Oxygen Is the High-Energy Molecule Powering Complex Multicellular Life: Fundamental Corrections to Traditional Bioenergetics
- Klaus Schmidt-Rohr*
Klaus Schmidt-RohrDepartment of Chemistry, Brandeis University, Waltham, Massachusetts 02465, United StatesMore by Klaus Schmidt-Rohr
Abstract
A fundamental re-assessment of the overall energetics of biochemical electron transfer chains and cycles is presented, highlighting the crucial role of the highest-energy molecule involved, O2. The chemical energy utilized by most complex multicellular organisms is not predominantly stored in glucose or fat, but rather in O2 with its relatively weak (i.e., high-energy) double bond. Accordingly, reactions of O2 with organic molecules are highly exergonic, while other reactions of glucose, fat, NAD(P)H, or ubiquinol (QH2) are not, as demonstrated in anaerobic respiration with its meager energy output. The notion that “reduced molecules” such as alkanes or fatty acids are energy-rich is shown to be incorrect; they only unlock the energy of more O2, compared to O-containing molecules of similar mass. Glucose contains a moderate amount of chemical energy per bond (<20% compared to O2), as confirmed by the relatively small energy output in glycolysis and the Krebs cycle converting glucose to CO2 and NADH. Only in the “terminal” aerobic respiration reaction with O2 does a large free energy change occur due to the release of oxygen’s stored chemical energy. The actual reaction of O2 in complex IV of the inner mitochondrial membrane does not even involve any organic fuel molecule and yet releases >1 MJ when 6 mol of O2 reacts. The traditional presentation that relegated O2 to the role of a low-energy terminal acceptor for depleted electrons has not explained these salient observations and must be abandoned. Its central notion that electrons release energy because they move from a high-energy donor to a low-energy acceptor is demonstrably false. The energies of (at least) two donor and two acceptor species come into play, and the low “terminal” negative reduction potential in aerobic respiration can be attributed to the unusually high energy of O2, the crucial reactant. This is confirmed by comparison with the corresponding half-reaction without O2, which is endergonic. In addition, the electrons are mostly not accepted by oxygen but by hydrogen. Redox energy transfer and release diagrams are introduced to provide a superior representation of the energetics of the various species in coupled half-reactions. Electron transport by movement of reduced molecules in the electron transfer chain is shown to run counter to the energy flow, which is carried by oxidized species. O2, rather than glucose, NAD(P)H, or ATP, is the molecule that provides the most energy to animals and plants and is crucial for sustaining large complex life forms. The analysis also highlights a significant discrepancy in the proposed energetics of reactions of aerobic respiration, which should be re-evaluated.
Introduction
Results and Discussion
Energetics of Molecules in Aerobic Respiration
Summary of the Traditional Presentation
(i) | Conceptual overviews of bioenergetics show naı̈ve statements and diagrams about sunlight and nutrients providing the energy organisms need, (1,2,8) and it is assumed without reflection that organic fuel molecules contain the energy released in aerobic respiration. (3−5,11) |
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(ii) | In more specific summaries of respiration and photosynthesis reactions, the Gibbs free energy changes ΔrGo′ in overall reactions, such as NADH + H+ + 1/2O2 → H2O + NAD+, are given but without meaningful explanation. (We have shown that their main component, ΔrHo, can be quantitatively explained in terms of the energy per electron-pair bond. (12) In combustion and aerobic respiration, most of the energy derives from the unusually weak double bond of O2.) |
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(iii) | An electron transfer description is given at length. (1−3,6) In the description of the electron transfer step by step, the origin of the large ΔrGo′ in aerobic respiration is not discussed. This analysis does not even explicitly refer to energies but rather to negative standard reduction potentials in volts. It is “explained” in terms of differential electron affinities or an “electron waterfall”. (6,24) |
Energy Released in Aerobic Respiration
High-Energy Molecules
O2 Is a High-Energy Molecule
Glucose Has Only Moderate Energy
Reduced Molecules Have Little Energy
NAD(P)H Is Not a High-Energy Molecule
Representing the Energetics of Redox Reactions in Respiration
Two Valid Views of Energy Release in a Redox Reaction
High-Energy Reactants to Lower-Energy Products
Half-Reaction Analysis
A Superior Representation of Half-Reaction Energetics: Redox Energy Transfer and Release Diagrams
Correcting Common Electron Transfer Misconceptions
The Higher the Energy of O2, the Lower Its Half-Reaction Free Energy Level
Hydrogen, Rather than Oxygen, Is the Main Terminal Electron Acceptor
An Electron Waterfall?
