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Magnetite Mineralization inside Cross-Linked Protein Crystals

  • Mariia Savchenko
    Mariia Savchenko
    Departamento de Química Orgánica, Facultad de Ciencias, Unidad de Excelencia de Química Aplicada a Biomedicina y Medioambiente (UEQ), Universidad de Granada, 18002 Granada, Spain
    Laboratorio de Estudios Cristalográficos, Instituto Andaluz de Ciencias de la Tierra (Consejo Superior de Investigaciones Científicas-Universidad de Granada), Avenida de las Palmeras 4, 18100 Armilla, Granada, Spain
    Departamento de Física Aplicada, Facultad de Ciencias, Universidad de Granada, 18002 Granada, Spain
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  • , 
  • Victor Sebastian
    Victor Sebastian
    Department of Chemical Engineering and Environmental Technology, Instituto de Nanociencia y Materiales de Aragón (INMA), CSIC-Universidad de Zaragoza, Zaragoza 50009, Spain
    Networking Research Center on Bioengineering Biomaterials and Nanomedicine (CIBER- BBN), Madrid 28029, Spain
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    Orcidhttps://orcid.org/0000-0002-6873-5244
  • , 
  • Modesto Torcuato Lopez-Lopez
    Modesto Torcuato Lopez-Lopez
    Departamento de Física Aplicada, Facultad de Ciencias, Universidad de Granada, 18002 Granada, Spain
    Instituto de Investigación Biosanitaria ibs, Granada 18012, Spain
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    Orcidhttps://orcid.org/0000-0002-9068-7795
  • , 
  • Alejandro Rodriguez-Navarro
    Alejandro Rodriguez-Navarro
    Departamento de Mineralogía y Petrología, Facultad de Ciencias, Universidad de Granada, 18002 Granada, Spain
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    Orcidhttps://orcid.org/0000-0003-2674-7383
  • , 
  • Luis Alvarez De Cienfuegos*
    Luis Alvarez De Cienfuegos
    Departamento de Química Orgánica, Facultad de Ciencias, Unidad de Excelencia de Química Aplicada a Biomedicina y Medioambiente (UEQ), Universidad de Granada, 18002 Granada, Spain
    Instituto de Investigación Biosanitaria ibs, Granada 18012, Spain
    *Email: [email protected]. Tel.: (+34) 958 248099.
    More by Luis Alvarez De Cienfuegos
    Orcidhttps://orcid.org/0000-0001-8910-4241
  • , 
  • Concepcion Jimenez-Lopez*
    Concepcion Jimenez-Lopez
    Departamento de Microbiología, Facultad de Ciencias, Universidad de Granada, Campus de Fuentenueva s/n, 18002 Granada, Spain
    *Email: [email protected]. Tel.: (+34) 958 249833.
    More by Concepcion Jimenez-Lopez
    Orcidhttps://orcid.org/0000-0002-5645-2079
  • , and 
  • José Antonio Gavira*
    José Antonio Gavira
    Laboratorio de Estudios Cristalográficos, Instituto Andaluz de Ciencias de la Tierra (Consejo Superior de Investigaciones Científicas-Universidad de Granada), Avenida de las Palmeras 4, 18100 Armilla, Granada, Spain
    *Email: [email protected]. Tel.: (+34) 958 525586.
    More by José Antonio Gavira
    Orcidhttps://orcid.org/0000-0002-7386-6484
Cite this: Cryst. Growth Des. 2023, 23, 6, 4032–4040
Publication Date (Web):April 28, 2023
https://doi.org/10.1021/acs.cgd.2c01436

Copyright © 2023 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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Crystallization in confined spaces is a widespread process in nature that also has important implications for the stability and durability of many man-made materials. It has been reported that confinement can alter essential crystallization events, such as nucleation and growth and, thus, have an impact on crystal size, polymorphism, morphology, and stability. Therefore, the study of nucleation in confined spaces can help us understand similar events that occur in nature, such as biomineralization, design new methods to control crystallization, and expand our knowledge in the field of crystallography. Although the fundamental interest is clear, basic models at the laboratory scale are scarce mainly due to the difficulty in obtaining well-defined confined spaces allowing a simultaneous study of the mineralization process outside and inside the cavities. Herein, we have studied magnetite precipitation in the channels of cross-linked protein crystals (CLPCs) with different channel pore sizes, as a model of crystallization in confined spaces. Our results show that nucleation of an Fe-rich phase occurs inside the protein channels in all cases, but, by a combination of chemical and physical effects, the channel diameter of CLPCs exerted a precise control on the size and stability of those Fe-rich nanoparticles. The small diameters of protein channels restrain the growth of metastable intermediates to around 2 nm and stabilize them over time. At larger pore diameters, recrystallization of the Fe-rich precursors into more stable phases was observed. This study highlights the impact that crystallization in confined spaces can have on the physicochemical properties of the resulting crystals and shows that CLPCs can be interesting substrates to study this process.

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Synopsis

Cross-linked protein crystals provide a well-ordered decorated channel array to study inorganic precipitation in confined space of modulable size and physicochemical properties.

1. Introduction

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There are a number of very relevant processes (nucleation, growth, phase transformation, etc.) that occur in confined spaces, such as those taking place during biomineralization, (1,2) methods to form nanomaterials, (3,4) frost heave scale formation, (5) etc., that require our attention and dipper understanding of how crystallization processes in these small cavities occur. These processes can provide valuable information about the weathering and decay of construction materials, (6) contribute to developing strategies for the remediation of contaminants, (7) and have a significant impact on different research areas such as pharmaceuticals, material science, nanomaterials, biomineralization, and geochemistry. (5,8) Additionally, crystallization in confinement can alter nucleation rates, as well as crystal size, polymorph, morphology, and orientation, (5,9−13) so research in this area contributes to increasing knowledge in the field of crystallization, and therefore, it is important from a fundamental point of view. One example of a nanocrystal formed in a confined space is the magnetosome of magnetotactic bacteria. Although the biomineralization process of the magnetosome is not well known, it has been proven that the nucleation and growth of the magnetic crystal forming the magnetosome occur in confined vesicles, modulated by the interaction with different magnetosome membrane proteins, resulting in crystals with a homogeneous size and morphology with excellent magnetic properties. (14) In particular, the formation of a ferrihydrite metastable precursor has been demonstrated during this biomineralization process, which later crystallizes into the stable mineral form (i.e., magnetite). (15−17) Little is, however, known about the formation of these precursors, their stability, their maturation, and whether or not their formation is linked to the confinement. A better understanding of the role of confinement in magnetite formation is not only interesting from a fundamental point of view, but also to produce novel magnetite nanoparticles with defined sizes that might be of potential interest in technological application.
One of the challenges in the study of crystallization in confined spaces is the selection of an appropriate experimental setup and analysis techniques. In fact, understanding the effects of confinement relies on the ability to analyze those effects on crystals isolated from this environment or preferably, to perform the analysis in situ, directly in the confined space. This analysis, in most of the cases, is not simple to do and is restrained to the use of few techniques such as electron microscopies, X-ray tomography, and X-ray or neutron diffraction. (5) Furthermore, to clearly understand the effects of confinement on crystallization, simultaneous analysis of the solution surrounding the confined space must be performed.
Another challenge is the nature or type of the confined space, which has to be able to modify the kinetics or thermodynamics of the crystallization by reducing the three dimensions of the system, preferably in a well-defined manner. Different systems have been studied, such as droplets/microfluidic devices, (18−23) as well as materials that have pores of different sizes, (24) like polymeric matrices, (25−28) microporous and mesoporous materials, glasses, (29,30) or carbon nanotubes. (31−33) In this context, porous protein crystals have the potential to become an interesting confined space to study crystallization thanks to their well-defined and regular distribution of pores (solvent channels), as well as their defined chemical composition reproduced regularly in the crystal lattice. (34,35)
Although protein crystals are mechanically unstable, cross-linking these crystals can improve their stability and maintain their shape and catalytic activity or being used as heterogeneous catalysts even after being dry for preservation. (36−38) In fact, cross-linked protein crystals (CLPCs) have been explored for the formation of new inorganic or hybrid materials (39) by a process that implies metal or chemical coordination with the amino acids exposed to the solvent channels and a subsequent reduction or precipitation of the particles. (34) This technique has been used to obtain well-ordered arrays of metallic nanoparticles of Pd/Pt, (40) Ag, (41−43) Au, (41,43−45) Co/Pt, (46) and CdS quantum dots, (47) giving rise to composite protein crystals with new catalytic and optical properties.
Herein, as a model to understand better crystal formation in confined spaces, we have studied the nucleation and growth of magnetite nanoparticles inside the channels of CLPCs formed by coprecipitation of ferrous and ferric iron in alkaline aqueous solution. CLPCs act as reaction vessels in which the nucleation and growth of magnetite can be affected by a confined growth modulated by chemical interactions. CLPCs of different pore sizes such as tetragonal lysozyme (2.0 nm Ø), orthorhombic glucose isomerase (3.5 nm Ø), and hexagonal lipase (8.0 nm Ø) have been used in this study (Figure 1). The characterization of magnetite particles has been carried out in situ directly from nanometric slides of CLPCs visualized by transmission electron microscopy (TEM). High-resolution transmission electron microscopy (HR-TEM) of thin slides of each mineralized CLPC was carried out to characterize the nanoparticles and for detection of diffraction using selected area electron diffraction (SAED).

Figure 1

Figure 1. (A) Optical micrograph of each protein crystal: A1─lysozyme; A2─glucose isomerase; A3─lipase. (B) Crystal structures: B1─lysozyme; B2─glucose isomerase; B3─lipase. (C) Schematic picture describing magnetite precipitation inside pores of CLPCs.

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2. Materials and Methods

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2.1. Reagents and Materials

2.1.1. Reagents for Protein Crystallization and Cross-Linking

Lysozyme (62971, HEWL, three-times crystallized powder), sodium acetate (AcONa 99%), sodium chloride (NaCl 99%), magnesium chloride (MgCl2 ≥98%), monopotassium phosphate (KH2PO4 ≥99.0%), monosodium phosphate (NaH2PO ≥99.0%), HEPES (≥99.5%), NaH2PO TRIS (99.9%), and glutaraldehyde solution (Grade II, 25% in H2O) were purchased from Sigma-Aldrich (Madrid, Spain). Glucose isomerase D-xylose-ketol-isomerase from Streptomyces rubiginosus was purchased as a crystal suspension from Hampton Research (HR7–100). Lipase (Aspergillus sp) was purchased from Biocon as Biolipasa-L (Barcelona, Spain).
Lysozyme was dissolved in 50 mM AcONa, dialyzed (24 h) against 50 mM AcONa (pH 4.5) in a ratio 1:1000 at 4 °C and concentrated by centrifugation at 4 °C (g = *5000/25 min) to ≈150 mg mL–1, using a theoretical value for the extinction coefficient at 280 nm of 2.56 mL mg–1. Glucose isomerase was dialyzed for 24 h against HEPES 100 mM pH 7.0 at a ratio 1:1000 at 4 °C and concentrated by centrifugation at 4 °C (g = *5000/1 h) to ≈75 mg mL–1 using a theoretical value for the extinction coefficient at 280 nm of 1.074 mL mg–1. Lipase was dialyzed for 24 h against Milli-Q water at a ratio 1:1000 at 4 °C and also concentrated by centrifugation at 4 °C (g = *5000/4 h) to ≈40 mg mL–1 using a theoretical value for the extinction coefficient at 280 nm of 1.2 mL mg–1. Prior to the experimental setup, all the protein solutions were filtered through a 0.45 μm pore-size filter membrane system (Millipore).
The precipitant solutions (NaCl, MgCl2, K/NaH2PO4) with desirable concentration were obtained from their stock solution by diluting with appropriate buffer (50 mM AcONa pH 4.5; 0.01 M HEPES pH 7.0; 0.1 M TRIS pH 7.0). Then, the solutions were filtered through a 0.45 μm pore-size filter membrane system (Millipore).
Agarose D-5 was purchased from Hispanagar (Madrid, Spain). Sol of agarose with desirable concentration was obtained by dissolving agarose in Milli-Q water and heating at 90 °C until obtaining a homogeneous transparent solution. Then the solution was cooled down to 70 °C.

2.1.2. Reagents for Magnetite Precipitation

NaHCO3, Na2CO3, NaOH, Fe(ClO4)2, and FeCl3 were purchased from Sigma-Aldrich. The stock solutions, NaHCO3/Na2CO3 (0.15 M/0.15 M), NaOH (1 M), Fe(ClO4)2 (0.5 M), and FeCl3 (1 M), were prepared with deoxygenated water inside an anaerobic chamber (Coy Laboratory Products, Grass Lake, MI) filled with 4% H2 in N2.

2.2. Production of CLPCs

Protein crystals were obtained by a batch method. Lysozyme crystals were grown in 0.2% w/v agarose using 30 mg mL–1 lysozyme solution, 3% NaCl, and 50 mM NaOAc buffer pH 4.5. Glucose isomerase crystals were obtained in 0.1% w/v agarose using 30 mg mL–1 of protein solution, 0.2 M solution of MgCl2, and 0.01 M HEPES buffer pH 7.0. Lipase crystals were obtained in 0.2% w/v agarose using 15 mg mL–1 lipase solution and 0.3 M solution of K/NaH2PO4 and 0.1 M TRIS buffer pH 7.0. All concentrations are final after mixing all components.
CLPCs (cross-linked protein crystals): CLLCs (cross-linked lysozyme crystals), CLGICs (cross-linked glucose isomerase crystals) and CLLPCs (cross-linked lipase crystals) were obtained by diffusion of isotonic 5% v/v glutaraldehyde solution through the agarose gel of the batches at 20 °C for 24 h. For enhanced cross-linking, in case of glucose isomerase and lipase crystals, they were additionally soaked in 10% v/v glutaraldehyde solution for 24 h at 20 °C. To avoid an osmotic shock, before using the CLPCs, crystals were sequentially transferred through a series of precipitant solutions at lower precipitant concentration than used for crystallization.

2.3. In Situ Formation of Magnetite

2.3.1. Precipitation of Magnetite in CLPCs

Two types of experiments (Types 1 and 2) were done to study magnetite precipitation in different environments. In both cases, CLPCs (lysozyme, glucose isomerase, and lipase crystals) were placed in a glass vial inside an anaerobic COY chamber filled with 4% H2 in N2.
The master solution was prepared inside the anaerobic chamber in 10 mL to a final concentration of 2.78 mM Fe(ClO4)2, 3.5 mM NaHCO3, 3.5 mM Na2CO3, and 5.56 mM FeCl3. The procedure is described by Perez-Gonzalez et al. (48)
Figure 2 represents schematically the two types of experiments. The initial one, named Type 1, in which CLPCs were exposed to the magnetite precipitation procedure only one time and Type 2 for which iron solution was freshly renewed “n” times.

Figure 2

Figure 2. Event sequence in protocol Type 1: (1) CLPCs are added to the master solution (NaHCO3/Na2CO3, Fe(ClO4)2, and FeCl3), (2) incubation of the CLPCs to allow iron diffusion, (3) initiation of the precipitation by the addition of NaOH and changing the pH to 12.5, (4) precipitation of magnetite, and (5) fishing out the CLPCs for the analysis. Type 2 “Cycles”: (1) 100 CLPCs are added in the master solution, (2) incubation, (3) initiation, (4) precipitation of magnetite, and (5) at least two CLPCs are preserved for characterization and the rest of the crystals are placed in a fresh master solution to start a new cycle, up to nine cycles.

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2.3.1.1. Type 1
CLPCs (min three crystals of each protein) were placed in a vial with the master solution and incubated for 4 to 12 days to allow iron ions to diffuse within crystal pores. Each experiment was set up in triplicate.
Precipitation was triggered by increasing the pH adding NaOH under anaerobic conditions (COY chamber), and the pH was recorded after each experiment. In the initial phase of the experiment, the pH was varied from 8.0 to 12.5 by increasing NaOH concentration. As expected, pH 12.5 (0.125 mL of 2.5 M NaOH) was chosen as the best condition to produce a higher number of nanoparticles inside CLPCs. This condition was established to further follow the precipitation of iron oxide particles within CLPCs. After adding NaOH, crystals were kept inside the anaerobic COY from 2 weeks to 6 months.
2.3.1.2. Type 2
In these experiments, iron solution was renewed to avoid its potential depletion due to, i.e., the growth of magnetite in the bulk solution. We followed a similar protocol to that in Type 1. CLPCs (100 crystals of each protein) were placed in the vial containing the master solution and incubated for 4 days (as determined in Type 1 experiments). The precipitation of iron oxides was triggered by increasing the pH to 12.5, adding 0.125 mL of 2.5 M NaOH, and kept inside the anaerobic COY for 10 days (Cycle 1). Then, at least two crystals of each protein were taken for characterization, and the rest was placed in a new vial containing the freshly prepared master solution to start the new cycle (Cycle 2). This process was repeated nine times except for lipase (CLLPCs), because crystals lost their integrity after the second cycle.

2.3.2. Precipitation of Magnetite in the Absence of CLPCs

To evaluate the formation and growth of magnetite nanoparticles in the absence of CLPC (control), a series of experiments were performed following the same protocol as explained above but in the absence of CLPC. Therefore, a vial containing 98,75 mL of master solution was prepared as detailed above, and 1.25 mL of 2.5 M NaOH was added to increase the pH of the master solution to 12.5. After adding NaOH, the sample was homogenized and aliquoted in 10 different bottles. After 14 days (the time equivalent to the full cycle in Type 2 experiments), a sample was collected out of the chamber for evaluation by (HR)TEM.

2.4. Characterization

2.4.1. (HR)TEM Sample Characterization

For TEM (FEI-TECNAI T20 at 200 kV and LIBRA 120 PLUS Carl Zeiss, Germany) observation, CLPCs were dehydrated with ethanol and embedded in Epoxy Resin: EMbed-812 from EMS (Electron Microscopy Sciences). Ultrathin sections (50–70 nm) were prepared using a Reichert Ultracut S microtome (Austria, Vienna) after which the cuts were deposited onto G300 Mesh Square Copper (Agar Scientific). The control magnetite nanoparticles were put onto CF200-Cu Carbon Film, Mesh 200 Copper (EMS) grids. The distribution, size, growth, and evolution of formed iron oxides nanoparticles inside the pores of CLPCs and in control samples were analyzed.
The elemental analysis and diffraction patterns (d-spacing by using SAED) of the iron oxide nanoparticles were analyzed with high-resolution HR-TEM, FEI TITAN G2 (The Netherlands) and Philips CM20 equipped with energy-dispersive X-ray microanalysis. To determine d-spacings from SAED patterns, measurements were taken horizontally and vertically and average to diminish camera distortions.

2.5. Statistical Analysis

The size, number, distribution, and diffraction patterns of the nanoparticles were analyzed with ImageJ 1.53e software from TEM micrographs. An average number of 100 nanoparticles per sample were measured to calculate size distribution from at least two different TEM micrographs. For nanoparticle distribution along the CLPCs, TEM micrographs were divided into 100 zones of equal area (182.5 nm2). From these 100 zones, we randomly pick three zones near the center of the crystal and another 3 near the border to count and measured all the particles. The statistical analyses were done with OriginPro 2021. The difference between the number of the nanoparticles near the border and in the center was evaluated by the one-way analysis of variance test and the size distribution by the Kruskal–Wallis test. The p-values have been compared with the significance level to evaluate the null hypothesis where there were no differences between means or when the null hypothesis indicates that the population means are all equal. A significance level type I error of 0.05 was considered to be the minimum accepted level that denotes a difference between means. The notation that we have included hereafter is * p < 0.05, ** p < 0.001, and *** p < 0.0001 when the differences between means are statistically significant.
Iron oxide nanoparticle distribution inside lysozyme crystals was evaluated from the border to the center of a CLLC along a crystal section. The TEM image was converted to a black and white image and divided the length of the crystal in eight sections of 135 nm (see Figure S3 for details). Then the black/white ratio was calculated using the image analysis software ImageJ 1.53e. The value “0” (black) was indicative of the presence of iron oxide particles, and the value “255” (white) corresponds to the absence of nanoparticles.

3. Results and Discussion

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CLLCs were studied in greater detail as a model to understand the evolution of the confined magnetite precipitation. TEM images of thin slides of CLLCs showed clearly distinct areas (Figure 3A). On one of these areas was the bulk (here referred as outside) in which magnetite crystals of size ∼3–15 nm and similar shape, even a bit smaller than those formed in the control sample (∼3–25 nm) were clearly observed (Figure 3A superior right corner versus Figure 3B). The mineral phase was determined by SAED analyses of those crystals (Figure 4A2), and d-spacing was calculated and compared to that in the relevant literature matching those referenced for magnetite. (28,49) This precipitation outside CLLCs acted as a positive control, showing that mineral formation was allowed in the system. A second area located along a semicircular border (Figure 3A) showed again the presence of particles of similar size to those obtained in the bulk (outside). This border was delimiting the area of the protein crystal.

Figure 3

Figure 3. TEM images of (A) iron oxide nanoparticles grown in CLLC experiments (four cycles) inside and outside the protein crystal and (B) in the bulk (protein free) experiment (four cycles).

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Figure 4

Figure 4. TEM images of magnetite grown outside (A1) and iron oxides nanoparticles inside (B1, C1, and D1) CLLCs after cycle number 2 (A1 and B1), 4 (C1), and 8 (D1). SAED diffraction images are shown in A2, B2, C2, and D2 (insets correspond to the diffraction area). Only crystals obtained outside CLLCs showed SAED diffraction pattern consistent with magnetite (A2) (see also Figure S2).

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Finally, a completely different third area was observed (Figure 3A, inside) in which iron oxide nanoparticles (Fe presence confirmed by EELS) of extremely small size (∼2 nm) were found. It is interesting to note that these nanoparticles were very homogenous in size and were distributed along the whole area inside the CLLCs, and this holds true for all the CLPCs studied. These results show that the conditions (supersaturation) under which this Fe phase was precipitating inside protein crystals were different from those occurring in the bulk. Moreover, given the homogeneity in the size of nanoparticles precipitated inside CLLCs, and considering that the pore size of lysozyme is also of approximately 2 nm, (50) these results also seem to point out a potential effect of the pore size on the particle formation inside CLLCs.
However, when the same experiment was identically performed but kept for a longer period of time (6 months), no nanoparticles were observed by TEM inside the CLLC. CLLCs did not show any signal of collapse or alteration. However, crystals were still obtained outside of the CLLC, again, showing a size and morphology that compare to that of the crystals formed in the control experiment (protein free) (Figures 3B and S3). These results indicate that those extremely small nanoparticles observed inside the CLLC at shorter period of times were, in fact, Fe-rich metastable intermediates that acted as the iron reservoir. During the time course experiment, and due to the mineral (magnetite) precipitation in the bulk, the supersaturation with respect to the relevant Fe-rich phase decreased outside of CLLCs, forcing the dissolution of these Fe-rich intermediates inside CLLCs.
To further study the process and to avoid Fe depletion in the bulk, a sequential time-lapse strategy was designed in which loading of the crystals with iron solution (4 days) and precipitation in basic media (10 days) were repeated nine times (here referred to as cycles) (Type 2 protocol). CLLPCs and CLGICs were also included in the set of experiments to further study the effect of the pore size on the growth of the Fe-rich phase inside the protein crystals, since they had wider pore channels than that of lysozymes (8.0 nm Ø for CLLPCs and 3.5 nm Ø for CLGICs, as determined from the crystal packing) (Figure 1).
Nanoparticle precipitation in the bulk (outside, Figure 4A1) was observed from the first cycle in all experiments, those nanoparticles having SAED patterns consistent with magnetite (Figure 4A2). On the contrary, nanoparticles inside CLLCs were only observed after the second cycle and held thereafter (Figure 4), and EDX analysis confirmed the presence of iron (Figure S1). These nanoparticles were similar in size (∼2.0 nm) to those obtained following the previous (Type 1) protocol and matched very well the channel diameter of the lysozyme crystals (∼2.0 nm Ø), suggesting a potential physical barrier restraint over nanoparticle growth. SAED patterns only show two diffuse rings that come from the carbon background, suggesting that the 2 nm nanoparticles are amorphous (Figure 4B2,C2,D2).
Similarly, after two cycles of incubation for CLGICs and one cycle for CLLPCs, Fe-rich nanoparticle formation was also detected (Figure 5A,B). TEM images of these nanoparticles showed similar results, in terms of size, homogeneity, and location distribution than those yielded for the nanoparticles inside lysozyme crystals (Figure 5C).

