Capturing the Moment of Emergence of Crystal Nucleus from Disorder
- Takayuki Nakamuro
Takayuki NakamuroDepartment of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Takayuki Nakamuro
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- Masaya Sakakibara
Masaya SakakibaraDepartment of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Masaya Sakakibara
- ,
- Hiroki Nada
Hiroki NadaEnvironmental Management Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba 305-8569, JapanMore by Hiroki Nada
- ,
- Koji Harano
Koji HaranoDepartment of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Koji Harano
- , and
- Eiichi Nakamura*
Eiichi Nakamura*[email protected]Department of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Eiichi Nakamura
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Abstract
Crystallization is the process of atoms or molecules forming an organized solid via nucleation and growth. Being intrinsically stochastic, the research at an atomistic level has been a huge experimental challenge. We report herein in situ detection of a crystal nucleus forming during nucleation/growth of a NaCl nanocrystal, as video recorded in the interior of a vibrating conical carbon nanotube at 20–40 ms frame–1 with localization precision of <0.1 nm. We saw NaCl units 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 mechanical vibration have been experimentally indicated.
Self-organization of atoms and molecules into crystals plays a key role in diverse areas of science and technology, (1) biology, (2,3) and the environment. (4) Crystallization occurs in two stages, nucleation and growth. Nucleation starts with a clustering of the constituents and phase transition at a saddle point of the potential energy surface (5,6) illustrated as a simple model in Figure 1a for homogeneous nucleation of NaCl in the gas phase. (7) As the size of a prenucleation cluster increases toward a critical radius rc, there forms a critical nucleus—a transient species so far undetectable by experiments. Theory has suggested that the nucleation process seen at an atomistic or molecular level is stochastic, (8) like any chemical reactions analyzed at this level. (9) Atomistic experimental studies of the nucleation process have therefore been a huge challenge, (10−13) and it has remained largely the subject of theory, (14) simulation, (15) and mimicry. (16,17) A step forward in this challenge has recently been provided by isolation from a bulk solution and ex situ characterization of prenucleation clusters using single-molecule atomic-resolution real-time electron microscopy (SMART-EM). (18,19) We report herein in situ atomic-resolution detection of a crystal nucleus forming during nucleation/growth of a NaCl nanocrystal, which took place at 298 K in a few tens of nm3 vacuum space of a vibrating conical carbon nanotube (CNT), (20) as recorded at 20–40 ms frame–1 with localization precision of <0.1 nm. (21) In a CNT at 298 K studied on a transmission electron microscope (TEM), the nucleation/growth took place nine times during 152 s (Figures 2 and 3). First, in the narrow apex region, (22) a few NaCl units gathered and grew to form a transient cluster with morphology fluctuating between featureless and semiordered states, (5) from which suddenly emerged a crystal nucleus over the nine times in a reproducible manner (Figure 2). The video images reveal that the two-step mechanism of crystal nucleation may include multiple nonproductive semiordered clusters forming before the final cluster that produces a crystalline nucleus (Figure 1d). (5) Homoepitaxial growth then took place stochastically as the crystal vibrated in the CNT. (8,23,24) At 473 K, a crystal was found to shrink in a stochastic manner (Figure 4). (25) We anticipate that the SMART-EM setup (26) provides a versatile platform for studies of self-assembly and other chemical events in atomistic details so far unachievable. (27,28)
Figure 1
Figure 1. Nucleation and growth of a NaCl nanocrystal in a vibrating CNT. (a) Schematic energy diagram of crystallization. The radius of a critical nucleus shown as rc. (b) TEM image of a NaCl nanocrystal at 298 K in an aminated CNT of a size denoted as (x, y, z) with x, y, and z (thickness) defined herein. Throughout this work, the assignment on which of Na+ and Cl– occupies the corners of a crystal is arbitrary, because the TEM image lacks this information. The amino groups on CNT are too small to be seen. Scale bar 1 nm. Acceleration voltage 80 kV and electron dose rate of 3.6 × 105 e– nm–2 s–1. Whenever necessary, the moiré pattern due to the graphitic lattice was removed by inverse fast Fourier transform (Figure 1 in Supporting Information Figure S1). (c) Model of a conical CNT shown with a curved arrow illustrating vibration. (d) Schematic diagram of the crystallization. NaCl molecules are supplied from a hidden reservoir. Vibrations of CNT and crystal are shown with curved arrows.
Figure 2
Figure 2. Nucleation/growth events taking place nine times. (a) Four representative snapshots in each event (40 ms frame–1). Time 0 is the time when a NaCl cluster first appeared. The crystal size in parentheses. Acceleration voltage 80 kV and electron dose rate 4.0 × 105 e– nm–2 s–1 with small dose fluctuation (Figure S7). Scale bar 1 nm. The position of the images in each frame is normalized for the outline of the vibrating CNT (cf. Movies S1–S4). See Figure S8 for a 318-frame data set. (b) Histogram of the time until the appearance of a (4,6) crystal (red) and growth until (6,8) crystal or its size equivalent (blue). (c) Normal distribution of nucleation time period (black line) with an average of 5.07 s and standard deviation (sd) of 2.18 s. (d) Distribution of initial growth time period (average of 3.94 s and sd of 2.33 s), during which the crystal grew from 48 to 144 NaCl with a rate of 24.4 NaCl s–1. (e) The course of the crystal growth in the nine events (column) and crystal sizes observed (+) during the growth (row).
Figure 3
Figure 3. Nucleation/growth at 298 K. (a) Cluster/crystal images in the first event shown in Figure 2a. White arrows indicate steps in contact with the CNT wall. (b) Time evolution of 2-D area of cluster/crystal images. The nucleation phase ended at the dotted line at 5.04 s, before which featureless (light blue) and semiordered clusters (dark blue) alternately appeared. Arrows indicate step formation, and red dots the snapshots shown in (a).
Figure 4
Figure 4. Shrinkage/collapse at 473 K. (a) Crystal shrinkage at 473 K (20 ms frame–1). Time 0 is set arbitrarily. See Figure S10 and Movie S5 for a 28-frame data set. Scale bar 1 nm. (b) Time evolution of the 2-D area of the images with the dotted line showing the end of the shrinkage stage.
Unlike previous works using a molten inorganic salt that penetrates the entire interior of a narrow CNT, (29) we introduced aqueous NaCl into a CNT and removed water in vacuo to grow a nanocrystal in the void space (e.g., Figure 1b). To this end, we soaked a water-soluble aggregate of aminated conical CNTs (carbon nanohorns) (30) in saturated aq. NaCl at 25 °C for 24 h, dried it in vacuo (298 K, 0.5 h) and, upon TEM analysis, found a single nanometer-sized NaCl crystal in a CNT as also characterized by energy-dispersive X-ray spectroscopic analysis (Figure S2). The crystals were found in approximately 10% of the CNTs (no crystal found after 1 h immersion in aq. NaCl). Thus, the diffusion of aq. NaCl into the CNTs through an undetected structural defect is slow. The CNT vibrated stochastically several times per second with an amplitude of ± <0.1 nm (cf. Figure 1c, Figure S3, Movie S1), (21) and this mechanical vibration was essential for the observed crystal growth (see below).
Approximately 5% of several tens of NaCl crystals examined were held tightly in cylindrical CNTs (always one crystal in one CNT), and neither grew nor shrank during observation. Figure 1b shows an example of such stable crystals seen as a rectangular array of 40 dots, 20 NaCl units (denoted as (5,8) crystal). The interatomic distance of 0.273(16)–0.277(8) nm is slightly shorter than the distance of 0.2820(1) nm in a bulk crystal at 298 K (31) (Figure S4) as theoretically predicted. (32) Note that the crystal packing of inorganic crystals grown from their molten salt in a CNT was strongly perturbed from the one in the corresponding bulk crystal. (29) The thickness (z) would be close to the width (x) because of the circular cross section of the CNT, minimization of surface energy (x ≈ y ≈ z), and neutrality of the crystal. Thus, the (5,8) crystal in Figure 1b would contain 100 NaCl units (i.e., (5,8,5) crystal). A preliminary gray value analysis, though the accuracy reduced by image blurring, indicated that the nanocrystals have a thickness of a few NaCl units, supporting the structure assignment stated above. (33)
The rest (95%) of the NaCl crystals were found in vibrating conical CNTs (cf. Figure 1c,d; Figure S5). In the conical CNTs, but not in the cylindrical ones, we made a striking observation—spontaneous crystal nucleation and growth taking place nine times at 298 K during 152 s (Figures 2 and 3). Figure 1d illustrates a rationale for the observed events. Based on an average crystal growth rate of 24.4 NaCl s–1 (Figure 2d), we consider that numerous neutral NaCl molecules translate back and forth in the CNT (the motions are too fast to be seen), and become trapped in the narrow and polarized conical apex. (22) Thus, in the beginning (ii), a short-lived semiordered cluster(s) made of several NaCl units forms, breaks down to a disordered cluster (iii), reorganizes into a larger semiordered cluster(s) (iv), and breaks down (v) until phase transition to a (4,6) crystal (vi). We consider that a (4,6) crystal is a (4,6,4) crystal comprising 48 NaCl units, in light of a report on a 48 NaCl cluster forming among a series of stable clusters of unassigned structures ((NaCl)n, n = 18, 20, 24, 30, 32, 40, 48, 50, 56, 60, and 72 (Figure S6) upon quenching of a NaCl vapor at 300 K at 133 Pa). (34) The crystal then grows larger layer-by-layer as the CNT vibrates stochastically (vii, viii), and gradually moves toward the more spacious bottom part that can accommodate a larger crystal. This crystal supplies NaCl molecules in the next cycle (back to (i)). This intriguing oscillation phenomenon suggests the presence of a thermal gradient created by the electron beam preferentially heating the CNT aggregates’ interior.
Figure 2a shows four TEM snapshots in each of the nine events, on which we performed statistical analysis (Figure 2b–e). The event repeated nine times over 152 s until the specimen drifted away from the view frame. In all events, a small cluster appeared, grew, and produced a (4,6) crystal, which grew larger and disappeared into the bottom of the CNT (cf. fourth and eighth events), and the process started again after several seconds. Note that in all nine events, the crystals that appeared after (4,6) grew irreversibly, while the prenucleation clusters before (4,6) formed reversibly. Thus, the emergence of the (4,6) crystal nucleus marks the end of the nucleation period.
Figure 2b shows the duration of the nucleation period in red, and the period of the initial stage of growth in blue (growth from (4,6) to (6,8), or from 48 to 144 NaCl). We find similarity in the duration of the two periods in each event, but diversity among the nine events. Shown in Figure 2c, the nucleation period over the nine events roughly follows a normal distribution with an average time of 5.07 s, since the nucleation process produced the same (4,6) crystal every time. The growth period distributes more randomly because the growth process produced a different crystal every time. The growth period averages to be 3.94 s, which indicates 24.4 NaCl units incorporated every second into the crystal (Figure 2d). This property of the initial growth is supported by the stochastic growth pathways shown in Figure 2e. For example, the first event went through (4,6), (5,6), (5,7), (6,7), and (6,8) crystals, and the other eight events took different courses. Given the growth rate of 24.4 NaCl s–1, we would expect that the nucleation period should have ended in 2 s instead of 5.07 s, indicating in turn the probabilistic nature of the nucleation process.
At 298 K, we saw exclusive crystal formation, and, at higher temperature, we saw crystal shrinkage. Figure 3 illustrates details of the first event of the nucleation/growth at 298 K shown in Figure 2a (Figure S9), and Figure 4 illustrates an example of the shrinkage at 473 K. In the initial 5 s of Figure 3a, featureless and semiordered morphology alternated before the formation of the (4,6) crystal at 5.04 s. (5,8) At 0–0.72 s, we saw a cluster growing up to approximately 2 × 3 in size near the apex that then disappeared quickly, and at 2.00–2.68 s, the appearance of a semiordered cluster made of several rows of NaCl along the graphitic wall, which also disappeared quickly. A sequence from 5.00 to 5.04 s is particularly noteworthy because a clear image of the (4,6) crystal nucleus suddenly emerged from a featureless object. Note that all of the semiordered prenucleation clusters before 5.04 s formed reversibly, while the crystals after 5.04 s grew irreversibly as found in the eight other events (cf. Figure S8). During the next 6 s, stochastic homoepitaxial growth of the (4,6) crystal occurred. (8,24) At 5.48 s, we saw the formation of a step in contact with the graphitic wall (arrow; (4,6)s with s denoting step), its disappearance to regenerate (4,6) in the next frame, and further growth to (5,6). As a note of caution, we assume that the crystal growth took place three-dimensionally, although the TEM information was limited to 2-D.
Finally, we examined the shrinkage of a NaCl crystal at 473 K. In a vibrating conical CNT, we found a NaCl crystal shrank in less than 1 s as shown in Figure 4a. A (7,11) crystal first shrank in a longitudinal direction into (7,9) (at 0.20 s) and gained width to form (8,7) to fit in a wider section of the CNT (0.32 s), which then shrank via step formation at 0.60 s into a crystal of a size approximately (6,3) at 0.82 s. The interatomic distance measured for the crystal between 0 and 0.82 s remained constant (0.278(4)–0.283(15) nm) until sudden collapse into a new crystal of an approximately (4,5) size (0.283(11)–0.285(6) nm) that we find in the tip of the CNT. The blurred lattice images often found in Figure 4a suggest dynamic defect formation during the degradation.
Supporting Information
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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c12100.