The Reduced “Electron-Carrying” Species Do Not Carry the Energy
Electron Transfer and Energy Release
Electron Transfer and Bond Energies
Local but Not Global Electron Flow
The Electron Transfer Chain in Aerobic Respiration
Energetics of the Aerobic Respiration Chain
Reconsidering the Number of Protons Pumped by the Energy of O2
Glycolysis and Citric Acid (Krebs) Cycle
The Calvin Cycle
Synopsis
The Traditional Description of Bioenergetics Is Incorrect
(i) | The traditional explanation in terms of electron transfer to oxygen is mechanistically incorrect: the electrons are mostly transferred to hydrogen, not oxygen (see above). |
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(ii) | The electron transfer or fuel energy description cannot explain why this reaction is highly exergonic and exothermic: no organic fuel is involved in this reaction, yet a lot of energy is produced (approximately –1350 kJ/mol per 6O2). Since Fe2+(cytc) is lower in energy than Fe3+(cytc), organisms are certainly not fueled by Fe2+(cytc) and, thus, the energy released by the reaction in eq 14 unquestionably comes from O2, a proven high-energy molecule. |
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(iii) | Any explanation connecting electron transfer between molecules with the energy released must include bond energies. These are quantities with energy units and real explanatory power unlike standard reduction potentials in volts. The energy stored in O2 can be attributed quantitatively to its relatively weak double bond, (12) which is less stable (higher in energy) by 250–410 kJ/mol relative to a double bond in CO2 or a pair of single bonds in organic molecules or in H2O (see Figure 1). |
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(iv) | The standard reduction potential levels in the electron waterfall picture (6,24) are not energies of chemical species but differences between such energies. Therefore, they do not reveal where chemical energy is stored. Specifically, the level of the terminal half-reaction is lowered as the energy of the electron acceptors, O2 + 4H+, is increased. Both changes would increase the energy released with the electron: the acceptors are reactants, and higher reactant energy increases the energy released by a reaction. |
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(v) | The traditional electron transfer analysis has ignored the (model-independent) large negative ΔrGo′ value of this reaction in eq 14, which was just another meaningless empirical value, and therefore overlooked that it is incompatible with the small number of protons supposedly pumped by complex IV. Recognizing O2 as a high-energy molecule, our analysis correctly predicts the large negative ΔrGo′ value and highlights the factor-of-two discrepancy in the number of H+ pumped. |
Limitations of the Electron Transfer Paradigm
Bond Energies as the Crucial Unifying Concept of Bioenergetics
O2 as the Major High-Energy Molecule in the Biosphere
Conclusions
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.9b03352.
Analyses of combustion energetics irrespective of the bond order of O2; a review of bonding in O2; a table of thermodynamic energies for biochemistry; the origin of data for Table S1 and Figure 1; conventional versus meaningful individual free energies of ions; evaluating free energies of reactants and products; discussions of “weak bonds to strong bonds” and of the small entropy of combustion; reduced molecules and their reaction energetics; the analogy of NAD(P)H + H+ and H2; O2 in the last or first step of respiration; more electron transfer to hydrogen than oxygen; presenting the electron transfer chain of aerobic respiration correctly, with reduced “electron-carrying” molecules not carrying the energy; “half-reaction free energy levels” and standard reduction potentials versus electron energies; energetics of the Calvin cycle; a review of biochemical energy in textbooks; and an example of correcting bioenergetics in a textbook (PDF)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgments
The author would like to acknowledge Gursu Culcu for raising the question of energetics of electron transfer chains and to thank Sam Darmstadt and Laura Schmidt-Hong for checking numerical values of free energies of reactions and stoichiometries. Dr. Chris Miller was kind enough to read through the paper and provide feedback on its arguments, which the author has much appreciated.