Figure 5

Figure 5. TEM images of iron oxides nanoparticles grown within CLGICs (A) and CLLPCs (B) after two and one cycles, respectively. The plot (C) shows the average nanoparticle particle size for the three proteins after the first cycle.

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SAED results confirmed that the iron oxide nanoparticles formed inside CLGICs were crystals of magnetite from the second cycle (Figure 6 and Table S1). Unfortunately, CLLPCs did not survive more than two cycles of iron oxide precipitation avoiding any further analysis and comparison (Figure S4). In all cases, the size of these magnetite nanoparticles formed inside the protein crystals channels is significantly different from that of the nanoparticles formed outside or in the control experiment, which grew over time (Figure 7). Interestingly, this growth over time that was observed in the magnetite nanoparticles formed outside the protein or in the control experiments was prevented inside the protein crystal channels (Figure 7).

Figure 6

Figure 6. HR-TEM images of magnetite grown inside CLGICs after cycle 2 (A1), cycle 4 (B1), cycle 6 (C1), and cycle 8 (D1) and the corresponding SAED diffraction images of selected regions (insets in A2, B2, C2, and D2). C2 shows single crystal spots corresponding to 111 magnetite reflections. Indexation of all images is shown in Table S1.

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Figure 7

Figure 7. Mean size of magnetite nanoparticles formed inside pores of CLLCs and CLGICs and in solution without CLPCs (control), big standard deviation in the controls appears due to the heterogeneous size of the particles.

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The nanoparticle growth process may be restricted by one and/or the combination of the following circumstances: (1) following upon Fe depletion due to an insufficient Fe flux; (2) by physical barrier constrain caused by the protein crystal porous size; and/or (3) by the stabilization of the nuclei (negatively charged) with the positively charged residues in the protein. It has been previously demonstrated that nuclei can be stabilized because of the electrostatic interaction between the protein positively charged functional groups and the negatively charged mineral surfaces. (51,52) In fact, while the hydrated surface of magnetite remains basically uncharged at neutral pH as a consequence of the dominant neutral surface species ≡Fe(II,III)OH, as the pH value increases, Fe(II,III)OH becomes dominant, and, at even higher pH values, the dominant species are Fe(II,III)O–, being, in these conditions, the surface of magnetite negatively charged (53) and thus able to interact and be stabilized by positively charged residues in the pore channel.
In the case of lysozyme crystals, once the bulk solution enters the channel system of the protein, a localized Fe-rich phase nucleation is expected following an ionotropic effect triggered by a local high supersaturation with respect to magnetite induced by the acidic residues present in the channel. Those nuclei keep growing as the income of Fe continues, but, once they reach the size of the CLLC pore channel (2 nm), (1) the mineral fills the pore and the surface of the nanoparticles start interacting with the residues in the channel (possibly positive residues) and (2) new Fe incomes are impeded because of pore clogging. The interaction between the mineral and the protein residues in the channel stabilizes the particles and prevents further growth. Under these conditions, Fe-rich particles formed inside lysozyme crystal are not able to grow any further. They stay stable as a metastable phase and may dissolve over time when the bulk becomes undersaturated with respect to magnetite, as it is well known that amorphous phases are more soluble than crystalline ones. Interestingly, our observation of the formation of an Fe-rich metastable phase is consistent with previous results, (15−17) which observed the formation of a ferrihydrite metastable precursor that later crystallized into magnetite. Therefore, in the case of lysozyme crystals, it seems that the diameter of the channel is determinant for the nanoparticle size and to avoid the transition from the metastable precursor to the crystalline phase.
Different is the scenario for CLLPCs and CLGICs. As in CLLCs, the nucleation of an Fe-rich phase induced by an ionotropic effect is expected due to the presence of acidic residues in the protein channels. However, being the channel pore size larger than in CLLC, two main differences can be pointed out with respect to what occurred in CLLC: (1) the flux of Fe into the protein crystal channel is not blocked, as the size of the nuclei (2–3 nm) is smaller than the diameter of the channel, and (2) the interaction between the mineral surface and the channel protein residues is more limited, as the mineral does not fill the pore. These facts would result in a lack of mineral stabilization and the possibility for a recrystallization of the potential precursor into the more stable phase. SAED-HR-TEM analysis (Figure 6) of the Fe-rich nanoparticles formed inside CLGICs (3.5 nm pore channel) showed that these nanoparticles presented diffraction peaks in all the evaluated cycles. The identification of (111) and (311) crystal faces from the diffraction pattern confirmed the presence of crystalline magnetite. This result is quite interesting since it shows that the nanoparticles are able to restructure from amorphous to crystalline, although a significant size change was not observed. Although, the most usual mechanism for this transformation is a dissolution-precipitation mechanism, in the case of the transformation within CLGICs, the transition from amorphous to magnetite may be triggered by the continuous increase of supersaturation since iron diffusion is not impeded. At this point, we cannot explain why magnetite particles grow to reach the pore size of CLGICs.
The flux of iron from the bulk solution to the protein channels induced a gradient in the concentration of nanoparticles from a higher concentration near the border of the crystal to a lower concentration the farther from the border going inside the protein crystal, as it can be seen in Figure 8A which is a TEM image of CLGICs after 8 cycles. Figure 8B shows that the number of particles near the border is practically the triple with respect to that of the particles inside the protein crystal, that holding true for both CLLCs and CLGICs. No statistically significant differences were observed in the size of the nanoparticles from each group among the two crystalline proteins, but differences were observed between the size of the crystals inside and in the border, pointing again to an effect of confinement during the precipitation of iron oxides particles (Figure 8C).

Figure 8

Figure 8. (A) TEM image of CLGICs after eight cycles which illustrates the distribution of magnetite nanoparticles. Particle distribution was calculated along the length of the crystal by determining the black/white ratio in eight regions of 135 nm each and plotted in the insert. (B) Number and (C) size of the magnetite nanoparticles formed near and far from the border of the CLPCs, based on TEM images from the ninth cycle.

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4. Conclusions

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Herein, we have studied the aqueous coprecipitation of iron oxide salts at room temperature inside CLPCs. The use of CLPCs has allowed us to study how chemical and physical factors can influence magnetite mineralization in a confined space. Our results have shown that nucleation of an Fe-rich phase occurs inside the protein channels in all cases, but the channel diameter size is important to stabilize metastable precursor, thus preventing their recrystallization into the more stable phases, magnetite. Smallest pore sizes impose physical barriers that make more likely the (1) stabilization of the metastable precursors by the chemical interaction of the nanoparticles with the protein functional groups and (2) restrained Fe diffusion into the channel system. A bigger pore size allows the transition from metastable precursor to crystalline particles as observed with CLGICs. These results have shown the drastic effects that crystallization inside CLPCs can have in the mineralization of magnetite. Finally, we have also proven that CLPCs can be interesting biomimetic porous materials to study crystallization processes in confined spaces.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.cgd.2c01436.

  • Figure S1: Elemental analysis of CLLCs, Figure S2 d-spacing values of the diffraction pattern shown in Figure 4A2; Table S1. d-spacing values of the diffraction pattern shown in Figure 6A2,B2,C2,D2; Figure S3: Protocol for iron oxide nanoparticle distribution determination; Figure S4: magnetite crystals grown in the bulk (protein free); Figure S5: HR-TEM and SAED of CLLPCs (PDF)

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Author Information

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  • Corresponding Authors
    • Luis Alvarez De Cienfuegos - Departamento de Química Orgánica, Facultad de Ciencias, Unidad de Excelencia de Química Aplicada a Biomedicina y Medioambiente (UEQ), Universidad de Granada, 18002 Granada, Spain;  Instituto de Investigación Biosanitaria ibs, Granada 18012, Spain;  Orcidhttps://orcid.org/0000-0001-8910-4241;  Email: [email protected]
    • Concepcion Jimenez-Lopez - Departamento de Microbiología, Facultad de Ciencias, Universidad de Granada, Campus de Fuentenueva s/n, 18002 Granada, Spain;  Orcidhttps://orcid.org/0000-0002-5645-2079;  Email: [email protected]
    • José Antonio Gavira - Laboratorio de Estudios Cristalográficos, Instituto Andaluz de Ciencias de la Tierra (Consejo Superior de Investigaciones Científicas-Universidad de Granada), Avenida de las Palmeras 4, 18100 Armilla, Granada, Spain;  Orcidhttps://orcid.org/0000-0002-7386-6484;  Email: [email protected]
  • Authors
    • Mariia Savchenko - Departamento de Química Orgánica, Facultad de Ciencias, Unidad de Excelencia de Química Aplicada a Biomedicina y Medioambiente (UEQ), Universidad de Granada, 18002 Granada, Spain;  Laboratorio de Estudios Cristalográficos, Instituto Andaluz de Ciencias de la Tierra (Consejo Superior de Investigaciones Científicas-Universidad de Granada), Avenida de las Palmeras 4, 18100 Armilla, Granada, Spain;  Departamento de Física Aplicada, Facultad de Ciencias, Universidad de Granada, 18002 Granada, Spain
    • Victor Sebastian - Department of Chemical Engineering and Environmental Technology, Instituto de Nanociencia y Materiales de Aragón (INMA), CSIC-Universidad de Zaragoza, Zaragoza 50009, Spain;  Networking Research Center on Bioengineering Biomaterials and Nanomedicine (CIBER- BBN), Madrid 28029, Spain;  Orcidhttps://orcid.org/0000-0002-6873-5244
    • Modesto Torcuato Lopez-Lopez - Departamento de Física Aplicada, Facultad de Ciencias, Universidad de Granada, 18002 Granada, Spain;  Instituto de Investigación Biosanitaria ibs, Granada 18012, Spain;  Orcidhttps://orcid.org/0000-0002-9068-7795
    • Alejandro Rodriguez-Navarro - Departamento de Mineralogía y Petrología, Facultad de Ciencias, Universidad de Granada, 18002 Granada, Spain;  Orcidhttps://orcid.org/0000-0003-2674-7383
  • Author Contributions

    M.S.: Formal analysis, investigation, and validation; V.S.: Investigation and validation; A.R.-N.: Investigation and validation; M.T.L.-L: Funding acquisition and formal analysis; L.A.d.C.: Conceptualization, funding acquisition, methodology, project administration, supervision, writing-original draft, and writing─review and editing; C.J.-L.: Conceptualization, funding acquisition, methodology, project administration, supervision, writing-original draft, and writing─review and editing; J.A.G.: Conceptualization, funding acquisition, methodology, project administration, supervision, writing-original draft, and writing─review and editing.

  • Funding

    This study was supported by projects PID2020-116261GB-I00 (J.A.G.), PID2020-118498GB-I00 (L.A.d.C.) and PDC2021-121135.100 (C.J.L.) of the Ministerio de Ciencia e Innovación, MCIN/AEI/10.13039/501100011033 and by projects P18-FR-3533 and A-FQM-340-UGR20 of the FEDER/Junta de Andalucía-Consejería de Transformación Económica, Industria, Conocimiento y Universidades (Spain). Thanks go to Unidad Cientifica de Excelencia UCE-PP2016-05 and Instituto de Biotecnología of the University of Granada for their assistance.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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Thanks go to the CIC personnel, Juan de Dios Bueno Pérez, Ma José Martínez Guerrero and Ma del Mar Abad Ortega, of the University of Granada for technical assistance. VS acknowledges the use of instrumentation as well as the technical advice provided by the National Facility ELECMI ICTS, node “Laboratorio de Microscopias Avanzadas (LMA)” at “Universidad de Zaragoza”. We are really thankful to Professor Helmut Cölfen for the careful reading of the manuscript, suggestions, and corrections.

References

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This article references 53 other publications.