Methods and Materials and Representative TEM images (PDF)
Movie S1: Vibration of a conical CNT at 298 K (MOV
Movie S2: Nine times crystallization of NaCl in a conical CNT at 298 K (0–44.40 s) (MOV)
Movie S3: Nine times crystallization of NaCl in a conical CNT at 298 K (44.44–88.84 s) (MOV)
Movie S4: Nine times crystallization of NaCl in a conical CNT at 298 K (88.88–133.28 s) (MOV)
Movie S5: Shrinkage/collapse of NaCl in a conical CNT at 473 K (MOV)
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Author Information
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Eiichi Nakamura - Department of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan;
http://orcid.org/0000-0002-4192-1741;
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Takayuki Nakamuro - Department of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan;http://orcid.org/0000-0002-0752-3475
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Hiroki Nada - Environmental Management Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba 305-8569, Japan;http://orcid.org/0000-0002-1744-2759
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Koji Harano - Department of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan;http://orcid.org/0000-0001-6800-8023
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Acknowledgments
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We thank Profs. Koichiro Saiki, Makio Uwaha, and Tatsuya Tsukuda for helpful discussion. We also thank Nobuya Mamizu, Hiromitsu Furukawa (SYSTEM IN FRONTIER Inc.), and Issei Tomotsuka for automated cross-correlation image analysis, and Ko Kamei for helpful discussion. This research is supported by JSPS KAKENHI (JP19H05459 (to E.N.) and JP20K15123 (to T.N.)), Japan Science and Technology Agency (SENTAN JPMJSN16B1 (to K.H.)), and Prof. Osafune memorial scholarship (to T.N.) by the Japanese Society of Microscopy.
References
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This article references 34 other publications.
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4Bartels-Rausch, T. Ten things we need to know about ice and snow. Nature 2013, 494, 27– 29, DOI: 10.1038/494027aGoogle Scholar4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXitFaqu7k%253D&md5=5da71af30b7a04b3edc38f53d3e3db74Chemistry Ten things we need to know about ice and snowBartels-Rausch, ThorstenNature (London, United Kingdom) (2013), 494 (7435), 27-29CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)Understanding the mol. behavior of frozen water is essential for predicting the future of our planet, says Thorsten Bartels-Rausch.
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5(a) Vekilov, P. G. Nucleation. Cryst. Growth Des. 2010, 10, 5007– 5019, DOI: 10.1021/cg1011633Google Scholar5ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhsVaisrnO&md5=760e7504daad63314fe654b75e113d29NucleationVekilov, Peter G.Crystal Growth & Design (2010), 10 (12), 5007-5019CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)A review. Crystn. starts with nucleation and control of nucleation is crucial for the control of the no., size, perfection, polymorphism, and other characteristics of cryst. materials. This is particularly true for crystn. in soln., which is an essential part of processes in the chem. and pharmaceutical industries and a major step in physiol. and pathol. phenomena. There were significant recent advances in the understanding of the mechanism of nucleation of crystals in soln. The foremost of these are the two-step mechanism of nucleation and the notion of the soln.-crystal spinodal. According to the two-step mechanism, the cryst. nucleus appears inside pre-existing metastable clusters of size several hundred nanometers, which consist of dense liq. and are suspended in the soln. While initially proposed for protein crystals, the applicability of this mechanism was demonstrated for small mol. org. materials, colloids, polymers, and biominerals. This mechanism helps to explain several long-standing puzzles of crystal nucleation in soln.: nucleation rates which are many orders of magnitude lower than theor. predictions, the significance of the dense protein liq., and others. At high supersaturations typical of most crystg. systems, the generation of crystal embryos occurs in the spinodal regime, where the nucleation barrier is negligible. The soln.-crystal spinodal helps to clarify the role of heterogeneous substrates in nucleation and the selection of cryst. polymorphs. Importantly, these ideas provide powerful tools for control of the nucleation process by varying the soln. thermodn. parameters.(b) Nielsen, M. H.; Aloni, S.; De Yoreo, J. J. In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways. Science 2014, 345, 1158– 1162, DOI: 10.1126/science.1254051Google Scholar5bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsVGhtLbF&md5=666d1f4ca29359e906a274ce68b9fd44In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathwaysNielsen, Michael H.; Aloni, Shaul; De Yoreo, James J.Science (Washington, DC, United States) (2014), 345 (6201), 1158-1162CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Multiple nucleation pathways were obsd. for the crystal nucleation of calcium carbonate (CaCO3) including formation both directly from soln. and indirectly through transformation of amorphous and cryst. precursors. In situ transmission electron microscopy (TEM) was used in a cell that enables reagent mixing. An amorphous-to-calcite transformation was not obsd. The behavior of amorphous calcium carbonate upon dissoln. suggests that it encompasses a spectrum of structures, including liqs. and solids. These observations of competing direct and indirect pathways are consistent with classical predictions, whereas the behavior of amorphous particles hints at an underlying commonality among recently proposed precursor-based mechanisms.
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6(a) Erdemir, D.; Lee, A. Y.; Myerson, A. S. Nucleation of crystals from solution: Classical and two-step models. Acc. Chem. Res. 2009, 42, 621– 629, DOI: 10.1021/ar800217xGoogle Scholar6ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXltFOltbs%253D&md5=1777175975e040b55a2c0a58bfd8fd5bNucleation of Crystals from Solution: Classical and Two-Step ModelsErdemir, Deniz; Lee, Alfred Y.; Myerson, Allan S.Accounts of Chemical Research (2009), 42 (5), 621-629CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Crystn. is vital to many processes occurring in nature and in the chem., pharmaceutical, and food industries. Notably, crystn. is an attractive isolation step for manufg. because this single process combines both particle formation and purifn. Almost all of the products based on fine chems., such as dyes, explosives, and photog. materials, require crystn. in their manuf., and more than 90% of all pharmaceutical products contain bioactive drug substances and excipients in the cryst. solid state. Hence control over the crystn. process allows manufacturers to obtain products with desired and reproducible properties. We judge the quality of a cryst. product based on four main properties: size, purity, morphol., and crystal structure. The pharmaceutical industry in particular requires prodn. of the desired crystal form (polymorph) to assure the bioavailability and stability of the drug substance. In soln. crystn., nucleation plays a decisive role in detg. the crystal structure and size distribution. Therefore, understanding the fundamentals of nucleation is crucial to achieve control over these properties. Because of its anal. simplicity, researchers have widely applied classical nucleation theory to soln. crystn. However, a no. of differences between theor. predictions and exptl. results suggest that nucleation of solids from soln. does not proceed via the classical pathway but follows more complex routes. In this Account, we discuss the shortcomings of classical nucleation theory and review studies contributing to the development of the modern two-step model. In the two-step model that was initially proposed for protein crystn., a sufficient-sized cluster of solute mols. forms first, followed by reorganization of that cluster into an ordered structure. In recent exptl. and theor. studies, we and other researchers have demonstrated the applicability of the two-step mechanism to both macromols. and small org. mols., suggesting that this mechanism may underlie most crystn. processes from solns. Because we have obsd. an increase in the organization time of appropriate lattice structures with greater mol. complexity, we propose that organization is the rate-detg. step. Further development of a clearer picture of nucleation may help det. the optimum conditions necessary for the effective organization within the clusters. In addn., greater understanding of these processes may lead to the design of auxiliaries that can increase the rate of nucleation and avoid the formation of undesired solid forms, allowing researchers to obtain the final product in a timely and reproducible manner.(b) De Yoreo, J. J.; Gilbert, P. U. P. A.; Sommerdijk, N. A. J. M.; Penn, R. L.; Whitelam, S.; Joester, D.; Zhang, H.; Rimer, J. D.; Navrotsky, A.; Banfield, J. F.; Wallace, A. F.; Michel, F. M.; Meldrum, F. C.; Cölfen, H.; Dove, P. M. Crystallization by particle attachment in synthetic, biogenic, and geologic environments. Science 2015, 349, aaa6760, DOI: 10.1126/science.aaa6760Google ScholarThere is no corresponding record for this reference.
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7Kalcher, I.; Dzubiella, J. NaCl crystallization in apolar nanometer-sized confinement studied by atomistic simulations. Phys. Rev. E 2013, 88, 062312 DOI: 10.1103/PhysRevE.88.062312Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitVOktrk%253D&md5=fc7668cb7c826173421d697aa3913896NaCl crystallization in apolar nanometer-sized confinement studied by atomistic simulationsKalcher, Immanuel; Dzubiella, JoachimPhysical Review E: Statistical, Nonlinear, and Soft Matter Physics (2013), 88 (6-A), 062312/1-062312/10CODEN: PRESCM; ISSN:1539-3755. (American Physical Society)The structure and growth of mol. NaCl crystals in bulk and in a narrow, nanometer-sized apolar confinement are examd. by explicit-water mol. dynamics computer simulations. Fast crystn. and subsequent diffusion-controlled cluster growth in bulk is triggered by supersaturations that exceed a certain threshold value. In confinement, simulated in a pseudo grand canonical setup, salt is shown to be expelled from the narrow apolar slab region, and the effective ion concn. inside the nanoconfinement is always considerably lower than the reservoir salt concn. so that no fast crystn. takes place. For very small slab widths (d < 1.5 nm) salt is almost entirely expelled while water remains in the slab, indicating a capillary evapn. phenomenon for the polar ions. If forced into the apolar confinement by simulating in a strictly canonical setup, we find stable crystals only if at least 3 cryst. planes fit into the slab, which happens above a 2-nm slab width. In this case the (100) plane of the bulk crystal is oriented parallel to the apolar surface delimited by a subnanometer thin hydration layer. This work presents mol.-level insight of salt crystn. in apolar confinements of a nanometer scale with possible implications in double-layer supercapacitor physics and geol. salt weathering.
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8Gladkov, S. O. On Mathematical Description of Crystallization as a Deterministic Chaos Problem. Tech. Phys. 2008, 53, 952– 955, DOI: 10.1134/S1063784208070219Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXptVyitb0%253D&md5=76c001fbf9ef10faa7a0c3e4a32934caOn mathematical description of crystallization as a deterministic chaos problemGladkov, S. O.Technical Physics (2008), 53 (7), 952-955CODEN: TEPHEX; ISSN:1063-7842. (Pleiades Publishing, Ltd.)The problem of anal. description of the space-time nucleation of the crystal phase is solved using the theory of nonuniform and nonstationary fluctuations of d. and temp. and the method of deterministic chaos.
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9Komatsuzaki, T.; Berry, R. S. Chemical reaction dynamics: Many-body chaos and regularity. Adv. Chem. Phys. 2003, 123, 79– 152, DOI: 10.1002/0471231509.ch2Google ScholarThere is no corresponding record for this reference.
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10Zheng, H.; Smith, R. K.; Jun, Y.-w.; Kisielowski, C.; Dahmen, U.; Alivisatos, A. P. Observation of single colloidal platinum nanocrystal growth trajectories. Science 2009, 324, 1309– 1312, DOI: 10.1126/science.1172104Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXms12gtbk%253D&md5=ac8ff7c442a75980accf254eb63b2d9cObservation of Single Colloidal Platinum Nanocrystal Growth TrajectoriesZheng, Haimei; Smith, Rachel K.; Jun, Young-wook; Kisielowski, Christian; Dahmen, Ulrich; Alivisatos, A. PaulScience (Washington, DC, United States) (2009), 324 (5932), 1309-1312CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Understanding of colloidal nanocrystal growth mechanisms is essential for the syntheses of nanocrystals with desired phys. properties. The classical model for the growth of monodisperse nanocrystals assumes a discrete nucleation stage followed by growth via monomer attachment, but has overlooked particle-particle interactions. Recent studies suggested that interactions between particles play an important role. Using in situ TEM, platinum nanocrystals can grow either by monomer attachment from soln. or by particle coalescence. Through the combination of these two processes, an initially broad size distribution can spontaneously narrow into a nearly monodisperse distribution. Probably colloidal nanocrystals take different pathways of growth based on their size- and morphol.-dependent internal energies.
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11Jonkheijm, P.; van der Schoot, P.; Schenning, A. P. H. J.; Meijer, E. W. Probing the solvent-assisted nucleation pathway in chemical self-assembly. Science 2006, 313, 80– 83, DOI: 10.1126/science.1127884Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XmsFWisr4%253D&md5=145a82543d9267d6bbbdbb5aa08e9b96Probing the Solvent-Assisted Nucleation Pathway in Chemical Self-AssemblyJonkheijm, Pascal; van der Schoot, Paul; Schenning, Albertus P. H. J.; Meijer, E. W.Science (Washington, DC, United States) (2006), 313 (5783), 80-83CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Hierarchical self-assembly offers a powerful strategy for producing mol. nanostructures. Although widely used, the mechanistic details of self-assembly processes are poorly understood. We spectroscopically monitored a nucleation process in the self-assembly of π-conjugated mols. into helical supramol. fibrillar structures. The data support a nucleation-growth pathway that gives rise to a remarkably high degree of cooperativity. Furthermore, we characterize a helical transition in the nucleating species before growth. The self-assembly process depends strongly on solvent structure, suggesting that an organized shell of solvent mols. plays an explicit role in rigidifying the aggregates and guiding them toward further assembly into bundles and/or gels.