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32Payne, W. J. Energy Yields and Growth of Heterotrophs. Annu. Rev. Microbiol. 1970, 24, 17– 52, DOI: 10.1146/annurev.mi.24.100170.000313Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE3MXjvFCmtw%253D%253D&md5=34f10bf3ff2a33f5b24f1f1ea998b40aEnergy yields and growth of heterotrophsPayne, William J.Annual Review of Microbiology (1970), 24 (), 17-52CODEN: ARMIAZ; ISSN:0066-4227.A review concerning the available energy yield of cells during growth of heterotrophic bacteria and yeasts in both aerobic and anaerobic cultures and in both simple and complex media. Generalizations concerning yields from ordinary substrates give an av. yield of 65% from growth on a hydrocarbon as compared with the productivity of a conventional substrate. As much as 60% of the enthalpy of the hydrocarbon may be lost in the conversion of these substances by the cells.
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33Schmidt-Rohr, K. How Batteries Store and Release Energy: Explaining Basic Electrochemistry. J. Chem. Educ. 2018, 95, 1801– 1810, DOI: 10.1021/acs.jchemed.8b00479Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsFGlu7jL&md5=24ef3fb883e8b3aaae48a673cec93cfdHow Batteries Store and Release Energy: Explaining Basic ElectrochemistrySchmidt-Rohr, KlausJournal of Chemical Education (2018), 95 (10), 1801-1810CODEN: JCEDA8; ISSN:0021-9584. (American Chemical Society and Division of Chemical Education, Inc.)A review. Batteries are valued as devices that store chem. energy and convert it into elec. energy. Unfortunately, the std. description of electrochem. does not explain specifically where or how the energy is stored in a battery; explanations just in terms of electron transfer are easily shown to be at odds with exptl. observations. Importantly, the Gibbs energy redn. in an electrochem. reaction in a battery also involves atom transfer between different phases. It is shown that, for simple galvanic cells or batteries with reactive metal electrodes, two intuitively meaningful contributions to the elec. energy are relevant: (i) the difference in the lattice cohesive energies of the bulk metals, reflecting metallic and covalent bonding and accounting for the atom transfer, and (ii) the difference in the ionization energies of the metals in water, assocd. with electron transfer. The ionization energy in water can be calcd. as the sum of gas-phase ionization energies and the hydration energy of the metal ion. Entropy plays only a limited role, for instance, driving the processes in concn. cells. The prediction of the energy of batteries in terms of cohesive and aq. ionization energies is in excellent agreement with expt. Since the elec. energy released is equal to the redn. in Gibbs energy, which is the hallmark of a spontaneous process, the anal. also explains why specific electrochem. processes occur. In several important cases, including the classical Zn/Cu battery, the difference in the bulk-metal cohesive energies is the origin of the elec. energy released. For instance, metallic Zn, Cd, or Mg lack stabilization by bonding via unoccupied d-orbitals and are therefore of higher energy than most transition metals. Indeed, metallic zinc is shown to be the high-energy material in the alk. household battery. The lead-acid car battery is recognized as an ingenious device that splits water into 2 H+(aq) and O2- during charging and derives much of its elec. energy from the formation of the strong O-H bonds of H2O during discharge. The anal. provides an explanation of basic electrochem. that will help students better understand this important topic.
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1Nelson, D. L.; Cox, M. M. Lehninger Principles of Biochemistry; 6th ed.; Worth Publishers: New York, 2013.There is no corresponding record for this reference.
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8Morowitz, H. J. Energy Flow in Biology; Ox Bow Press: Woodbridge, CT, 1979.There is no corresponding record for this reference.