  1. 1
    Mann, S. Biomineralization: Principles and Concepts in Bioinorganic Materials Chemistry; Oxford chemistry masters; Oxford University Press, 2001.
    Google Scholar
    There is no corresponding record for this reference.
  2. 2
    Mañas-Torres, M. C.; Ramírez-Rodríguez, G. B.; García-Peiro, J. I.; Parra-Torrejón, B.; Cuerva, J. M.; Lopez-Lopez, M. T.; Álvarez De Cienfuegos, L.; Delgado-López, J. M. Organic/Inorganic Hydrogels by Simultaneous Self-Assembly and Mineralization of Aromatic Short-Peptides. Inorg. Chem. Front. 2022, 9, 743– 752,  DOI: 10.1039/d1qi01249e
    Google Scholar
    2
    Organic/inorganic hydrogels by simultaneous self-assembly and mineralization of aromatic short-peptides
    Manas-Torres, Mari C.; Ramirez-Rodriguez, Gloria B.; Garcia-Peiro, Jose I.; Parra-Torrejon, Belen; Cuerva, Juan M.; Lopez-Lopez, Modesto T.; Alvarez de Cienfuegos, Luis; Delgado-Lopez, Jose M.
    Inorganic Chemistry Frontiers (2022), 9 (4), 743-752CODEN: ICFNAW; ISSN:2052-1553. (Royal Society of Chemistry)
    Self-assembled peptides and proteins have turned out to be excellent templates for the growth of inorg. minerals and can be used to emulate natural biomineralization processes. Doing this, researchers have developed complex sophisticated materials with properties, in some cases, similar to those found in nature. Of special interest is the development of scaffolds able to guide bone regeneration. The bone tissue comprises an org. matrix composed of aligned collagen fibers contg. nanoapatite crystals oriented along the fiber direction. During bone mineralization, both processes, the self-assembly of collagen fibrils and mineralization occur simultaneously. Collagen fibers are able to control calcium phosphate nucleation and subsequent apatite crystal growth at a very limited range of collagen d. and ionic concn. In this study, we reproduced the simultaneity of both processes using an artificial peptide fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF) that has the ability to self-assemble in water after the addn. of Ca2+ ions. Therefore, the peptide self-assembly process and the mineralization of apatite are Ca-demanding processes and occur simultaneously. The role of peptide and ionic concns. has been investigated affording org./inorg. hybrid hydrogels with different degrees of homogeneity and mineralization. Interestingly, at very low Ca2+ concns., we found that apatite nanocrystals are integrated into Fmoc-FF fibrils and oriented as in biol. mineralized collagen fibrils, the basic building blocks of bone.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhsVWru7w%253D&md5=930373b1d8fb5346a38a16dead224e9c
  3. 3
    Meldrum, F. C.; Cölfen, H. Controlling Mineral Morphologies and Structures in Biological and Synthetic Systems. Chem. Rev. 2008, 108, 4332– 4432,  DOI: 10.1021/cr8002856
    Google Scholar
    3
    Controlling Mineral Morphologies and Structures in Biological and Synthetic Systems
    Meldrum, Fiona C.; Colfen, Helmut
    Chemical Reviews (Washington, DC, United States) (2008), 108 (11), 4332-4432CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtlOrs77N&md5=bd35b770d4028a5cbace58f7bf55e4b3
  4. 4
    Liu, Y.; Goebl, J.; Yin, Y. Templated Synthesis of Nanostructured Materials. Chem. Soc. Rev. 2013, 42, 2610– 2653,  DOI: 10.1039/c2cs35369e
    Google Scholar
    4
    Templated synthesis of nanostructured materials
    Liu, Yiding; Goebl, James; Yin, Yadong
    Chemical Society Reviews (2013), 42 (7), 2610-2653CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review. Templating is one of the most important techniques for the controlled synthesis of nanostructured materials. This powerful tool uses a pre-existing guide with desired nanoscale features to direct the formation of nanomaterials into forms that are otherwise difficult to obtain. As a result, templated synthesis is capable of producing nanostructures with unique structures, morphologies and properties. In this review, we summarize the general principles of templated synthesis and cover recent developments in this area. As a wide variety of synthesis techniques are utilized to produce nanomaterials using template-based methods, the discussion is organized around the various types of common templates. We examine the use of both phys. and chem. hard colloidal templates, soft templates, and other non-colloidal templates, followed by our perspective on the state of the field and potential future directions.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXmsFWnsL4%253D&md5=fdb40269482893466dbb120300637777
  5. 5
    Meldrum, F. F. C.; O’Shaughnessy, C.; O’Shaughnessy, C. Crystallization in Confinement. Adv. Mater. 2020, 32, 2001068  DOI: 10.1002/adma.202001068
    Google Scholar
    5
    Crystallization in Confinement
    Meldrum, Fiona C.; O'Shaughnessy, Cedrick
    Advanced Materials (Weinheim, Germany) (2020), 32 (31), 2001068CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Many crystn. processes of great importance, including frost heave, biomineralization, the synthesis of nanomaterials, and scale formation, occur in small vols. rather than bulk soln. Here, the influence of confinement on crystn. processes is described, drawing together information from fields as diverse as bioinspired mineralization, templating, pharmaceuticals, colloidal crystn., and geochem. Expts. are principally conducted within confining systems that offer well-defined environments, varying from droplets in microfluidic devices, to cylindrical pores in filtration membranes, to nanoporous glasses and carbon nanotubes. Dramatic effects are obsd., including a stabilization of metastable polymorphs, a depression of f.ps., and the formation of crystals with preferred orientations, modified morphologies, and even structures not seen in bulk. Confinement is also shown to influence crystn. processes over length scales ranging from the at. to hundreds of micrometers, and to originate from a wide range of mechanisms. The development of an enhanced understanding of the influence of confinement on crystal nucleation and growth will not only provide superior insight into crystn. processes in many real-world environments, but will also enable this phenomenon to be used to control crystn. in applications including nanomaterial synthesis, heavy metal remediation, and the prevention of weathering.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXht1Kisr%252FI&md5=7d9c8e72ef9e1c37c1eb582984bb2ab1
  6. 6
    Espinosa-Marzal, R. M.; Scherer, G. W. Advances in Understanding Damage by Salt Crystallization. Acc. Chem. Res. 2010, 43, 897– 905,  DOI: 10.1021/ar9002224
    Google Scholar
    6
    Advances in Understanding Damage by Salt Crystallization
    Espinosa-Marzal, Rosa M.; Scherer, George W.
    Accounts of Chemical Research (2010), 43 (6), 897-905CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
    A review. The single most important cause of the deterioration of monuments in the Mediterranean basin, and elsewhere around the world, is the crystn. of salt within the pores of the stone. Considerable advances have been made in recent years in elucidating the fundamental mechanisms responsible for salt damage. As a result, new methods of treatment are being proposed that offer the possibility of attacking the cause of the problem, rather than simply treating the symptoms. In this Account, we review the thermodn. and kinetics of crystn., then examine how a range of technol. innovations have been applied exptl. to further the current understanding of in-pore crystn. We close with a discussion of how computer modeling now provides particularly valuable insight, including quant. ests. of both the interaction forces between the mineral and the crystal and the stresses induced in the material. Analyzing the kinetics and thermodn. of crystal growth within the pores of a stone requires sensitive tools used in combination. For example, calorimetry quantifies the amt. of salt that ppts. in the pores of a stone during cooling, and dilatometric measurements on a companion sample reveal the stress exerted by the salt. Synchrotron X-rays can penetrate the stone and identify the metastable phases that often appear in the first stages of crystn. Atomic force microscopy and environmental SEM permit study of the nanometric liq. film that typically lies between salt and stone; this film controls the magnitude of the pressure exerted and the kinetics of relaxation of the stress. These exptl. advances provide validation for increasingly advanced simulations, using continuum models of reactive transport on a macroscopic scale and mol. dynamics on the at. scale. Because of the fundamental understanding of the damage mechanisms that is beginning to emerge, it is possible to devise methods for protecting monuments and sculptures. For example, chem. modification of the stone can alter the repulsive forces that stabilize the liq. film between the salt and mineral surfaces, thereby reducing the stress that the salt can generate. Alternatively, mols. can be introduced into the pores of the stone that inhibit the nucleation or growth of salt crystals. Many challenges remain, however, particularly in understanding the complex interactions between salts, the role of metastable phases, the mechanism of crack initiation and growth, and the role of biofilms.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXjtVyit74%253D&md5=4d98950284278e96893c9d8d7808f2bb
  7. 7
    Liang, Y.; Tsuji, S.; Jia, J.; Tsuji, T.; Matsuoka, T. Modeling CO2-Water-Mineral Wettability and Mineralization for Carbon Geosequestration. Acc. Chem. Res. 2017, 50, 1530– 1540,  DOI: 10.1021/acs.accounts.7b00049
    Google Scholar
    7
    Modeling CO2-Water-Mineral Wettability and Mineralization for Carbon Geosequestration
    Liang, Yunfeng; Tsuji, Shinya; Jia, Jihui; Tsuji, Takeshi; Matsuoka, Toshifumi
    Accounts of Chemical Research (2017), 50 (7), 1530-1540CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
    A review. Carbon dioxide (CO2) capture and storage (CCS) is an important climate change mitigation option along with improved energy efficiency, renewable energy, and nuclear energy. CO2 geosequestration, i.e., to store CO2 under the subsurface of Earth, is feasible because the world's sedimentary basins have high capacity and are often located in the same region of the world as emission sources. How CO2 interacts with the connate water and minerals is the focus of this Account. There are four trapping mechanisms that keep CO2 in the pores of subsurface rocks: (1) structural trapping, (2) residual trapping, (3) dissoln. trapping, and (4) mineral trapping. The first two are dominated by capillary action, where wettability controls CO2 and water two-phase flow in porous media. We review state-of-the-art studies on CO2/water/mineral wettability, which was found to depend on pressure and temp. conditions, salt concn. in aq. solns., mineral surface chem., and geometry. We then review some recent advances in mineral trapping. First, we show that it is possible to reproduce the CO2/water/mineral wettability at a wide range of pressures using mol. dynamics (MD) simulations. As the pressure increases, CO2 gas transforms into a supercrit. fluid or liq. at ∼7.4 MPa depending on the environmental temp. This transition leads to a substantial decrease of the interfacial tension between CO2 and reservoir brine (or pure water). However, the wettability of CO2/water/rock systems depends on the type of rock surface. Recently, we investigated the contact angle of CO2/water/silica systems with two different silica surfaces using MD simulations. We found that contact angle increased with pressure for the hydrophobic (siloxane) surface while it was almost const. for the hydrophilic (silanol) surface, in excellent agreement with exptl. observations. Furthermore, we found that the CO2 thin films at the CO2-hydrophilic silica and CO2-H2O interfaces displayed a linear correlation, which can in turn explain the const. contact angle on the hydrophilic silica surface. In view of the literature and our study results, a few recommendations seem necessary to construct a mol. system suitable to study wettability with MD simulations. Future work should be conducted to det. the influence of brine salinity on the wettability of minerals with high cation exchange capacity. Mineral trapping is believed to be an extremely slow process, likely taking thousands of years. However, a recent pilot study demonstrated that CO2 mineralization occurs within 2 years in highly reactive basalt reservoirs. A first-principles MD study has also shown that carbonation reactions occur rapidly at the surface oxygen sites of a reactive mineral. We obsd. carbonate ions on both a newly cleaved quartz surface (without hydrolysis), and a basalt andesine surface after hydrolysis in a CO2-rich environment. Future work should consider the influence of water, gas impurities, and mineral cation type on carbonation.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVOitLbF&md5=af210ff53b3eb73cb043fecce37315be
  8. 8
    Jiang, Q.; Ward, M. D. Crystallization under Nanoscale Confinement. Chem. Soc. Rev. 2014, 43, 2066– 2079,  DOI: 10.1039/c3cs60234f
    Google Scholar
    8
    Crystallization under nanoscale confinement
    Jiang, Qi; Ward, Michael D.
    Chemical Society Reviews (2014), 43 (7), 2066-2079CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review. Classical crystal growth models posit that crystn. outcomes are detd. by nuclei that resemble mature crystal phases, but at a crit. size where the vol. free energy of nuclei begins to offset the unfavorable surface free energy arising from the interface with the growth medium. Crystn. under nanoscale confinement offers an opportunity to examine nucleation and phase transformations at length scales corresponding to the crit. size, at which kinetics and thermodn. of nucleation and growth intersect and dramatic departures in stability compared to bulk crystals can appear. This tutorial review focuses on recent investigations of the crystn. of org. compds. in nanoporous matrixes that effectively provide millions of nanoscale reactors in a single sample, ranging from controlled porous glass (CPG) beads to nanoporous block-copolymer monoliths to anodic Al2O3 membranes. Confinement of crystal growth in this manner provides a snapshot of the earliest stages of crystal growth, with insights into nucleation, size-dependent polymorphism, and thermotropic behavior of nanoscale crystals. Moreover, these matrixes can be used to screen for crystal polymorphs and assess their stability as nanocrystals. The well-aligned cylindrical nanoscale pores of polymer monoliths or AAO also allow detn. of preferred orientation of embedded nanocrystals, affording insight into the competitive nature of nucleation, crit. sizes, and phase transition mechanisms. Collectively, these investigations have increased our understanding of crystn. at length scales that are deterministic while suggesting strategies for controlling crystn. outcomes.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXjvVygtLs%253D&md5=7e0e054644f866d61484e7a937ba3507
  9. 9
    Li, C.; Qi, L. Bioinspired Fabrication of 3D Ordered Macroporous Single Crystals of Calcite from a Transient Amorphous Phase. Angew. Chem., Int. Ed. 2008, 47, 2388– 2393,  DOI: 10.1002/anie.200705403
    Google Scholar
    9
    Bioinspired fabrication of 3D ordered macroporous single crystals of calcite from a transient amorphous phase
    Li, Cheng; Qi, Limin
    Angewandte Chemie, International Edition (2008), 47 (13), 2388-2393CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Filling the gaps: Unique 3D ordered macroporous (3DOM) calcium carbonate single crystals with controlled orientation and well-defined nanopatterns are fabricated by introducing amorphous calcium carbonate into a colloidal crystal template of polymer spheres (see picture). Such a bioinspired strategy suggests a route to functional single-cryst. materials and sheds light on biomineralization mechanisms.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXktFGmu7s%253D&md5=698bbe747b8e9a6624bb377d3016d130
  10. 10
    Yoo, W. C.; Kumar, S.; Penn, R. L.; Tsapatsis, M.; Stein, A. Growth Patterns and Shape Development of Zeolite Nanocrystals in Confined Syntheses. J. Am. Chem. Soc. 2009, 131, 12377– 12383,  DOI: 10.1021/ja904466v
    Google Scholar
    10
    Growth Patterns and Shape Development of Zeolite Nanocrystals in Confined Syntheses
    Yoo, Won Cheol; Kumar, Sandeep; Penn, R. Lee; Tsapatsis, Michael; Stein, Andreas
    Journal of the American Chemical Society (2009), 131 (34), 12377-12383CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The effects of confinement on the morphol. development of the zeolite silicalite-1 were studied during hydrothermal synthesis in three-dimensionally ordered macroporous (3DOM) carbon monoliths. By scheduling multiple infiltration/hydrothermal reaction (IHT) steps using precursor solns. with high (H) or low nutrient content (L) in specific sequences, it was possible to obtain various zeolite morphologies of interest for technol. applications. The special morphologies are also functions of shaping and templating effects by the 3DOM carbon reactor and functions of limited mass transport in the confined reaction environment. IHT steps employing high nutrient concns. favor nucleation, whereas those using low nutrient concns. provide growth-dominant conditions. Obsd. product morphologies include polycryst. spherical arrays for the sequence HHH..., single crystal domains spanning dozens of macropores for the sequence LLL..., and faceted silicalite-1 crystallites with dimensions less than 100 nm with the sequence HLLL. Most of these crystallites have dimensions less than 100 nm and woul.d be suitable building blocks for seeded zeolite membrane growth. The sequence LLL...H introduces a secondary population of particles with smaller size, so that the size distribution of zeolite crystallites in the combined population may be tuned to optimize packing of particles. By choosing the appropriate infiltration program, it is possible to control grain sizes in polycryst. particles (spheres and opaline arrays of spheres), which alters the concn. of grain boundaries in the particles and is expected to influence transport properties through the zeolite.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXps1ektbk%253D&md5=d0a6f4135daf1b3c95902a04234f1363
  11. 11
    Hetherington, N. B. J.; Kulak, A. N.; Kim, Y. Y.; Noel, E. H.; Snoswell, D.; Butler, M.; Meldrum, F. C. Porous Single Crystals of Calcite from Colloidal Crystal Templates: ACC Is Not Required for Nanoscale Templating. Adv. Funct. Mater. 2011, 21, 948– 954,  DOI: 10.1002/adfm.201001366
    Google Scholar
    11
    Porous Single Crystals of Calcite from Colloidal Crystal Templates: ACC Is Not Required for Nanoscale Templating
    Hetherington, Nicola B. J.; Kulak, Alex N.; Kim, Yi-Yeoun; Noel, Elizabeth H.; Snoswell, David; Butler, Michael; Meldrum, Fiona C.
    Advanced Functional Materials (2011), 21 (5), 948-954CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The formation of nanostructured single crystals of calcite via direct, ion-by-ion pptn. methods has been studied. Single crystals with complex morphologies and curved surfaces were obtained using this technique. Calcite crystals with inverse opal and direct opal structures were prepd. using templates of colloidal crystals and polystyrene reverse opals, resp., and excellent replication of the template structures were achieved, including the formation of 200-nm spheres of calcite in the direct opal structure. These highly porous crystals also displayed extremely regular, cryst. morphologies. The results are also discussed in light of alternative templating methods using amorphous calcium carbonate (ACC) as a precursor phase and provide insight into the role of ACC in biol. calcification processes.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXisFWkt7g%253D&md5=ab909e7a07eb0b5584b927dde5316f4b
  12. 12
    Crossland, E. J. W.; Noel, N.; Sivaram, V.; Leijtens, T.; Alexander-Webber, J. A.; Snaith, H. J. Mesoporous TiO 2 Single Crystals Delivering Enhanced Mobility and Optoelectronic Device Performance. Nature 2013, 495, 215– 219,  DOI: 10.1038/nature11936
    Google Scholar
    12
    Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance
    Crossland, Edward J. W.; Noel, Nakita; Sivaram, Varun; Leijtens, Tomas; Alexander-Webber, Jack A.; Snaith, Henry J.
    Nature (London, United Kingdom) (2013), 495 (7440), 215-219CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
    Mesoporous ceramics and semiconductors enable low-cost solar power, solar fuel, (photo)catalyst and elec. energy storage technologies. State-of-the-art, printable high-surface-area electrodes are fabricated from thermally sintered pre-formed nanocrystals. Mesoporosity provides the desired highly accessible surfaces but many applications also demand long-range electronic connectivity and structural coherence. A mesoporous single-crystal (MSC) semiconductor can meet both criteria. Here the authors demonstrate a general synthetic method of growing semiconductor MSCs of anatase TiO2 based on seeded nucleation and growth inside a mesoporous template immersed in a dil. reaction soln. Both isolated MSCs and ensembles incorporated into films have higher conductivities and electron mobilities than nanocryst. TiO2. Conventional nanocrystals, unlike MSCs, require in-film thermal sintering to reinforce electronic contact between particles, thus increasing fabrication cost, limiting the use of flexible substrates and precluding, for instance, multi-junction solar cell processing. Using MSC films processed entirely <150°, the authors have fabricated all-solid-state, low-temp. sensitized solar cells that have 7.3% efficiency, the highest efficiency yet reported. These high-surface-area anatase single crystals will find application in many different technologies, and this generic synthetic strategy extends the possibility of mesoporous single-crystal growth to a range of functional ceramics and semiconductors.
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  13. 13
    Huber, P. Soft Matter in Hard Confinement: Phase Transition Thermodynamics, Structure, Texture, Diffusion and Flow in Nanoporous Media. J. Phys. Condens. Matter 2015, 27, 103102  DOI: 10.1088/0953-8984/27/10/103102
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    13
    Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media
    Huber, Patrick
    Journal of Physics: Condensed Matter (2015), 27 (10), 103102/1-103102/43CODEN: JCOMEL; ISSN:0953-8984. (IOP Publishing Ltd.)
    A review. Spatial confinement in nanoporous media affects the structure, thermodn. and mobility of mol. soft matter often markedly. This article reviews thermodn. equil. phenomena, such as physisorption, capillary condensation, crystn., self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equil. physics, i.e. the rheol. of liqs., capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined mol. species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcs. to liq. crystals, polymers, ionic liqs., proteins and water. Mostly, expts. with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diams. ranging from a few up to 50 nm are presented. The obsd. peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystn. in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnol. importance, e.g. for the synthesis of org./inorg. hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochem. deposition of nanostructures.
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  14. 14
    Komeili, A. Molecular Mechanisms of Compartmentalization and Biomineralization in Magnetotactic Bacteria. FEMS Microbiol. Rev. 2012, 36, 232– 255,  DOI: 10.1111/j.1574-6976.2011.00315.x
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    14
    Molecular mechanisms of compartmentalization and biomineralization in magnetotactic bacteria
    Komeili, Arash
    FEMS Microbiology Reviews (2012), 36 (1), 232-255CODEN: FMREE4; ISSN:0168-6445. (Wiley-Blackwell)
    A review. Magnetotactic bacteria (MB) are remarkable organisms with the ability to exploit the earth's magnetic field for navigational purposes. To do this, they build specialized compartments called magnetosomes that consist of a lipid membrane and a cryst. magnetic mineral. These organisms have the potential to serve as models for the study of compartmentalization as well as biomineralization in bacteria. Addnl., they offer the opportunity to design applications that take advantage of the particular properties of magnetosomes. In recent years, a sustained effort to identify the mol. basis of this process has resulted in a clearer understanding of the magnetosome formation and biomineralization. Here, I present an overview of MB and explore the possible mol. mechanisms of membrane remodeling, protein sorting, cytoskeletal organization, iron transport, and biomineralization that lead to the formation of a functional magnetosome organelle.
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  15. 15
    Baumgartner, J.; Morin, G.; Menguy, N.; Gonzalez, T. P.; Widdrat, M.; Cosmidis, J.; Faivre, D. Magnetotactic Bacteria Form Magnetite from a Phosphate-Rich Ferric Hydroxide via Nanometric Ferric (Oxyhydr)Oxide Intermediates. Proc. Natl. Acad. Sci. U. S. A. 2013, 110, 14883– 14888,  DOI: 10.1073/pnas.1307119110
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    15
    Magnetotactic bacteria form magnetite from a phosphate-rich ferric hydroxide via nanometric ferric (oxyhydr)oxide intermediates
    Baumgartner, Jens; Morin, Guillaume; Menguy, Nicolas; Gonzalez, Teresa Perez; Widdrat, Marc; Cosmidis, Julie; Faivre, Damien
    Proceedings of the National Academy of Sciences of the United States of America (2013), 110 (37), 14883-14888,S14883/1-S14883/8CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
    The iron oxide mineral magnetite (Fe3O4) is produced by various organisms to exploit magnetic and mech. properties. Magnetotactic bacteria have become one of the best model organisms for studying magnetite biomineralization, as their genomes are sequenced and tools are available for their genetic manipulation. However, the chem. route by which magnetite is formed intracellularly within the so-called magnetosomes has remained a matter of debate. Here, the authors used X-ray absorption spectroscopy at cryogenic temps. and transmission electron microscopic imaging techniques to chem. characterize and spatially resolve the mechanism of biomineralization in those microorganisms. They show that magnetite forms through phase transformation from a highly disordered phosphate-rich ferric hydroxide phase, consistent with prokaryotic ferritins, via transient nanometric ferric (oxyhydr)oxide intermediates within the magnetosome organelle. This pathway remarkably resembles recent results on synthetic magnetite formation and bears a high similarity to suggested mineralization mechanisms in higher organisms.
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  16. 16
    Siponen, M. I.; Legrand, P.; Widdrat, M.; Jones, S. R.; Zhang, W. J.; Chang, M. C. Y.; Faivre, D.; Arnoux, P.; Pignol, D. Structural Insight into Magnetochrome-Mediated Magnetite Biomineralization. Nature 2013, 502, 681– 684,  DOI: 10.1038/nature12573
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    16
    Structural insight into magnetochrome-mediated magnetite biomineralization
    Siponen, Marina I.; Legrand, Pierre; Widdrat, Marc; Jones, Stephanie R.; Zhang, Wei-Jia; Chang, Michelle C. Y.; Faivre, Damien; Arnoux, Pascal; Pignol, David
    Nature (London, United Kingdom) (2013), 502 (7473), 681-684CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
    Magnetotactic bacteria align along the Earth's magnetic field using an organelle called the magnetosome, a biomineralized magnetite (Fe(II)Fe(III)2O4) or greigite (Fe(II)Fe(III)2S4) crystal embedded in a lipid vesicle. Although the need for both iron(II) and iron(III) is clear, little is known about the biol. mechanisms controlling their ratio. Here we present the structure of the magnetosome-assocd. protein MamP and find that it is built on a unique arrangement of a self-plugged PDZ domain fused to two magnetochrome domains, defining a new class of c-type cytochrome exclusively found in magnetotactic bacteria. Mutational anal., enzyme kinetics, co-crystn. with iron(II) and an in vitro MamP-assisted magnetite prodn. assay establish MamP as an iron oxidase that contributes to the formation of iron(III) ferrihydrite eventually required for magnetite crystal growth in vivo. These results demonstrate the mol. mechanisms of iron management taking place inside the magnetosome and highlight the role of magnetochrome in iron biomineralization.
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  17. 17
    Lenders, J. J. M.; Altan, C. L.; Bomans, P. H. H.; Arakaki, A.; Bucak, S.; De With, G.; Sommerdijk, N. A. J. M. A Bioinspired Coprecipitation Method for the Controlled Synthesis of Magnetite Nanoparticles. Cryst. Growth Des. 2014, 14, 5561– 5568,  DOI: 10.1021/cg500816z