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12Zhou, J.; Yang, Y.; Yang, Y.; Kim, D. S.; Yuan, A.; Tian, X.; Ophus, C.; Sun, F.; Schmid, A. K.; Nathanson, M.; Heinz, H.; An, Q.; Zeng, H.; Ercius, P.; Miao, J. Observing crystal nucleation in four dimensions using atomic electron tomography. Nature 2019, 570, 500– 503, DOI: 10.1038/s41586-019-1317-xGoogle Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXht1yktbjO&md5=f2933a85ef1ddcac8d55986dd716564dObserving crystal nucleation in four dimensions using atomic electron tomographyZhou, Jihan; Yang, Yongsoo; Yang, Yao; Kim, Dennis S.; Yuan, Andrew; Tian, Xuezeng; Ophus, Colin; Sun, Fan; Schmid, Andreas K.; Nathanson, Michael; Heinz, Hendrik; An, Qi; Zeng, Hao; Ercius, Peter; Miao, JianweiNature (London, United Kingdom) (2019), 570 (7762), 500-503CODEN: NATUAS; ISSN:0028-0836. (Nature Research)Nucleation plays a crit. role in many phys. and biol. phenomena that range from crystn., melting and evapn. to the formation of clouds and the initiation of neurodegenerative diseases1-3. However, nucleation is a challenging process to study exptl., esp. in its early stages, when several atoms or mols. start to form a new phase from a parent phase. A no. of exptl. and computational methods have been used to study nucleation processes4-17, but exptl. detn. of the three-dimensional at. structure and the dynamics of early-stage nuclei has been unachievable. Here the authors use at. electron tomog. to study early-stage nucleation in four dimensions (i.e., including time) at at. resoln. Using FePt nanoparticles as a model system, early-stage nuclei are irregularly shaped, each has a core of one to a few atoms with the max. order parameter, and the order parameter gradient points from the core to the boundary of the nucleus. The authors capture the structure and dynamics of the same nuclei undergoing growth, fluctuation, dissoln., merging and/or division, which are regulated by the order parameter distribution and its gradient. These exptl. observations are corroborated by mol. dynamics simulations of heterogeneous and homogeneous nucleation in liq.-solid phase transitions of Pt. The authors' exptl. and mol. dynamics results indicate that a theory beyond classical nucleation theory1,2,18 is needed to describe early-stage nucleation at the at. scale. The authors anticipate that the reported approach will open the door to the study of many fundamental problems in materials science, nanoscience, condensed matter physics and chem., such as phase transition, at. diffusion, grain boundary dynamics, interface motion, defect dynamics and surface reconstruction with four-dimensional at. resoln.
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13Zeng, Z.; Zheng, W.; Zheng, H. Visualization of colloidal nanocrystal formation and electrode-electrolyte interfaces in liquids using TEM. Acc. Chem. Res. 2017, 50, 1808– 1817, DOI: 10.1021/acs.accounts.7b00161Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1Olsb3E&md5=73b7461245dd630b1271d9be1cc4fc2fVisualization of Colloidal Nanocrystal Formation and Electrode-Electrolyte Interfaces in Liquids Using TEMZeng, Zhiyuan; Zheng, Wenjing; Zheng, HaimeiAccounts of Chemical Research (2017), 50 (8), 1808-1817CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Transmission electron microscopy (TEM) has become a powerful anal. tool for addressing unique scientific problems in chem. sciences as well as in materials sciences and other disciplines. There has been a lot of recent interest in the development and applications of liq. phase environmental TEM. In this Account, we review the development and applications of liq. cell TEM for the study of dynamic phenomena at liq.-solid interfaces, focusing on two areas: (1) nucleation, growth, and self-assembly of colloidal nanocrystals and (2) electrode-electrolyte interfaces during charge and discharge processes. We highlight the achievements and progress that have been made in these two topical areas of our studies. For example, tracking single platinum particle growth trajectories revealed that two different pathways of growth, either by monomer attachment or coalescence between nanoparticles, led to the same particle size. With the improved spatial resoln. and fast electron detection, we were able to trace individual facet development during platinum nanocube platinum nanocube growth. The results showed that different from the surface energy minimization rule prediction, the growth rates of all low-energy facets, such as {100}, {110}, and {111}, were similar. The {100} facets stopped growth early, and the continuous growth of the rest facets resulted in a nanocube. D. functional theory calcns. showed that the amine ligands with low mobility on the {100} facets blocked the further growth of the facets. The effect of the ligand on nanoparticle shape evolution were further studied systematically using a Pt-Fe nanoparticle system by changing the oleylamine concn. With 20%, 30%, or 50% oleylamine, Pt-Fe nanowires or nanoparticles with different morphologies and stabilities were achieved. Real-time imaging of nanoparticles in soln. also enabled the study of interactions between nanoparticles during self-assembly. We further compared the study of noble-metal nanoparticles and transition-metal oxides in a liq. cell to elucidate the nanoparticle formation mechanisms. In the second part of this Account, we review the study of electrolyte-electrode interfaces by the development of electrochem. liq. cell TEM. The formation of single-cryst. Pb dendrites from polycryst. branches and Li dendrite growth in a com. electrolyte for Li ion batteries were obsd. We also studied lithiation reactions of MoS2 and Au electrodes. MoS2 nanoflakes on the Ti electrode underwent irreversible decompn., resulting in the vanishing of the MoS2 active nanoflakes. More detailed study using nanobeam diffraction indicated that the MoS2 nanoflakes were broken down into small nanoparticles as a result of the fast discharge. For the lithiation of Au electrodes, three distinct types of morphol. changes during reactions were revealed, including gradual dissoln., explosive reaction, and local expansion/shrinkage. Addnl., we studied electrolyte decompn. reactions such as bubble formation and solid electrolyte interphase formation. At the end, our perspective on the challenges and opportunities in the applications of liq. phase environmental TEM for the study of liq. chem. reactions is provided.
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14Durán-Olivencia, M. A.; Lutsko, J. F. Mesoscopic nucleation theory for confined systems: A one-parameter model. Phys. Rev. E 2015, 91, 022402 DOI: 10.1103/PhysRevE.91.022402Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXlsVyqs7Y%253D&md5=94d60860b2787565a373c8db41b1a712Mesoscopic nucleation theory for confined systems: a one-parameter modelDuran-Olivencia, Miguel A.; Lutsko, James F.Physical Review E: Statistical, Nonlinear, and Soft Matter Physics (2015), 91 (2-A), 022402/1-022402/16CODEN: PRESCM; ISSN:1539-3755. (American Physical Society)Classical nucleation theory has been recently reformulated based on fluctuating hydrodynamics. The present work extends this effort to the case of nucleation in confined systems such as small pores and vesicles. The finite available mass imposes a maximal supercrit. cluster size and prohibits nucleation altogether if the system is too small. We quantity the effect of system size on the nucleation rate. We also discuss the effect of relaxing the capillary-model assumption of zero interfacial width resulting in significant changes in the nucleation barrier and nucleation rate.
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15Wallace, A. F.; Hedges, L. O.; Fernandez-Martinez, A.; Raiteri, P.; Gale, J. D.; Waychunas, G. A.; Whitelam, S.; Banfield, J. F.; De Yoreo, J. J. Microscopic evidence for liquid-liquid separation in supersaturated CaCO3 solutions. Science 2013, 341, 885– 889, DOI: 10.1126/science.1230915Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXht12gsL%252FL&md5=d12279e06d1fe47a5ef9ca743c4f89cfMicroscopic Evidence for Liquid-Liquid Separation in Supersaturated CaCO3 SolutionsWallace, Adam F.; Hedges, Lester O.; Fernandez-Martinez, Alejandro; Raiteri, Paolo; Gale, Julian D.; Waychunas, Glenn A.; Whitelam, Stephen; Banfield, Jillian F.; De Yoreo, James J.Science (Washington, DC, United States) (2013), 341 (6148), 885-889CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Recent exptl. observations of the onset of calcium carbonate (CaCO3) mineralization suggest the emergence of a population of clusters that are stable rather than unstable as predicted by classical nucleation theory. Mol. dynamics simulations were used to probe the structure, dynamics, and energetics of hydrated CaCO3 clusters and lattice gas simulations to explore the behavior of cluster populations before nucleation. The simulations predict the formation of a dense liq. phase through liq.-liq. sepn. within the concn. range in which clusters are obsd. Coalescence and solidification of nanoscale droplets results in formation of a solid phase, the structure of which is consistent with amorphous CaCO3. The presence of a liq.-liq. binodal enables a diverse set of exptl. observations to be reconciled within the context of established phase-sepn. mechanisms.
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16Grzybowski, B. A.; Winkleman, A.; Wiles, J. A.; Brumer, Y.; Whitesides, G. M. Electrostatic self-assembly of macroscopic crystals using contact electrification. Nat. Mater. 2003, 2, 241– 245, DOI: 10.1038/nmat860Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXisFWgs78%253D&md5=6291995a48069dc57a36536f33b91a74Electrostatic self-assembly of macroscopic crystals using contact electrificationGrzybowski, Bartosz A.; Winkleman, Adam; Wiles, Jason A.; Brumer, Yisroel; Whitesides, George M.Nature Materials (2003), 2 (4), 241-245CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Self-assembly of components larger than mols. into ordered arrays is an efficient way of prepg. microstructured materials with interesting mech. and optical properties. Although crystn. of identical particles or particles of different sizes or shapes can be readily achieved, the repertoire of methods to assemble binary lattices of particles of the same sizes but with different properties is very limited. This paper describes electrostatic self-assembly of two types of macroscopic components of identical dimensions using interactions that are generated by contact electrification. The systems we have examd. comprise two kinds of objects (usually spheres) made of different polymeric materials that charge with opposite elec. polarities when agitated on flat, metallic surfaces. The interplay of repulsive interactions between like-charged objects and attractive interactions between unlike-charged ones results in the self-assembly of these objects into highly ordered, closed arrays. Remarkably, some of the assemblies that form are not electroneutral, i.e., they possess a net charge. The authors suggest that the stability of these unusual structures can be explained by accounting for the interactions between elec. dipoles that the particles in the aggregates induce in their neighbors.
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17Girard, M.; Wang, S.; Du, J. S.; Das, A.; Huang, Z.; Dravid, V. P.; Lee, B.; Mirkin, C. A.; de la Cruz, M. O. Particle analogs of electrons in colloidal crystals. Science 2019, 364, 1174– 1178, DOI: 10.1126/science.aaw8237Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtlKqsL7M&md5=e2767780ae789f4b14ef9f93710ffcd1Particle analogs of electrons in colloidal crystalsGirard, Martin; Wang, Shunzhi; Du, Jingshan S.; Das, Anindita; Huang, Ziyin; Dravid, Vinayak P.; Lee, Byeongdu; Mirkin, Chad A.; Olvera de la Cruz, MonicaScience (Washington, DC, United States) (2019), 364 (6446), 1174-1178CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A versatile method for the design of colloidal crystals involves the use of DNA as a particle-directing ligand. With such systems, DNA-nanoparticle conjugates are considered programmable atom equiv. (PAEs), and design rules have been devised to engineer crystn. outcomes. This work shows that when reduced in size and DNA grafting d., PAEs behave as electron equiv. (EEs), roaming through and stabilizing the lattices defined by larger PAEs, as electrons do in metals in the classical picture. This discovery defines a new property of colloidal crystals-metallicity-that is characterized by the extent of EE delocalization and diffusion. As the no. of strands increases or the temp. decreases, the EEs localize, which is structurally reminiscent of a metal-insulator transition. Colloidal crystal metallicity, therefore, provides new routes to metallic, intermetallic, and compd. phases.
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18Harano, K.; Homma, T.; Niimi, Y.; Koshino, M.; Suenaga, K.; Leibler, L.; Nakamura, E. Heterogeneous nucleation of organic crystals mediated by single-molecule templates. Nat. Mater. 2012, 11, 877– 881, DOI: 10.1038/nmat3408Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtlGjsrfP&md5=e52d4b8049ad9f0b941740fe54fb4254Heterogeneous nucleation of organic crystals mediated by single-molecule templatesHarano, Koji; Homma, Tatsuya; Niimi, Yoshiko; Koshino, Masanori; Suenaga, Kazu; Leibler, Ludwik; Nakamura, EiichiNature Materials (2012), 11 (10), 877-881CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Fundamental understanding of how crystals of org. mols. nucleate on a surface remains limited because of the difficulty of probing rare events at the mol. scale. Single-mol. templates on the surface of carbon nanohorns can nucleate the crystn. of two org. compds. from a supersatd. soln. by mediating the formation of disordered and mobile mol. nanoclusters on the templates. Single-mol. real-time transmission electron microscopy indicates that each nanocluster consists of a max. of approx. 15 mols., that there are fewer nanoclusters than crystals in soln., and that in the absence of templates physisorption, but not crystal formation, occurs. These findings suggest that template-induced heterogeneous nucleation mechanistically resembles two-step homogeneous nucleation.
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19Xing, J.; Schweighauser, L.; Okada, S.; Harano, K.; Nakamura, E. Atomistic Structures and Dynamics of Prenucleation Clusters in MOF-2 and MOF-5 Syntheses. Nat. Commun. 2019, 10, 3608, DOI: 10.1038/s41467-019-11564-4Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BB3MrhtFagtA%253D%253D&md5=27f67359d053519ee2b0d06c51457192Atomistic structures and dynamics of prenucleation clusters in MOF-2 and MOF-5 synthesesXing Junfei; Schweighauser Luca; Okada Satoshi; Harano Koji; Nakamura EiichiNature communications (2019), 10 (1), 3608 ISSN:.Chemical reactions in solution almost always take place via a series of minute intermediates that are often in rapid equilibrium with each other, and hence hardly characterizable at the level of atomistic molecular structures. We found that single-molecule atomic-resolution real-time electron microscopic (SMART-EM) video imaging provides a unique methodology for capturing and analyzing the minute reaction intermediates, as illustrated here for single prenucleation clusters (PNCs) in the reaction mixture of metal-organic frameworks (MOFs). Specifically, we found two different types of PNCs are involved in the formation of MOF-2 and MOF-5 from a mixture of zinc nitrate and benzene dicarboxylates at 95 °C and 120 °C, respectively. SMART-EM identified a small amount of 1-nm-sized cube and cube-like PNCs in the MOF-5 synthesis, but not in the MOF-2 synthesis. In the latter, we instead found only linear and square PNCs, suggesting that the MOF-2/-5 bifurcation takes place at the PNC stage.
