Remote control of flavin reactivities by an intramolecular crown ring serving as a metal-binding site

Shinkai, Seiji; Kameoka, Kei; Ueda, Kaori; Manabe, Osamu

doi:10.1021/ja00237a061

Cited by 24 publications

(7 citation statements)

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“…31 Earlier examples described how an intramolecular reaction can be modulated by the addition of well-chosen effectors. 33,[629][630][631][632][633][634] Mirkin and co-workers 376 recently reviewed allosteric catalysts including several examples of allosteric enzyme mimics (NAD(P)H mimic), 631,632 Flavin coenzyme mimics [635][636][637] and several nuclease mimics. 42,[638][639][640][641][642][643][644][645][646][647] We already mentioned in Part 1 of this review 315 how ions can alter the chiral ability 648,649 or the coordination mode of classical covalent ligands.…”

Section: Allosteric Catalysismentioning

confidence: 99%

Supramolecular catalysis. Part 2: artificial enzyme mimics

et al. 2014

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The design of artificial catalysts able to compete with the catalytic proficiency of enzymes is an intense subject of research. Non-covalent interactions are thought to be involved in several properties of enzymatic catalysis, notably (i) the confinement of the substrates and the active site within a catalytic pocket, (ii) the creation of a hydrophobic pocket in water, (iii) self-replication properties and (iv) allosteric properties. The origins of the enhanced rates and high catalytic selectivities associated with these properties are still a matter of debate. Stabilisation of the transition state and favourable conformations of the active site and the product(s) are probably part of the answer. We present here artificial catalysts and biomacromolecule hybrid catalysts which constitute good models towards the development of truly competitive artificial enzymes.

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Section: Allosteric Catalysismentioning

confidence: 99%

Supramolecular catalysis. Part 2: artificial enzyme mimics

et al. 2014

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“…The first one involves the "remote control" of flavin reactivities by an intramolecular crown ether ring serving as a metal-binding site (558,559). The intermediate could then be converted Among the more recent coenzyme models of flavin, two deserve special attention.…”

Section: T T Ho Tmentioning

confidence: 99%

Bioorganic Chemistry

Dugas¹

1989

Springer Advanced Texts in Chemistry

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“…Similar systems containing a crown ether unit covalently linked to a flavin moiety have already been reported 15. In these cases, however, the crown ether is not a binding site for a substrate but only coordinates alkali metal or alkaline‐earth metal ions, thus modulating the flavin redox potential and resulting in changes in the oxidation quantum yields of benzyl alcohol15a or alkali mandelates 15b…”

Section: Resultsmentioning

confidence: 99%

Catalytic Photooxidation of 4‐Methoxybenzyl Alcohol with a Flavin–Zinc(II)‐Cyclen Complex

Cibulka

Vasold

König

2004

Chemistry A European J

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Flavin-zinc(II)-cyclen 10 contains a covalently linked substrate binding site (zinc(II)-cyclen) and a chromophore unit (flavin). Upon irradiation, compound 10 effectively oxidizes 4-methoxybenzyl alcohol (11-OCH3) to the corresponding benzaldehyde both in water and in acetonitrile. In the presence of air, the reduced flavin 10-H2 is reoxidized, and so catalytic amounts of 10 are sufficient for alcohol conversion. The mechanism of oxidation is based on photoinduced electron transfer from the coordinated benzyl alcohol to the flavin chromophore. This intramolecular process provides a much higher photooxidation efficiency, with quantum yields 30 times those of the comparable intermolecular process with a flavin chromophore without a binding site. For the reaction in buffered aqueous solution a quantum yield of Phi = 0.4 is observed. The turnover number in acetonitrile is increased (up to 20) by high benzyl alcohol concentrations. The results show that the covalent combination of a chromophore and a suitable binding site may lead to photomediators more efficient than classical sensitizer molecules.

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Remote control of flavin reactivities by an intramolecular crown ring serving as a metal-binding site

Cited by 24 publications

References 0 publications

Supramolecular catalysis. Part 2: artificial enzyme mimics

Supramolecular catalysis. Part 2: artificial enzyme mimics

Bioorganic Chemistry

Catalytic Photooxidation of 4‐Methoxybenzyl Alcohol with a Flavin–Zinc(II)‐Cyclen Complex

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