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    17
    A Bioinspired Coprecipitation Method for the Controlled Synthesis of Magnetite Nanoparticles
    Lenders, Jos J. M.; Altan, Cem L.; Bomans, Paul H. H.; Arakaki, Atsushi; Bucak, Seyda; de With, Gijsbertus; Sommerdijk, Nico A. J. M.
    Crystal Growth & Design (2014), 14 (11), 5561-5568CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
    Nature often uses precursor phases for the controlled development of cryst. materials with well-defined morphologies and unusual properties. Mimicking such a strategy in in vitro model systems would potentially lead to the H2O-based, room-temp. synthesis of superior materials. In the case of magnetite (Fe3O4), which in biol. generally is formed through a ferrihydrite precursor, such approaches have remained largely unexplored. Here the authors report on a simple protocol that involves the slow copptn. of FeIII/FeII salts through NH3 diffusion, during which ferrihydrite ppts. 1st at low pH values and is converted to magnetite at high pH values. Direct copptn. often leads to small crystals with superparamagnetic properties. Conversely, in this approach, the crystn. kinetics-and thereby the resulting crystal sizes-can be controlled through the NH3 influx and the Fe concn., which results in single crystals with sizes well in the ferrimagnetic domain. Also, this strategy provides a convenient platform for the screening of org. additives as nucleation and growth controllers, which the authors demonstrate for the biol. derived M6A peptide.
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  18. 18
    Laval, P.; Crombez, A.; Salmon, J. B. Microfluidic Droplet Method for Nucleation Kinetics Measurements. Langmuir 2009, 25, 1836– 1841,  DOI: 10.1021/la802695r
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    18
    Microfluidic Droplet Method for Nucleation Kinetics Measurements
    Laval, Philippe; Crombez, Aurore; Salmon, Jean-Baptiste
    Langmuir (2009), 25 (3), 1836-1841CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
    The authors developed a microfluidic equiv. of the classical droplet method for studying nucleation kinetics. Microfluidic device allows one to store hundreds of droplets of small vol. (∼100 nL) and to accurately control their temp. The authors also monitor directly all the stored droplets, and thus perform statistical measurements on a large no. of nucleation events. In the case of aq. solns. of KNO3, the authors manage to study nucleation kinetics and polymorphs and quantify the influence of impurities. The use of small droplets is crucial in such expts., since it allows the sample to reach high supersaturations and to sep. all the nucleation events. Also, the authors compare results to the classical nucleation theory, and the authors demonstrate unambiguously using direct observations of the droplets that nucleation in aq. solns. of KNO3 always occurs using heterogeneous mechanisms.
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  19. 19
    Selzer, D.; Tüllmann, N.; Kiselev, A.; Leisner, T.; Kind, M. Investigation of Crystal Nucleation of Highly Supersaturated Aqueous KNO3 Solution from Single Levitated Droplet Experiments. Cryst. Growth Des. 2018, 18, 4896– 4905,  DOI: 10.1021/acs.cgd.7b01778
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    19
    Investigation of Crystal Nucleation of Highly Supersaturated Aqueous KNO3 Solution from Single Levitated Droplet Experiments
    Selzer, Daniel; Tuellmann, Nadine; Kiselev, Alexei; Leisner, Thomas; Kind, Matthias
    Crystal Growth & Design (2018), 18 (9), 4896-4905CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
    In this work, we use an electrodynamic balance (EDB) to study primary crystal nucleation from single levitated aq. potassium nitrate (KNO3) soln. droplets under isothermal conditions. We investigate crystn. in droplets with vols. less than one nanoliter. From induction time distributions we derive nucleation rates of KNO3. Nucleation processes were found to occur at different mechanisms. Results are interpreted based on the classical nucleation theory (CNT) to gain more information about the prevailing nucleation mechanism. We also investigate the shape and morphol. of crystals using SEM. Two typical morphol. types of crystd. particles could be identified, depending on whether nucleation occurred during the evapn. phase or at const. supersatn. of solute.
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  20. 20
    Selzer, D.; Frank, C.; Kind, M. On the Effect of the Continuous Phase on Primary Crystal Nucleation of Aqueous KNO 3 Solution Droplets. J. Cryst. Growth 2019, 517, 39– 47,  DOI: 10.1016/j.jcrysgro.2019.04.004
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    20
    On the effect of the continuous phase on primary crystal nucleation of aqueous KNO3 solution droplets
    Selzer, Daniel; Frank, Corinna; Kind, Matthias
    Journal of Crystal Growth (2019), 517 (), 39-47CODEN: JCRGAE; ISSN:0022-0248. (Elsevier B.V.)
    In this work, we study the effect of the continuous phase on crystal nucleation of potassium nitrate (KNO3) from aq. soln. by carrying out isothermal crystn. expts. on a set of soln. droplets in a microfluidic device. To this end, rates of primary crystal nucleation of KNO3 are derived from induction time measurements. Nucleation is found to follow different heterogeneous nucleation mechanisms, regardless of the continuous phase used. Depending on supersatn., heterogeneous nucleation centers provoke fast nucleation in a fraction of droplets, whereas slow nucleation is obsd. in the remaining fraction of droplets. Furthermore, our results suggest that nucleation occurs preferentially at the liq.-liq. interface of the droplets. Based on our results, we derive kinetic parameters and discuss them in the context of classical nucleation theory (CNT).
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  21. 21
    Weidinger, I.; Klein, J.; Stöckel, P.; Baumgärtel, H.; Leisner, T. Nucleation Behavior of N-Alkane Microdroplets in an Electrodynamic Balance. J. Phys. Chem. B 2003, 107, 3636– 3643,  DOI: 10.1021/jp0205362
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    21
    Nucleation Behavior of n-Alkane Microdroplets in an Electrodynamic Balance
    Weidinger, I.; Klein, J.; Stoeckel, P.; Baumgaertel, H.; Leisner, T.
    Journal of Physical Chemistry B (2003), 107 (v 15), 3636-3643CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
    The nucleation behavior of n-alkane droplets with C nos. ranging from 14 to 17 was obsd. in an electrodynamic balance. Changes in the elastic light-scattering pattern of the single levitated microdroplets indicate the phase transition from liq. to solid. Cooling/heating expts. showed larger supercooling temps. than expected for alkane droplets with an alkane/air interface. Measurements of the nucleation rates of C15H32 and C17H36 gave addnl. information about the dynamics of the nucleation process and allowed us to distinguish homogeneous from heterogeneous nucleation.
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  22. 22
    Chen, D. L.; Gerdts, G. J.; Ismagilov, R. F. Using Microfluidics to Observe the Effect of Mixing on Nucleation of Protein Crystals. J. Am. Chem. Soc. 2005, 127, 9672– 9673,  DOI: 10.1021/ja052279v
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    22
    Using microfluidics to observe the effect of mixing on nucleation of protein crystals
    Chen, Delai L.; Gerdts, Cory J.; Ismagilov, Rustem F.
    Journal of the American Chemical Society (2005), 127 (27), 9672-9673CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    This paper analyzes the effect of mixing on nucleation of protein crystals. The mixing of protein and precipitant was controlled by changing the flow rate in a plug-based microfluidic system. The nucleation rate inversely depended on the flow rate, and flow rate could be used to control nucleation. For example, at higher supersaturations, pptn. happened at low flow rates while large crystals grew at high flow rates. Mixing at low flow velocities in a winding channel induces nucleation more effectively than mixing in straight channels. A qual. scaling argument that relies on a no. of assumptions is presented to understand the exptl. results. In addn. to helping fundamental understanding, this result may be used to control nucleation, using rapid chaotic mixing to eliminate formation of ppts. at high supersatn. and using slow chaotic mixing to induce nucleation at lower supersatn.
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  23. 23
    Stephens, C. J.; Kim, Y. Y.; Evans, S. D.; Meldrum, F. C.; Christenson, H. K. Early Stages of Crystallization of Calcium Carbonate Revealed in Picoliter Droplets. J. Am. Chem. Soc. 2011, 133, 5210– 5213,  DOI: 10.1021/ja200309m
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    23
    Early Stages of Crystallization of Calcium Carbonate Revealed in Picoliter Droplets
    Stephens, Christopher J.; Kim, Yi-Yeoun; Evans, Stephen D.; Meldrum, Fiona C.; Christenson, Hugo K.
    Journal of the American Chemical Society (2011), 133 (14), 5210-5213CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The authors studied the heterogeneous nucleation and growth of CaCO3 within regular arrays of picoliter droplets created on patterned self-assembled monolayers (SAMs). The SAMs provide well-defined substrates that offer control over CaCO3 nucleation, and the authors used these impurity-free droplet arrays to study crystal growth in spatially and chem. controlled, finite-reservoir environments. The results demonstrate a no. of remarkable features of pptn. within these confined vols. CaCO3 crystn. proceeds significantly more slowly in the droplets than in the bulk, allowing the mechanism of crystn., which progresses via amorphous Ca carbonate, to be easily obsd. The pptn. reaction terminates at an earlier stage than in the bulk soln., revealing intermediate growth forms. Confinement can therefore be used as a straightforward method for studying the mechanisms of crystn. on a substrate without the requirement for specialized anal. techniques. The results are also of significance to biomineralization processes, where crystn. typically occurs in confinement and in assocn. with org. matrixes, and it is envisaged that the method is applicable to many crystg. systems.
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  24. 24
    Stack, A. G. Precipitation in Pores: A Geochemical Frontier. Rev. Mineral. Geochem. 2015, 80, 165– 190,  DOI: 10.2138/rmg.2015.80.05
    Google Scholar
    There is no corresponding record for this reference.
  25. 25
    Bae, C.; Kim, S.; Ahn, B.; Kim, J.; Sung, M. M.; Shin, H. Template-Directed Gas-Phase Fabrication of Oxide Nanotubes. Chem. Mater. 2008, 20, 756– 767,  DOI: 10.1039/b716652d
    Google Scholar
    25
    Template-Directed Synthesis of Oxide Nanotubes: Fabrication, Characterization, and Applications
    Bae, Changdeuck; Yoo, Hyunjun; Kim, Sihyeong; Lee, Kyungeun; Kim, Jiyoung; Sung, Myung M.; Shin, Hyunjung
    Chemistry of Materials (2008), 20 (3), 756-767CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    A review. A template-directed synthesis strategy is an ideal tool to fabricate oxide nanotubes in that their phys. dimensions can be precisely controlled and monodisperse samples can be harvested in large quantity. The wall thickness of the oxide nanotubes is controllable by varying the deposition conditions, and the length and diam. can be tailored in accordance with the templates used. A wealth of functional oxide materials with the controlled polymorphs can be deposited to be nanotubular structures by various synthesis methods. This short review article describes the recent progress made in the field of the template synthesis of oxide nanotubes. We begin this review with the comprehensive survey on the research activities of the template-directed oxide nanotubes. We then focus on the template synthesis that combines porous membrane templates with various deposition techniques and discuss the processing issues assocd. with coating inside nanoscale pores, selective etching of oxide nanotubes from the templates, and dispersion against the formation of nanotubes' bundle-up. Structures and phys. properties of the oxide nanotubes prepd. by template synthesis are also summarized. Their potential for application in drug-delivery systems, sensors, and solar energy conversion devices, which could be facilitated by the template synthesis, is discussed. Finally, we conclude this review by providing our perspectives to the future directions in the template-directed oxide nanotubes.
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  26. 26
    Hurst, S. J.; Payne, E. K.; Qin, L.; Mirkin, C. A. Multisegmented One-Dimensional Nanorods Prepared by Hard-Template Synthetic Methods. Angew. Chem., Int. Ed. 2006, 45, 2672– 2692,  DOI: 10.1002/anie.200504025
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    26
    Multisegmented one-dimensional nanorods prepared by hard-template synthetic methods
    Hurst, Sarah J.; Payne, Emma Kathryn; Qin, Lidong; Mirkin, Chad A.
    Angewandte Chemie, International Edition (2006), 45 (17), 2672-2692CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. In the science and engineering communities, the nanoscience revolution is intensifying. As many types of nanomaterials are becoming more reliably synthesized, they are being used for novel applications in all branches of nanoscience and nanotechnol. Since it is sometimes desirable for single nanomaterials to perform multiple functions simultaneously, multicomponent nanomaterials, such as core-shell, alloyed, and striped nanoparticles, are being more extensively researched. Nanoscientists hope to design multicomponent nanostructures and exploit their inherent multiple functionalities for use in many novel applications. This review highlights recent advances in the synthesis of multisegmented one-dimensional nanorods and nanowires with metal, semiconductor, polymer, mol., and even gapped components. It also discusses the applications of these multicomponent nanomaterials in magnetism, self-assembly, electronics, biol., catalysis, and optics. Particular emphasis is placed on the new materials and devices achievable using these multicomponent, rather than single-component, nanowire structures.
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  27. 27
    Zhou, H.; Wong, S. S. A Facile and Mild Synthesis of 1-D ZnO, CuO, and α-Fe2O3 Nanostructures and Nanostructured Arrays. ACS Nano 2008, 2, 944– 958,  DOI: 10.1021/nn700428x
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    27
    A Facile and Mild Synthesis of 1-D ZnO, CuO, and α-Fe2O3 Nanostructures and Nanostructured Arrays
    Zhou, Hongjun; Wong, Stanislaus S.
    ACS Nano (2008), 2 (5), 944-958CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    ZnO nanowires, CuO nanowires, and α-Fe2O3 nanotubes as well as their corresponding arrays have been successfully synthesized via a low cost, generalizable, and simplistic template method. Diams. of one-dimensional (1-D) metal oxide nanostructures (∼60-260 nm), measuring micrometers in length, can be reliably and reproducibly controlled by the template pore channel dimensions. Assocd. vertically aligned arrays have been attached to the surfaces of a no. of geometrically significant substrates, such as curved plastic and glass rod motifs. The methodol. reported herein relies on the initial formation of an insol. metal hydroxide precursor, initially resulting from the reaction of the corresponding metal soln. and sodium hydroxide, and its subsequent transformation under mild conditions into the desired metal oxide nanostructures. Size- and shape-dependent optical, magnetic, and catalytic properties of as-prepd. 1-D metal oxides were investigated and noted to be mainly comparable to or better than the assocd. properties of the corresponding bulk oxides. A plausible mechanism for as-obsd. wire and tube-like motifs is also discussed.
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  28. 28
    Wang, Y.; Li, B.; Zhou, Y.; Jia, D. In Situ Mineralization of Magnetite Nanoparticles in Chitosan Hydrogel. Nanoscale Res. Lett. 2009, 4, 1041– 1046,  DOI: 10.1007/s11671-009-9355-1
    Google Scholar
    28
    In situ mineralization of magnetite nanoparticles in chitosan hydrogel
    Wang, Yongliang; Li, Baoqiang; Zhou, Yu; Jia, Dechang
    Nanoscale Research Letters (2009), 4 (9), 1041-1046CODEN: NRLAAD; ISSN:1556-276X. (Springer)
    Based on chelation effect between iron ions and amino groups of chitosan, in situ mineralization of magnetite nanoparticles in chitosan hydrogel under ambient conditions was carried out. The chelation effect between iron ions and amino groups in CS-Fe complex, which indicated that the chitosan hydrogel exerted a crucial control on the magnetite mineralization, was proved by X-ray photoelectron spectrum. The compn., morphol. and size of the mineralized magnetite nanoparticles were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy and thermal gravity. The mineralized nanoparticles were nonstoichiometric magnetite with a unit formula of Fe2.85O4 and coated by a thin layer of chitosan. The mineralized magnetite nanoparticles with mean diam. of 13 nm were dispersed in chitosan hydrogel uniformly. Magnetization measurement indicated that superparamagnetism behavior was exhibited. These magnetite nanoparticles mineralized in chitosan hydrogel have potential applications in the field of biotechnol. Moreover, this method can also be used to synthesize other kinds of inorg. nanoparticles, such as ZnO, Fe2O3 and hydroxyapatite.
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  29. 29
    Liefferink, R. W.; Naillon, A.; Bonn, D.; Prat, M.; Shahidzadeh, N. Single Layer Porous Media with Entrapped Minerals for Microscale Studies of Multiphase Flow. Lab Chip 2018, 18, 1094– 1104,  DOI: 10.1039/c7lc01377a
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    29
    Single layer porous media with entrapped minerals for microscale studies of multiphase flow
    Liefferink, R. W.; Naillon, A.; Bonn, D.; Prat, M.; Shahidzadeh, N.
    Lab on a Chip (2018), 18 (7), 1094-1104CODEN: LCAHAM; ISSN:1473-0189. (Royal Society of Chemistry)
    The behavior of minerals (i.e. salts) such as sodium chloride and calcite in porous media is very important in various applications such as weathering of artworks, oil recovery and CO2 sequestration. We report a novel method for manufg. single layer porous media in which minerals can be entrapped in a controlled way in order to study their dissoln. and recrystn. In addn., our manufg. method is a versatile tool for creating monomodal, bimodal or multimodal pore size microporous media with controlled porosity ranging from 25% to 50%. These micromodels allow multiphase flows to be quant. studied with different microscopy techniques and can serve to validate numerical models that can subsequently be extended to the 3D situation where visualization is exptl. difficult. As an example of their use, deliquescence (dissoln. by moisture absorption) of entrapped NaCl crystals is studied; our results show that the invasion of the resulting salt soln. is controlled by the capillary pressure within the porous network. For hydrophilic porous media, the liq. preferentially invades the small pores whereas in a hydrophobic network the large pores are filled. Consequently, after several deliquescence/drying cycles in the hydrophilic system, the salt is transported towards the outside of the porous network via small pores; in hydrophobic micromodels, no salt migration is obsd. Numerical simulations based on the characteristics of our single layer pore network agree very well with the exptl. results and give more insight into the dynamics of salt transport through porous media.
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  30. 30
    Manno, R.; Ranjan, P.; Sebastian, V.; Mallada, R.; Irusta, S.; Sharma, U. K.; Van der Eycken, E. V.; Santamaria, J. Continuous Microwave-Assisted Synthesis of Silver Nanoclusters Confined in Mesoporous SBA-15: Application in Alkyne Cyclizations. Chem. Mater. 2020, 32, 2874– 2883,  DOI: 10.1021/acs.chemmater.9b04935
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    30
    Continuous Microwave-Assisted Synthesis of Silver Nanoclusters Confined in Mesoporous SBA-15: Application in Alkyne Cyclizations
    Manno, Roberta; Ranjan, Prabhat; Sebastian, Victor; Mallada, Reyes; Irusta, Silvia; Sharma, Upendra K.; Van der Eycken, Erik V.; Santamaria, Jesus
    Chemistry of Materials (2020), 32 (7), 2874-2883CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    Metal nanoclusters are becoming exciting candidates as highly efficient catalysts for heterogeneous processes in view of their extraordinary surface to vol. ratio and the high concn. of uncoordinated atoms that contribute to enhanced catalytic activity. For this reason, the development of accurate and reliable procedures for the synthesis of stable and supported metal nanoclusters is highly desirable. Although Ag-nanoclusters (Ag-NCs) stabilized by anion templates with a structure like Ag(n + m)m + and a long lifetime have been widely investigated, supported clusters present significant advantages regarding their recovery and recyclability. In spite of their potential, the stabilization of clusters of precious metals on porous substrates is scarcely investigated. Herein, we present an innovative approach for the synthesis of stable Ag nanoclusters designed with the aim of achieving a strict control of key phases such as mixing, microwave heating and quenching. The catalyst was used for the activation of alkynes showing excellent activity for the formation of C-O, C-N and C-C bonds. When compared with commonly used homogeneous Ag-salts, Ag-NCs enhanced the catalytic activity toward the cyclization of a wide range of substrates, thereby minimizing the metal loading and allowing the sepn. as well as the reuse of the catalyst for multiple cycles.
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  31. 31
    Meyer, R. R.; Sloan, J.; Dunin-Borkowski, R. E.; Kirkland, A. I.; Novotny, M. C.; Bailey, S. R.; Hutchison, J. L.; Green, M. L. H. Discrete Atom Imaging of One-Dimensional Crystals Formed within Single-Walled Carbon Nanotubes. Science 2000, 289, 1324– 1326,  DOI: 10.1126/science.289.5483.1324
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    31
    Discrete atom imaging of one-dimensional crystals formed within single-walled carbon nanotube
    Meyer, Riidiger R.; Sloan, Jeremy; Dunin-Borkowski, Rafal E.; Kirkland, Angus I.; Novotny, Miles C.; Bailey, Sam R.; Hutchison, John L.; Green, Malcolm L. H.
    Science (Washington, D. C.) (2000), 289 (5483), 1324-1326CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    The complete crystallog. of a 1-dimensional crystal of KI encapsulated within a 1.6-nm-diam. single-walled C nanotube was detd. with high-resoln. TEM. Individual atoms of K and I within the crystal were identified from a phase image that was reconstructed with a modified focal series restoration approach. The lattice spacings within the crystal are substantially different from those in bulk KI. This is attributed to the reduced coordination of the surface atoms of the crystal and the close proximity of the van der Waals surface of the confining nanotube.
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  32. 32
    Guan, L.; Suenaga, K.; Shi, Z.; Gu, Z.; Iijima, S. Polymorphic Structures of Iodine and Their Phase Transition in Confined Nanospace. Nano Lett. 2007, 7, 1532– 1535,  DOI: 10.1021/nl070313t
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    32
    Polymorphic Structures of Iodine and Their Phase Transition in Confined Nanospace
    Guan, Lunhui; Suenaga, Kazu; Shi, Zujin; Gu, Zhennan; Iijima, Sumio
    Nano Letters (2007), 7 (6), 1532-1535CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
    At. chains and crystal of I were successfully generated in a controlled manner inside single-walled C nanotubes (SWNTs). The structure is strongly dependent on the diam. of SWNTs; the single, double, and triple helical structures became quite stable when the diam. of SWNTs matches the certain size. More than three chains of I are not very stable, and they often crystallize inside the C nanotube when the diam. is larger than 1.45 nm. The crystn. or phase transition in a confined nanospace is thus directly obsd., and there is indeed a crit. size of the hollow nanospace for the stable formation of the at. chains of I.
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  33. 33
    Nakamuro, T.; Sakakibara, M.; Nada, H.; Harano, K.; Nakamura, E. Capturing the Moment of Emergence of Crystal Nucleus from Disorder. J. Am. Chem. Soc. 2021, 143, 1763– 1767,  DOI: 10.1021/jacs.0c12100
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    33
    Capturing the Moment of Emergence of Crystal Nucleus from Disorder
    Nakamuro, Takayuki; Sakakibara, Masaya; Nada, Hiroki; Harano, Koji; Nakamura, Eiichi
    Journal of the American Chemical Society (2021), 143 (4), 1763-1767CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Crystn. is the process of atoms or mols. forming an organized solid via nucleation and growth. Being intrinsically stochastic, the research at an atomistic level was a huge exptl. challenge. In situ detection is reported of a crystal nucleus forming during nucleation/growth of a NaCl nanocrystal, as video recorded in the interior of a vibrating conical C nanotube at 20-40 ms/frame with localization precision of <0.1 nm. NaCl units were seen assembled to form a cluster fluctuating between featureless and semiordered states, which suddenly formed a crystal. Subsequent crystal growth at 298 K and shrinkage at 473 K took place also in a stochastic manner. Productive contributions of the graphitic surface and its mech. vibration were exptl. indicated.
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  34. 34
    Ueno, T. Porous Protein Crystals as Reaction Vessels. Chem. -Eur. J. 2013, 19, 9096– 9102,  DOI: 10.1002/chem.201300250
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    34
    Porous Protein Crystals as Reaction Vessels
    Ueno, Takafumi
    Chemistry - A European Journal (2013), 19 (28), 9096-9102CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Porous protein crystals have the potential to provide new porous materials due to their unique chem. environments composed of amino acid residues periodically exposed at the surface of the solvent channels in the crystal lattice. This enables accumulation of external compds. in special arrangements by metal coordination interactions or by chem. modifications. This article presents a review of advances in the recently established field of porous protein crystals.
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  35. 35
    Ding, Y.; Shi, L.; Wei, H. Protein-Directed Approaches to Functional Nanomaterials: A Case Study of Lysozyme. J. Mater. Chem. B 2014, 2, 8268– 8291,  DOI: 10.1039/c4tb01235f
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    35
    Protein-directed approaches to functional nanomaterials: a case study of lysozyme
    Ding, Yubin; Shi, Leilei; Wei, Hui
    Journal of Materials Chemistry B: Materials for Biology and Medicine (2014), 2 (47), 8268-8291CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
    A review. Functional nanomaterials have found wide applications in diverse areas because of their intrinsically different properties compared to their bulk counterparts. To achieve the goal of prepg. functional nanomaterials, various strategies have been successfully developed. Among them, the biomol.-directed approach has been extensively explored to synthesize many functional nanomaterials owing to their programmability, self-assembly and recognition capabilities. This Feature Article highlights the use of lysozyme as a model protein to the direct synthesis of nanomaterials. Future advances in rational de novo design and synthesis of functional nanomaterials with proteins will depend on a deep understanding of the synthetic strategies and the formation mechanisms. This Feature Article discusses the synthesis of nanomaterials with lysozyme in both the soln. phase and crystal form. The synthetic strategies, formation mechanisms and wide applications of several kinds of materials, such as metals, oxides, metal sulfides, and composites, are covered. The lessons from this case study will provide invaluable guidance in future materials design using proteins and other biomols. Rational design of personalized functional nanomaterials will be possible in the future (366 refs.).
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  36. 36
    Margolin, A. L.; Navia, M. A. Protein Crystals as Novel Catalytic Materials. Angew. Chem., Int. Ed. 2001, 40, 2204– 2222,  DOI: 10.1002/1521-3773(20010618)40:12<2204::aid-anie2204>3.0.co;2-j
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    36
    Protein crystals as novel catalytic materials