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20Isobe, H.; Tanaka, T.; Maeda, R.; Noiri, E.; Solin, N.; Yudasaka, M.; Iijima, S.; Nakamura, E. Preparation, purification, characterization, and cytotoxicity assessment of water-soluble, transition-metal-free carbon nanotube aggregates. Angew. Chem., Int. Ed. 2006, 45, 6676– 6680, DOI: 10.1002/anie.200601718Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFCltLfP&md5=62ccf1248c238b8eabc451f528adaac5Preparation, purification, characterization, and cytotoxicity assessment of water-soluble, transition-metal-free carbon nanotube aggregatesIsobe, Hiroyuki; Tanaka, Takatsugu; Maeda, Rui; Noiri, Eisei; Solin, Niclas; Yudasaka, Masako; Iijima, Sumio; Nakamura, EiichiAngewandte Chemie, International Edition (2006), 45 (40), 6676-6680CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)The risk assessment of carbon materials, an important topic in nanomaterials research, has been hampered by the lack of characterizable samples. Transition-metal-free carbon nanohorn aggregates have been prepd. that are covalently bonded aggregates of single-walled nanotubes. They were functionalized to give water-sol. derivs., which were incubated with cells in cytotoxicity assessments.
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21Shimizu, T.; Lungerich, D.; Stuckner, J.; Murayama, M.; Harano, K.; Nakamura, E. Real-time video imaging of mechanical motions of a single molecular shuttle with sub-millisecond sub-angstrom precision. Bull. Chem. Soc. Jpn. 2020, 93, 1079– 1085, DOI: 10.1246/bcsj.20200134Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhs1ensLzF&md5=da606721713cb90663dd5d292b3bc3c5Real-Time Video Imaging of Mechanical Motions of a Single Molecular Shuttle with Sub-Millisecond Sub-Angstrom Precision#Shimizu, Toshiki; Lungerich, Dominik; Stuckner, Joshua; Murayama, Mitsuhiro; Harano, Koji; Nakamura, EiichiBulletin of the Chemical Society of Japan (2020), 93 (9), 1079-1085CODEN: BCSJA8; ISSN:0009-2673. (Chemical Society of Japan)Miniaturized machines have open up a new dimension of chem., studied usually as an av. over numerous mols. or for a single mol. bound on a robust substrate. Mech. motions at a single mol. level, however, are under quantum control, strongly coupled with fluctuations of its environment - a system rarely addressed because an efficient way of observing the nanomech. motions in real time is lacking. Here, we report sub-millisecond sub-Å precision in situ video imaging of a single fullerene mol. shuttling, rotating, and interacting with a vibrating carbon nanotube at 0.625 ms(ms)/frame or 1600 fps, using an electron microscope, a fast camera, and a denoising algorithm. We have achieved in situ observation of the mech. motions of a mol. coupled with vibration of a carbon nanotube with std. error as small as 0.9 ms in time and 0.01 nm in space. We have revealed rich mol. dynamics, where motions are non-linear, stochastic and often non-repeatable, and a work and energy relationship at a mol. level previously undetected by time-averaged measurements or microscopy. The mol. video recording at a 1600-fps rate exceeds by 100 times the previous records of continuous recording of mol. motions.
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22Kvashnin, A. G.; Sorokin, P. B.; Yakobson, B. I. Flexoelectricity in Carbon Nanostructures: Nanotubes, Fullerenes, and Nanocones. J. Phys. Chem. Lett. 2015, 6, 2740– 2744, DOI: 10.1021/acs.jpclett.5b01041Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtVKit7rE&md5=1959845defc8feb4011ac35ac088b38dFlexoelectricity in Carbon Nanostructures: Nanotubes, Fullerenes, and NanoconesKvashnin, Alexander G.; Sorokin, Pavel B.; Yakobson, Boris I.Journal of Physical Chemistry Letters (2015), 6 (14), 2740-2744CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)We report theor. anal. of the electronic flexoelec. effect assocd. with nanostructures of sp2 carbon (curved graphene). Through the d. functional theory calcns., we establish the universality of the linear dependence of flexoelec. at. dipole moments on local curvature in various carbon networks (carbon nanotubes, fullerenes with high and low symmetry, and nanocones). The usefulness of such dependence is in the possibility to extend the anal. of any carbon systems with local deformations with respect to their electronic properties. This result is exemplified by exploring of flexoelec. effect in carbon nanocones that display large dipole moment, cumulative over their surface yet surprisingly scaling exactly linearly with the length, and with sine-law dependence on the apex angle, dflex ∼ L sin(α). Our study points out the opportunity of predicting the elec. dipole moment distribution on complex graphene-based nanostructures based only on the local curvature information.
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23Liao, H.-G.; Zherebetskyy, D.; Xin, H.; Czarnik, C.; Ercius, P.; Elmlund, H.; Pan, M.; Wang, L.-W.; Zheng, H. Facet development during platinum nanocube growth. Science 2014, 345, 916– 919, DOI: 10.1126/science.1253149Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtlOmsr7L&md5=53d93e7204a661efbf68b986c117174dFacet development during platinum nanocube growthLiao, Hong-Gang; Zherebetskyy, Danylo; Xin, Huolin; Czarnik, Cory; Ercius, Peter; Elmlund, Hans; Pan, Ming; Wang, Lin-Wang; Zheng, HaimeiScience (Washington, DC, United States) (2014), 345 (6199), 916-919CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)An understanding of how facets of a nanocrystal develop is crit. for controlling nanocrystal shape and designing novel functional materials. However, the at. pathways of nanocrystal facet development are mostly unknown because of the lack of direct observation. The authors report the imaging of Pt nanocube growth in a liq. cell using TEM with high spatial and temporal resoln. The growth rates of all low index facets are similar until the {100} facets stop growth. The continuous growth of the rest facets leads to a nanocube. The authors' calcn. shows that the much lower ligand mobility on the {100} facets is responsible for the arresting of {100} growing facets. These findings shed light on nanocrystal shape-control mechanisms and future design of nanomaterials.
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24Saiki, K. Fabrication and characterization of epitaxial films of ionic materials. Appl. Surf. Sci. 1997, 113/114, 9– 17, DOI: 10.1016/S0169-4332(96)00888-4Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXitVSqurw%253D&md5=4ab6f6feb781ddb25278457fc23e3df0Fabrication and characterization of epitaxial films of ionic materialsSaiki, KoichiroApplied Surface Science (1997), 113/114 (), 9-17CODEN: ASUSEE; ISSN:0169-4332. (Elsevier)The authors have investigated hetero-epitaxial growth of alkali halides, the most typical ionic material, on various kinds of substrates. In the case of growth of alkali halide on foreign alkali halide, layer by layer growth with or without coherent interface and island growth are obsd. according to the misfit value. In contrast, the lattice matching condition works for the growth of alkali halide on GaAs and Si substrates. Alkali halide/GaAs or Si system provides several basic problems such as ionic/covalent interface. On the other hand, it provides flat and conductive alkali-halide surfaces. The authors have used this surface as a substrate for the growth of some org. materials. The thickness dependence of surface phonon polariton of LiBr thin films grown on Si has been investigated. These results might open a new field in research of ionic material surfaces, interfaces, and thin films.
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25Siwick, B. J.; Dwyer, J. R.; Jordan, R. E.; Miller, R. J. D. An atomic-level view of melting using femtosecond electron diffraction. Science 2003, 302, 1382– 1385, DOI: 10.1126/science.1090052Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXptVCqu7c%253D&md5=12666d4b0fd23c35b665b188591e2b6fAn Atomic-Level View of Melting Using Femtosecond Electron DiffractionSiwick, Bradley J.; Dwyer, Jason R.; Jordan, Robert E.; Miller, R. J. DwayneScience (Washington, DC, United States) (2003), 302 (5649), 1382-1385CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)600-Fs electron pulses was used to study the structural evolution of Al as it underwent an ultrafast laser-induced solid-liq. phase transition. Real-time observations showed the loss of long-range order that was present in the cryst. phase and the emergence of the liq. structure where only short-range at. correlations were present; this transition occurred in 3.5 ps for thin-film Al with an excitation fluence of 70 mJ per square centimeter. The sensitivity and time resoln. were sufficient to capture the time-dependent pair correlation function as the system evolved from the solid to the liq. state. These observations provide an at.-level description of the melting process, in which the dynamics are best understood as a thermal phase transition under strongly driven conditions.
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26Nakamura, E. Atomic-resolution transmission electron microscopic movies for study of organic molecules, assemblies, and reactions: The first 10 years of development. Acc. Chem. Res. 2017, 50, 1281– 1292, DOI: 10.1021/acs.accounts.7b00076Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXntFChsrc%253D&md5=1240b08d7ecb940920769731df781215Atomic-Resolution Transmission Electron Microscopic Movies for Study of Organic Molecules, Assemblies, and Reactions: The First 10 Years of DevelopmentNakamura, EiichiAccounts of Chemical Research (2017), 50 (6), 1281-1292CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. A mol. is a quantum mech. entity. Watching motions and reactions of a mol. with eyes has therefore been a dream of chemists for a century. This dream has come true with the aid of the movies of at.-resoln. transmission electron microscopic (AR-TEM) mol. images through real-time observation of dynamic motions of single org. mols. (denoted hereafter as single-mol. at.-resoln. real-time (SMART) TEM imaging). Since 2007, the authors have reported movies of a variety of single org. mols., organometallic mols., and their assemblies, which are rotating, stretching, and reacting. Like movies in the theater, the at.-resoln. mol. movies provide us information on the 3-dimensional structures of the mols. and also their time evolution. The success of the SMART-TEM imaging crucially depends on the development of chem. fishhooks with which fish (org. mols.) in soln. can be captured on a single-walled carbon nanotube (CNT, serving as a fishing rod). The captured mols. are connected to a slowly vibrating CNT, and their motions are displayed on a monitor in real time. A fishing line connecting the fish and the rod may be a σ-bond, a van der Waals force, or other weak connections. Here, the mol./CNT system behaves as a coupled oscillator, where the low-frequency anisotropic vibration of the CNT is transmitted to the mols. via the weak chem. connections that act as an energy filter. Interpretation of the obsd. motions of the mols. at at. resoln. needs us to consider the quantum mech. nature of electrons as well as bond rotation, letting us deviate from the conventional statistical world of chem. What new horizons can the authors explore. The authors have so far carried out conformational studies of individual mols., assigning anti or gauche conformations to each C-C bond in conformers that the authors saw. The authors can also det. the structures of van der Waals assemblies of org. mols., thereby providing mechanistic insights into crystal formation-phenomena of general significance in science, engineering, and daily life. Whereas many of the single org. mols. in a vacuum seen by SMART-TEM are sufficiently long-lived for detailed studies, mols. with low ionization potentials (<6 eV) undergo chem. reactions, for example, [60]fullerene and organometallic compds. possibly via a hole catalysis mechanism, where a radical cation of CNT generated under electron irradn. catalyzes the transformation via an electron transfer mechanism. Common org. mols. whose ionization potentials are much higher (>8 eV) than that of CNT (5 eV) remain stable for a time long enough for observation at 60-120 kV acceleration voltage, as they are not oxidized by the CNT radical cation. Alternatively, the reaction may have taken place via an excited state of a mol. produced by energy transfer from CNT possessing excess energy provided by the electron beam. SMART-TEM imaging is a simple approach to the study of the structures and reactions of mols. and their assemblies and will serve as a gateway to the research and education of the science connecting the quantum mech. world and the real world.
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27Okada, S.; Kowashi, S.; Schweighauser, L.; Yamanouchi, K.; Harano, K.; Nakamura, E. Direct microscopic analysis of individual C60 dimerization events: Kinetics and mechanisms. J. Am. Chem. Soc. 2017, 139, 18281– 18287, DOI: 10.1021/jacs.7b09776Google Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvVKitrvL&md5=ce28ae5fd9d062c9c8a048c3abf6e624Direct Microscopic Analysis of Individual C60 Dimerization Events: Kinetics and MechanismsOkada, Satoshi; Kowashi, Satori; Schweighauser, Luca; Yamanouchi, Kaoru; Harano, Koji; Nakamura, EiichiJournal of the American Chemical Society (2017), 139 (50), 18281-18287CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Modern transition state theory states that the statistical behavior of a chem. reaction is the sum of individual chem. events that occur randomly. Statistical anal. of each event for individual mols. in a three-dimensional space however is practically impossible. We report here that kinetics and mechanisms of chem. reactions can be investigated by using a one-dimensional system where reaction events can be obsd. in situ and counted one by one using variable-temp. (VT) at.-resoln. transmission electron microscopy (TEM). We thereby provide direct proof that the ensemble behavior of random events conforms to the Rice-Ramsperger-Kassel-Marcus theory, as illustrated for [2+2] cycloaddn. of C60 mols. in carbon nanotubes (CNTs). This method gives kinetic and structural information for different types of reactions occurring simultaneously in the microscopic view field, suggesting that the VT-TEM opens a new dimension of chem. kinetics research on mols. and their assemblies in their excited and ionized states. The study carried out at 393-493 K showed that pristine CNT primarily acts as a singlet sensitizer of the cycloaddn. reaction that takes place with an activation energy of 33.5 ± 6.8 kJ/mol. On the other hand, CNT suffers electron damage of the conjugated system at 103-203 K and promotes a reactive radical cation path that takes place with an activation energy of only 1.9 ± 0.7 kJ/mol. The pre-exponential factor of the Arrhenius plot gave us further mechanistic insights.
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28Nakamura, E.; Harano, K. Chemical kinetics study through observation of individual reaction events with atomic-resolution electron microscopy. Proc. Jpn. Acad., Ser. B 2018, 94, 428– 440, DOI: 10.2183/pjab.94.028Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXktFOis78%253D&md5=63ec851a28abf3c5a0d969e905750616Chemical kinetics study through observation of individual reaction events with atomic-resolution electron microscopyNakamura, Eiichi; Harano, KojiProceedings of the Japan Academy, Series B: Physical and Biological Sciences (2018), 94 (10), 428-440CODEN: PJABDW; ISSN:0386-2208. (Nippon Gakushiin)Single-mol. at.-resoln. real-time electron microscopic movie imaging is an emerging new tool for obtaining dynamic structural information on mols. and mol. assemblies. This method provides a hitherto inaccessible possibility to in situ observe the time evolution of chem. events at various temps. from the beginning till the end, as demonstrated for the kinetics study of [2 + 2] cycloaddn. of [60]fullerene mols., which was found to occur via an excited state or via radical cation depending on the temp. One unique feature of this methodol. is that, by observing directly the reaction events, one can obtain information on the frequency of events unperturbed by mol. diffusion. With the obtained exptl. data set, we provided the first exptl. proof of what the quantum mech. transition state theory predicted, in that isolated mols. behave as if all their accessible states were occupied in a random order. We also found that, under the 1-D reaction conditions, mol.-level information on a few hundred mols. suffices to deduce statistically meaningful kinetics data that match with those obtained by bulk expts.