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9Hedges, S.; Blair, J. E.; Venturi, M. L.; Shoe, J. L. A molecular timescale of eukaryote evolution and the rise of complex multicellular life. BMC Evol. Biol 2004, 4, 2, DOI: 10.1186/1471-2148-4-29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BD2c3js1eqsg%253D%253D&md5=992e9729979fe8d769d360d3169b6301A molecular timescale of eukaryote evolution and the rise of complex multicellular lifeHedges S Blair; Blair Jaime E; Venturi Maria L; Shoe Jason LBMC evolutionary biology (2004), 4 (), 2 ISSN:.BACKGROUND: The pattern and timing of the rise in complex multicellular life during Earth's history has not been established. Great disparity persists between the pattern suggested by the fossil record and that estimated by molecular clocks, especially for plants, animals, fungi, and the deepest branches of the eukaryote tree. Here, we used all available protein sequence data and molecular clock methods to place constraints on the increase in complexity through time. RESULTS: Our phylogenetic analyses revealed that (i) animals are more closely related to fungi than to plants, (ii) red algae are closer to plants than to animals or fungi, (iii) choanoflagellates are closer to animals than to fungi or plants, (iv) diplomonads, euglenozoans, and alveolates each are basal to plants+animals+fungi, and (v) diplomonads are basal to other eukaryotes (including alveolates and euglenozoans). Divergence times were estimated from global and local clock methods using 20-188 proteins per node, with data treated separately (multigene) and concatenated (supergene). Different time estimation methods yielded similar results (within 5%): vertebrate-arthropod (964 million years ago, Ma), Cnidaria-Bilateria (1,298 Ma), Porifera-Eumetozoa (1,351 Ma), Pyrenomycetes-Plectomycetes (551 Ma), Candida-Saccharomyces (723 Ma), Hemiascomycetes-filamentous Ascomycota (982 Ma), Basidiomycota-Ascomycota (968 Ma), Mucorales-Basidiomycota (947 Ma), Fungi-Animalia (1,513 Ma), mosses-vascular plants (707 Ma), Chlorophyta-Tracheophyta (968 Ma), Rhodophyta-Chlorophyta+Embryophyta (1,428 Ma), Plantae-Animalia (1,609 Ma), Alveolata-plants+animals+fungi (1,973 Ma), Euglenozoa-plants+animals+fungi (1,961 Ma), and Giardia-plants+animals+fungi (2,309 Ma). By extrapolation, mitochondria arose approximately 2300-1800 Ma and plastids arose 1600-1500 Ma. Estimates of the maximum number of cell types of common ancestors, combined with divergence times, showed an increase from two cell types at 2500 Ma to approximately 10 types at 1500 Ma and 50 cell types at approximately 1000 Ma. CONCLUSIONS: The results suggest that oxygen levels in the environment, and the ability of eukaryotes to extract energy from oxygen, as well as produce oxygen, were key factors in the rise of complex multicellular life. Mitochondria and organisms with more than 2-3 cell types appeared soon after the initial increase in oxygen levels at 2300 Ma. The addition of plastids at 1500 Ma, allowing eukaryotes to produce oxygen, preceded the major rise in complexity.
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10Bender, D. A.; Botham, K. M.; Kennelly, P. J.; Rodwell, V. W.; Weil, P. A. Harper’s Illustrated Biochemistry; 29th ed.; McGraw Hill: New York, 2012.There is no corresponding record for this reference.
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11Reece, J. B.; Urry, L. A.; Cain, M. L.; Wasserman, S. A.; Minorsky, P. V.; Jackson, R. B. Campbell Biology; 7th ed.; Pearson / Benjamin Cummings: Boston, 2011.There is no corresponding record for this reference.
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12Schmidt-Rohr, K. Why Combustions Are Always Exothermic, Yielding About 418 kJ per Mole of O2. J. Chem. Educ. 2015, 92, 2094– 2099, DOI: 10.1021/acs.jchemed.5b0033312https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsVWqtLrF&md5=423b81d5afcf0e452e23c23797912192Why Combustions Are Always Exothermic, Yielding About 418 kJ per Mole of O2Schmidt-Rohr, KlausJournal of Chemical Education (2015), 92 (12), 2094-2099CODEN: JCEDA8; ISSN:0021-9584. (American Chemical Society and Division of Chemical Education, Inc.)The strongly exothermic nature of reactions between mol. oxygen and all org. mols. as well as many other substances is explained in simple, general terms. The double bond in O2 is much weaker than other double bonds or pairs of single bonds, and therefore the formation of the stronger bonds in CO2 and H2O results in the release of energy, which is given off as heat or increases thermal motion. This explains why fire is hot regardless of fuel compn. The bond energies in the fuel play only a minor role; for example, the total bond energy of CH4 is nearly the same as that of CO2. A careful anal. in terms of bond enthalpies, counting double bonds as two bonds to keep the total no. of bonds unchanged, gives the heat of combustion close to -418 kJ/mol (i.e., -100 kcal/mol) for each mole of O2, in good agreement (±3.1%) with data for >500 org. compds.; the heat of condensation of H2O, -44 kJ/mol, is also included in the anal. For 268 mols. with ≥ 8 carbon atoms, the std. deviation from the predicted value is even smaller, 2.1%. This enables an instant est. of the heat of combustion simply from the elemental compn. of the fuel, even for a complex mixt. or unknown mol. structure, and explains principles of biofuels prodn. The anal. indicates that O2, rather than fuels like octane, H2, ethanol, or glucose, is the crucial "energy-rich" mol.; we briefly explain why O2 is abundant in air despite its high enthalpy.