    Margolin, Alexey L.; Navia, Manuel A.
    Angewandte Chemie, International Edition (2001), 40 (12), 2204-2222CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH)
    A review, with 146 refs. In this era of mol. biol., protein crystn. is often considered to be a necessary first step in obtaining structural information through x-ray diffraction anal. In a different light, protein crystals can also be thought of as materials, whose chem. and phys. properties make them broadly attractive and useful across a larger spectrum of disciplines. The full potential of these protein cryst. materials has been severely restricted in practice, however, both by their inherent fragility, and by strongly held skepticism concerning their routine and predictable growth, formulation, and practical application. Fortunately, these problems have turned out to be solvable. A systematic exploration of the biophysics and biochem. of protein crystn. has shown that one can dependably create new protein cryst. materials more or less at will. In turn, these crystals can be readily strengthened, both chem. and mech., to make them suitable for practical commercialization. Today, these novel materials are used as industrial catalysts on a com. scale, in bioremediation and "green chem." applications, and in enantioselective chromatog. of pharmaceuticals and fine chems. In the near future, their utility will expand, to include the purifn. of protein drugs, formulation of direct protein therapeutics, and development of adjuvant-less vaccines.
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  37. 37
    Fernández-Penas, R.; Verdugo-Escamilla, C.; Martínez-Rodríguez, S.; Gavira, J. A. Production of Cross-Linked Lipase Crystals at a Preparative Scale. Cryst. Growth Des. 2021, 21, 1698– 1707,  DOI: 10.1021/acs.cgd.0c01608
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    37
    Production of Cross-Linked Lipase Crystals at a Preparative Scale
    Fernandez-Penas, Raquel; Verdugo-Escamilla, Cristobal; Martinez-Rodriguez, Sergio; Gavira, Jose A.
    Crystal Growth & Design (2021), 21 (3), 1698-1707CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
    The autoimmobilization of enzymes via cross-linked enzyme crystals (CLECs) has regained interest in recent years, boosted by the extensive knowledge gained in protein crystn., the decrease of cost and laboriousness of the process, and the development of potential applications. In this work, we present the crystn. and preparative-scale prodn. of reinforced cross-linked lipase crystals (RCLLCs) using a com. detergent additive as a raw material. Bulk crystn. was carried out in 500 mL of agarose media using the batch technique. Agarose facilitates the homogeneous prodn. of crystals, their crosslinking treatment, and their extn. RCLLCs were active in an aq. soln. and in hexane, as shown by the hydrolysis of p-nitrophenol butyrate and α-methylbenzyl acetate, resp. RCLLCs presented both high thermal and robust operational stability, allowing the prepn. of a packed-bed chromatog. column to work in a continuous flow. Finally, we detd. the three-dimensional (3D) models of this com. lipase crystd. with and without phosphate at 2.0 and 1.7 Å resolns., resp.
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  38. 38
    Conejero-Muriel, M.; Rodríguez-Ruiz, I.; Verdugo-Escamilla, C.; Llobera, A.; Gavira, J. A. Continuous Sensing Photonic Lab-on-a-Chip Platform Based on Cross-Linked Enzyme Crystals. Anal. Chem. 2016, 88, 11919– 11923,  DOI: 10.1021/acs.analchem.6b03793
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    38
    Continuous Sensing Photonic Lab-on-a-Chip Platform Based on Cross-Linked Enzyme Crystals
    Conejero-Muriel, Mayte; Rodriguez-Ruiz, Isaac; Verdugo-Escamilla, Cristobal; Llobera, Andreu; Gavira, Jose A.
    Analytical Chemistry (Washington, DC, United States) (2016), 88 (23), 11919-11923CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
    Microfluidics or lab-on-a-chip technol. offer clear advantages over conventional systems such as a dramatic redn. of reagent consumption or a shorter anal. time, which are translated into costs effective systems. In this work, we present a photonic enzymic lab on a chip reactor based on Cross-Linked Enzyme Crystals (CLECs), able to work in continuous flow, as a highly sensitive, robust, reusable and stable platform for continuous sensing with superior performance as compared to the state of the art. The microreactor is designed to facilitate the in situ crystn. and crystal crosslinking generating enzymically active material that can be stored for months/years. Thus, and by means of monolithically integrated micro-optics elements, continuous enzymic reactions can be spectrophotometrically monitored. Lipase, an enzyme with industrial significance for catalyzed transesterification, hydrolysis and esterification reactions, is used to demonstrate the potential of the microplatforms as both a continuous biosensor or as a microreactor for the synthesis of high value compds.
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    Contreras-Montoya, R.; Escolano, G.; Roy, S.; Lopez-Lopez, M. T.; Delgado-López, J. M.; Cuerva, J. M.; Díaz-Mochón, J. J.; Ashkenasy, N.; Gavira, J. A.; Álvarez de Cienfuegos, L. Catalytic and Electron Conducting Carbon Nanotube–Reinforced Lysozyme Crystals. Adv. Funct. Mater. 2018, 29, 1807351  DOI: 10.1002/adfm.201807351
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    There is no corresponding record for this reference.
  40. 40
    Falkner, J. C.; Turner, M. E.; Bosworth, J. K.; Trentler, T. J.; Johnson, J. E.; Lin, T.; Colvin, V. L. Virus Crystals as Nanocomposite Scaffolds. J. Am. Chem. Soc. 2005, 127, 5274– 5275,  DOI: 10.1021/ja044496m
    Google Scholar
    40
    Virus Crystals as Nanocomposite Scaffolds
    Falkner, Joshua C.; Turner, Mary E.; Bosworth, Joan K.; Trentler, Timothy J.; Johnson, John E.; Lin, Tianwei; Colvin, Vicki L.
    Journal of the American Chemical Society (2005), 127 (15), 5274-5275CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The generation of long-range three-dimensional nanoscopic patterns is a major goal in materials chem. Here we report a strategy for creating such systems using virus crystals as scaffolds which can be infiltrated with metal specifically palladium and platinum. The inorg. component effectively packs within the porous macromol. crystal architecture, providing a route for patterning these materials on the nanometer length scale. To verify the quality of the metal infiltration, SEM-EDX was used to det. the homogeneous distribution of metal across the crystal, and TEM was used to confirm that the metal was confined within the porous structure of the crystal.
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  41. 41
    Guli, M.; Lambert, E. M.; Li, M.; Mann, S. Template-Directed Synthesis of Nanoplasmonic Arrays by Intracrystalline Metalization of Cross-Linked Lysozyme Crystals. Angew. Chem., Int. Ed. 2010, 49, 520– 523,  DOI: 10.1002/anie.200905070
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    41
    Template-Directed Synthesis of Nanoplasmonic Arrays by Intracrystalline Metalization of Cross-Linked Lysozyme Crystals
    Guli, Mina; Lambert, Elizabeth M.; Li, Mei; Mann, Stephen
    Angewandte Chemie, International Edition (2010), 49 (3), 520-523, S520/1-S520/6CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Here, we extend the above strategies for the sequestration of metal ions and their redn. products within the solvent channels of glutaraldehyde crosslinked lysozyme single crystals. Herein, we exploit this structural arrangement as an ordered 1-D intracryst. reaction environment for the periodic organization and nanoscale confinement of plasmonic nanowires of Ag or Au. Arrays of metallic nanofilaments are produced within the protein crystals by in situ redox reactions involving photoredn. of sequestered Ag' ions or chem. redn. of AuCl4- by BH4- ions pre-organized into the solvent channels. The resulting metalized protein crystals are phys. robust, regular in external morphol., and uniform in size. Such materials represent a new class of hybrid monoliths with patterned nanostructured interiors, and may find uses as waveguides, sensors, and catalysts.
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  42. 42
    Liang, M.; Wang, L.; Su, R.; Qi, W.; Wang, M.; Yu, Y.; He, Z. Synthesis of Silver Nanoparticles within Cross-Linked Lysozyme Crystals as Recyclable Catalysts for 4-Nitrophenol Reduction. Catal. Sci. Technol. 2013, 3, 1910– 1914,  DOI: 10.1039/c3cy00157a
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    42
    Synthesis of silver nanoparticles within cross-linked lysozyme crystals as recyclable catalysts for 4-nitrophenol reduction
    Liang, Miao; Wang, Libing; Su, Rongxin; Qi, Wei; Wang, Mengfan; Yu, Yanjun; He, Zhimin
    Catalysis Science & Technology (2013), 3 (8), 1910-1914CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
    For the first time, we demonstrated the fabrication of silver nanoparticles (NPs) in cross-linked protein crystal hybrid material with catalytic properties using a facile chem. redn. method. The macroscopic porous lysozyme crystals can be used as excellent templates for the incorporation of Ag nanoparticles. The resulting AgNP-in-lysozyme crystal composites exhibited a good catalytic activity toward nitrophenol redn. Notably, these catalysts could be easily recovered and reused for at least five successive cycles with almost const. activity and conversion efficiency.
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  43. 43
    Muskens, O. L.; England, M. W.; Danos, L.; Li, M.; Mann, S. Plasmonic Response of Ag- and Au-Infiltrated Cross-Linked Lysozyme Crystals. Adv. Funct. Mater. 2013, 23, 281– 290,  DOI: 10.1002/adfm.201201718
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    43
    Plasmonic Response of Ag- and Au-Infiltrated Cross-Linked Lysozyme Crystals
    Muskens, Otto L.; England, Matt W.; Danos, Lefteris; Li, Mei; Mann, Stephen
    Advanced Functional Materials (2013), 23 (3), 281-290CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Metal-infiltrated protein crystals form a novel class of bio-nanomaterials of great interest for applications in biomedicine, chem., and optoelectronics. As yet, very little is known about the internal structure of these materials and the interconnectivity of the metallic network. Here, the optical response of individual Au- and Ag-infiltrated cross-linked lysozyme crystals is investigated using angle- and polarization-dependent spectroscopy. The measurements unequivocally show that metallic inclusions formed inside the nanoporous solvent channels do not connect into continuous nanowires, but rather consist of ensembles of isolated spheroidal nanoclusters with aspect ratios as high as a value of four, and which exhibit a pronounced plasmonic response that is isotropic on a macroscopic length scale. Fluorescence measurement in the visible range show a strong contribution from the protein host, which is quenched by the Au inclusions, and a weaker contribution attributed to the mol.-like emission from small Au-clusters.
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  44. 44
    Wei, H.; Wang, Z.; Zhang, J.; House, S.; Gao, Y. G.; Yang, L.; Robinson, H.; Tan, L. H.; Xing, H.; Hou, C.; Robertson, I. M.; Zuo, J. M.; Lu, Y. Time-Dependent, Protein-Directed Growth of Gold Nanoparticles within a Single Crystal of Lysozyme. Nat. Nanotechnol. 2011, 6, 93– 97,  DOI: 10.1038/nnano.2010.280
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    44
    Time-dependent, protein-directed growth of gold nanoparticles within a single crystal of lysozyme
    Wei, Hui; Wang, Zidong; Zhang, Jiong; House, Stephen; Gao, Yi-Gui; Yang, Limin; Robinson, Howard; Tan, Li Huey; Xing, Hang; Hou, Changjun; Robertson, Ian M.; Zuo, Jian-Min; Lu, Yi
    Nature Nanotechnology (2011), 6 (2), 93-97CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)
    Gold nanoparticles are useful in biomedical applications due to their distinct optical properties and high chem. stability. Reports of the biogenic formation of gold colloids from gold complexes has also led to an increased level of interest in the biomineralization of gold. However, the mechanism responsible for biomol.-directed gold nanoparticle formation remains unclear due to the lack of structural information about biol. systems and the fast kinetics of biomimetic chem. systems in soln. Here the authors show that intact single crystals of lysozyme can be used to study the time-dependent, protein-directed growth of gold nanoparticles. The protein crystals slow down the growth of the gold nanoparticles, allowing detailed kinetic studies to be carried out, and permit a three-dimensional structural characterization that would be difficult to achieve in soln. Furthermore, the authors show that addnl. chem. species can be used to fine-tune the growth rate of the gold nanoparticles.
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  45. 45
    Wei, H.; Lu, Y. Catalysis of Gold Nanoparticles within Lysozyme Single Crystals. Chem. -Asian J. 2012, 7, 680– 683,  DOI: 10.1002/asia.201100942
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    45
    Catalysis of Gold Nanoparticles within Lysozyme Single Crystals
    Wei, Hui; Lu, Yi
    Chemistry - An Asian Journal (2012), 7 (4), 680-683CODEN: CAAJBI; ISSN:1861-4728. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Bio-nano hybrid materials have been the focus of numerous studies because they combine the merits of both biomols. and nanomaterials, with potential for a wide range of applications in catalysis, electronic devices, energy conversion and storage, drug delivery, imaging, and sensing. Here we have demonstrated that AuNPs grown in situ within a lysozyme protein crystal could be used as efficient catalyst to catalyze the redn. of p-nitrophenol by NaBH4. The precise control of the AuNP sizes by the single crystals of lysozyme allowed us to elucidate the relationship between the catalytic activity and the size of the crystals. Furthermore, we showed that the catalytic activity of the AuNPs@Lys could be modulated by fine-tuning the AuNPs growth with addnl. chems. to either accelerate or inhibit the AuNP growth. This work provides insights into the development of new highly efficient catalysts by incorporating inorg. materials within protein crystals.
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  46. 46
    Abe, S.; Tsujimoto, M.; Yoneda, K.; Ohba, M.; Hikage, T.; Takano, M.; Kitagawa, S.; Ueno, T. Porous Protein Crystals as Reaction Vessels for Controlling Magnetic Properties of Nanoparticles. Small 2012, 8, 1314– 1319,  DOI: 10.1002/smll.201101866
    Google Scholar
    46
    Porous Protein Crystals as Reaction Vessels for Controlling Magnetic Properties of Nanoparticles
    Abe, Satoshi; Tsujimoto, Masahiko; Yoneda, Ko; Ohba, Masaaki; Hikage, Tatsuo; Takano, Mikio; Kitagawa, Susumu; Ueno, Takafumi
    Small (2012), 8 (9), 1314-1319CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The authors have demonstrated the synthesis of magnetic bimetallic CoPt-NPs within porous HEWL crystals and succeeded in controlling magnetic properties of CoPt-NPs by using different crystal systems of HEWL. This represents the first example of using protein crystals as solid biomol. templates for the synthesis of magnetic nanoparticles. The authors succeeded in obtaining CoPt-NPs with the largest coercivity values among previously reported protein assemblies in soln. The high coercivity of CoPt*0 is due to the rigid reaction channels where metal ions can accumulate and where the size-restricted CoPt-NPs independentally align affecting the magnetic anisotropy.
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  47. 47
    Wei, H.; House, S.; Wu, J.; Zhang, J.; Wang, Z.; He, Y.; Gao, E. J.; Gao, Y.; Robinson, H.; Li, W.; Zuo, J.; Robertson, I. M.; Lu, Y. Enhanced and Tunable Fluorescent Quantum Dots within a Single Crystal of Protein. Nano Res. 2013, 6, 627– 634,  DOI: 10.1007/s12274-013-0348-0
    Google Scholar
    47
    Enhanced and tunable fluorescent quantum dots within a single crystal of protein
    Wei, Hui; House, Stephen; Wu, Jiangjiexing; Zhang, Jiong; Wang, Zidong; He, Ying; Gao, Elizabeth J.; Gao, Yigui; Robinson, Howard; Li, Wei; Zuo, Jianmin; Robertson, Ian M.; Lu, Yi
    Nano Research (2013), 6 (9), 627-634CODEN: NRAEB5; ISSN:1998-0000. (Springer GmbH)
    The design and synthesis of bio-nano hybrid materials can not only provide new materials with novel properties, but also advance our fundamental understanding of interactions between biomols. and their abiotic counterparts. Here, we report a new approach to achieving such a goal by growing CdS quantum dots (QDs) within single crystals of lysozyme protein. This bio-nano hybrid emitted much stronger red fluorescence than its counterpart without the crystal, and such fluorescence properties could be either enhanced or suppressed by the addn. of Ag(I) or Hg(II), resp. The three-dimensional incorporation of CdS QDs within the lysozyme crystals was revealed by scanning transmission electron microscopy with electron tomog. More importantly, since our approach did not disrupt the cryst. nature of the lysozyme crystals, the metal and protein interactions were able to be studied by X-ray crystallog., thus providing insight into the role of Cd(II) in the CdS QDs formation. [Figure not available: see fulltext.].
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  48. 48
    Perez-Gonzalez, T.; Rodriguez-Navarro, A.; Jimenez-Lopez, C. Inorganic Magnetite Precipitation at 25 °C: A Low-Cost Inorganic Coprecipitation Method. J. Supercond. Novel Magn. 2011, 24, 549– 557,  DOI: 10.1007/s10948-010-0999-y
    Google Scholar
    48
    Inorganic Magnetite Precipitation at 25°C. A Low-Cost Inorganic Coprecipitation Method
    Perez-Gonzalez, T.; Rodriguez-Navarro, A.; Jimenez-Lopez, C.
    Journal of Superconductivity and Novel Magnetism (2011), 24 (1-2), 549-557CODEN: JSNMBN; ISSN:1557-1939. (Springer)
    An easy, low-cost copptn. method to inorganically produce magnetite nanoparticles from solns., in free-drift expts., under anoxic conditions, at 25° and 1 atm pressure is here presented. By using this method, pure magnetite is obtained as the final solid, which shows the typical magnetic properties and thermal stability behavior of magnetite produced by other methods. The size of the magnetite crystals produced by the present method varies from relatively big sizes (200-300 nm), to sizes within the single magnetic domain range, just depending on the incubation time. The soln. from which magnetite ppts. may be representative of certain natural environments where bacteria that produce magnetite may live and, thus, our magnetite may be used as an inorg. ref. to compare to biol. produced magnetites.
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  49. 49
    Downs, R. T.; Bartelmehs, K. L.; Gibbs, G. V.; Boisen, M. B. Interactive Software for Calculating and Displaying X-Ray or Neutron Powder Diffractometer Patterns of Crystalline Materials. Am. Mineral. 1993, 78, 1104– 1107
    Google Scholar
    49
    Interactive software for calculating and displaying x-ray or neutron powder diffractometer patterns of crystalline materials
    Downs, R. T.; Bartelmehs, K. L.; Gibbs, G. V.; Boisen, M. B., Jr.
    American Mineralogist (1993), 78 (9-10), 1104-7CODEN: AMMIAY; ISSN:0003-004X.
    Two computer programs, XPOW and XPOWPLOT, that generate and graph x-ray or neutron powder diffractometer patterns of cryst. materials are described. The input for XPOW requires only the radiation wavelength, cell dimensions, space group, and positional parameters for the atoms in the asym. unit. The output includes a listing of the d values, 2θ values, and the relative intensities for the nonequiv. Bragg reflections within a given 2θ interval. Using the XPOW output, the XPOWPLOT program creates menu-aided interactive color displays of up to five powder diffractometer patterns simultaneously on the PC monitor.
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  50. 50
    Uwada, T.; Kouno, K.; Ishikawa, M. In Situ Absorption and Fluorescence Microspectroscopy Investigation of the Molecular Incorporation Process into Single Nanoporous Protein Crystals. ACS Omega 2020, 5, 9605– 9613,  DOI: 10.1021/acsomega.0c01038
    Google Scholar
    50
    In Situ Absorption and Fluorescence Microspectroscopy Investigation of the Molecular Incorporation Process into Single Nanoporous Protein Crystals
    Uwada, Takayuki; Kouno, Kohei; Ishikawa, Mitsuru
    ACS Omega (2020), 5 (16), 9605-9613CODEN: ACSODF; ISSN:2470-1343. (American Chemical Society)
    Protein crystals exhibit distinct three-dimensional structures, which contain well-ordered nanoporous solvent channels, providing a chem. heterogeneous environment. In this paper, the incorporation of various mols. into the solvent channels of native hen egg-white lysozyme crystals was demonstrated using fluorescent dyes, including acridine yellow G, rhodamine 6G, and eosin Y. The process was evaluated on the basis of absorption and fluorescence microspectroscopy at a single-crystal level. The mol. loading process was clearly visualized as a function of time, and it was detd. that the protein crystals could act as nanoporous materials. It was found that the incorporation process is strongly dependent on the mol. charge, leading to heterogeneous mol. aggregation, which suggests host-guest interaction of protein crystals from the viewpoint of nanoporous materials.
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  51. 51
    Bereczk-Tompa, É.; Vonderviszt, F.; Horváth, B.; Szalai, I.; Pósfai, M. Biotemplated Synthesis of Magnetic Filaments. Nanoscale 2017, 9, 15062– 15069,  DOI: 10.1039/c7nr04842d
    Google Scholar
    51
    Biotemplated synthesis of magnetic filaments
    Bereczk-Tompa, Eva; Vonderviszt, Ferenc; Horvath, Barnabas; Szalai, Istvan; Posfai, Mihaly
    Nanoscale (2017), 9 (39), 15062-15069CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
    With the aim of creating one-dimensional magnetic nanostructures, we genetically engineered flagellar filaments produced by Salmonella bacteria to display iron- or magnetite-binding sites, and used the mutant filaments as templates for both nucleation and attachment of the magnetic iron oxide magnetite. Although nucleation from soln. and attachment of nanoparticles to a pre-existing surface are two different processes, non-classical crystal nucleation pathways have been increasingly recognized in biol. systems, and in many cases nucleation and particle attachment cannot be clearly distinguished. In this study we tested the magnetite-nucleating ability of four types of mutant flagella previously shown to be efficient binders of magnetite nanoparticles, and we used two other mutant flagella that were engineered to periodically display known iron-binding oligopeptides on their surfaces. All mutant filaments were demonstrated to be efficient as templates for the synthesis of one-dimensional magnetic nanostructures under ambient conditions. Both approaches resulted in similar final products, with randomly oriented magnetite nanoparticles partially covering the filamentous biol. templates. In an external magnetic field, the viscosity of a suspension of the produced magnetic filaments showed a twofold increase relative to the control sample. The results of magnetic susceptibility measurements were also consistent with the magnetic nanoparticles occurring in linear structures. Our study demonstrates that biol. templating can be used to produce one-dimensional magnetic nanostructures under benign conditions, and that modified flagellar filaments can be used for creating model systems in which crystal nucleation from soln. can be exptl. studied.
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  52. 52
    Contreras-Montoya, R.; Jabalera, Y.; Blanco, V.; Cuerva, J. M.; Jimenez-Lopez, C.; Alvarez De Cienfuegos, L. Lysine as Size-Control Additive in a Bioinspired Synthesis of Pure Superparamagnetic Magnetite Nanoparticles. Cryst. Growth Des. 2020, 20, 533– 542,  DOI: 10.1021/acs.cgd.9b00169
    Google Scholar
    52
    Lysine as Size-Control Additive in a Bioinspired Synthesis of Pure Superparamagnetic Magnetite Nanoparticles
    Contreras-Montoya, Rafael; Jabalera, Ylenia; Blanco, Victor; Cuerva, Juan Manuel; Jimenez-Lopez, Concepcion; Alvarez de Cienfuegos, Luis
    Crystal Growth & Design (2020), 20 (2), 533-542CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
    Magnetite nanoparticles (MNPs) are being used in a no. of nanotechnol. applications, esp. biomedical, both in diagnosis and in therapeutics such as hyperthermia agents and as drug nanocarriers for targeted chemotherapy. However, the development of efficient methodologies to produce novel MNPs with the specific requirements needed for biomedical applications is still challenging. In this context, biomimetic approaches taking use of magnetosome proteins expressed as recombinant and/or polyamino acids are becoming of great interest. In fact, these protocols give rise to magnetite nanoparticles of adequate size, magnetic properties and surface functionalization that make them compatible for biomedical applications. In this respect, herein lysine (Lys), unlike other amino acids like arginine (Arg), is able to exert a control over the size of MNPs produced in H2O and at room temp. This control occurs through the stabilization of the magnetite nuclei by the lateral NH4+ group of Lys. The strength of such stabilization allows a further release of these previously bonded nuclei to allow the further growth of the larger ones, thus resulting in larger crystals compared to those obtained by using Arg or no amino acids at all. MNPs obtained by the mediation of this amino acid are fairly large (30 nm) while being superparamagnetic at room temp. They present an isoelec. point of 4, which may allow the coupling/release of these MNPs to other mols. based on electrostatic interaction, a large magnetic moment per particle and high magnetization satn. This study highlights the effects that biol. additives have in the process of magnetite biomineralization and goes along the line of previous reports using magnetosome proteins and polyamino acids. Lysine is able to exert a control over the size of magnetite nanoparticles obtained from aq. solns. in free-drift expts. performed at room temp. These magnetites show well-faceted faces and sizes at 20-30 nm. Lysine adsorbs on the surface of the magnetites, making them neg. charged at physiol. pH and suitable for biotechnol. applications.
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  53. 53
    García Rubia, G.; Peigneux, A.; Jabalera, Y.; Puerma, J.; Oltolina, F.; Elert, K.; Colangelo, D.; Gómez Morales, J.; Prat, M.; Jimenez-Lopez, C. PH-Dependent Adsorption Release of Doxorubicin on MamC-Biomimetic Magnetite Nanoparticles. Langmuir 2018, 34, 13713– 13724,  DOI: 10.1021/acs.langmuir.8b03109
    Google Scholar
    53
    pH-Dependent Adsorption Release of Doxorubicin on MamC-Biomimetic Magnetite Nanoparticles
    Garcia Rubia, German; Peigneux, Ana; Jabalera, Ylenia; Puerma, Javier; Oltolina, Francesca; Elert, Kerstin; Colangelo, Donato; Gomez Morales, Jaime; Prat, Maria; Jimenez-Lopez, Concepcion
    Langmuir (2018), 34 (45), 13713-13724CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
    New biomimetic magnetite nanoparticles (hereafter BMNPs) with sizes larger than most common superparamagnetic nanoparticles were produced in the presence of the recombinant MamC protein from Magnetococcus marinus MC-1 and functionalized with doxorubicin (DOXO) intended as potential drug nanocarriers. Unlike inorg. magnetite nanoparticles, in BMNPs the MamC protein controls their size and morphol., providing them with magnetic properties consistent with a large magnetic moment per particle; moreover, it provides the nanoparticles with novel surface properties. BMNPs display the isoelec. point at pH 4.4, being strongly neg. charged at physiol. pH (pH 7.4). This allows both (i) their functionalization with DOXO, which is pos. charged at pH 7.4, and (ii) the stability of the DOXO-surface bond and DOXO release to be pH dependent and governed by electrostatic interactions. DOXO adsorption follows a Langmuir-Freundlich model, and the coupling of DOXO to BMNPs (binary biomimetic nanoparticles) is very stable at physiol. pH (max. release of 5% of the drug adsorbed). Conversely, when pH decreases, these electrostatic interactions weaken, and at pH 5, DOXO is released up to ∼35% of the amt. initially adsorbed. The DOXO-BMNPs display cytotoxicity on the GTL-16 human gastric carcinoma cell line in a dose-dependent manner, reaching about ∼70% of mortality at the max. amt. tested, while the nonloaded BMNPs are fully cytocompatible. The present data suggest that BMNPs could be useful as potential drug nanocarriers with a drug adsorption-release governed by changes in local pH values.
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  • Abstract

