Quantum Effects in Enzyme Kinetics

Sen, Arundhuti; Kohen, Amnon

doi:10.1039/9781847559975-00161

Cited by 11 publications

(18 citation statements)

References 43 publications

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“…The contribution of DAD sampling to enzyme systems that are optimized for H-tunneling, as determined from the temperature dependence of the KIE, is generally quite weak (31, 32, 115), with the temperature-independent KIEs easily fitted to Equation 4 within a single population of protein (50) displaying a high frequency for DAD sampling (95, 96). Such apparent active-site compaction/compression could arise, in principle, from ground-state interactions within the dominant E-S complex.…”

Section: Interrelationship Between Donor-acceptor Distance Sampling Amentioning

confidence: 99%

Hydrogen Tunneling Links Protein Dynamics to Enzyme Catalysis

Klinman

Kohen

2013

Annu. Rev. Biochem.

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311

474

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The relationship between protein dynamics and function is a subject of considerable contemporary interest. Although protein motions are frequently observed during ligand binding and release steps, the contribution of protein motions to the catalysis of bond making/breaking processes is more difficult to probe and verify. Here, we show how the quantum mechanical hydrogen tunneling associated with enzymatic C–H bond cleavage provides a unique window into the necessity of protein dynamics for achieving optimal catalysis. Experimental findings support a hierarchy of thermodynamically equilibrated motions that control the H-donor and -acceptor distance and active-site electrostatics, creating an ensemble of conformations suitable for H-tunneling. A possible extension of this view to methyl transfer and other catalyzed reactions is also presented. The impact of understanding these dynamics on the conceptual framework for enzyme activity, inhibitor/drug design, and biomimetic catalyst design is likely to be substantial.

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Section: Interrelationship Between Donor-acceptor Distance Sampling Amentioning

confidence: 99%

Hydrogen Tunneling Links Protein Dynamics to Enzyme Catalysis

Klinman

Kohen

2013

Annu. Rev. Biochem.

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311

474

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“…Now, what can be stated so far about hydrogen tunnelling in enzyme-catalysed reactions? Large isotope effects are observed in many enzymatic reactions that involve hydrogen transfer [117,121,122]. These observations indicate that tunnelling occurs in enzymatic reactions.…”

Section: Quantum Tunnelling In Molecular Biologymentioning

confidence: 99%

Quantum Tunnelling to the Origin and Evolution of Life

Trixler

2013

COC

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Quantum tunnelling is a phenomenon which becomes relevant at the nanoscale and below. It is a paradox from the classical point of view as it enables elementary particles and atoms to permeate an energetic barrier without the need for sufficient energy to overcome it. Tunnelling might seem to be an exotic process only important for special physical effects and applications such as the Tunnel Diode, Scanning Tunnelling Microscopy (electron tunnelling) or Near-field Optical Microscopy operating in photon tunnelling mode. However, this review demonstrates that tunnelling can do far more, being of vital importance for life: physical and chemical processes which are crucial in theories about the origin and evolution of life can be traced directly back to the effects of quantum tunnelling. These processes include the chemical evolution in stellar interiors and within the cold interstellar medium, prebiotic chemistry in the atmosphere and subsurface of planetary bodies, planetary habitability via insolation and geothermal heat as well as the function of biomolecular nanomachines. This review shows that quantum tunnelling has many highly important implications to the field of molecular and biological evolution, prebiotic chemistry and astrobiology.

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“…Approaches to analyze the data of these biochemical reactions are known [80][81][82][83]. Furthermore, quantum effects, including tunneling, have been reported to influence enzyme kinetics [84].…”

Section: Activation Parametersmentioning

confidence: 99%