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13Alberty, R. A.; Silbey, R. J. Physical Chemistry; 2nd ed.; Wiley: New York, 1997. p.Table 8.3.There is no corresponding record for this reference.
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14Alberty, R. A. Thermodynamics of Biochemical Reactions; Wiley: Hoboken, NJ, 2003. p. 211– 213.There is no corresponding record for this reference.
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15Oxtoby, D. W.; Gillis, H. P.; Butler, L. J. Principles of Modern Chemistry; 8th ed.; CENGAGE Learning: Boston, MA, 2015.There is no corresponding record for this reference.
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16Atkins, P.; de Paula, J. Physical Chemistry; 8th ed.; Freeman: New York, 2006. pp. 225– 229.There is no corresponding record for this reference.
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17Thornton, W. M. The Relation of Oxygen to the Heat of Combustion of Organic Compounds. Philos. Mag., Ser. 1917, 33, 196– 203, DOI: 10.1080/14786440208635627There is no corresponding record for this reference.
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18Huggett, C. Estimation of Rate of Heat Release by Means of Oxygen Consumption Measurements. Fire Mater. 1980, 4, 61– 65, DOI: 10.1002/fam.81004020218https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3MXhslyktw%253D%253D&md5=838519d41fdd6860ba0000bfc190c1c4Estimation of rate of heat release by means of oxygen consumption measurementsHuggett, ClaytonFire and Materials (1980), 4 (2), 61-5CODEN: FMATDV; ISSN:0308-0501.Measurement of the rate of O consumption provides a simple, versatile, and powerful tool for estg. the rate of heat release in fire expts. and fire tests. The method is based on the generalization that the heats of combustion per unit of O consumed are approx. the same for most fuels commonly encountered in fires. A measurement of the rate of O consumption can then be converted to a measure of rate of heat release. Data on heats of combustion are presented to support this generalization. The applicability of the technique to combustion under fire conditions is examd., possible sources of error in the measurements are discussed, and applications of the method are reviewed. The accuracy of O consumption based rate of heat release measurements should compare favorably with those derived from conventional calorimetric measurements.
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19Cordier, J.-L.; Butsch, B. M.; Birou, B.; von Stockar, U. The relationship between elemental composition and heat of combustion of microbial biomass. Appl. Microbiol. Biotechnol. 1987, 25, 305– 312, DOI: 10.1007/BF0025253819https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2sXhslCltb8%253D&md5=04549bf22682ed4758e61f23a5bec91bThe relationship between elemental composition and heat of combustion of microbial biomassCordier, Jean Louis; Butsch, Bertram M.; Birou, Bernard; Von Stockar, UrsApplied Microbiology and Biotechnology (1987), 25 (4), 305-12CODEN: AMBIDG; ISSN:0175-7598.Four models taken from the literature, which permit calcn. of heats of combustion from elemental anal., are evaluated from a theor. point of view. In order to obtain exptl. values of heat of combustion with a higher degree of accuracy than that in the literature, an improved sample prepn. technique based on lyophilization of microbial biomass was developed. Heat of combustion was detd. by direct measurement in a calorimeter and compared to calcd. values from each of the literature models. Giese's formula predicted heat of combustion the most accurately. The enthalpy content of the bacteria investigated (23.13 kJ/g) significantly differs from that of yeasts (21.21 kJ/g).