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    Figure 1

    Figure 1. (A) Optical micrograph of each protein crystal: A1─lysozyme; A2─glucose isomerase; A3─lipase. (B) Crystal structures: B1─lysozyme; B2─glucose isomerase; B3─lipase. (C) Schematic picture describing magnetite precipitation inside pores of CLPCs.

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    Figure 2

    Figure 2. Event sequence in protocol Type 1: (1) CLPCs are added to the master solution (NaHCO3/Na2CO3, Fe(ClO4)2, and FeCl3), (2) incubation of the CLPCs to allow iron diffusion, (3) initiation of the precipitation by the addition of NaOH and changing the pH to 12.5, (4) precipitation of magnetite, and (5) fishing out the CLPCs for the analysis. Type 2 “Cycles”: (1) 100 CLPCs are added in the master solution, (2) incubation, (3) initiation, (4) precipitation of magnetite, and (5) at least two CLPCs are preserved for characterization and the rest of the crystals are placed in a fresh master solution to start a new cycle, up to nine cycles.

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    Figure 3

    Figure 3. TEM images of (A) iron oxide nanoparticles grown in CLLC experiments (four cycles) inside and outside the protein crystal and (B) in the bulk (protein free) experiment (four cycles).

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    Figure 4

    Figure 4. TEM images of magnetite grown outside (A1) and iron oxides nanoparticles inside (B1, C1, and D1) CLLCs after cycle number 2 (A1 and B1), 4 (C1), and 8 (D1). SAED diffraction images are shown in A2, B2, C2, and D2 (insets correspond to the diffraction area). Only crystals obtained outside CLLCs showed SAED diffraction pattern consistent with magnetite (A2) (see also Figure S2).

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    Figure 5

    Figure 5. TEM images of iron oxides nanoparticles grown within CLGICs (A) and CLLPCs (B) after two and one cycles, respectively. The plot (C) shows the average nanoparticle particle size for the three proteins after the first cycle.

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    Figure 6

    Figure 6. HR-TEM images of magnetite grown inside CLGICs after cycle 2 (A1), cycle 4 (B1), cycle 6 (C1), and cycle 8 (D1) and the corresponding SAED diffraction images of selected regions (insets in A2, B2, C2, and D2). C2 shows single crystal spots corresponding to 111 magnetite reflections. Indexation of all images is shown in Table S1.

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    Figure 7

    Figure 7. Mean size of magnetite nanoparticles formed inside pores of CLLCs and CLGICs and in solution without CLPCs (control), big standard deviation in the controls appears due to the heterogeneous size of the particles.

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    Figure 8

    Figure 8. (A) TEM image of CLGICs after eight cycles which illustrates the distribution of magnetite nanoparticles. Particle distribution was calculated along the length of the crystal by determining the black/white ratio in eight regions of 135 nm each and plotted in the insert. (B) Number and (C) size of the magnetite nanoparticles formed near and far from the border of the CLPCs, based on TEM images from the ninth cycle.

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    This article references 53 other publications.

