H-transfers in Photosystem II: what can we learn from recent lessons in the enzyme community?

Hay, Sam; Scrutton, Nigel S.

doi:10.1007/s11120-008-9326-x

Cited by 6 publications

(3 citation statements)

References 71 publications

(97 reference statements)

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“…Consequently, it would appear that inflated α‐2° KIEs may be indicative of a tunnelling contribution to the H transfer, but normal KIEs do not rule out tunnelling [43]. A similar argument can be made for 1° KIEs – although KIEs ≤ 7 can be explained using transition state theory, the KIE arising from a full tunnelling reaction (described by ) can be any value [10,46].…”

Section: Measurement Of H‐transfer Reactions In Oyesmentioning

confidence: 99%

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Structural and mechanistic aspects of flavoproteins: probes of hydrogen tunnelling

2009

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At least half of all enzyme‐catalysed reactions are thought to involve a hydrogen transfer. In the last 10 years, it has become apparent that many of these reactions will occur, in part, or in full, by quantum mechanical tunnelling. We are particularly interested in the role of promoting vibrations on H transfer, and the Old Yellow Enzyme family of flavoproteins has proven to be an excellent model system with which to examine such reactions. In this minireview, we describe new and established experimental methods used to study H‐tunnelling in these enzymes and we consider some practical issues important to such studies. The application of these methods has provided strong evidence linking protein dynamics and H‐tunnelling in biological systems.

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Section: Measurement Of H‐transfer Reactions In Oyesmentioning

confidence: 99%

“…IEs -although KIEs £ 7 can be explained using transition state theory, the KIE arising from a full tunnelling reaction (described by Eqns 1-3) can be any value [10,46].…”

Section: Measurement Of H-transfer Reactions In Oyesmentioning

confidence: 99%

Structural and mechanistic aspects of flavoproteins: probes of hydrogen tunnelling

2009

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“…Hydrogen atom abstraction reactions from phenols have attracted considerable interest as these substrates represent the most extensive class of natural and synthetic radical scavenging antioxidants − and these reactions play a key role in a variety of enzymatic reactions. − …”

Section: Introductionmentioning

confidence: 99%

Kinetic Solvent Effects on Hydrogen Abstraction from Phenol by the Cumyloxyl Radical. Toward an Understanding of the Role of Protic Solvents

et al. 2012

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A time-resolved kinetic study of the hydrogen atom abstraction reactions from phenol by the cumyloxyl radical (CumO • ) was carried out in different solvents. The hydrogen atom abstraction rate constant (k H ) was observed to decrease by almost 3 orders of magnitude on going from isooctane to MeOH. In TFE, MeCN/H 2 O 2:1, and MeOH, the measured k H values were lower than expected on the basis of the Snelgrove−Ingold (SI) equation that correlates log k H to the solvent hydrogen bond acceptor (HBA) ability parameter β 2 H . As these solvents also act as hydrogen bond donors (HBDs), we explored the notion that a more thorough description of solvent effects could be provided by including a solvent HBD ability term, α 2 H , into the SI equation via β 2 H (1 + α 2 H ). The inclusion of such a term greatly improves the fitting for TFE, MeCN/H 2 O 2:1, and MeOH but at the expense of that for tertiary alkanols. This finding suggests that, for the reaction of CumO • with phenol, the HBA and HBD abilities of both the solvent and the substrate could be responsible for the observed KSEs. but this requires that primary and tertiary alkanols exhibit different solvation behaviors. Possible explanations for this different behavior are explored.

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Mechanistics of Enzyme Catalysis: From Small to Large Active‐Site Models

Llano

Gauld

2010

Quantum Biochemistry

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H-transfers in Photosystem II: what can we learn from recent lessons in the enzyme community?

Cited by 6 publications

References 71 publications

Structural and mechanistic aspects of flavoproteins: probes of hydrogen tunnelling

Structural and mechanistic aspects of flavoproteins: probes of hydrogen tunnelling

Kinetic Solvent Effects on Hydrogen Abstraction from Phenol by the Cumyloxyl Radical. Toward an Understanding of the Role of Protic Solvents

Mechanistics of Enzyme Catalysis: From Small to Large Active‐Site Models

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