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20Weiss, H. M. Appreciating Oxygen. J. Chem. Educ. 2008, 85, 1218– 1219, DOI: 10.1021/ed085p121820https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXpvVSitbo%253D&md5=afa38d854478550b8bd656bfd934fef1Appreciating oxygenWeiss, Hilton M.Journal of Chemical Education (2008), 85 (9), 1218-1219CODEN: JCEDA8; ISSN:0021-9584. (Journal of Chemical Education, Dept. of Chemistry)The article describes the property of oxygen. Oxygen is the unique mol. that stores energy coming from the sun and provides the energy for life on earth.
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21Ross, K. Fuel and food are not made of energy - a constructive view of respiration and combustion. Sch Sci. Rev. 2013, 94, 60– 6921https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtVais7vL&md5=4e74ac47136c514be7d0321ee5656e59Fuel and food are not made of energy - a constructive view of respiration and combustionRoss, KeithSchool Science Review (2013), 94 (349), 60-69CODEN: SSCRAD; ISSN:0036-6811. (Association for Science Education)A review. We often say that food and fuels contain energy, whereas energy is stored in the fuel-oxygen system generated during photosynthesis. This article suggests revised approaches to teaching that make a clear distinction between matter (food, fuel, oxygen) and energy.
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22Borden, W. T.; Hoffmann, R.; Stuyver, T.; Chen, B. Dioxygen: What Makes This Triplet Diradical Kinetically Persistent?. J. Am. Chem. Soc. 2017, 139, 9010– 9018, DOI: 10.1021/jacs.7b0423222https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXpslKhtL8%253D&md5=da374ba6c834caedc5073f5214ffec69Dioxygen: What Makes This Triplet Diradical Kinetically Persistent?Borden, Weston Thatcher; Hoffmann, Roald; Stuyver, Thijs; Chen, BoJournal of the American Chemical Society (2017), 139 (26), 9010-9018CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Exptl. heats of formation and enthalpies obtained from G4 calcns. both find that the resonance stabilization of the two unpaired electrons in triplet O2, relative to the unpaired electrons in two hydroxyl radicals, amts. to 100 kcal/mol. The origin of this huge stabilization energy is described within the contexts of both MO and valence-bond (VB) theory. Although O2 is a triplet diradical, the thermodn. unfavorability of both its hydrogen atom abstraction and oligomerization reactions can be attributed to its very large resonance stabilization energy. The unreactivity of O2 toward both these modes of self-destruction maintains its abundance in the ecosphere and thus its availability to support aerobic life. However, despite the resonance stabilization of the π system of triplet O2, the weakness of the O-O σ bond makes reactions of O2, which eventually lead to cleavage of this bond, very favorable thermodynamically.
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23Ori, J. In Sciencing.com; https://sciencing.com/oxygen-release-energy-cellular-respiration-6362797.html, 2018.There is no corresponding record for this reference.
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24Dill, K. A.; Bromberg, S. Molecular Driving Forces; 2nd ed.; Garland Science: London/New York, 2011.There is no corresponding record for this reference.
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25Chase, M. W.; Davies, C. A.; Downey, J. R.; Frurip, D. J.; McDonald, R. A.; Syverud, A. N. https://janaf.nist.gov/, 1998; Vol.There is no corresponding record for this reference.
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26Heimann, A.; Jakobsen, R.; Blodau, C. Energetic Constraints on H2-Dependent Terminal Electron Accepting Processes in Anoxic Environments: A Review of Observations and Model Approaches. Environ. Sci. Technol. 2010, 44, 24– 33, DOI: 10.1021/es901820726https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtl2iurbN&md5=d9571b836cd6d3c3031c0361889f9f90Energetic Constraints on H2-Dependent Terminal Electron Accepting Processes in Anoxic Environments: A Review of Observations and Model ApproachesHeimann, Axel; Jakobsen, Rasmus; Blodau, ChristianEnvironmental Science & Technology (2010), 44 (1), 24-33CODEN: ESTHAG; ISSN:0013-936X. (American Chemical Society)A review is given. Microbially mediated terminal electron accepting processes (TEAPs) to a large extent control the fate of redox reactive elements and assocd. reactions in anoxic soils, sediments, and aquifers. This review focuses on thermodn. controls and regulation of H-dependent TEAPs, case studies illustrating this concept, and the quant. description of thermodn. controls in modeling. Other electron transfer processes are considered where appropriate. The work reviewed shows that thermodn. and microbial kinetics are connected near thermodn. equil. Free energy thresholds for terminal respiration are physiol. based and often near -20 KJ/mol, depending on the mechanism of ATP generation; more pos. free energy values have been reported under starvation conditions for methanogenesis and lower values for TEAPs that provide more energy. H-dependent methanogenesis and sulfate redn. are under direct thermodn. control in soils and sediments and generally approach theor. min. energy thresholds. If H concns. are lowered by thermodynamically more potent TEAPs, these processes are inhibited. This principle is also valid for TEAPS providing more free energy, such as denitrification and arsenate redn., but electron donor concn. cannot be lowered so that the processes reach theor. energy thresholds. Thermodn. and kinetics have been integrated by combining traditional descriptions of microbial kinetics with the equil. const. K and reaction quotient Q of a process, taking into account process-specific threshold energies. This approach is dynamically evolving toward a general concept of microbially driven electron transfer in anoxic environments and has been used successfully in applications ranging from bioreactor regulation to groundwater and sediment biogeochem.