    1. 1
      Mann, S. Biomineralization: Principles and Concepts in Bioinorganic Materials Chemistry; Oxford chemistry masters; Oxford University Press, 2001.
      There is no corresponding record for this reference.
    2. 2
      Mañas-Torres, M. C.; Ramírez-Rodríguez, G. B.; García-Peiro, J. I.; Parra-Torrejón, B.; Cuerva, J. M.; Lopez-Lopez, M. T.; Álvarez De Cienfuegos, L.; Delgado-López, J. M. Organic/Inorganic Hydrogels by Simultaneous Self-Assembly and Mineralization of Aromatic Short-Peptides. Inorg. Chem. Front. 2022, 9, 743– 752,  DOI: 10.1039/d1qi01249e
      2
      Organic/inorganic hydrogels by simultaneous self-assembly and mineralization of aromatic short-peptides
      Manas-Torres, Mari C.; Ramirez-Rodriguez, Gloria B.; Garcia-Peiro, Jose I.; Parra-Torrejon, Belen; Cuerva, Juan M.; Lopez-Lopez, Modesto T.; Alvarez de Cienfuegos, Luis; Delgado-Lopez, Jose M.
      Inorganic Chemistry Frontiers (2022), 9 (4), 743-752CODEN: ICFNAW; ISSN:2052-1553. (Royal Society of Chemistry)
      Self-assembled peptides and proteins have turned out to be excellent templates for the growth of inorg. minerals and can be used to emulate natural biomineralization processes. Doing this, researchers have developed complex sophisticated materials with properties, in some cases, similar to those found in nature. Of special interest is the development of scaffolds able to guide bone regeneration. The bone tissue comprises an org. matrix composed of aligned collagen fibers contg. nanoapatite crystals oriented along the fiber direction. During bone mineralization, both processes, the self-assembly of collagen fibrils and mineralization occur simultaneously. Collagen fibers are able to control calcium phosphate nucleation and subsequent apatite crystal growth at a very limited range of collagen d. and ionic concn. In this study, we reproduced the simultaneity of both processes using an artificial peptide fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF) that has the ability to self-assemble in water after the addn. of Ca2+ ions. Therefore, the peptide self-assembly process and the mineralization of apatite are Ca-demanding processes and occur simultaneously. The role of peptide and ionic concns. has been investigated affording org./inorg. hybrid hydrogels with different degrees of homogeneity and mineralization. Interestingly, at very low Ca2+ concns., we found that apatite nanocrystals are integrated into Fmoc-FF fibrils and oriented as in biol. mineralized collagen fibrils, the basic building blocks of bone.
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    3. 3
      Meldrum, F. C.; Cölfen, H. Controlling Mineral Morphologies and Structures in Biological and Synthetic Systems. Chem. Rev. 2008, 108, 4332– 4432,  DOI: 10.1021/cr8002856
      3
      Controlling Mineral Morphologies and Structures in Biological and Synthetic Systems
      Meldrum, Fiona C.; Colfen, Helmut
      Chemical Reviews (Washington, DC, United States) (2008), 108 (11), 4332-4432CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtlOrs77N&md5=bd35b770d4028a5cbace58f7bf55e4b3
    4. 4
      Liu, Y.; Goebl, J.; Yin, Y. Templated Synthesis of Nanostructured Materials. Chem. Soc. Rev. 2013, 42, 2610– 2653,  DOI: 10.1039/c2cs35369e
      4
      Templated synthesis of nanostructured materials
      Liu, Yiding; Goebl, James; Yin, Yadong
      Chemical Society Reviews (2013), 42 (7), 2610-2653CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. Templating is one of the most important techniques for the controlled synthesis of nanostructured materials. This powerful tool uses a pre-existing guide with desired nanoscale features to direct the formation of nanomaterials into forms that are otherwise difficult to obtain. As a result, templated synthesis is capable of producing nanostructures with unique structures, morphologies and properties. In this review, we summarize the general principles of templated synthesis and cover recent developments in this area. As a wide variety of synthesis techniques are utilized to produce nanomaterials using template-based methods, the discussion is organized around the various types of common templates. We examine the use of both phys. and chem. hard colloidal templates, soft templates, and other non-colloidal templates, followed by our perspective on the state of the field and potential future directions.
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    5. 5
      Meldrum, F. F. C.; O’Shaughnessy, C.; O’Shaughnessy, C. Crystallization in Confinement. Adv. Mater. 2020, 32, 2001068  DOI: 10.1002/adma.202001068
      5
      Crystallization in Confinement
      Meldrum, Fiona C.; O'Shaughnessy, Cedrick
      Advanced Materials (Weinheim, Germany) (2020), 32 (31), 2001068CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Many crystn. processes of great importance, including frost heave, biomineralization, the synthesis of nanomaterials, and scale formation, occur in small vols. rather than bulk soln. Here, the influence of confinement on crystn. processes is described, drawing together information from fields as diverse as bioinspired mineralization, templating, pharmaceuticals, colloidal crystn., and geochem. Expts. are principally conducted within confining systems that offer well-defined environments, varying from droplets in microfluidic devices, to cylindrical pores in filtration membranes, to nanoporous glasses and carbon nanotubes. Dramatic effects are obsd., including a stabilization of metastable polymorphs, a depression of f.ps., and the formation of crystals with preferred orientations, modified morphologies, and even structures not seen in bulk. Confinement is also shown to influence crystn. processes over length scales ranging from the at. to hundreds of micrometers, and to originate from a wide range of mechanisms. The development of an enhanced understanding of the influence of confinement on crystal nucleation and growth will not only provide superior insight into crystn. processes in many real-world environments, but will also enable this phenomenon to be used to control crystn. in applications including nanomaterial synthesis, heavy metal remediation, and the prevention of weathering.
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    6. 6
      Espinosa-Marzal, R. M.; Scherer, G. W. Advances in Understanding Damage by Salt Crystallization. Acc. Chem. Res. 2010, 43, 897– 905,  DOI: 10.1021/ar9002224
      6
      Advances in Understanding Damage by Salt Crystallization
      Espinosa-Marzal, Rosa M.; Scherer, George W.
      Accounts of Chemical Research (2010), 43 (6), 897-905CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. The single most important cause of the deterioration of monuments in the Mediterranean basin, and elsewhere around the world, is the crystn. of salt within the pores of the stone. Considerable advances have been made in recent years in elucidating the fundamental mechanisms responsible for salt damage. As a result, new methods of treatment are being proposed that offer the possibility of attacking the cause of the problem, rather than simply treating the symptoms. In this Account, we review the thermodn. and kinetics of crystn., then examine how a range of technol. innovations have been applied exptl. to further the current understanding of in-pore crystn. We close with a discussion of how computer modeling now provides particularly valuable insight, including quant. ests. of both the interaction forces between the mineral and the crystal and the stresses induced in the material. Analyzing the kinetics and thermodn. of crystal growth within the pores of a stone requires sensitive tools used in combination. For example, calorimetry quantifies the amt. of salt that ppts. in the pores of a stone during cooling, and dilatometric measurements on a companion sample reveal the stress exerted by the salt. Synchrotron X-rays can penetrate the stone and identify the metastable phases that often appear in the first stages of crystn. Atomic force microscopy and environmental SEM permit study of the nanometric liq. film that typically lies between salt and stone; this film controls the magnitude of the pressure exerted and the kinetics of relaxation of the stress. These exptl. advances provide validation for increasingly advanced simulations, using continuum models of reactive transport on a macroscopic scale and mol. dynamics on the at. scale. Because of the fundamental understanding of the damage mechanisms that is beginning to emerge, it is possible to devise methods for protecting monuments and sculptures. For example, chem. modification of the stone can alter the repulsive forces that stabilize the liq. film between the salt and mineral surfaces, thereby reducing the stress that the salt can generate. Alternatively, mols. can be introduced into the pores of the stone that inhibit the nucleation or growth of salt crystals. Many challenges remain, however, particularly in understanding the complex interactions between salts, the role of metastable phases, the mechanism of crack initiation and growth, and the role of biofilms.
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    7. 7
      Liang, Y.; Tsuji, S.; Jia, J.; Tsuji, T.; Matsuoka, T. Modeling CO2-Water-Mineral Wettability and Mineralization for Carbon Geosequestration. Acc. Chem. Res. 2017, 50, 1530– 1540,  DOI: 10.1021/acs.accounts.7b00049
      7
      Modeling CO2-Water-Mineral Wettability and Mineralization for Carbon Geosequestration
      Liang, Yunfeng; Tsuji, Shinya; Jia, Jihui; Tsuji, Takeshi; Matsuoka, Toshifumi
      Accounts of Chemical Research (2017), 50 (7), 1530-1540CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. Carbon dioxide (CO2) capture and storage (CCS) is an important climate change mitigation option along with improved energy efficiency, renewable energy, and nuclear energy. CO2 geosequestration, i.e., to store CO2 under the subsurface of Earth, is feasible because the world's sedimentary basins have high capacity and are often located in the same region of the world as emission sources. How CO2 interacts with the connate water and minerals is the focus of this Account. There are four trapping mechanisms that keep CO2 in the pores of subsurface rocks: (1) structural trapping, (2) residual trapping, (3) dissoln. trapping, and (4) mineral trapping. The first two are dominated by capillary action, where wettability controls CO2 and water two-phase flow in porous media. We review state-of-the-art studies on CO2/water/mineral wettability, which was found to depend on pressure and temp. conditions, salt concn. in aq. solns., mineral surface chem., and geometry. We then review some recent advances in mineral trapping. First, we show that it is possible to reproduce the CO2/water/mineral wettability at a wide range of pressures using mol. dynamics (MD) simulations. As the pressure increases, CO2 gas transforms into a supercrit. fluid or liq. at ∼7.4 MPa depending on the environmental temp. This transition leads to a substantial decrease of the interfacial tension between CO2 and reservoir brine (or pure water). However, the wettability of CO2/water/rock systems depends on the type of rock surface. Recently, we investigated the contact angle of CO2/water/silica systems with two different silica surfaces using MD simulations. We found that contact angle increased with pressure for the hydrophobic (siloxane) surface while it was almost const. for the hydrophilic (silanol) surface, in excellent agreement with exptl. observations. Furthermore, we found that the CO2 thin films at the CO2-hydrophilic silica and CO2-H2O interfaces displayed a linear correlation, which can in turn explain the const. contact angle on the hydrophilic silica surface. In view of the literature and our study results, a few recommendations seem necessary to construct a mol. system suitable to study wettability with MD simulations. Future work should be conducted to det. the influence of brine salinity on the wettability of minerals with high cation exchange capacity. Mineral trapping is believed to be an extremely slow process, likely taking thousands of years. However, a recent pilot study demonstrated that CO2 mineralization occurs within 2 years in highly reactive basalt reservoirs. A first-principles MD study has also shown that carbonation reactions occur rapidly at the surface oxygen sites of a reactive mineral. We obsd. carbonate ions on both a newly cleaved quartz surface (without hydrolysis), and a basalt andesine surface after hydrolysis in a CO2-rich environment. Future work should consider the influence of water, gas impurities, and mineral cation type on carbonation.
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    8. 8
      Jiang, Q.; Ward, M. D. Crystallization under Nanoscale Confinement. Chem. Soc. Rev. 2014, 43, 2066– 2079,  DOI: 10.1039/c3cs60234f
      8
      Crystallization under nanoscale confinement
      Jiang, Qi; Ward, Michael D.
      Chemical Society Reviews (2014), 43 (7), 2066-2079CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. Classical crystal growth models posit that crystn. outcomes are detd. by nuclei that resemble mature crystal phases, but at a crit. size where the vol. free energy of nuclei begins to offset the unfavorable surface free energy arising from the interface with the growth medium. Crystn. under nanoscale confinement offers an opportunity to examine nucleation and phase transformations at length scales corresponding to the crit. size, at which kinetics and thermodn. of nucleation and growth intersect and dramatic departures in stability compared to bulk crystals can appear. This tutorial review focuses on recent investigations of the crystn. of org. compds. in nanoporous matrixes that effectively provide millions of nanoscale reactors in a single sample, ranging from controlled porous glass (CPG) beads to nanoporous block-copolymer monoliths to anodic Al2O3 membranes. Confinement of crystal growth in this manner provides a snapshot of the earliest stages of crystal growth, with insights into nucleation, size-dependent polymorphism, and thermotropic behavior of nanoscale crystals. Moreover, these matrixes can be used to screen for crystal polymorphs and assess their stability as nanocrystals. The well-aligned cylindrical nanoscale pores of polymer monoliths or AAO also allow detn. of preferred orientation of embedded nanocrystals, affording insight into the competitive nature of nucleation, crit. sizes, and phase transition mechanisms. Collectively, these investigations have increased our understanding of crystn. at length scales that are deterministic while suggesting strategies for controlling crystn. outcomes.
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    9. 9
      Li, C.; Qi, L. Bioinspired Fabrication of 3D Ordered Macroporous Single Crystals of Calcite from a Transient Amorphous Phase. Angew. Chem., Int. Ed. 2008, 47, 2388– 2393,  DOI: 10.1002/anie.200705403
      9
      Bioinspired fabrication of 3D ordered macroporous single crystals of calcite from a transient amorphous phase
      Li, Cheng; Qi, Limin
      Angewandte Chemie, International Edition (2008), 47 (13), 2388-2393CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Filling the gaps: Unique 3D ordered macroporous (3DOM) calcium carbonate single crystals with controlled orientation and well-defined nanopatterns are fabricated by introducing amorphous calcium carbonate into a colloidal crystal template of polymer spheres (see picture). Such a bioinspired strategy suggests a route to functional single-cryst. materials and sheds light on biomineralization mechanisms.
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    10. 10
      Yoo, W. C.; Kumar, S.; Penn, R. L.; Tsapatsis, M.; Stein, A. Growth Patterns and Shape Development of Zeolite Nanocrystals in Confined Syntheses. J. Am. Chem. Soc. 2009, 131, 12377– 12383,  DOI: 10.1021/ja904466v
      10
      Growth Patterns and Shape Development of Zeolite Nanocrystals in Confined Syntheses
      Yoo, Won Cheol; Kumar, Sandeep; Penn, R. Lee; Tsapatsis, Michael; Stein, Andreas
      Journal of the American Chemical Society (2009), 131 (34), 12377-12383CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The effects of confinement on the morphol. development of the zeolite silicalite-1 were studied during hydrothermal synthesis in three-dimensionally ordered macroporous (3DOM) carbon monoliths. By scheduling multiple infiltration/hydrothermal reaction (IHT) steps using precursor solns. with high (H) or low nutrient content (L) in specific sequences, it was possible to obtain various zeolite morphologies of interest for technol. applications. The special morphologies are also functions of shaping and templating effects by the 3DOM carbon reactor and functions of limited mass transport in the confined reaction environment. IHT steps employing high nutrient concns. favor nucleation, whereas those using low nutrient concns. provide growth-dominant conditions. Obsd. product morphologies include polycryst. spherical arrays for the sequence HHH..., single crystal domains spanning dozens of macropores for the sequence LLL..., and faceted silicalite-1 crystallites with dimensions less than 100 nm with the sequence HLLL. Most of these crystallites have dimensions less than 100 nm and woul.d be suitable building blocks for seeded zeolite membrane growth. The sequence LLL...H introduces a secondary population of particles with smaller size, so that the size distribution of zeolite crystallites in the combined population may be tuned to optimize packing of particles. By choosing the appropriate infiltration program, it is possible to control grain sizes in polycryst. particles (spheres and opaline arrays of spheres), which alters the concn. of grain boundaries in the particles and is expected to influence transport properties through the zeolite.
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    11. 11
      Hetherington, N. B. J.; Kulak, A. N.; Kim, Y. Y.; Noel, E. H.; Snoswell, D.; Butler, M.; Meldrum, F. C. Porous Single Crystals of Calcite from Colloidal Crystal Templates: ACC Is Not Required for Nanoscale Templating. Adv. Funct. Mater. 2011, 21, 948– 954,  DOI: 10.1002/adfm.201001366
      11
      Porous Single Crystals of Calcite from Colloidal Crystal Templates: ACC Is Not Required for Nanoscale Templating
      Hetherington, Nicola B. J.; Kulak, Alex N.; Kim, Yi-Yeoun; Noel, Elizabeth H.; Snoswell, David; Butler, Michael; Meldrum, Fiona C.
      Advanced Functional Materials (2011), 21 (5), 948-954CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The formation of nanostructured single crystals of calcite via direct, ion-by-ion pptn. methods has been studied. Single crystals with complex morphologies and curved surfaces were obtained using this technique. Calcite crystals with inverse opal and direct opal structures were prepd. using templates of colloidal crystals and polystyrene reverse opals, resp., and excellent replication of the template structures were achieved, including the formation of 200-nm spheres of calcite in the direct opal structure. These highly porous crystals also displayed extremely regular, cryst. morphologies. The results are also discussed in light of alternative templating methods using amorphous calcium carbonate (ACC) as a precursor phase and provide insight into the role of ACC in biol. calcification processes.
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    12. 12
      Crossland, E. J. W.; Noel, N.; Sivaram, V.; Leijtens, T.; Alexander-Webber, J. A.; Snaith, H. J. Mesoporous TiO 2 Single Crystals Delivering Enhanced Mobility and Optoelectronic Device Performance. Nature 2013, 495, 215– 219,  DOI: 10.1038/nature11936
      12
      Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance
      Crossland, Edward J. W.; Noel, Nakita; Sivaram, Varun; Leijtens, Tomas; Alexander-Webber, Jack A.; Snaith, Henry J.
      Nature (London, United Kingdom) (2013), 495 (7440), 215-219CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      Mesoporous ceramics and semiconductors enable low-cost solar power, solar fuel, (photo)catalyst and elec. energy storage technologies. State-of-the-art, printable high-surface-area electrodes are fabricated from thermally sintered pre-formed nanocrystals. Mesoporosity provides the desired highly accessible surfaces but many applications also demand long-range electronic connectivity and structural coherence. A mesoporous single-crystal (MSC) semiconductor can meet both criteria. Here the authors demonstrate a general synthetic method of growing semiconductor MSCs of anatase TiO2 based on seeded nucleation and growth inside a mesoporous template immersed in a dil. reaction soln. Both isolated MSCs and ensembles incorporated into films have higher conductivities and electron mobilities than nanocryst. TiO2. Conventional nanocrystals, unlike MSCs, require in-film thermal sintering to reinforce electronic contact between particles, thus increasing fabrication cost, limiting the use of flexible substrates and precluding, for instance, multi-junction solar cell processing. Using MSC films processed entirely <150°, the authors have fabricated all-solid-state, low-temp. sensitized solar cells that have 7.3% efficiency, the highest efficiency yet reported. These high-surface-area anatase single crystals will find application in many different technologies, and this generic synthetic strategy extends the possibility of mesoporous single-crystal growth to a range of functional ceramics and semiconductors.
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    13. 13
      Huber, P. Soft Matter in Hard Confinement: Phase Transition Thermodynamics, Structure, Texture, Diffusion and Flow in Nanoporous Media. J. Phys. Condens. Matter 2015, 27, 103102  DOI: 10.1088/0953-8984/27/10/103102
      13
      Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media
      Huber, Patrick
      Journal of Physics: Condensed Matter (2015), 27 (10), 103102/1-103102/43CODEN: JCOMEL; ISSN:0953-8984. (IOP Publishing Ltd.)
      A review. Spatial confinement in nanoporous media affects the structure, thermodn. and mobility of mol. soft matter often markedly. This article reviews thermodn. equil. phenomena, such as physisorption, capillary condensation, crystn., self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equil. physics, i.e. the rheol. of liqs., capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined mol. species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcs. to liq. crystals, polymers, ionic liqs., proteins and water. Mostly, expts. with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diams. ranging from a few up to 50 nm are presented. The obsd. peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystn. in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnol. importance, e.g. for the synthesis of org./inorg. hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochem. deposition of nanostructures.
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    14. 14
      Komeili, A. Molecular Mechanisms of Compartmentalization and Biomineralization in Magnetotactic Bacteria. FEMS Microbiol. Rev. 2012, 36, 232– 255,  DOI: 10.1111/j.1574-6976.2011.00315.x
      14
      Molecular mechanisms of compartmentalization and biomineralization in magnetotactic bacteria
      Komeili, Arash
      FEMS Microbiology Reviews (2012), 36 (1), 232-255CODEN: FMREE4; ISSN:0168-6445. (Wiley-Blackwell)
      A review. Magnetotactic bacteria (MB) are remarkable organisms with the ability to exploit the earth's magnetic field for navigational purposes. To do this, they build specialized compartments called magnetosomes that consist of a lipid membrane and a cryst. magnetic mineral. These organisms have the potential to serve as models for the study of compartmentalization as well as biomineralization in bacteria. Addnl., they offer the opportunity to design applications that take advantage of the particular properties of magnetosomes. In recent years, a sustained effort to identify the mol. basis of this process has resulted in a clearer understanding of the magnetosome formation and biomineralization. Here, I present an overview of MB and explore the possible mol. mechanisms of membrane remodeling, protein sorting, cytoskeletal organization, iron transport, and biomineralization that lead to the formation of a functional magnetosome organelle.
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    15. 15
      Baumgartner, J.; Morin, G.; Menguy, N.; Gonzalez, T. P.; Widdrat, M.; Cosmidis, J.; Faivre, D. Magnetotactic Bacteria Form Magnetite from a Phosphate-Rich Ferric Hydroxide via Nanometric Ferric (Oxyhydr)Oxide Intermediates. Proc. Natl. Acad. Sci. U. S. A. 2013, 110, 14883– 14888,  DOI: 10.1073/pnas.1307119110
      15
      Magnetotactic bacteria form magnetite from a phosphate-rich ferric hydroxide via nanometric ferric (oxyhydr)oxide intermediates
      Baumgartner, Jens; Morin, Guillaume; Menguy, Nicolas; Gonzalez, Teresa Perez; Widdrat, Marc; Cosmidis, Julie; Faivre, Damien
      Proceedings of the National Academy of Sciences of the United States of America (2013), 110 (37), 14883-14888,S14883/1-S14883/8CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
      The iron oxide mineral magnetite (Fe3O4) is produced by various organisms to exploit magnetic and mech. properties. Magnetotactic bacteria have become one of the best model organisms for studying magnetite biomineralization, as their genomes are sequenced and tools are available for their genetic manipulation. However, the chem. route by which magnetite is formed intracellularly within the so-called magnetosomes has remained a matter of debate. Here, the authors used X-ray absorption spectroscopy at cryogenic temps. and transmission electron microscopic imaging techniques to chem. characterize and spatially resolve the mechanism of biomineralization in those microorganisms. They show that magnetite forms through phase transformation from a highly disordered phosphate-rich ferric hydroxide phase, consistent with prokaryotic ferritins, via transient nanometric ferric (oxyhydr)oxide intermediates within the magnetosome organelle. This pathway remarkably resembles recent results on synthetic magnetite formation and bears a high similarity to suggested mineralization mechanisms in higher organisms.
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    16. 16
      Siponen, M. I.; Legrand, P.; Widdrat, M.; Jones, S. R.; Zhang, W. J.; Chang, M. C. Y.; Faivre, D.; Arnoux, P.; Pignol, D. Structural Insight into Magnetochrome-Mediated Magnetite Biomineralization. Nature 2013, 502, 681– 684,  DOI: 10.1038/nature12573
      16
      Structural insight into magnetochrome-mediated magnetite biomineralization
      Siponen, Marina I.; Legrand, Pierre; Widdrat, Marc; Jones, Stephanie R.; Zhang, Wei-Jia; Chang, Michelle C. Y.; Faivre, Damien; Arnoux, Pascal; Pignol, David
      Nature (London, United Kingdom) (2013), 502 (7473), 681-684CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      Magnetotactic bacteria align along the Earth's magnetic field using an organelle called the magnetosome, a biomineralized magnetite (Fe(II)Fe(III)2O4) or greigite (Fe(II)Fe(III)2S4) crystal embedded in a lipid vesicle. Although the need for both iron(II) and iron(III) is clear, little is known about the biol. mechanisms controlling their ratio. Here we present the structure of the magnetosome-assocd. protein MamP and find that it is built on a unique arrangement of a self-plugged PDZ domain fused to two magnetochrome domains, defining a new class of c-type cytochrome exclusively found in magnetotactic bacteria. Mutational anal., enzyme kinetics, co-crystn. with iron(II) and an in vitro MamP-assisted magnetite prodn. assay establish MamP as an iron oxidase that contributes to the formation of iron(III) ferrihydrite eventually required for magnetite crystal growth in vivo. These results demonstrate the mol. mechanisms of iron management taking place inside the magnetosome and highlight the role of magnetochrome in iron biomineralization.
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    17. 17
      Lenders, J. J. M.; Altan, C. L.; Bomans, P. H. H.; Arakaki, A.; Bucak, S.; De With, G.; Sommerdijk, N. A. J. M. A Bioinspired Coprecipitation Method for the Controlled Synthesis of Magnetite Nanoparticles. Cryst. Growth Des. 2014, 14, 5561– 5568,  DOI: 10.1021/cg500816z
      17
      A Bioinspired Coprecipitation Method for the Controlled Synthesis of Magnetite Nanoparticles
      Lenders, Jos J. M.; Altan, Cem L.; Bomans, Paul H. H.; Arakaki, Atsushi; Bucak, Seyda; de With, Gijsbertus; Sommerdijk, Nico A. J. M.
      Crystal Growth & Design (2014), 14 (11), 5561-5568CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      Nature often uses precursor phases for the controlled development of cryst. materials with well-defined morphologies and unusual properties. Mimicking such a strategy in in vitro model systems would potentially lead to the H2O-based, room-temp. synthesis of superior materials. In the case of magnetite (Fe3O4), which in biol. generally is formed through a ferrihydrite precursor, such approaches have remained largely unexplored. Here the authors report on a simple protocol that involves the slow copptn. of FeIII/FeII salts through NH3 diffusion, during which ferrihydrite ppts. 1st at low pH values and is converted to magnetite at high pH values. Direct copptn. often leads to small crystals with superparamagnetic properties. Conversely, in this approach, the crystn. kinetics-and thereby the resulting crystal sizes-can be controlled through the NH3 influx and the Fe concn., which results in single crystals with sizes well in the ferrimagnetic domain. Also, this strategy provides a convenient platform for the screening of org. additives as nucleation and growth controllers, which the authors demonstrate for the biol. derived M6A peptide.
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    18. 18
      Laval, P.; Crombez, A.; Salmon, J. B. Microfluidic Droplet Method for Nucleation Kinetics Measurements. Langmuir 2009, 25, 1836– 1841,  DOI: 10.1021/la802695r
      18
      Microfluidic Droplet Method for Nucleation Kinetics Measurements
      Laval, Philippe; Crombez, Aurore; Salmon, Jean-Baptiste
      Langmuir (2009), 25 (3), 1836-1841CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      The authors developed a microfluidic equiv. of the classical droplet method for studying nucleation kinetics. Microfluidic device allows one to store hundreds of droplets of small vol. (∼100 nL) and to accurately control their temp. The authors also monitor directly all the stored droplets, and thus perform statistical measurements on a large no. of nucleation events. In the case of aq. solns. of KNO3, the authors manage to study nucleation kinetics and polymorphs and quantify the influence of impurities. The use of small droplets is crucial in such expts., since it allows the sample to reach high supersaturations and to sep. all the nucleation events. Also, the authors compare results to the classical nucleation theory, and the authors demonstrate unambiguously using direct observations of the droplets that nucleation in aq. solns. of KNO3 always occurs using heterogeneous mechanisms.
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    19. 19
      Selzer, D.; Tüllmann, N.; Kiselev, A.; Leisner, T.; Kind, M. Investigation of Crystal Nucleation of Highly Supersaturated Aqueous KNO3 Solution from Single Levitated Droplet Experiments. Cryst. Growth Des. 2018, 18, 4896– 4905,  DOI: 10.1021/acs.cgd.7b01778
      19
      Investigation of Crystal Nucleation of Highly Supersaturated Aqueous KNO3 Solution from Single Levitated Droplet Experiments
      Selzer, Daniel; Tuellmann, Nadine; Kiselev, Alexei; Leisner, Thomas; Kind, Matthias
      Crystal Growth & Design (2018), 18 (9), 4896-4905CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      In this work, we use an electrodynamic balance (EDB) to study primary crystal nucleation from single levitated aq. potassium nitrate (KNO3) soln. droplets under isothermal conditions. We investigate crystn. in droplets with vols. less than one nanoliter. From induction time distributions we derive nucleation rates of KNO3. Nucleation processes were found to occur at different mechanisms. Results are interpreted based on the classical nucleation theory (CNT) to gain more information about the prevailing nucleation mechanism. We also investigate the shape and morphol. of crystals using SEM. Two typical morphol. types of crystd. particles could be identified, depending on whether nucleation occurred during the evapn. phase or at const. supersatn. of solute.
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    20. 20
      Selzer, D.; Frank, C.; Kind, M. On the Effect of the Continuous Phase on Primary Crystal Nucleation of Aqueous KNO 3 Solution Droplets. J. Cryst. Growth 2019, 517, 39– 47,  DOI: 10.1016/j.jcrysgro.2019.04.004
      20
      On the effect of the continuous phase on primary crystal nucleation of aqueous KNO3 solution droplets
      Selzer, Daniel; Frank, Corinna; Kind, Matthias
      Journal of Crystal Growth (2019), 517 (), 39-47CODEN: JCRGAE; ISSN:0022-0248. (Elsevier B.V.)
      In this work, we study the effect of the continuous phase on crystal nucleation of potassium nitrate (KNO3) from aq. soln. by carrying out isothermal crystn. expts. on a set of soln. droplets in a microfluidic device. To this end, rates of primary crystal nucleation of KNO3 are derived from induction time measurements. Nucleation is found to follow different heterogeneous nucleation mechanisms, regardless of the continuous phase used. Depending on supersatn., heterogeneous nucleation centers provoke fast nucleation in a fraction of droplets, whereas slow nucleation is obsd. in the remaining fraction of droplets. Furthermore, our results suggest that nucleation occurs preferentially at the liq.-liq. interface of the droplets. Based on our results, we derive kinetic parameters and discuss them in the context of classical nucleation theory (CNT).
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    21. 21
      Weidinger, I.; Klein, J.; Stöckel, P.; Baumgärtel, H.; Leisner, T. Nucleation Behavior of N-Alkane Microdroplets in an Electrodynamic Balance. J. Phys. Chem. B 2003, 107, 3636– 3643,  DOI: 10.1021/jp0205362
      21
      Nucleation Behavior of n-Alkane Microdroplets in an Electrodynamic Balance
      Weidinger, I.; Klein, J.; Stoeckel, P.; Baumgaertel, H.; Leisner, T.
      Journal of Physical Chemistry B (2003), 107 (v 15), 3636-3643CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
      The nucleation behavior of n-alkane droplets with C nos. ranging from 14 to 17 was obsd. in an electrodynamic balance. Changes in the elastic light-scattering pattern of the single levitated microdroplets indicate the phase transition from liq. to solid. Cooling/heating expts. showed larger supercooling temps. than expected for alkane droplets with an alkane/air interface. Measurements of the nucleation rates of C15H32 and C17H36 gave addnl. information about the dynamics of the nucleation process and allowed us to distinguish homogeneous from heterogeneous nucleation.
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    22. 22
      Chen, D. L.; Gerdts, G. J.; Ismagilov, R. F. Using Microfluidics to Observe the Effect of Mixing on Nucleation of Protein Crystals. J. Am. Chem. Soc. 2005, 127, 9672– 9673,  DOI: 10.1021/ja052279v
      22
      Using microfluidics to observe the effect of mixing on nucleation of protein crystals
      Chen, Delai L.; Gerdts, Cory J.; Ismagilov, Rustem F.
      Journal of the American Chemical Society (2005), 127 (27), 9672-9673CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      This paper analyzes the effect of mixing on nucleation of protein crystals. The mixing of protein and precipitant was controlled by changing the flow rate in a plug-based microfluidic system. The nucleation rate inversely depended on the flow rate, and flow rate could be used to control nucleation. For example, at higher supersaturations, pptn. happened at low flow rates while large crystals grew at high flow rates. Mixing at low flow velocities in a winding channel induces nucleation more effectively than mixing in straight channels. A qual. scaling argument that relies on a no. of assumptions is presented to understand the exptl. results. In addn. to helping fundamental understanding, this result may be used to control nucleation, using rapid chaotic mixing to eliminate formation of ppts. at high supersatn. and using slow chaotic mixing to induce nucleation at lower supersatn.
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    23. 23
      Stephens, C. J.; Kim, Y. Y.; Evans, S. D.; Meldrum, F. C.; Christenson, H. K. Early Stages of Crystallization of Calcium Carbonate Revealed in Picoliter Droplets. J. Am. Chem. Soc. 2011, 133, 5210– 5213,  DOI: 10.1021/ja200309m
      23
      Early Stages of Crystallization of Calcium Carbonate Revealed in Picoliter Droplets
      Stephens, Christopher J.; Kim, Yi-Yeoun; Evans, Stephen D.; Meldrum, Fiona C.; Christenson, Hugo K.
      Journal of the American Chemical Society (2011), 133 (14), 5210-5213CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The authors studied the heterogeneous nucleation and growth of CaCO3 within regular arrays of picoliter droplets created on patterned self-assembled monolayers (SAMs). The SAMs provide well-defined substrates that offer control over CaCO3 nucleation, and the authors used these impurity-free droplet arrays to study crystal growth in spatially and chem. controlled, finite-reservoir environments. The results demonstrate a no. of remarkable features of pptn. within these confined vols. CaCO3 crystn. proceeds significantly more slowly in the droplets than in the bulk, allowing the mechanism of crystn., which progresses via amorphous Ca carbonate, to be easily obsd. The pptn. reaction terminates at an earlier stage than in the bulk soln., revealing intermediate growth forms. Confinement can therefore be used as a straightforward method for studying the mechanisms of crystn. on a substrate without the requirement for specialized anal. techniques. The results are also of significance to biomineralization processes, where crystn. typically occurs in confinement and in assocn. with org. matrixes, and it is envisaged that the method is applicable to many crystg. systems.
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    24. 24
      Stack, A. G. Precipitation in Pores: A Geochemical Frontier. Rev. Mineral. Geochem. 2015, 80, 165– 190,  DOI: 10.2138/rmg.2015.80.05
      There is no corresponding record for this reference.
    25. 25
      Bae, C.; Kim, S.; Ahn, B.; Kim, J.; Sung, M. M.; Shin, H. Template-Directed Gas-Phase Fabrication of Oxide Nanotubes. Chem. Mater. 2008, 20, 756– 767,  DOI: 10.1039/b716652d
      25
      Template-Directed Synthesis of Oxide Nanotubes: Fabrication, Characterization, and Applications
      Bae, Changdeuck; Yoo, Hyunjun; Kim, Sihyeong; Lee, Kyungeun; Kim, Jiyoung; Sung, Myung M.; Shin, Hyunjung
      Chemistry of Materials (2008), 20 (3), 756-767CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      A review. A template-directed synthesis strategy is an ideal tool to fabricate oxide nanotubes in that their phys. dimensions can be precisely controlled and monodisperse samples can be harvested in large quantity. The wall thickness of the oxide nanotubes is controllable by varying the deposition conditions, and the length and diam. can be tailored in accordance with the templates used. A wealth of functional oxide materials with the controlled polymorphs can be deposited to be nanotubular structures by various synthesis methods. This short review article describes the recent progress made in the field of the template synthesis of oxide nanotubes. We begin this review with the comprehensive survey on the research activities of the template-directed oxide nanotubes. We then focus on the template synthesis that combines porous membrane templates with various deposition techniques and discuss the processing issues assocd. with coating inside nanoscale pores, selective etching of oxide nanotubes from the templates, and dispersion against the formation of nanotubes' bundle-up. Structures and phys. properties of the oxide nanotubes prepd. by template synthesis are also summarized. Their potential for application in drug-delivery systems, sensors, and solar energy conversion devices, which could be facilitated by the template synthesis, is discussed. Finally, we conclude this review by providing our perspectives to the future directions in the template-directed oxide nanotubes.
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    26. 26
      Hurst, S. J.; Payne, E. K.; Qin, L.; Mirkin, C. A. Multisegmented One-Dimensional Nanorods Prepared by Hard-Template Synthetic Methods. Angew. Chem., Int. Ed. 2006, 45, 2672– 2692,  DOI: 10.1002/anie.200504025
      26
      Multisegmented one-dimensional nanorods prepared by hard-template synthetic methods
      Hurst, Sarah J.; Payne, Emma Kathryn; Qin, Lidong; Mirkin, Chad A.
      Angewandte Chemie, International Edition (2006), 45 (17), 2672-2692CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. In the science and engineering communities, the nanoscience revolution is intensifying. As many types of nanomaterials are becoming more reliably synthesized, they are being used for novel applications in all branches of nanoscience and nanotechnol. Since it is sometimes desirable for single nanomaterials to perform multiple functions simultaneously, multicomponent nanomaterials, such as core-shell, alloyed, and striped nanoparticles, are being more extensively researched. Nanoscientists hope to design multicomponent nanostructures and exploit their inherent multiple functionalities for use in many novel applications. This review highlights recent advances in the synthesis of multisegmented one-dimensional nanorods and nanowires with metal, semiconductor, polymer, mol., and even gapped components. It also discusses the applications of these multicomponent nanomaterials in magnetism, self-assembly, electronics, biol., catalysis, and optics. Particular emphasis is placed on the new materials and devices achievable using these multicomponent, rather than single-component, nanowire structures.
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    27. 27
      Zhou, H.; Wong, S. S. A Facile and Mild Synthesis of 1-D ZnO, CuO, and α-Fe2O3 Nanostructures and Nanostructured Arrays. ACS Nano 2008, 2, 944– 958,  DOI: 10.1021/nn700428x
      27
      A Facile and Mild Synthesis of 1-D ZnO, CuO, and α-Fe2O3 Nanostructures and Nanostructured Arrays
      Zhou, Hongjun; Wong, Stanislaus S.