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29
Recent review;
Sandoval, S.; Tobias, G.; Flahaut, E. Structure of inorganic nanocrystals confined within carbon nanotubes. Inorg. Chim. Acta 2019, 492, 66– 75, DOI: 10.1016/j.ica.2019.04.004Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXnsFGhsLs%253D&md5=e15e3b5ed07e7ba9417ac6b5b98462c9Structure of inorganic nanocrystals confined within carbon nanotubesSandoval, Stefania; Tobias, Gerard; Flahaut, EmmanuelInorganica Chimica Acta (2019), 492 (), 66-75CODEN: ICHAA3; ISSN:0020-1693. (Elsevier B.V.)A review. There are many examples in which the cavities of carbon nanotubes have been filled with a variety of compds. Unprecedented structures compared to those of the same material in the bulk are obsd., such as low dimensional crystals. Such encapsulated materials can have unusual properties that differ from those of the bulk material. The scope of this review is to give a brief approach to the different nanostructures formed after encapsulation of inorg. compds. within the inner cavities of carbon nanotubes. The confined materials can take the form of one-dimensional nanowires, nanoclusters or even inorg. nanotubes. This review is part of the special issue of the journal dedicated to Prof. Malcolm L. H. Green, and special emphasis is thus given to the work performed by the group of Prof. Green. -
30Hanayama, H.; Yamada, J.; Harano, K.; Nakamura, E. Cyclodextrins as surfactants for solubilization and purification of carbon nanohorn aggregates. Chem. - Asian J. 2020, 15, 1549– 1552, DOI: 10.1002/asia.202000273Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXmvFSku7s%253D&md5=1b3aa00d74a50b131a9350eb80daadddCyclodextrins as Surfactants for Solubilization and Purification of Carbon Nanohorn AggregatesHanayama, Hiroki; Yamada, Junya; Harano, Koji; Nakamura, EiichiChemistry - An Asian Journal (2020), 15 (10), 1549-1552CODEN: CAAJBI; ISSN:1861-4728. (Wiley-VCH Verlag GmbH & Co. KGaA)Nano- to micrometer-scale surface roughness contributes to the hydrophobicity of materials as discussed often in terms of superhydrophobicity. We report here that as little as 1 wt.% of α, β, and γ-cyclodextrins (CDs) can disperse carbon nanohorn aggregates (CNHa) as surfactants in water by binding on their pointed tips. The binding mode was visually demonstrated using single-mol. at. resoln. real-time electron microscopy (SMART-EM). The SMART-EM data provided an estn. of the equil. const. of the CD binding to be close to that of adamantane ammonium chloride to β-CD. A qual. study on the rate of decomplexation of α, β, and γ-CDs from CNHa suggests a substantial mechanistic difference in their binding mode to the CNH tips. A sequence of α-CD complexation and decomplexation allows us to purify CNHa by selectively removing graphitic ball-shaped impurity (GB). Upon treatment with NaNH2, the purified CNHa produce GB-free amino-CNHa where the tips are functionalized with NH2 groups.
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31Barrett, W. T.; Wallace, W. E. Studies of NaCl-KCl solid solutions. I. Heats of formation, lattice spacings, densities, Schottky defects and mutual solubilities. J. Am. Chem. Soc. 1954, 76, 366– 369, DOI: 10.1021/ja01631a014Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG2cXjtFartg%253D%253D&md5=0a7dd75f8057267e0c0676359c383c8bSodium chloride-potassium chloride solid solutions. I. Heats of formation, lattice spacings, densities, Schottky defects, and mutual solubilitiesBarrett, W. T.; Wallace, W. E.Journal of the American Chemical Society (1954), 76 (), 366-9CODEN: JACSAT; ISSN:0002-7863.Heats of formation, lattice spacings, and ds. of a series of NaCl-KCl solid solns. homogenized at 630° and quenched to room temp. were detd. Data are included showing the no. of Schottky defects in this system, and the solid-soly. curve was redetd.
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32Lai, J.; Lu, X.; Zheng, L. Convergence from clusters to the bulk solid: An ab initio investigation of clusters NanCln (n = 2–40). PhysChemComm 2002, 5, 82– 87, DOI: 10.1039/B202278HGoogle ScholarThere is no corresponding record for this reference.
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33Cowley, J. M.; Iijima, S. Electron Microscope Image Contrast for Thin Crystals. Z. Naturforsch., A: Phys. Sci. 1972, 27a, 445– 451, DOI: 10.1515/zna-1972-0312Google ScholarThere is no corresponding record for this reference.
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34Pflaum, R.; Sattler, K.; Recknagel, E. Multiphoton stimulated desorption: the magic numbers of neutral sodium chloride clusters. Chem. Phys. Lett. 1987, 138, 8– 12, DOI: 10.1016/0009-2614(87)80333-0Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2sXlt1ekurs%253D&md5=33f9e2beeda35575d2701ed7a946e997Multiphoton stimulated desorption: the magic numbers of neutral sodium chloride clustersPflaum, R.; Sattler, K.; Recknagel, E.Chemical Physics Letters (1987), 138 (1), 8-12CODEN: CHPLBC; ISSN:0009-2614.Multiphoton ionization of warm NaCl clusters generates magic nos. which are different from the anomalies reported after electron ionization of sputtering. They can be explained by assuming the desorption of all Na halide mols. outside rectangular neutral cluster cores before ionization takes place. In contrast, cold clusters show the magic nos. of ion cuboids.
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Abstract
Figure 1
Figure 1. Nucleation and growth of a NaCl nanocrystal in a vibrating CNT. (a) Schematic energy diagram of crystallization. The radius of a critical nucleus shown as rc. (b) TEM image of a NaCl nanocrystal at 298 K in an aminated CNT of a size denoted as (x, y, z) with x, y, and z (thickness) defined herein. Throughout this work, the assignment on which of Na+ and Cl– occupies the corners of a crystal is arbitrary, because the TEM image lacks this information. The amino groups on CNT are too small to be seen. Scale bar 1 nm. Acceleration voltage 80 kV and electron dose rate of 3.6 × 105 e– nm–2 s–1. Whenever necessary, the moiré pattern due to the graphitic lattice was removed by inverse fast Fourier transform (Figure 1 in Supporting Information Figure S1). (c) Model of a conical CNT shown with a curved arrow illustrating vibration. (d) Schematic diagram of the crystallization. NaCl molecules are supplied from a hidden reservoir. Vibrations of CNT and crystal are shown with curved arrows.
Figure 2
Figure 2. Nucleation/growth events taking place nine times. (a) Four representative snapshots in each event (40 ms frame–1). Time 0 is the time when a NaCl cluster first appeared. The crystal size in parentheses. Acceleration voltage 80 kV and electron dose rate 4.0 × 105 e– nm–2 s–1 with small dose fluctuation (Figure S7). Scale bar 1 nm. The position of the images in each frame is normalized for the outline of the vibrating CNT (cf. Movies S1–S4). See Figure S8 for a 318-frame data set. (b) Histogram of the time until the appearance of a (4,6) crystal (red) and growth until (6,8) crystal or its size equivalent (blue). (c) Normal distribution of nucleation time period (black line) with an average of 5.07 s and standard deviation (sd) of 2.18 s. (d) Distribution of initial growth time period (average of 3.94 s and sd of 2.33 s), during which the crystal grew from 48 to 144 NaCl with a rate of 24.4 NaCl s–1. (e) The course of the crystal growth in the nine events (column) and crystal sizes observed (+) during the growth (row).
Figure 3
Figure 3. Nucleation/growth at 298 K. (a) Cluster/crystal images in the first event shown in Figure 2a. White arrows indicate steps in contact with the CNT wall. (b) Time evolution of 2-D area of cluster/crystal images. The nucleation phase ended at the dotted line at 5.04 s, before which featureless (light blue) and semiordered clusters (dark blue) alternately appeared. Arrows indicate step formation, and red dots the snapshots shown in (a).
Figure 4
Figure 4. Shrinkage/collapse at 473 K. (a) Crystal shrinkage at 473 K (20 ms frame–1). Time 0 is set arbitrarily. See Figure S10 and Movie S5 for a 28-frame data set. Scale bar 1 nm. (b) Time evolution of the 2-D area of the images with the dotted line showing the end of the shrinkage stage.
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References
ARTICLE SECTIONS
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4Bartels-Rausch, T. Ten things we need to know about ice and snow. Nature 2013, 494, 27– 29, DOI: 10.1038/494027a4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXitFaqu7k%253D&md5=5da71af30b7a04b3edc38f53d3e3db74Chemistry Ten things we need to know about ice and snowBartels-Rausch, ThorstenNature (London, United Kingdom) (2013), 494 (7435), 27-29CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)Understanding the mol. behavior of frozen water is essential for predicting the future of our planet, says Thorsten Bartels-Rausch.
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5(a) Vekilov, P. G. Nucleation. Cryst. Growth Des. 2010, 10, 5007– 5019, DOI: 10.1021/cg10116335ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhsVaisrnO&md5=760e7504daad63314fe654b75e113d29NucleationVekilov, Peter G.Crystal Growth & Design (2010), 10 (12), 5007-5019CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)A review. Crystn. starts with nucleation and control of nucleation is crucial for the control of the no., size, perfection, polymorphism, and other characteristics of cryst. materials. This is particularly true for crystn. in soln., which is an essential part of processes in the chem. and pharmaceutical industries and a major step in physiol. and pathol. phenomena. There were significant recent advances in the understanding of the mechanism of nucleation of crystals in soln. The foremost of these are the two-step mechanism of nucleation and the notion of the soln.-crystal spinodal. According to the two-step mechanism, the cryst. nucleus appears inside pre-existing metastable clusters of size several hundred nanometers, which consist of dense liq. and are suspended in the soln. While initially proposed for protein crystals, the applicability of this mechanism was demonstrated for small mol. org. materials, colloids, polymers, and biominerals. This mechanism helps to explain several long-standing puzzles of crystal nucleation in soln.: nucleation rates which are many orders of magnitude lower than theor. predictions, the significance of the dense protein liq., and others. At high supersaturations typical of most crystg. systems, the generation of crystal embryos occurs in the spinodal regime, where the nucleation barrier is negligible. The soln.-crystal spinodal helps to clarify the role of heterogeneous substrates in nucleation and the selection of cryst. polymorphs. Importantly, these ideas provide powerful tools for control of the nucleation process by varying the soln. thermodn. parameters.(b) Nielsen, M. H.; Aloni, S.; De Yoreo, J. J. In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways. Science 2014, 345, 1158– 1162, DOI: 10.1126/science.12540515bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsVGhtLbF&md5=666d1f4ca29359e906a274ce68b9fd44In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathwaysNielsen, Michael H.; Aloni, Shaul; De Yoreo, James J.Science (Washington, DC, United States) (2014), 345 (6201), 1158-1162CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Multiple nucleation pathways were obsd. for the crystal nucleation of calcium carbonate (CaCO3) including formation both directly from soln. and indirectly through transformation of amorphous and cryst. precursors. In situ transmission electron microscopy (TEM) was used in a cell that enables reagent mixing. An amorphous-to-calcite transformation was not obsd. The behavior of amorphous calcium carbonate upon dissoln. suggests that it encompasses a spectrum of structures, including liqs. and solids. These observations of competing direct and indirect pathways are consistent with classical predictions, whereas the behavior of amorphous particles hints at an underlying commonality among recently proposed precursor-based mechanisms.
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6(a) Erdemir, D.; Lee, A. Y.; Myerson, A. S. Nucleation of crystals from solution: Classical and two-step models. Acc. Chem. Res. 2009, 42, 621– 629, DOI: 10.1021/ar800217x6ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXltFOltbs%253D&md5=1777175975e040b55a2c0a58bfd8fd5bNucleation of Crystals from Solution: Classical and Two-Step ModelsErdemir, Deniz; Lee, Alfred Y.; Myerson, Allan S.Accounts of Chemical Research (2009), 42 (5), 621-629CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Crystn. is vital to many processes occurring in nature and in the chem., pharmaceutical, and food industries. Notably, crystn. is an attractive isolation step for manufg. because this single process combines both particle formation and purifn. Almost all of the products based on fine chems., such as dyes, explosives, and photog. materials, require crystn. in their manuf., and more than 90% of all pharmaceutical products contain bioactive drug substances and excipients in the cryst. solid state. Hence control over the crystn. process allows manufacturers to obtain products with desired and reproducible properties. We judge the quality of a cryst. product based on four main properties: size, purity, morphol., and crystal structure. The pharmaceutical industry in particular requires prodn. of the desired crystal form (polymorph) to assure the bioavailability and stability of the drug substance. In soln. crystn., nucleation plays a decisive role in detg. the crystal structure and size distribution. Therefore, understanding the fundamentals of nucleation is crucial to achieve control over these properties. Because of its anal. simplicity, researchers have widely applied classical nucleation theory to soln. crystn. However, a no. of differences between theor. predictions and exptl. results suggest that nucleation of solids from soln. does not proceed via the classical pathway but follows more complex routes. In this Account, we discuss the shortcomings of classical nucleation theory and review studies contributing to the development of the modern two-step model. In the two-step model that was initially proposed for protein crystn., a sufficient-sized cluster of solute mols. forms first, followed by reorganization of that cluster into an ordered structure. In recent exptl. and theor. studies, we and other researchers have demonstrated the applicability of the two-step mechanism to both macromols. and small org. mols., suggesting that this mechanism may underlie most crystn. processes from solns. Because we have obsd. an increase in the organization time of appropriate lattice structures with greater mol. complexity, we propose that organization is the rate-detg. step. Further development of a clearer picture of nucleation may help det. the optimum conditions necessary for the effective organization within the clusters. In addn., greater understanding of these processes may lead to the design of auxiliaries that can increase the rate of nucleation and avoid the formation of undesired solid forms, allowing researchers to obtain the final product in a timely and reproducible manner.(b) De Yoreo, J. J.; Gilbert, P. U. P. A.; Sommerdijk, N. A. J. M.; Penn, R. L.; Whitelam, S.; Joester, D.; Zhang, H.; Rimer, J. D.; Navrotsky, A.; Banfield, J. F.; Wallace, A. F.; Michel, F. M.; Meldrum, F. C.; Cölfen, H.; Dove, P. M. Crystallization by particle attachment in synthetic, biogenic, and geologic environments. Science 2015, 349, aaa6760, DOI: 10.1126/science.aaa6760There is no corresponding record for this reference.