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27Taiz, L.; Zeiger, E.; Møller, I. M.; Murphy, A. Plant Physiology and Development; 6th ed.; Oxford University Press: Oxford, 2014. Topic 8.4: Energy Demands for Photosynthesis in Land Plants.There is no corresponding record for this reference.
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28Mentzer, A. P. In Sciencing.com; https://sciencing.com/nadph-photosynthesis-5799755.html 2019; Vol. 2019.There is no corresponding record for this reference.
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29Bockris, J. O.; Reddy, A. K. N.; Gamboa-Aldeco, M. Modern Electrochemistry 2A, Fundamentals of Electrodics; 2nd ed.; Kluwer Academic / Plenum: New York, 2001.There is no corresponding record for this reference.
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30Martin, F.; Zipse, H. Charge Distribution in the Water Molecule - A Comparison of Methods. J. Comput. Chem. 2004, 26, 97– 105, DOI: 10.1002/jcc.2015730https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXhtFaiurrI&md5=8ac76995b2a34f00e743a679e4c0d2d6Charge distribution in the water molecule - a comparison of methodsMartin, F.; Zipse, H.Journal of Computational Chemistry (2004), 26 (1), 97-105CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)The charge distribution in the water mol. has been analyzed using a broad variety of basis sets, four different quantum mech. methods (Hartree-Fock, Becke3LYP, MP2, and QCISD), and six population anal. methods (Mulliken, NPA, AIM, CHELPG, Merz-Kollman, and Resp). The influence of the mol. structure on the calcd. at. charges has been studied using small perturbations of the exptl. detd. structure.
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31Kharasch, M. S.; Sher, B. The Electronic Conception of Valence and Heats of Combustion of Organic Compounds. J. Phys. Chem. 1925, 29, 625– 658, DOI: 10.1021/j150252a00131https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaB2MXhslyjtA%253D%253D&md5=c3375c716fa53edcc7e868657ade3905Electronic conception of valence and heats of combustion of organic compoundsKharasch, M. S.; Sher, BenJournal of Physical Chemistry (1925), 29 (), 625-58CODEN: JPCHAX; ISSN:0022-3654.The heat of combustion of org. compds. is assumed to be the energy given out when an electron pair shifts from its relatively non-polar position in the org. bond to the relatively polar positions occupied in H2O and CO2. The no. of possible degrees of polarity, i. e., the no. of possible energy levels in the Bohr sense is supposed to be finite, not infinite as in the older form of the Lewis theory. The differences in the energy of an electron in nonpolar bonds and in the polar bonds of the CO2 type are sub-multiple of 26.05 kg. cal. per mol. per electron. Thus the heat of combustion of liquid satd. hydrocarbons is 26.05 N, where N is the number of valence electrons in the compd. If 0 is taken as the energy level of an electron in the polar CO2 and H2O type of bond, the electrons in the non-polar C-H, C-C, N-H and conjugate double bonds, are in energy level 1; the electrons in the partially polar bonds C.dbd.C, (non-conjugate), C-OH, C-NO2, C-NH2 (primary), are in energy level 1/2; the electrons in .dbd.C.sbd.OH, .dbd.C.dbd.O are in energy level 1/4; the electrons in tertiary alcohols, phenols, anilides and acids O.sbd.H and N.dbd.O are in levels 0-1/8, the data not being sufficient to decide. These formulas have been tested for 278 org. compds., the agreement being most striking.
