Application of the Theory of Diffusion-controlled Reactions to Enzyme Kinetics

Alberty, Robert A.; Hammes, Gordon G.

doi:10.1021/j150560a005

Cited by 356 publications

(237 citation statements)

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“…The detection of hydrogen tunneling often relies on the observation of large KIEs. However, some reactions on condensed phases can be studied only around room temperature or within a limited range of temperatures, and they are often controlled by the diffusion processes of the reactants, as in aerosol chemistry (40,41), and enzyme catalysis (42,43). The present findings indicate that tunneling should be considered in the study of chemical reactions involving hydrogen and deuterium on condensed phases, even when an anomalously large reaction efficiency is observed alongside a small KIE.…”

Section: Discussionmentioning

confidence: 74%

Quantum tunneling observed without its characteristic large kinetic isotope effects

Hama

Ueta

Kouchi

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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Classical transition-state theory is fundamental to describing chemical kinetics; however, quantum tunneling is also important in explaining the unexpectedly large reaction efficiencies observed in many chemical systems. Tunneling is often indicated by anomalously large kinetic isotope effects (KIEs), because a particle's ability to tunnel decreases significantly with its increasing mass. Here we experimentally demonstrate that cold hydrogen (H) and deuterium (D) atoms can add to solid benzene by tunneling; however, the observed H/D KIE was very small (1-1.5) despite the large intrinsic H/D KIE of tunneling (≳100). This strong reduction is due to the chemical kinetics being controlled not by tunneling but by the surface diffusion of the H/D atoms, a process not greatly affected by the isotope type. Because tunneling need not be accompanied by a large KIE in surface and interfacial chemical systems, it might be overlooked in other systems such as aerosols or enzymes. Our results suggest that surface tunneling reactions on interstellar dust may contribute to the deuteration of interstellar aromatic and aliphatic hydrocarbons, which could represent a major source of the deuterium enrichment observed in carbonaceous meteorites and interplanetary dust particles. These findings could improve our understanding of interstellar physicochemical processes, including those during the formation of the solar system. quantum tunneling | kinetic isotope effect | heterogeneous reactions | reaction dynamics | astrochemistry

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Section: Discussionmentioning

confidence: 74%

Quantum tunneling observed without its characteristic large kinetic isotope effects

Hama

Ueta

Kouchi

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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“…The screening of coulombic interactions by electrolyte solutions was analyzed in terms of the electrostatic attraction of two oppositely charged spheres with radii r, a center-center separation of 2r, and charges ϮZ. Relative to infinite separation, the potential energy, V, is given by the expression (61,62),…”

Section: Resultsmentioning

confidence: 99%

Electrostatic Interactions in the Binding Pathway of a Transient Protein Complex Studied by NMR and Isothermal Titration Calorimetry

Meneses

Mittermaier

2014

Journal of Biological Chemistry

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Background: Electrostatic interactions are known accelerate binding in protein complexes with long lifetimes (minutes to hours). Results: NMR and calorimetry were used to characterize binding kinetics in short lived (ϳ1 ms) protein-peptide complexes. Conclusion: Electrostatic enhancement is much less and basal (electrostatic-free) association rates are greater than previously observed. Significance: Electrostatics may play different roles in short lived and long lived protein complexes.

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“…Whereas ␣ 1 PI inhibits free cat G in two steps (12), it reacts in one step with the 30bp DNA-cat G complex. The value of k ass (21 M Ϫ1 s Ϫ1 ) is, however, several orders of magnitude lower than the maximum rate constant for a bimolecular diffusion-controlled reaction (21). It may, therefore, be assumed that the reaction involves an intermediate even if the latter is not seen kinetically.…”

Section: Discussionmentioning

confidence: 99%

DNA Strongly Impairs the Inhibition of Cathepsin G by α1-Antichymotrypsin and α1-Proteinase Inhibitor

Duranton

Boudier

Belorgey

et al. 2000

Journal of Biological Chemistry

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Application of the Theory of Diffusion-controlled Reactions to Enzyme Kinetics

Cited by 356 publications

References 1 publication

Quantum tunneling observed without its characteristic large kinetic isotope effects

Quantum tunneling observed without its characteristic large kinetic isotope effects

Electrostatic Interactions in the Binding Pathway of a Transient Protein Complex Studied by NMR and Isothermal Titration Calorimetry

DNA Strongly Impairs the Inhibition of Cathepsin G by α1-Antichymotrypsin and α1-Proteinase Inhibitor

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