      ACS Nano (2008), 2 (5), 944-958CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      ZnO nanowires, CuO nanowires, and α-Fe2O3 nanotubes as well as their corresponding arrays have been successfully synthesized via a low cost, generalizable, and simplistic template method. Diams. of one-dimensional (1-D) metal oxide nanostructures (∼60-260 nm), measuring micrometers in length, can be reliably and reproducibly controlled by the template pore channel dimensions. Assocd. vertically aligned arrays have been attached to the surfaces of a no. of geometrically significant substrates, such as curved plastic and glass rod motifs. The methodol. reported herein relies on the initial formation of an insol. metal hydroxide precursor, initially resulting from the reaction of the corresponding metal soln. and sodium hydroxide, and its subsequent transformation under mild conditions into the desired metal oxide nanostructures. Size- and shape-dependent optical, magnetic, and catalytic properties of as-prepd. 1-D metal oxides were investigated and noted to be mainly comparable to or better than the assocd. properties of the corresponding bulk oxides. A plausible mechanism for as-obsd. wire and tube-like motifs is also discussed.
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    28. 28
      Wang, Y.; Li, B.; Zhou, Y.; Jia, D. In Situ Mineralization of Magnetite Nanoparticles in Chitosan Hydrogel. Nanoscale Res. Lett. 2009, 4, 1041– 1046,  DOI: 10.1007/s11671-009-9355-1
      28
      In situ mineralization of magnetite nanoparticles in chitosan hydrogel
      Wang, Yongliang; Li, Baoqiang; Zhou, Yu; Jia, Dechang
      Nanoscale Research Letters (2009), 4 (9), 1041-1046CODEN: NRLAAD; ISSN:1556-276X. (Springer)
      Based on chelation effect between iron ions and amino groups of chitosan, in situ mineralization of magnetite nanoparticles in chitosan hydrogel under ambient conditions was carried out. The chelation effect between iron ions and amino groups in CS-Fe complex, which indicated that the chitosan hydrogel exerted a crucial control on the magnetite mineralization, was proved by X-ray photoelectron spectrum. The compn., morphol. and size of the mineralized magnetite nanoparticles were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy and thermal gravity. The mineralized nanoparticles were nonstoichiometric magnetite with a unit formula of Fe2.85O4 and coated by a thin layer of chitosan. The mineralized magnetite nanoparticles with mean diam. of 13 nm were dispersed in chitosan hydrogel uniformly. Magnetization measurement indicated that superparamagnetism behavior was exhibited. These magnetite nanoparticles mineralized in chitosan hydrogel have potential applications in the field of biotechnol. Moreover, this method can also be used to synthesize other kinds of inorg. nanoparticles, such as ZnO, Fe2O3 and hydroxyapatite.
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    29. 29
      Liefferink, R. W.; Naillon, A.; Bonn, D.; Prat, M.; Shahidzadeh, N. Single Layer Porous Media with Entrapped Minerals for Microscale Studies of Multiphase Flow. Lab Chip 2018, 18, 1094– 1104,  DOI: 10.1039/c7lc01377a
      29
      Single layer porous media with entrapped minerals for microscale studies of multiphase flow
      Liefferink, R. W.; Naillon, A.; Bonn, D.; Prat, M.; Shahidzadeh, N.
      Lab on a Chip (2018), 18 (7), 1094-1104CODEN: LCAHAM; ISSN:1473-0189. (Royal Society of Chemistry)
      The behavior of minerals (i.e. salts) such as sodium chloride and calcite in porous media is very important in various applications such as weathering of artworks, oil recovery and CO2 sequestration. We report a novel method for manufg. single layer porous media in which minerals can be entrapped in a controlled way in order to study their dissoln. and recrystn. In addn., our manufg. method is a versatile tool for creating monomodal, bimodal or multimodal pore size microporous media with controlled porosity ranging from 25% to 50%. These micromodels allow multiphase flows to be quant. studied with different microscopy techniques and can serve to validate numerical models that can subsequently be extended to the 3D situation where visualization is exptl. difficult. As an example of their use, deliquescence (dissoln. by moisture absorption) of entrapped NaCl crystals is studied; our results show that the invasion of the resulting salt soln. is controlled by the capillary pressure within the porous network. For hydrophilic porous media, the liq. preferentially invades the small pores whereas in a hydrophobic network the large pores are filled. Consequently, after several deliquescence/drying cycles in the hydrophilic system, the salt is transported towards the outside of the porous network via small pores; in hydrophobic micromodels, no salt migration is obsd. Numerical simulations based on the characteristics of our single layer pore network agree very well with the exptl. results and give more insight into the dynamics of salt transport through porous media.
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    30. 30
      Manno, R.; Ranjan, P.; Sebastian, V.; Mallada, R.; Irusta, S.; Sharma, U. K.; Van der Eycken, E. V.; Santamaria, J. Continuous Microwave-Assisted Synthesis of Silver Nanoclusters Confined in Mesoporous SBA-15: Application in Alkyne Cyclizations. Chem. Mater. 2020, 32, 2874– 2883,  DOI: 10.1021/acs.chemmater.9b04935
      30
      Continuous Microwave-Assisted Synthesis of Silver Nanoclusters Confined in Mesoporous SBA-15: Application in Alkyne Cyclizations
      Manno, Roberta; Ranjan, Prabhat; Sebastian, Victor; Mallada, Reyes; Irusta, Silvia; Sharma, Upendra K.; Van der Eycken, Erik V.; Santamaria, Jesus
      Chemistry of Materials (2020), 32 (7), 2874-2883CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      Metal nanoclusters are becoming exciting candidates as highly efficient catalysts for heterogeneous processes in view of their extraordinary surface to vol. ratio and the high concn. of uncoordinated atoms that contribute to enhanced catalytic activity. For this reason, the development of accurate and reliable procedures for the synthesis of stable and supported metal nanoclusters is highly desirable. Although Ag-nanoclusters (Ag-NCs) stabilized by anion templates with a structure like Ag(n + m)m + and a long lifetime have been widely investigated, supported clusters present significant advantages regarding their recovery and recyclability. In spite of their potential, the stabilization of clusters of precious metals on porous substrates is scarcely investigated. Herein, we present an innovative approach for the synthesis of stable Ag nanoclusters designed with the aim of achieving a strict control of key phases such as mixing, microwave heating and quenching. The catalyst was used for the activation of alkynes showing excellent activity for the formation of C-O, C-N and C-C bonds. When compared with commonly used homogeneous Ag-salts, Ag-NCs enhanced the catalytic activity toward the cyclization of a wide range of substrates, thereby minimizing the metal loading and allowing the sepn. as well as the reuse of the catalyst for multiple cycles.
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    31. 31
      Meyer, R. R.; Sloan, J.; Dunin-Borkowski, R. E.; Kirkland, A. I.; Novotny, M. C.; Bailey, S. R.; Hutchison, J. L.; Green, M. L. H. Discrete Atom Imaging of One-Dimensional Crystals Formed within Single-Walled Carbon Nanotubes. Science 2000, 289, 1324– 1326,  DOI: 10.1126/science.289.5483.1324
      31
      Discrete atom imaging of one-dimensional crystals formed within single-walled carbon nanotube
      Meyer, Riidiger R.; Sloan, Jeremy; Dunin-Borkowski, Rafal E.; Kirkland, Angus I.; Novotny, Miles C.; Bailey, Sam R.; Hutchison, John L.; Green, Malcolm L. H.
      Science (Washington, D. C.) (2000), 289 (5483), 1324-1326CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      The complete crystallog. of a 1-dimensional crystal of KI encapsulated within a 1.6-nm-diam. single-walled C nanotube was detd. with high-resoln. TEM. Individual atoms of K and I within the crystal were identified from a phase image that was reconstructed with a modified focal series restoration approach. The lattice spacings within the crystal are substantially different from those in bulk KI. This is attributed to the reduced coordination of the surface atoms of the crystal and the close proximity of the van der Waals surface of the confining nanotube.
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    32. 32
      Guan, L.; Suenaga, K.; Shi, Z.; Gu, Z.; Iijima, S. Polymorphic Structures of Iodine and Their Phase Transition in Confined Nanospace. Nano Lett. 2007, 7, 1532– 1535,  DOI: 10.1021/nl070313t
      32
      Polymorphic Structures of Iodine and Their Phase Transition in Confined Nanospace
      Guan, Lunhui; Suenaga, Kazu; Shi, Zujin; Gu, Zhennan; Iijima, Sumio
      Nano Letters (2007), 7 (6), 1532-1535CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
      At. chains and crystal of I were successfully generated in a controlled manner inside single-walled C nanotubes (SWNTs). The structure is strongly dependent on the diam. of SWNTs; the single, double, and triple helical structures became quite stable when the diam. of SWNTs matches the certain size. More than three chains of I are not very stable, and they often crystallize inside the C nanotube when the diam. is larger than 1.45 nm. The crystn. or phase transition in a confined nanospace is thus directly obsd., and there is indeed a crit. size of the hollow nanospace for the stable formation of the at. chains of I.
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    33. 33
      Nakamuro, T.; Sakakibara, M.; Nada, H.; Harano, K.; Nakamura, E. Capturing the Moment of Emergence of Crystal Nucleus from Disorder. J. Am. Chem. Soc. 2021, 143, 1763– 1767,  DOI: 10.1021/jacs.0c12100
      33
      Capturing the Moment of Emergence of Crystal Nucleus from Disorder
      Nakamuro, Takayuki; Sakakibara, Masaya; Nada, Hiroki; Harano, Koji; Nakamura, Eiichi
      Journal of the American Chemical Society (2021), 143 (4), 1763-1767CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Crystn. is the process of atoms or mols. forming an organized solid via nucleation and growth. Being intrinsically stochastic, the research at an atomistic level was a huge exptl. challenge. In situ detection is reported of a crystal nucleus forming during nucleation/growth of a NaCl nanocrystal, as video recorded in the interior of a vibrating conical C nanotube at 20-40 ms/frame with localization precision of <0.1 nm. NaCl units were seen assembled to form a cluster fluctuating between featureless and semiordered states, which suddenly formed a crystal. Subsequent crystal growth at 298 K and shrinkage at 473 K took place also in a stochastic manner. Productive contributions of the graphitic surface and its mech. vibration were exptl. indicated.
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    34. 34
      Ueno, T. Porous Protein Crystals as Reaction Vessels. Chem. -Eur. J. 2013, 19, 9096– 9102,  DOI: 10.1002/chem.201300250
      34
      Porous Protein Crystals as Reaction Vessels
      Ueno, Takafumi
      Chemistry - A European Journal (2013), 19 (28), 9096-9102CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Porous protein crystals have the potential to provide new porous materials due to their unique chem. environments composed of amino acid residues periodically exposed at the surface of the solvent channels in the crystal lattice. This enables accumulation of external compds. in special arrangements by metal coordination interactions or by chem. modifications. This article presents a review of advances in the recently established field of porous protein crystals.
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    35. 35
      Ding, Y.; Shi, L.; Wei, H. Protein-Directed Approaches to Functional Nanomaterials: A Case Study of Lysozyme. J. Mater. Chem. B 2014, 2, 8268– 8291,  DOI: 10.1039/c4tb01235f
      35
      Protein-directed approaches to functional nanomaterials: a case study of lysozyme
      Ding, Yubin; Shi, Leilei; Wei, Hui
      Journal of Materials Chemistry B: Materials for Biology and Medicine (2014), 2 (47), 8268-8291CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
      A review. Functional nanomaterials have found wide applications in diverse areas because of their intrinsically different properties compared to their bulk counterparts. To achieve the goal of prepg. functional nanomaterials, various strategies have been successfully developed. Among them, the biomol.-directed approach has been extensively explored to synthesize many functional nanomaterials owing to their programmability, self-assembly and recognition capabilities. This Feature Article highlights the use of lysozyme as a model protein to the direct synthesis of nanomaterials. Future advances in rational de novo design and synthesis of functional nanomaterials with proteins will depend on a deep understanding of the synthetic strategies and the formation mechanisms. This Feature Article discusses the synthesis of nanomaterials with lysozyme in both the soln. phase and crystal form. The synthetic strategies, formation mechanisms and wide applications of several kinds of materials, such as metals, oxides, metal sulfides, and composites, are covered. The lessons from this case study will provide invaluable guidance in future materials design using proteins and other biomols. Rational design of personalized functional nanomaterials will be possible in the future (366 refs.).
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    36. 36
      Margolin, A. L.; Navia, M. A. Protein Crystals as Novel Catalytic Materials. Angew. Chem., Int. Ed. 2001, 40, 2204– 2222,  DOI: 10.1002/1521-3773(20010618)40:12<2204::aid-anie2204>3.0.co;2-j
      36
      Protein crystals as novel catalytic materials
      Margolin, Alexey L.; Navia, Manuel A.
      Angewandte Chemie, International Edition (2001), 40 (12), 2204-2222CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH)
      A review, with 146 refs. In this era of mol. biol., protein crystn. is often considered to be a necessary first step in obtaining structural information through x-ray diffraction anal. In a different light, protein crystals can also be thought of as materials, whose chem. and phys. properties make them broadly attractive and useful across a larger spectrum of disciplines. The full potential of these protein cryst. materials has been severely restricted in practice, however, both by their inherent fragility, and by strongly held skepticism concerning their routine and predictable growth, formulation, and practical application. Fortunately, these problems have turned out to be solvable. A systematic exploration of the biophysics and biochem. of protein crystn. has shown that one can dependably create new protein cryst. materials more or less at will. In turn, these crystals can be readily strengthened, both chem. and mech., to make them suitable for practical commercialization. Today, these novel materials are used as industrial catalysts on a com. scale, in bioremediation and "green chem." applications, and in enantioselective chromatog. of pharmaceuticals and fine chems. In the near future, their utility will expand, to include the purifn. of protein drugs, formulation of direct protein therapeutics, and development of adjuvant-less vaccines.
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    37. 37
      Fernández-Penas, R.; Verdugo-Escamilla, C.; Martínez-Rodríguez, S.; Gavira, J. A. Production of Cross-Linked Lipase Crystals at a Preparative Scale. Cryst. Growth Des. 2021, 21, 1698– 1707,  DOI: 10.1021/acs.cgd.0c01608
      37
      Production of Cross-Linked Lipase Crystals at a Preparative Scale
      Fernandez-Penas, Raquel; Verdugo-Escamilla, Cristobal; Martinez-Rodriguez, Sergio; Gavira, Jose A.
      Crystal Growth & Design (2021), 21 (3), 1698-1707CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      The autoimmobilization of enzymes via cross-linked enzyme crystals (CLECs) has regained interest in recent years, boosted by the extensive knowledge gained in protein crystn., the decrease of cost and laboriousness of the process, and the development of potential applications. In this work, we present the crystn. and preparative-scale prodn. of reinforced cross-linked lipase crystals (RCLLCs) using a com. detergent additive as a raw material. Bulk crystn. was carried out in 500 mL of agarose media using the batch technique. Agarose facilitates the homogeneous prodn. of crystals, their crosslinking treatment, and their extn. RCLLCs were active in an aq. soln. and in hexane, as shown by the hydrolysis of p-nitrophenol butyrate and α-methylbenzyl acetate, resp. RCLLCs presented both high thermal and robust operational stability, allowing the prepn. of a packed-bed chromatog. column to work in a continuous flow. Finally, we detd. the three-dimensional (3D) models of this com. lipase crystd. with and without phosphate at 2.0 and 1.7 Å resolns., resp.
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    38. 38
      Conejero-Muriel, M.; Rodríguez-Ruiz, I.; Verdugo-Escamilla, C.; Llobera, A.; Gavira, J. A. Continuous Sensing Photonic Lab-on-a-Chip Platform Based on Cross-Linked Enzyme Crystals. Anal. Chem. 2016, 88, 11919– 11923,  DOI: 10.1021/acs.analchem.6b03793
      38
      Continuous Sensing Photonic Lab-on-a-Chip Platform Based on Cross-Linked Enzyme Crystals
      Conejero-Muriel, Mayte; Rodriguez-Ruiz, Isaac; Verdugo-Escamilla, Cristobal; Llobera, Andreu; Gavira, Jose A.
      Analytical Chemistry (Washington, DC, United States) (2016), 88 (23), 11919-11923CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
      Microfluidics or lab-on-a-chip technol. offer clear advantages over conventional systems such as a dramatic redn. of reagent consumption or a shorter anal. time, which are translated into costs effective systems. In this work, we present a photonic enzymic lab on a chip reactor based on Cross-Linked Enzyme Crystals (CLECs), able to work in continuous flow, as a highly sensitive, robust, reusable and stable platform for continuous sensing with superior performance as compared to the state of the art. The microreactor is designed to facilitate the in situ crystn. and crystal crosslinking generating enzymically active material that can be stored for months/years. Thus, and by means of monolithically integrated micro-optics elements, continuous enzymic reactions can be spectrophotometrically monitored. Lipase, an enzyme with industrial significance for catalyzed transesterification, hydrolysis and esterification reactions, is used to demonstrate the potential of the microplatforms as both a continuous biosensor or as a microreactor for the synthesis of high value compds.
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    39. 39
      Contreras-Montoya, R.; Escolano, G.; Roy, S.; Lopez-Lopez, M. T.; Delgado-López, J. M.; Cuerva, J. M.; Díaz-Mochón, J. J.; Ashkenasy, N.; Gavira, J. A.; Álvarez de Cienfuegos, L. Catalytic and Electron Conducting Carbon Nanotube–Reinforced Lysozyme Crystals. Adv. Funct. Mater. 2018, 29, 1807351  DOI: 10.1002/adfm.201807351
      There is no corresponding record for this reference.
    40. 40
      Falkner, J. C.; Turner, M. E.; Bosworth, J. K.; Trentler, T. J.; Johnson, J. E.; Lin, T.; Colvin, V. L. Virus Crystals as Nanocomposite Scaffolds. J. Am. Chem. Soc. 2005, 127, 5274– 5275,  DOI: 10.1021/ja044496m
      40
      Virus Crystals as Nanocomposite Scaffolds
      Falkner, Joshua C.; Turner, Mary E.; Bosworth, Joan K.; Trentler, Timothy J.; Johnson, John E.; Lin, Tianwei; Colvin, Vicki L.
      Journal of the American Chemical Society (2005), 127 (15), 5274-5275CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The generation of long-range three-dimensional nanoscopic patterns is a major goal in materials chem. Here we report a strategy for creating such systems using virus crystals as scaffolds which can be infiltrated with metal specifically palladium and platinum. The inorg. component effectively packs within the porous macromol. crystal architecture, providing a route for patterning these materials on the nanometer length scale. To verify the quality of the metal infiltration, SEM-EDX was used to det. the homogeneous distribution of metal across the crystal, and TEM was used to confirm that the metal was confined within the porous structure of the crystal.
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    41. 41
      Guli, M.; Lambert, E. M.; Li, M.; Mann, S. Template-Directed Synthesis of Nanoplasmonic Arrays by Intracrystalline Metalization of Cross-Linked Lysozyme Crystals. Angew. Chem., Int. Ed. 2010, 49, 520– 523,  DOI: 10.1002/anie.200905070
      41
      Template-Directed Synthesis of Nanoplasmonic Arrays by Intracrystalline Metalization of Cross-Linked Lysozyme Crystals
      Guli, Mina; Lambert, Elizabeth M.; Li, Mei; Mann, Stephen
      Angewandte Chemie, International Edition (2010), 49 (3), 520-523, S520/1-S520/6CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Here, we extend the above strategies for the sequestration of metal ions and their redn. products within the solvent channels of glutaraldehyde crosslinked lysozyme single crystals. Herein, we exploit this structural arrangement as an ordered 1-D intracryst. reaction environment for the periodic organization and nanoscale confinement of plasmonic nanowires of Ag or Au. Arrays of metallic nanofilaments are produced within the protein crystals by in situ redox reactions involving photoredn. of sequestered Ag' ions or chem. redn. of AuCl4- by BH4- ions pre-organized into the solvent channels. The resulting metalized protein crystals are phys. robust, regular in external morphol., and uniform in size. Such materials represent a new class of hybrid monoliths with patterned nanostructured interiors, and may find uses as waveguides, sensors, and catalysts.
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    42. 42
      Liang, M.; Wang, L.; Su, R.; Qi, W.; Wang, M.; Yu, Y.; He, Z. Synthesis of Silver Nanoparticles within Cross-Linked Lysozyme Crystals as Recyclable Catalysts for 4-Nitrophenol Reduction. Catal. Sci. Technol. 2013, 3, 1910– 1914,  DOI: 10.1039/c3cy00157a
      42
      Synthesis of silver nanoparticles within cross-linked lysozyme crystals as recyclable catalysts for 4-nitrophenol reduction
      Liang, Miao; Wang, Libing; Su, Rongxin; Qi, Wei; Wang, Mengfan; Yu, Yanjun; He, Zhimin
      Catalysis Science & Technology (2013), 3 (8), 1910-1914CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
      For the first time, we demonstrated the fabrication of silver nanoparticles (NPs) in cross-linked protein crystal hybrid material with catalytic properties using a facile chem. redn. method. The macroscopic porous lysozyme crystals can be used as excellent templates for the incorporation of Ag nanoparticles. The resulting AgNP-in-lysozyme crystal composites exhibited a good catalytic activity toward nitrophenol redn. Notably, these catalysts could be easily recovered and reused for at least five successive cycles with almost const. activity and conversion efficiency.
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    43. 43
      Muskens, O. L.; England, M. W.; Danos, L.; Li, M.; Mann, S. Plasmonic Response of Ag- and Au-Infiltrated Cross-Linked Lysozyme Crystals. Adv. Funct. Mater. 2013, 23, 281– 290,  DOI: 10.1002/adfm.201201718
      43
      Plasmonic Response of Ag- and Au-Infiltrated Cross-Linked Lysozyme Crystals
      Muskens, Otto L.; England, Matt W.; Danos, Lefteris; Li, Mei; Mann, Stephen
      Advanced Functional Materials (2013), 23 (3), 281-290CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Metal-infiltrated protein crystals form a novel class of bio-nanomaterials of great interest for applications in biomedicine, chem., and optoelectronics. As yet, very little is known about the internal structure of these materials and the interconnectivity of the metallic network. Here, the optical response of individual Au- and Ag-infiltrated cross-linked lysozyme crystals is investigated using angle- and polarization-dependent spectroscopy. The measurements unequivocally show that metallic inclusions formed inside the nanoporous solvent channels do not connect into continuous nanowires, but rather consist of ensembles of isolated spheroidal nanoclusters with aspect ratios as high as a value of four, and which exhibit a pronounced plasmonic response that is isotropic on a macroscopic length scale. Fluorescence measurement in the visible range show a strong contribution from the protein host, which is quenched by the Au inclusions, and a weaker contribution attributed to the mol.-like emission from small Au-clusters.
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    44. 44
      Wei, H.; Wang, Z.; Zhang, J.; House, S.; Gao, Y. G.; Yang, L.; Robinson, H.; Tan, L. H.; Xing, H.; Hou, C.; Robertson, I. M.; Zuo, J. M.; Lu, Y. Time-Dependent, Protein-Directed Growth of Gold Nanoparticles within a Single Crystal of Lysozyme. Nat. Nanotechnol. 2011, 6, 93– 97,  DOI: 10.1038/nnano.2010.280
      44
      Time-dependent, protein-directed growth of gold nanoparticles within a single crystal of lysozyme
      Wei, Hui; Wang, Zidong; Zhang, Jiong; House, Stephen; Gao, Yi-Gui; Yang, Limin; Robinson, Howard; Tan, Li Huey; Xing, Hang; Hou, Changjun; Robertson, Ian M.; Zuo, Jian-Min; Lu, Yi
      Nature Nanotechnology (2011), 6 (2), 93-97CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)
      Gold nanoparticles are useful in biomedical applications due to their distinct optical properties and high chem. stability. Reports of the biogenic formation of gold colloids from gold complexes has also led to an increased level of interest in the biomineralization of gold. However, the mechanism responsible for biomol.-directed gold nanoparticle formation remains unclear due to the lack of structural information about biol. systems and the fast kinetics of biomimetic chem. systems in soln. Here the authors show that intact single crystals of lysozyme can be used to study the time-dependent, protein-directed growth of gold nanoparticles. The protein crystals slow down the growth of the gold nanoparticles, allowing detailed kinetic studies to be carried out, and permit a three-dimensional structural characterization that would be difficult to achieve in soln. Furthermore, the authors show that addnl. chem. species can be used to fine-tune the growth rate of the gold nanoparticles.
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    45. 45
      Wei, H.; Lu, Y. Catalysis of Gold Nanoparticles within Lysozyme Single Crystals. Chem. -Asian J. 2012, 7, 680– 683,  DOI: 10.1002/asia.201100942
      45
      Catalysis of Gold Nanoparticles within Lysozyme Single Crystals
      Wei, Hui; Lu, Yi
      Chemistry - An Asian Journal (2012), 7 (4), 680-683CODEN: CAAJBI; ISSN:1861-4728. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Bio-nano hybrid materials have been the focus of numerous studies because they combine the merits of both biomols. and nanomaterials, with potential for a wide range of applications in catalysis, electronic devices, energy conversion and storage, drug delivery, imaging, and sensing. Here we have demonstrated that AuNPs grown in situ within a lysozyme protein crystal could be used as efficient catalyst to catalyze the redn. of p-nitrophenol by NaBH4. The precise control of the AuNP sizes by the single crystals of lysozyme allowed us to elucidate the relationship between the catalytic activity and the size of the crystals. Furthermore, we showed that the catalytic activity of the AuNPs@Lys could be modulated by fine-tuning the AuNPs growth with addnl. chems. to either accelerate or inhibit the AuNP growth. This work provides insights into the development of new highly efficient catalysts by incorporating inorg. materials within protein crystals.
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    46. 46
      Abe, S.; Tsujimoto, M.; Yoneda, K.; Ohba, M.; Hikage, T.; Takano, M.; Kitagawa, S.; Ueno, T. Porous Protein Crystals as Reaction Vessels for Controlling Magnetic Properties of Nanoparticles. Small 2012, 8, 1314– 1319,  DOI: 10.1002/smll.201101866
      46
      Porous Protein Crystals as Reaction Vessels for Controlling Magnetic Properties of Nanoparticles
      Abe, Satoshi; Tsujimoto, Masahiko; Yoneda, Ko; Ohba, Masaaki; Hikage, Tatsuo; Takano, Mikio; Kitagawa, Susumu; Ueno, Takafumi
      Small (2012), 8 (9), 1314-1319CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The authors have demonstrated the synthesis of magnetic bimetallic CoPt-NPs within porous HEWL crystals and succeeded in controlling magnetic properties of CoPt-NPs by using different crystal systems of HEWL. This represents the first example of using protein crystals as solid biomol. templates for the synthesis of magnetic nanoparticles. The authors succeeded in obtaining CoPt-NPs with the largest coercivity values among previously reported protein assemblies in soln. The high coercivity of CoPt*0 is due to the rigid reaction channels where metal ions can accumulate and where the size-restricted CoPt-NPs independentally align affecting the magnetic anisotropy.
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    47. 47
      Wei, H.; House, S.; Wu, J.; Zhang, J.; Wang, Z.; He, Y.; Gao, E. J.; Gao, Y.; Robinson, H.; Li, W.; Zuo, J.; Robertson, I. M.; Lu, Y. Enhanced and Tunable Fluorescent Quantum Dots within a Single Crystal of Protein. Nano Res. 2013, 6, 627– 634,  DOI: 10.1007/s12274-013-0348-0
      47
      Enhanced and tunable fluorescent quantum dots within a single crystal of protein
      Wei, Hui; House, Stephen; Wu, Jiangjiexing; Zhang, Jiong; Wang, Zidong; He, Ying; Gao, Elizabeth J.; Gao, Yigui; Robinson, Howard; Li, Wei; Zuo, Jianmin; Robertson, Ian M.; Lu, Yi
      Nano Research (2013), 6 (9), 627-634CODEN: NRAEB5; ISSN:1998-0000. (Springer GmbH)
      The design and synthesis of bio-nano hybrid materials can not only provide new materials with novel properties, but also advance our fundamental understanding of interactions between biomols. and their abiotic counterparts. Here, we report a new approach to achieving such a goal by growing CdS quantum dots (QDs) within single crystals of lysozyme protein. This bio-nano hybrid emitted much stronger red fluorescence than its counterpart without the crystal, and such fluorescence properties could be either enhanced or suppressed by the addn. of Ag(I) or Hg(II), resp. The three-dimensional incorporation of CdS QDs within the lysozyme crystals was revealed by scanning transmission electron microscopy with electron tomog. More importantly, since our approach did not disrupt the cryst. nature of the lysozyme crystals, the metal and protein interactions were able to be studied by X-ray crystallog., thus providing insight into the role of Cd(II) in the CdS QDs formation. [Figure not available: see fulltext.].
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    48. 48
      Perez-Gonzalez, T.; Rodriguez-Navarro, A.; Jimenez-Lopez, C. Inorganic Magnetite Precipitation at 25 °C: A Low-Cost Inorganic Coprecipitation Method. J. Supercond. Novel Magn. 2011, 24, 549– 557,  DOI: 10.1007/s10948-010-0999-y
      48
      Inorganic Magnetite Precipitation at 25°C. A Low-Cost Inorganic Coprecipitation Method
      Perez-Gonzalez, T.; Rodriguez-Navarro, A.; Jimenez-Lopez, C.
      Journal of Superconductivity and Novel Magnetism (2011), 24 (1-2), 549-557CODEN: JSNMBN; ISSN:1557-1939. (Springer)
      An easy, low-cost copptn. method to inorganically produce magnetite nanoparticles from solns., in free-drift expts., under anoxic conditions, at 25° and 1 atm pressure is here presented. By using this method, pure magnetite is obtained as the final solid, which shows the typical magnetic properties and thermal stability behavior of magnetite produced by other methods. The size of the magnetite crystals produced by the present method varies from relatively big sizes (200-300 nm), to sizes within the single magnetic domain range, just depending on the incubation time. The soln. from which magnetite ppts. may be representative of certain natural environments where bacteria that produce magnetite may live and, thus, our magnetite may be used as an inorg. ref. to compare to biol. produced magnetites.
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    49. 49
      Downs, R. T.; Bartelmehs, K. L.; Gibbs, G. V.; Boisen, M. B. Interactive Software for Calculating and Displaying X-Ray or Neutron Powder Diffractometer Patterns of Crystalline Materials. Am. Mineral. 1993, 78, 1104– 1107
      49
      Interactive software for calculating and displaying x-ray or neutron powder diffractometer patterns of crystalline materials
      Downs, R. T.; Bartelmehs, K. L.; Gibbs, G. V.; Boisen, M. B., Jr.
      American Mineralogist (1993), 78 (9-10), 1104-7CODEN: AMMIAY; ISSN:0003-004X.
      Two computer programs, XPOW and XPOWPLOT, that generate and graph x-ray or neutron powder diffractometer patterns of cryst. materials are described. The input for XPOW requires only the radiation wavelength, cell dimensions, space group, and positional parameters for the atoms in the asym. unit. The output includes a listing of the d values, 2θ values, and the relative intensities for the nonequiv. Bragg reflections within a given 2θ interval. Using the XPOW output, the XPOWPLOT program creates menu-aided interactive color displays of up to five powder diffractometer patterns simultaneously on the PC monitor.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3sXmsFektLg%253D&md5=3744e7b44cda261d28e38e08c85092d5
    50. 50
      Uwada, T.; Kouno, K.; Ishikawa, M. In Situ Absorption and Fluorescence Microspectroscopy Investigation of the Molecular Incorporation Process into Single Nanoporous Protein Crystals. ACS Omega 2020, 5, 9605– 9613,  DOI: 10.1021/acsomega.0c01038
      50
      In Situ Absorption and Fluorescence Microspectroscopy Investigation of the Molecular Incorporation Process into Single Nanoporous Protein Crystals
      Uwada, Takayuki; Kouno, Kohei; Ishikawa, Mitsuru
      ACS Omega (2020), 5 (16), 9605-9613CODEN: ACSODF; ISSN:2470-1343. (American Chemical Society)
      Protein crystals exhibit distinct three-dimensional structures, which contain well-ordered nanoporous solvent channels, providing a chem. heterogeneous environment. In this paper, the incorporation of various mols. into the solvent channels of native hen egg-white lysozyme crystals was demonstrated using fluorescent dyes, including acridine yellow G, rhodamine 6G, and eosin Y. The process was evaluated on the basis of absorption and fluorescence microspectroscopy at a single-crystal level. The mol. loading process was clearly visualized as a function of time, and it was detd. that the protein crystals could act as nanoporous materials. It was found that the incorporation process is strongly dependent on the mol. charge, leading to heterogeneous mol. aggregation, which suggests host-guest interaction of protein crystals from the viewpoint of nanoporous materials.
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    51. 51
      Bereczk-Tompa, É.; Vonderviszt, F.; Horváth, B.; Szalai, I.; Pósfai, M. Biotemplated Synthesis of Magnetic Filaments. Nanoscale 2017, 9, 15062– 15069,  DOI: 10.1039/c7nr04842d
      51
      Biotemplated synthesis of magnetic filaments
      Bereczk-Tompa, Eva; Vonderviszt, Ferenc; Horvath, Barnabas; Szalai, Istvan; Posfai, Mihaly
      Nanoscale (2017), 9 (39), 15062-15069CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
      With the aim of creating one-dimensional magnetic nanostructures, we genetically engineered flagellar filaments produced by Salmonella bacteria to display iron- or magnetite-binding sites, and used the mutant filaments as templates for both nucleation and attachment of the magnetic iron oxide magnetite. Although nucleation from soln. and attachment of nanoparticles to a pre-existing surface are two different processes, non-classical crystal nucleation pathways have been increasingly recognized in biol. systems, and in many cases nucleation and particle attachment cannot be clearly distinguished. In this study we tested the magnetite-nucleating ability of four types of mutant flagella previously shown to be efficient binders of magnetite nanoparticles, and we used two other mutant flagella that were engineered to periodically display known iron-binding oligopeptides on their surfaces. All mutant filaments were demonstrated to be efficient as templates for the synthesis of one-dimensional magnetic nanostructures under ambient conditions. Both approaches resulted in similar final products, with randomly oriented magnetite nanoparticles partially covering the filamentous biol. templates. In an external magnetic field, the viscosity of a suspension of the produced magnetic filaments showed a twofold increase relative to the control sample. The results of magnetic susceptibility measurements were also consistent with the magnetic nanoparticles occurring in linear structures. Our study demonstrates that biol. templating can be used to produce one-dimensional magnetic nanostructures under benign conditions, and that modified flagellar filaments can be used for creating model systems in which crystal nucleation from soln. can be exptl. studied.
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    52. 52
      Contreras-Montoya, R.; Jabalera, Y.; Blanco, V.; Cuerva, J. M.; Jimenez-Lopez, C.; Alvarez De Cienfuegos, L. Lysine as Size-Control Additive in a Bioinspired Synthesis of Pure Superparamagnetic Magnetite Nanoparticles. Cryst. Growth Des. 2020, 20, 533– 542,  DOI: 10.1021/acs.cgd.9b00169
      52
      Lysine as Size-Control Additive in a Bioinspired Synthesis of Pure Superparamagnetic Magnetite Nanoparticles
      Contreras-Montoya, Rafael; Jabalera, Ylenia; Blanco, Victor; Cuerva, Juan Manuel; Jimenez-Lopez, Concepcion; Alvarez de Cienfuegos, Luis
      Crystal Growth & Design (2020), 20 (2), 533-542CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      Magnetite nanoparticles (MNPs) are being used in a no. of nanotechnol. applications, esp. biomedical, both in diagnosis and in therapeutics such as hyperthermia agents and as drug nanocarriers for targeted chemotherapy. However, the development of efficient methodologies to produce novel MNPs with the specific requirements needed for biomedical applications is still challenging. In this context, biomimetic approaches taking use of magnetosome proteins expressed as recombinant and/or polyamino acids are becoming of great interest. In fact, these protocols give rise to magnetite nanoparticles of adequate size, magnetic properties and surface functionalization that make them compatible for biomedical applications. In this respect, herein lysine (Lys), unlike other amino acids like arginine (Arg), is able to exert a control over the size of MNPs produced in H2O and at room temp. This control occurs through the stabilization of the magnetite nuclei by the lateral NH4+ group of Lys. The strength of such stabilization allows a further release of these previously bonded nuclei to allow the further growth of the larger ones, thus resulting in larger crystals compared to those obtained by using Arg or no amino acids at all. MNPs obtained by the mediation of this amino acid are fairly large (30 nm) while being superparamagnetic at room temp. They present an isoelec. point of 4, which may allow the coupling/release of these MNPs to other mols. based on electrostatic interaction, a large magnetic moment per particle and high magnetization satn. This study highlights the effects that biol. additives have in the process of magnetite biomineralization and goes along the line of previous reports using magnetosome proteins and polyamino acids. Lysine is able to exert a control over the size of magnetite nanoparticles obtained from aq. solns. in free-drift expts. performed at room temp. These magnetites show well-faceted faces and sizes at 20-30 nm. Lysine adsorbs on the surface of the magnetites, making them neg. charged at physiol. pH and suitable for biotechnol. applications.
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    53. 53
      García Rubia, G.; Peigneux, A.; Jabalera, Y.; Puerma, J.; Oltolina, F.; Elert, K.; Colangelo, D.; Gómez Morales, J.; Prat, M.; Jimenez-Lopez, C. PH-Dependent Adsorption Release of Doxorubicin on MamC-Biomimetic Magnetite Nanoparticles. Langmuir 2018, 34, 13713– 13724,  DOI: 10.1021/acs.langmuir.8b03109
      53
      pH-Dependent Adsorption Release of Doxorubicin on MamC-Biomimetic Magnetite Nanoparticles
      Garcia Rubia, German; Peigneux, Ana; Jabalera, Ylenia; Puerma, Javier; Oltolina, Francesca; Elert, Kerstin; Colangelo, Donato; Gomez Morales, Jaime; Prat, Maria; Jimenez-Lopez, Concepcion
      Langmuir (2018), 34 (45), 13713-13724CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      New biomimetic magnetite nanoparticles (hereafter BMNPs) with sizes larger than most common superparamagnetic nanoparticles were produced in the presence of the recombinant MamC protein from Magnetococcus marinus MC-1 and functionalized with doxorubicin (DOXO) intended as potential drug nanocarriers. Unlike inorg. magnetite nanoparticles, in BMNPs the MamC protein controls their size and morphol., providing them with magnetic properties consistent with a large magnetic moment per particle; moreover, it provides the nanoparticles with novel surface properties. BMNPs display the isoelec. point at pH 4.4, being strongly neg. charged at physiol. pH (pH 7.4). This allows both (i) their functionalization with DOXO, which is pos. charged at pH 7.4, and (ii) the stability of the DOXO-surface bond and DOXO release to be pH dependent and governed by electrostatic interactions. DOXO adsorption follows a Langmuir-Freundlich model, and the coupling of DOXO to BMNPs (binary biomimetic nanoparticles) is very stable at physiol. pH (max. release of 5% of the drug adsorbed). Conversely, when pH decreases, these electrostatic interactions weaken, and at pH 5, DOXO is released up to ∼35% of the amt. initially adsorbed. The DOXO-BMNPs display cytotoxicity on the GTL-16 human gastric carcinoma cell line in a dose-dependent manner, reaching about ∼70% of mortality at the max. amt. tested, while the nonloaded BMNPs are fully cytocompatible. The present data suggest that BMNPs could be useful as potential drug nanocarriers with a drug adsorption-release governed by changes in local pH values.
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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.cgd.2c01436.

    • Figure S1: Elemental analysis of CLLCs, Figure S2 d-spacing values of the diffraction pattern shown in Figure 4A2; Table S1. d-spacing values of the diffraction pattern shown in Figure 6A2,B2,C2,D2; Figure S3: Protocol for iron oxide nanoparticle distribution determination; Figure S4: magnetite crystals grown in the bulk (protein free); Figure S5: HR-TEM and SAED of CLLPCs (PDF)


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