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32Payne, W. J. Energy Yields and Growth of Heterotrophs. Annu. Rev. Microbiol. 1970, 24, 17– 52, DOI: 10.1146/annurev.mi.24.100170.00031332https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaE3MXjvFCmtw%253D%253D&md5=34f10bf3ff2a33f5b24f1f1ea998b40aEnergy yields and growth of heterotrophsPayne, William J.Annual Review of Microbiology (1970), 24 (), 17-52CODEN: ARMIAZ; ISSN:0066-4227.A review concerning the available energy yield of cells during growth of heterotrophic bacteria and yeasts in both aerobic and anaerobic cultures and in both simple and complex media. Generalizations concerning yields from ordinary substrates give an av. yield of 65% from growth on a hydrocarbon as compared with the productivity of a conventional substrate. As much as 60% of the enthalpy of the hydrocarbon may be lost in the conversion of these substances by the cells.
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33Schmidt-Rohr, K. How Batteries Store and Release Energy: Explaining Basic Electrochemistry. J. Chem. Educ. 2018, 95, 1801– 1810, DOI: 10.1021/acs.jchemed.8b0047933https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsFGlu7jL&md5=24ef3fb883e8b3aaae48a673cec93cfdHow Batteries Store and Release Energy: Explaining Basic ElectrochemistrySchmidt-Rohr, KlausJournal of Chemical Education (2018), 95 (10), 1801-1810CODEN: JCEDA8; ISSN:0021-9584. (American Chemical Society and Division of Chemical Education, Inc.)A review. Batteries are valued as devices that store chem. energy and convert it into elec. energy. Unfortunately, the std. description of electrochem. does not explain specifically where or how the energy is stored in a battery; explanations just in terms of electron transfer are easily shown to be at odds with exptl. observations. Importantly, the Gibbs energy redn. in an electrochem. reaction in a battery also involves atom transfer between different phases. It is shown that, for simple galvanic cells or batteries with reactive metal electrodes, two intuitively meaningful contributions to the elec. energy are relevant: (i) the difference in the lattice cohesive energies of the bulk metals, reflecting metallic and covalent bonding and accounting for the atom transfer, and (ii) the difference in the ionization energies of the metals in water, assocd. with electron transfer. The ionization energy in water can be calcd. as the sum of gas-phase ionization energies and the hydration energy of the metal ion. Entropy plays only a limited role, for instance, driving the processes in concn. cells. The prediction of the energy of batteries in terms of cohesive and aq. ionization energies is in excellent agreement with expt. Since the elec. energy released is equal to the redn. in Gibbs energy, which is the hallmark of a spontaneous process, the anal. also explains why specific electrochem. processes occur. In several important cases, including the classical Zn/Cu battery, the difference in the bulk-metal cohesive energies is the origin of the elec. energy released. For instance, metallic Zn, Cd, or Mg lack stabilization by bonding via unoccupied d-orbitals and are therefore of higher energy than most transition metals. Indeed, metallic zinc is shown to be the high-energy material in the alk. household battery. The lead-acid car battery is recognized as an ingenious device that splits water into 2 H+(aq) and O2- during charging and derives much of its elec. energy from the formation of the strong O-H bonds of H2O during discharge. The anal. provides an explanation of basic electrochem. that will help students better understand this important topic.
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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/acsomega.9b03352.
Analyses of combustion energetics irrespective of the bond order of O2; a review of bonding in O2; a table of thermodynamic energies for biochemistry; the origin of data for Table S1 and Figure 1; conventional versus meaningful individual free energies of ions; evaluating free energies of reactants and products; discussions of “weak bonds to strong bonds” and of the small entropy of combustion; reduced molecules and their reaction energetics; the analogy of NAD(P)H + H+ and H2; O2 in the last or first step of respiration; more electron transfer to hydrogen than oxygen; presenting the electron transfer chain of aerobic respiration correctly, with reduced “electron-carrying” molecules not carrying the energy; “half-reaction free energy levels” and standard reduction potentials versus electron energies; energetics of the Calvin cycle; a review of biochemical energy in textbooks; and an example of correcting bioenergetics in a textbook (PDF)
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