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7Kalcher, I.; Dzubiella, J. NaCl crystallization in apolar nanometer-sized confinement studied by atomistic simulations. Phys. Rev. E 2013, 88, 062312 DOI: 10.1103/PhysRevE.88.0623127https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitVOktrk%253D&md5=fc7668cb7c826173421d697aa3913896NaCl crystallization in apolar nanometer-sized confinement studied by atomistic simulationsKalcher, Immanuel; Dzubiella, JoachimPhysical Review E: Statistical, Nonlinear, and Soft Matter Physics (2013), 88 (6-A), 062312/1-062312/10CODEN: PRESCM; ISSN:1539-3755. (American Physical Society)The structure and growth of mol. NaCl crystals in bulk and in a narrow, nanometer-sized apolar confinement are examd. by explicit-water mol. dynamics computer simulations. Fast crystn. and subsequent diffusion-controlled cluster growth in bulk is triggered by supersaturations that exceed a certain threshold value. In confinement, simulated in a pseudo grand canonical setup, salt is shown to be expelled from the narrow apolar slab region, and the effective ion concn. inside the nanoconfinement is always considerably lower than the reservoir salt concn. so that no fast crystn. takes place. For very small slab widths (d < 1.5 nm) salt is almost entirely expelled while water remains in the slab, indicating a capillary evapn. phenomenon for the polar ions. If forced into the apolar confinement by simulating in a strictly canonical setup, we find stable crystals only if at least 3 cryst. planes fit into the slab, which happens above a 2-nm slab width. In this case the (100) plane of the bulk crystal is oriented parallel to the apolar surface delimited by a subnanometer thin hydration layer. This work presents mol.-level insight of salt crystn. in apolar confinements of a nanometer scale with possible implications in double-layer supercapacitor physics and geol. salt weathering.
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8Gladkov, S. O. On Mathematical Description of Crystallization as a Deterministic Chaos Problem. Tech. Phys. 2008, 53, 952– 955, DOI: 10.1134/S10637842080702198https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXptVyitb0%253D&md5=76c001fbf9ef10faa7a0c3e4a32934caOn mathematical description of crystallization as a deterministic chaos problemGladkov, S. O.Technical Physics (2008), 53 (7), 952-955CODEN: TEPHEX; ISSN:1063-7842. (Pleiades Publishing, Ltd.)The problem of anal. description of the space-time nucleation of the crystal phase is solved using the theory of nonuniform and nonstationary fluctuations of d. and temp. and the method of deterministic chaos.
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9Komatsuzaki, T.; Berry, R. S. Chemical reaction dynamics: Many-body chaos and regularity. Adv. Chem. Phys. 2003, 123, 79– 152, DOI: 10.1002/0471231509.ch2There is no corresponding record for this reference.
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10Zheng, H.; Smith, R. K.; Jun, Y.-w.; Kisielowski, C.; Dahmen, U.; Alivisatos, A. P. Observation of single colloidal platinum nanocrystal growth trajectories. Science 2009, 324, 1309– 1312, DOI: 10.1126/science.117210410https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXms12gtbk%253D&md5=ac8ff7c442a75980accf254eb63b2d9cObservation of Single Colloidal Platinum Nanocrystal Growth TrajectoriesZheng, Haimei; Smith, Rachel K.; Jun, Young-wook; Kisielowski, Christian; Dahmen, Ulrich; Alivisatos, A. PaulScience (Washington, DC, United States) (2009), 324 (5932), 1309-1312CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Understanding of colloidal nanocrystal growth mechanisms is essential for the syntheses of nanocrystals with desired phys. properties. The classical model for the growth of monodisperse nanocrystals assumes a discrete nucleation stage followed by growth via monomer attachment, but has overlooked particle-particle interactions. Recent studies suggested that interactions between particles play an important role. Using in situ TEM, platinum nanocrystals can grow either by monomer attachment from soln. or by particle coalescence. Through the combination of these two processes, an initially broad size distribution can spontaneously narrow into a nearly monodisperse distribution. Probably colloidal nanocrystals take different pathways of growth based on their size- and morphol.-dependent internal energies.
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11Jonkheijm, P.; van der Schoot, P.; Schenning, A. P. H. J.; Meijer, E. W. Probing the solvent-assisted nucleation pathway in chemical self-assembly. Science 2006, 313, 80– 83, DOI: 10.1126/science.112788411https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XmsFWisr4%253D&md5=145a82543d9267d6bbbdbb5aa08e9b96Probing the Solvent-Assisted Nucleation Pathway in Chemical Self-AssemblyJonkheijm, Pascal; van der Schoot, Paul; Schenning, Albertus P. H. J.; Meijer, E. W.Science (Washington, DC, United States) (2006), 313 (5783), 80-83CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Hierarchical self-assembly offers a powerful strategy for producing mol. nanostructures. Although widely used, the mechanistic details of self-assembly processes are poorly understood. We spectroscopically monitored a nucleation process in the self-assembly of π-conjugated mols. into helical supramol. fibrillar structures. The data support a nucleation-growth pathway that gives rise to a remarkably high degree of cooperativity. Furthermore, we characterize a helical transition in the nucleating species before growth. The self-assembly process depends strongly on solvent structure, suggesting that an organized shell of solvent mols. plays an explicit role in rigidifying the aggregates and guiding them toward further assembly into bundles and/or gels.
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12Zhou, J.; Yang, Y.; Yang, Y.; Kim, D. S.; Yuan, A.; Tian, X.; Ophus, C.; Sun, F.; Schmid, A. K.; Nathanson, M.; Heinz, H.; An, Q.; Zeng, H.; Ercius, P.; Miao, J. Observing crystal nucleation in four dimensions using atomic electron tomography. Nature 2019, 570, 500– 503, DOI: 10.1038/s41586-019-1317-x12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXht1yktbjO&md5=f2933a85ef1ddcac8d55986dd716564dObserving crystal nucleation in four dimensions using atomic electron tomographyZhou, Jihan; Yang, Yongsoo; Yang, Yao; Kim, Dennis S.; Yuan, Andrew; Tian, Xuezeng; Ophus, Colin; Sun, Fan; Schmid, Andreas K.; Nathanson, Michael; Heinz, Hendrik; An, Qi; Zeng, Hao; Ercius, Peter; Miao, JianweiNature (London, United Kingdom) (2019), 570 (7762), 500-503CODEN: NATUAS; ISSN:0028-0836. (Nature Research)Nucleation plays a crit. role in many phys. and biol. phenomena that range from crystn., melting and evapn. to the formation of clouds and the initiation of neurodegenerative diseases1-3. However, nucleation is a challenging process to study exptl., esp. in its early stages, when several atoms or mols. start to form a new phase from a parent phase. A no. of exptl. and computational methods have been used to study nucleation processes4-17, but exptl. detn. of the three-dimensional at. structure and the dynamics of early-stage nuclei has been unachievable. Here the authors use at. electron tomog. to study early-stage nucleation in four dimensions (i.e., including time) at at. resoln. Using FePt nanoparticles as a model system, early-stage nuclei are irregularly shaped, each has a core of one to a few atoms with the max. order parameter, and the order parameter gradient points from the core to the boundary of the nucleus. The authors capture the structure and dynamics of the same nuclei undergoing growth, fluctuation, dissoln., merging and/or division, which are regulated by the order parameter distribution and its gradient. These exptl. observations are corroborated by mol. dynamics simulations of heterogeneous and homogeneous nucleation in liq.-solid phase transitions of Pt. The authors' exptl. and mol. dynamics results indicate that a theory beyond classical nucleation theory1,2,18 is needed to describe early-stage nucleation at the at. scale. The authors anticipate that the reported approach will open the door to the study of many fundamental problems in materials science, nanoscience, condensed matter physics and chem., such as phase transition, at. diffusion, grain boundary dynamics, interface motion, defect dynamics and surface reconstruction with four-dimensional at. resoln.
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13Zeng, Z.; Zheng, W.; Zheng, H. Visualization of colloidal nanocrystal formation and electrode-electrolyte interfaces in liquids using TEM. Acc. Chem. Res. 2017, 50, 1808– 1817, DOI: 10.1021/acs.accounts.7b0016113https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1Olsb3E&md5=73b7461245dd630b1271d9be1cc4fc2fVisualization of Colloidal Nanocrystal Formation and Electrode-Electrolyte Interfaces in Liquids Using TEMZeng, Zhiyuan; Zheng, Wenjing; Zheng, HaimeiAccounts of Chemical Research (2017), 50 (8), 1808-1817CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Transmission electron microscopy (TEM) has become a powerful anal. tool for addressing unique scientific problems in chem. sciences as well as in materials sciences and other disciplines. There has been a lot of recent interest in the development and applications of liq. phase environmental TEM. In this Account, we review the development and applications of liq. cell TEM for the study of dynamic phenomena at liq.-solid interfaces, focusing on two areas: (1) nucleation, growth, and self-assembly of colloidal nanocrystals and (2) electrode-electrolyte interfaces during charge and discharge processes. We highlight the achievements and progress that have been made in these two topical areas of our studies. For example, tracking single platinum particle growth trajectories revealed that two different pathways of growth, either by monomer attachment or coalescence between nanoparticles, led to the same particle size. With the improved spatial resoln. and fast electron detection, we were able to trace individual facet development during platinum nanocube platinum nanocube growth. The results showed that different from the surface energy minimization rule prediction, the growth rates of all low-energy facets, such as {100}, {110}, and {111}, were similar. The {100} facets stopped growth early, and the continuous growth of the rest facets resulted in a nanocube. D. functional theory calcns. showed that the amine ligands with low mobility on the {100} facets blocked the further growth of the facets. The effect of the ligand on nanoparticle shape evolution were further studied systematically using a Pt-Fe nanoparticle system by changing the oleylamine concn. With 20%, 30%, or 50% oleylamine, Pt-Fe nanowires or nanoparticles with different morphologies and stabilities were achieved. Real-time imaging of nanoparticles in soln. also enabled the study of interactions between nanoparticles during self-assembly. We further compared the study of noble-metal nanoparticles and transition-metal oxides in a liq. cell to elucidate the nanoparticle formation mechanisms. In the second part of this Account, we review the study of electrolyte-electrode interfaces by the development of electrochem. liq. cell TEM. The formation of single-cryst. Pb dendrites from polycryst. branches and Li dendrite growth in a com. electrolyte for Li ion batteries were obsd. We also studied lithiation reactions of MoS2 and Au electrodes. MoS2 nanoflakes on the Ti electrode underwent irreversible decompn., resulting in the vanishing of the MoS2 active nanoflakes. More detailed study using nanobeam diffraction indicated that the MoS2 nanoflakes were broken down into small nanoparticles as a result of the fast discharge. For the lithiation of Au electrodes, three distinct types of morphol. changes during reactions were revealed, including gradual dissoln., explosive reaction, and local expansion/shrinkage. Addnl., we studied electrolyte decompn. reactions such as bubble formation and solid electrolyte interphase formation. At the end, our perspective on the challenges and opportunities in the applications of liq. phase environmental TEM for the study of liq. chem. reactions is provided.
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14Durán-Olivencia, M. A.; Lutsko, J. F. Mesoscopic nucleation theory for confined systems: A one-parameter model. Phys. Rev. E 2015, 91, 022402 DOI: 10.1103/PhysRevE.91.02240214https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXlsVyqs7Y%253D&md5=94d60860b2787565a373c8db41b1a712Mesoscopic nucleation theory for confined systems: a one-parameter modelDuran-Olivencia, Miguel A.; Lutsko, James F.Physical Review E: Statistical, Nonlinear, and Soft Matter Physics (2015), 91 (2-A), 022402/1-022402/16CODEN: PRESCM; ISSN:1539-3755. (American Physical Society)Classical nucleation theory has been recently reformulated based on fluctuating hydrodynamics. The present work extends this effort to the case of nucleation in confined systems such as small pores and vesicles. The finite available mass imposes a maximal supercrit. cluster size and prohibits nucleation altogether if the system is too small. We quantity the effect of system size on the nucleation rate. We also discuss the effect of relaxing the capillary-model assumption of zero interfacial width resulting in significant changes in the nucleation barrier and nucleation rate.
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15Wallace, A. F.; Hedges, L. O.; Fernandez-Martinez, A.; Raiteri, P.; Gale, J. D.; Waychunas, G. A.; Whitelam, S.; Banfield, J. F.; De Yoreo, J. J. Microscopic evidence for liquid-liquid separation in supersaturated CaCO3 solutions. Science 2013, 341, 885– 889, DOI: 10.1126/science.123091515https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXht12gsL%252FL&md5=d12279e06d1fe47a5ef9ca743c4f89cfMicroscopic Evidence for Liquid-Liquid Separation in Supersaturated CaCO3 SolutionsWallace, Adam F.; Hedges, Lester O.; Fernandez-Martinez, Alejandro; Raiteri, Paolo; Gale, Julian D.; Waychunas, Glenn A.; Whitelam, Stephen; Banfield, Jillian F.; De Yoreo, James J.Science (Washington, DC, United States) (2013), 341 (6148), 885-889CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Recent exptl. observations of the onset of calcium carbonate (CaCO3) mineralization suggest the emergence of a population of clusters that are stable rather than unstable as predicted by classical nucleation theory. Mol. dynamics simulations were used to probe the structure, dynamics, and energetics of hydrated CaCO3 clusters and lattice gas simulations to explore the behavior of cluster populations before nucleation. The simulations predict the formation of a dense liq. phase through liq.-liq. sepn. within the concn. range in which clusters are obsd. Coalescence and solidification of nanoscale droplets results in formation of a solid phase, the structure of which is consistent with amorphous CaCO3. The presence of a liq.-liq. binodal enables a diverse set of exptl. observations to be reconciled within the context of established phase-sepn. mechanisms.
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16Grzybowski, B. A.; Winkleman, A.; Wiles, J. A.; Brumer, Y.; Whitesides, G. M. Electrostatic self-assembly of macroscopic crystals using contact electrification. Nat. Mater. 2003, 2, 241– 245, DOI: 10.1038/nmat86016https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXisFWgs78%253D&md5=6291995a48069dc57a36536f33b91a74Electrostatic self-assembly of macroscopic crystals using contact electrificationGrzybowski, Bartosz A.; Winkleman, Adam; Wiles, Jason A.; Brumer, Yisroel; Whitesides, George M.Nature Materials (2003), 2 (4), 241-245CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Self-assembly of components larger than mols. into ordered arrays is an efficient way of prepg. microstructured materials with interesting mech. and optical properties. Although crystn. of identical particles or particles of different sizes or shapes can be readily achieved, the repertoire of methods to assemble binary lattices of particles of the same sizes but with different properties is very limited. This paper describes electrostatic self-assembly of two types of macroscopic components of identical dimensions using interactions that are generated by contact electrification. The systems we have examd. comprise two kinds of objects (usually spheres) made of different polymeric materials that charge with opposite elec. polarities when agitated on flat, metallic surfaces. The interplay of repulsive interactions between like-charged objects and attractive interactions between unlike-charged ones results in the self-assembly of these objects into highly ordered, closed arrays. Remarkably, some of the assemblies that form are not electroneutral, i.e., they possess a net charge. The authors suggest that the stability of these unusual structures can be explained by accounting for the interactions between elec. dipoles that the particles in the aggregates induce in their neighbors.
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17Girard, M.; Wang, S.; Du, J. S.; Das, A.; Huang, Z.; Dravid, V. P.; Lee, B.; Mirkin, C. A.; de la Cruz, M. O. Particle analogs of electrons in colloidal crystals. Science 2019, 364, 1174– 1178, DOI: 10.1126/science.aaw823717https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtlKqsL7M&md5=e2767780ae789f4b14ef9f93710ffcd1Particle analogs of electrons in colloidal crystalsGirard, Martin; Wang, Shunzhi; Du, Jingshan S.; Das, Anindita; Huang, Ziyin; Dravid, Vinayak P.; Lee, Byeongdu; Mirkin, Chad A.; Olvera de la Cruz, MonicaScience (Washington, DC, United States) (2019), 364 (6446), 1174-1178CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A versatile method for the design of colloidal crystals involves the use of DNA as a particle-directing ligand. With such systems, DNA-nanoparticle conjugates are considered programmable atom equiv. (PAEs), and design rules have been devised to engineer crystn. outcomes. This work shows that when reduced in size and DNA grafting d., PAEs behave as electron equiv. (EEs), roaming through and stabilizing the lattices defined by larger PAEs, as electrons do in metals in the classical picture. This discovery defines a new property of colloidal crystals-metallicity-that is characterized by the extent of EE delocalization and diffusion. As the no. of strands increases or the temp. decreases, the EEs localize, which is structurally reminiscent of a metal-insulator transition. Colloidal crystal metallicity, therefore, provides new routes to metallic, intermetallic, and compd. phases.
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18Harano, K.; Homma, T.; Niimi, Y.; Koshino, M.; Suenaga, K.; Leibler, L.; Nakamura, E. Heterogeneous nucleation of organic crystals mediated by single-molecule templates. Nat. Mater. 2012, 11, 877– 881, DOI: 10.1038/nmat340818https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtlGjsrfP&md5=e52d4b8049ad9f0b941740fe54fb4254Heterogeneous nucleation of organic crystals mediated by single-molecule templatesHarano, Koji; Homma, Tatsuya; Niimi, Yoshiko; Koshino, Masanori; Suenaga, Kazu; Leibler, Ludwik; Nakamura, EiichiNature Materials (2012), 11 (10), 877-881CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Fundamental understanding of how crystals of org. mols. nucleate on a surface remains limited because of the difficulty of probing rare events at the mol. scale. Single-mol. templates on the surface of carbon nanohorns can nucleate the crystn. of two org. compds. from a supersatd. soln. by mediating the formation of disordered and mobile mol. nanoclusters on the templates. Single-mol. real-time transmission electron microscopy indicates that each nanocluster consists of a max. of approx. 15 mols., that there are fewer nanoclusters than crystals in soln., and that in the absence of templates physisorption, but not crystal formation, occurs. These findings suggest that template-induced heterogeneous nucleation mechanistically resembles two-step homogeneous nucleation.
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19Xing, J.; Schweighauser, L.; Okada, S.; Harano, K.; Nakamura, E. Atomistic Structures and Dynamics of Prenucleation Clusters in MOF-2 and MOF-5 Syntheses. Nat. Commun. 2019, 10, 3608, DOI: 10.1038/s41467-019-11564-419https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BB3MrhtFagtA%253D%253D&md5=27f67359d053519ee2b0d06c51457192Atomistic structures and dynamics of prenucleation clusters in MOF-2 and MOF-5 synthesesXing Junfei; Schweighauser Luca; Okada Satoshi; Harano Koji; Nakamura EiichiNature communications (2019), 10 (1), 3608 ISSN:.Chemical reactions in solution almost always take place via a series of minute intermediates that are often in rapid equilibrium with each other, and hence hardly characterizable at the level of atomistic molecular structures. We found that single-molecule atomic-resolution real-time electron microscopic (SMART-EM) video imaging provides a unique methodology for capturing and analyzing the minute reaction intermediates, as illustrated here for single prenucleation clusters (PNCs) in the reaction mixture of metal-organic frameworks (MOFs). Specifically, we found two different types of PNCs are involved in the formation of MOF-2 and MOF-5 from a mixture of zinc nitrate and benzene dicarboxylates at 95 °C and 120 °C, respectively. SMART-EM identified a small amount of 1-nm-sized cube and cube-like PNCs in the MOF-5 synthesis, but not in the MOF-2 synthesis. In the latter, we instead found only linear and square PNCs, suggesting that the MOF-2/-5 bifurcation takes place at the PNC stage.
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20Isobe, H.; Tanaka, T.; Maeda, R.; Noiri, E.; Solin, N.; Yudasaka, M.; Iijima, S.; Nakamura, E. Preparation, purification, characterization, and cytotoxicity assessment of water-soluble, transition-metal-free carbon nanotube aggregates. Angew. Chem., Int. Ed. 2006, 45, 6676– 6680, DOI: 10.1002/anie.20060171820https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFCltLfP&md5=62ccf1248c238b8eabc451f528adaac5Preparation, purification, characterization, and cytotoxicity assessment of water-soluble, transition-metal-free carbon nanotube aggregatesIsobe, Hiroyuki; Tanaka, Takatsugu; Maeda, Rui; Noiri, Eisei; Solin, Niclas; Yudasaka, Masako; Iijima, Sumio; Nakamura, EiichiAngewandte Chemie, International Edition (2006), 45 (40), 6676-6680CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)The risk assessment of carbon materials, an important topic in nanomaterials research, has been hampered by the lack of characterizable samples. Transition-metal-free carbon nanohorn aggregates have been prepd. that are covalently bonded aggregates of single-walled nanotubes. They were functionalized to give water-sol. derivs., which were incubated with cells in cytotoxicity assessments.
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21Shimizu, T.; Lungerich, D.; Stuckner, J.; Murayama, M.; Harano, K.; Nakamura, E. Real-time video imaging of mechanical motions of a single molecular shuttle with sub-millisecond sub-angstrom precision. Bull. Chem. Soc. Jpn. 2020, 93, 1079– 1085, DOI: 10.1246/bcsj.2020013421https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhs1ensLzF&md5=da606721713cb90663dd5d292b3bc3c5Real-Time Video Imaging of Mechanical Motions of a Single Molecular Shuttle with Sub-Millisecond Sub-Angstrom Precision#Shimizu, Toshiki; Lungerich, Dominik; Stuckner, Joshua; Murayama, Mitsuhiro; Harano, Koji; Nakamura, EiichiBulletin of the Chemical Society of Japan (2020), 93 (9), 1079-1085CODEN: BCSJA8; ISSN:0009-2673. (Chemical Society of Japan)Miniaturized machines have open up a new dimension of chem., studied usually as an av. over numerous mols. or for a single mol. bound on a robust substrate. Mech. motions at a single mol. level, however, are under quantum control, strongly coupled with fluctuations of its environment - a system rarely addressed because an efficient way of observing the nanomech. motions in real time is lacking. Here, we report sub-millisecond sub-Å precision in situ video imaging of a single fullerene mol. shuttling, rotating, and interacting with a vibrating carbon nanotube at 0.625 ms(ms)/frame or 1600 fps, using an electron microscope, a fast camera, and a denoising algorithm. We have achieved in situ observation of the mech. motions of a mol. coupled with vibration of a carbon nanotube with std. error as small as 0.9 ms in time and 0.01 nm in space. We have revealed rich mol. dynamics, where motions are non-linear, stochastic and often non-repeatable, and a work and energy relationship at a mol. level previously undetected by time-averaged measurements or microscopy. The mol. video recording at a 1600-fps rate exceeds by 100 times the previous records of continuous recording of mol. motions.
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22Kvashnin, A. G.; Sorokin, P. B.; Yakobson, B. I. Flexoelectricity in Carbon Nanostructures: Nanotubes, Fullerenes, and Nanocones. J. Phys. Chem. Lett. 2015, 6, 2740– 2744, DOI: 10.1021/acs.jpclett.5b0104122https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtVKit7rE&md5=1959845defc8feb4011ac35ac088b38dFlexoelectricity in Carbon Nanostructures: Nanotubes, Fullerenes, and NanoconesKvashnin, Alexander G.; Sorokin, Pavel B.; Yakobson, Boris I.Journal of Physical Chemistry Letters (2015), 6 (14), 2740-2744CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)We report theor. anal. of the electronic flexoelec. effect assocd. with nanostructures of sp2 carbon (curved graphene). Through the d. functional theory calcns., we establish the universality of the linear dependence of flexoelec. at. dipole moments on local curvature in various carbon networks (carbon nanotubes, fullerenes with high and low symmetry, and nanocones). The usefulness of such dependence is in the possibility to extend the anal. of any carbon systems with local deformations with respect to their electronic properties. This result is exemplified by exploring of flexoelec. effect in carbon nanocones that display large dipole moment, cumulative over their surface yet surprisingly scaling exactly linearly with the length, and with sine-law dependence on the apex angle, dflex ∼ L sin(α). Our study points out the opportunity of predicting the elec. dipole moment distribution on complex graphene-based nanostructures based only on the local curvature information.
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23Liao, H.-G.; Zherebetskyy, D.; Xin, H.; Czarnik, C.; Ercius, P.; Elmlund, H.; Pan, M.; Wang, L.-W.; Zheng, H. Facet development during platinum nanocube growth. Science 2014, 345, 916– 919, DOI: 10.1126/science.125314923https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtlOmsr7L&md5=53d93e7204a661efbf68b986c117174dFacet development during platinum nanocube growthLiao, Hong-Gang; Zherebetskyy, Danylo; Xin, Huolin; Czarnik, Cory; Ercius, Peter; Elmlund, Hans; Pan, Ming; Wang, Lin-Wang; Zheng, HaimeiScience (Washington, DC, United States) (2014), 345 (6199), 916-919CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)An understanding of how facets of a nanocrystal develop is crit. for controlling nanocrystal shape and designing novel functional materials. However, the at. pathways of nanocrystal facet development are mostly unknown because of the lack of direct observation. The authors report the imaging of Pt nanocube growth in a liq. cell using TEM with high spatial and temporal resoln. The growth rates of all low index facets are similar until the {100} facets stop growth. The continuous growth of the rest facets leads to a nanocube. The authors' calcn. shows that the much lower ligand mobility on the {100} facets is responsible for the arresting of {100} growing facets. These findings shed light on nanocrystal shape-control mechanisms and future design of nanomaterials.
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24Saiki, K. Fabrication and characterization of epitaxial films of ionic materials. Appl. Surf. Sci. 1997, 113/114, 9– 17, DOI: 10.1016/S0169-4332(96)00888-424https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXitVSqurw%253D&md5=4ab6f6feb781ddb25278457fc23e3df0Fabrication and characterization of epitaxial films of ionic materialsSaiki, KoichiroApplied Surface Science (1997), 113/114 (), 9-17CODEN: ASUSEE; ISSN:0169-4332. (Elsevier)The authors have investigated hetero-epitaxial growth of alkali halides, the most typical ionic material, on various kinds of substrates. In the case of growth of alkali halide on foreign alkali halide, layer by layer growth with or without coherent interface and island growth are obsd. according to the misfit value. In contrast, the lattice matching condition works for the growth of alkali halide on GaAs and Si substrates. Alkali halide/GaAs or Si system provides several basic problems such as ionic/covalent interface. On the other hand, it provides flat and conductive alkali-halide surfaces. The authors have used this surface as a substrate for the growth of some org. materials. The thickness dependence of surface phonon polariton of LiBr thin films grown on Si has been investigated. These results might open a new field in research of ionic material surfaces, interfaces, and thin films.
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25Siwick, B. J.; Dwyer, J. R.; Jordan, R. E.; Miller, R. J. D. An atomic-level view of melting using femtosecond electron diffraction. Science 2003, 302, 1382– 1385, DOI: 10.1126/science.109005225https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXptVCqu7c%253D&md5=12666d4b0fd23c35b665b188591e2b6fAn Atomic-Level View of Melting Using Femtosecond Electron DiffractionSiwick, Bradley J.; Dwyer, Jason R.; Jordan, Robert E.; Miller, R. J. DwayneScience (Washington, DC, United States) (2003), 302 (5649), 1382-1385CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)600-Fs electron pulses was used to study the structural evolution of Al as it underwent an ultrafast laser-induced solid-liq. phase transition. Real-time observations showed the loss of long-range order that was present in the cryst. phase and the emergence of the liq. structure where only short-range at. correlations were present; this transition occurred in 3.5 ps for thin-film Al with an excitation fluence of 70 mJ per square centimeter. The sensitivity and time resoln. were sufficient to capture the time-dependent pair correlation function as the system evolved from the solid to the liq. state. These observations provide an at.-level description of the melting process, in which the dynamics are best understood as a thermal phase transition under strongly driven conditions.
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26Nakamura, E. Atomic-resolution transmission electron microscopic movies for study of organic molecules, assemblies, and reactions: The first 10 years of development. Acc. Chem. Res. 2017, 50, 1281– 1292, DOI: 10.1021/acs.accounts.7b0007626https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXntFChsrc%253D&md5=1240b08d7ecb940920769731df781215Atomic-Resolution Transmission Electron Microscopic Movies for Study of Organic Molecules, Assemblies, and Reactions: The First 10 Years of DevelopmentNakamura, EiichiAccounts of Chemical Research (2017), 50 (6), 1281-1292CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. A mol. is a quantum mech. entity. Watching motions and reactions of a mol. with eyes has therefore been a dream of chemists for a century. This dream has come true with the aid of the movies of at.-resoln. transmission electron microscopic (AR-TEM) mol. images through real-time observation of dynamic motions of single org. mols. (denoted hereafter as single-mol. at.-resoln. real-time (SMART) TEM imaging). Since 2007, the authors have reported movies of a variety of single org. mols., organometallic mols., and their assemblies, which are rotating, stretching, and reacting. Like movies in the theater, the at.-resoln. mol. movies provide us information on the 3-dimensional structures of the mols. and also their time evolution. The success of the SMART-TEM imaging crucially depends on the development of chem. fishhooks with which fish (org. mols.) in soln. can be captured on a single-walled carbon nanotube (CNT, serving as a fishing rod). The captured mols. are connected to a slowly vibrating CNT, and their motions are displayed on a monitor in real time. A fishing line connecting the fish and the rod may be a σ-bond, a van der Waals force, or other weak connections. Here, the mol./CNT system behaves as a coupled oscillator, where the low-frequency anisotropic vibration of the CNT is transmitted to the mols. via the weak chem. connections that act as an energy filter. Interpretation of the obsd. motions of the mols. at at. resoln. needs us to consider the quantum mech. nature of electrons as well as bond rotation, letting us deviate from the conventional statistical world of chem. What new horizons can the authors explore. The authors have so far carried out conformational studies of individual mols., assigning anti or gauche conformations to each C-C bond in conformers that the authors saw. The authors can also det. the structures of van der Waals assemblies of org. mols., thereby providing mechanistic insights into crystal formation-phenomena of general significance in science, engineering, and daily life. Whereas many of the single org. mols. in a vacuum seen by SMART-TEM are sufficiently long-lived for detailed studies, mols. with low ionization potentials (<6 eV) undergo chem. reactions, for example, [60]fullerene and organometallic compds. possibly via a hole catalysis mechanism, where a radical cation of CNT generated under electron irradn. catalyzes the transformation via an electron transfer mechanism. Common org. mols. whose ionization potentials are much higher (>8 eV) than that of CNT (5 eV) remain stable for a time long enough for observation at 60-120 kV acceleration voltage, as they are not oxidized by the CNT radical cation. Alternatively, the reaction may have taken place via an excited state of a mol. produced by energy transfer from CNT possessing excess energy provided by the electron beam. SMART-TEM imaging is a simple approach to the study of the structures and reactions of mols. and their assemblies and will serve as a gateway to the research and education of the science connecting the quantum mech. world and the real world.
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27Okada, S.; Kowashi, S.; Schweighauser, L.; Yamanouchi, K.; Harano, K.; Nakamura, E. Direct microscopic analysis of individual C60 dimerization events: Kinetics and mechanisms. J. Am. Chem. Soc. 2017, 139, 18281– 18287, DOI: 10.1021/jacs.7b0977627https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvVKitrvL&md5=ce28ae5fd9d062c9c8a048c3abf6e624Direct Microscopic Analysis of Individual C60 Dimerization Events: Kinetics and MechanismsOkada, Satoshi; Kowashi, Satori; Schweighauser, Luca; Yamanouchi, Kaoru; Harano, Koji; Nakamura, EiichiJournal of the American Chemical Society (2017), 139 (50), 18281-18287CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Modern transition state theory states that the statistical behavior of a chem. reaction is the sum of individual chem. events that occur randomly. Statistical anal. of each event for individual mols. in a three-dimensional space however is practically impossible. We report here that kinetics and mechanisms of chem. reactions can be investigated by using a one-dimensional system where reaction events can be obsd. in situ and counted one by one using variable-temp. (VT) at.-resoln. transmission electron microscopy (TEM). We thereby provide direct proof that the ensemble behavior of random events conforms to the Rice-Ramsperger-Kassel-Marcus theory, as illustrated for [2+2] cycloaddn. of C60 mols. in carbon nanotubes (CNTs). This method gives kinetic and structural information for different types of reactions occurring simultaneously in the microscopic view field, suggesting that the VT-TEM opens a new dimension of chem. kinetics research on mols. and their assemblies in their excited and ionized states. The study carried out at 393-493 K showed that pristine CNT primarily acts as a singlet sensitizer of the cycloaddn. reaction that takes place with an activation energy of 33.5 ± 6.8 kJ/mol. On the other hand, CNT suffers electron damage of the conjugated system at 103-203 K and promotes a reactive radical cation path that takes place with an activation energy of only 1.9 ± 0.7 kJ/mol. The pre-exponential factor of the Arrhenius plot gave us further mechanistic insights.
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28Nakamura, E.; Harano, K. Chemical kinetics study through observation of individual reaction events with atomic-resolution electron microscopy. Proc. Jpn. Acad., Ser. B 2018, 94, 428– 440, DOI: 10.2183/pjab.94.02828https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXktFOis78%253D&md5=63ec851a28abf3c5a0d969e905750616Chemical kinetics study through observation of individual reaction events with atomic-resolution electron microscopyNakamura, Eiichi; Harano, KojiProceedings of the Japan Academy, Series B: Physical and Biological Sciences (2018), 94 (10), 428-440CODEN: PJABDW; ISSN:0386-2208. (Nippon Gakushiin)Single-mol. at.-resoln. real-time electron microscopic movie imaging is an emerging new tool for obtaining dynamic structural information on mols. and mol. assemblies. This method provides a hitherto inaccessible possibility to in situ observe the time evolution of chem. events at various temps. from the beginning till the end, as demonstrated for the kinetics study of [2 + 2] cycloaddn. of [60]fullerene mols., which was found to occur via an excited state or via radical cation depending on the temp. One unique feature of this methodol. is that, by observing directly the reaction events, one can obtain information on the frequency of events unperturbed by mol. diffusion. With the obtained exptl. data set, we provided the first exptl. proof of what the quantum mech. transition state theory predicted, in that isolated mols. behave as if all their accessible states were occupied in a random order. We also found that, under the 1-D reaction conditions, mol.-level information on a few hundred mols. suffices to deduce statistically meaningful kinetics data that match with those obtained by bulk expts.
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29
Recent review;
Sandoval, S.; Tobias, G.; Flahaut, E. Structure of inorganic nanocrystals confined within carbon nanotubes. Inorg. Chim. Acta 2019, 492, 66– 75, DOI: 10.1016/j.ica.2019.04.00429https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXnsFGhsLs%253D&md5=e15e3b5ed07e7ba9417ac6b5b98462c9Structure of inorganic nanocrystals confined within carbon nanotubesSandoval, Stefania; Tobias, Gerard; Flahaut, EmmanuelInorganica Chimica Acta (2019), 492 (), 66-75CODEN: ICHAA3; ISSN:0020-1693. (Elsevier B.V.)A review. There are many examples in which the cavities of carbon nanotubes have been filled with a variety of compds. Unprecedented structures compared to those of the same material in the bulk are obsd., such as low dimensional crystals. Such encapsulated materials can have unusual properties that differ from those of the bulk material. The scope of this review is to give a brief approach to the different nanostructures formed after encapsulation of inorg. compds. within the inner cavities of carbon nanotubes. The confined materials can take the form of one-dimensional nanowires, nanoclusters or even inorg. nanotubes. This review is part of the special issue of the journal dedicated to Prof. Malcolm L. H. Green, and special emphasis is thus given to the work performed by the group of Prof. Green. -
30Hanayama, H.; Yamada, J.; Harano, K.; Nakamura, E. Cyclodextrins as surfactants for solubilization and purification of carbon nanohorn aggregates. Chem. - Asian J. 2020, 15, 1549– 1552, DOI: 10.1002/asia.20200027330https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXmvFSku7s%253D&md5=1b3aa00d74a50b131a9350eb80daadddCyclodextrins as Surfactants for Solubilization and Purification of Carbon Nanohorn AggregatesHanayama, Hiroki; Yamada, Junya; Harano, Koji; Nakamura, EiichiChemistry - An Asian Journal (2020), 15 (10), 1549-1552CODEN: CAAJBI; ISSN:1861-4728. (Wiley-VCH Verlag GmbH & Co. KGaA)Nano- to micrometer-scale surface roughness contributes to the hydrophobicity of materials as discussed often in terms of superhydrophobicity. We report here that as little as 1 wt.% of α, β, and γ-cyclodextrins (CDs) can disperse carbon nanohorn aggregates (CNHa) as surfactants in water by binding on their pointed tips. The binding mode was visually demonstrated using single-mol. at. resoln. real-time electron microscopy (SMART-EM). The SMART-EM data provided an estn. of the equil. const. of the CD binding to be close to that of adamantane ammonium chloride to β-CD. A qual. study on the rate of decomplexation of α, β, and γ-CDs from CNHa suggests a substantial mechanistic difference in their binding mode to the CNH tips. A sequence of α-CD complexation and decomplexation allows us to purify CNHa by selectively removing graphitic ball-shaped impurity (GB). Upon treatment with NaNH2, the purified CNHa produce GB-free amino-CNHa where the tips are functionalized with NH2 groups.
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31Barrett, W. T.; Wallace, W. E. Studies of NaCl-KCl solid solutions. I. Heats of formation, lattice spacings, densities, Schottky defects and mutual solubilities. J. Am. Chem. Soc. 1954, 76, 366– 369, DOI: 10.1021/ja01631a01431https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG2cXjtFartg%253D%253D&md5=0a7dd75f8057267e0c0676359c383c8bSodium chloride-potassium chloride solid solutions. I. Heats of formation, lattice spacings, densities, Schottky defects, and mutual solubilitiesBarrett, W. T.; Wallace, W. E.Journal of the American Chemical Society (1954), 76 (), 366-9CODEN: JACSAT; ISSN:0002-7863.Heats of formation, lattice spacings, and ds. of a series of NaCl-KCl solid solns. homogenized at 630° and quenched to room temp. were detd. Data are included showing the no. of Schottky defects in this system, and the solid-soly. curve was redetd.
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32Lai, J.; Lu, X.; Zheng, L. Convergence from clusters to the bulk solid: An ab initio investigation of clusters NanCln (n = 2–40). PhysChemComm 2002, 5, 82– 87, DOI: 10.1039/B202278HThere is no corresponding record for this reference.
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33Cowley, J. M.; Iijima, S. Electron Microscope Image Contrast for Thin Crystals. Z. Naturforsch., A: Phys. Sci. 1972, 27a, 445– 451, DOI: 10.1515/zna-1972-0312There is no corresponding record for this reference.
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34Pflaum, R.; Sattler, K.; Recknagel, E. Multiphoton stimulated desorption: the magic numbers of neutral sodium chloride clusters. Chem. Phys. Lett. 1987, 138, 8– 12, DOI: 10.1016/0009-2614(87)80333-034https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2sXlt1ekurs%253D&md5=33f9e2beeda35575d2701ed7a946e997Multiphoton stimulated desorption: the magic numbers of neutral sodium chloride clustersPflaum, R.; Sattler, K.; Recknagel, E.Chemical Physics Letters (1987), 138 (1), 8-12CODEN: CHPLBC; ISSN:0009-2614.Multiphoton ionization of warm NaCl clusters generates magic nos. which are different from the anomalies reported after electron ionization of sputtering. They can be explained by assuming the desorption of all Na halide mols. outside rectangular neutral cluster cores before ionization takes place. In contrast, cold clusters show the magic nos. of ion cuboids.
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Supporting Information
Supporting Information
ARTICLE SECTIONS
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c12100.
Methods and Materials and Representative TEM images (PDF)
Movie S1: Vibration of a conical CNT at 298 K (MOV
Movie S2: Nine times crystallization of NaCl in a conical CNT at 298 K (0–44.40 s) (MOV)
Movie S3: Nine times crystallization of NaCl in a conical CNT at 298 K (44.44–88.84 s) (MOV)
Movie S4: Nine times crystallization of NaCl in a conical CNT at 298 K (88.88–133.28 s) (MOV)
Movie S5: Shrinkage/collapse of NaCl in a conical CNT at 473 K (MOV)
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