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Volumn , Issue 12, 2001, Pages 2297-2303

A model system for flavoenzyme activity - Binding of flavin and modulation of its redox potentials through coordination to a Lewis-acidic azamacrocyclic zinc(II) complex

Author keywords

Electrochemistry; Electron transfer; Enzyme models; Macrocycles; Molecular recognition

Indexed keywords

FLAVOPROTEIN; QUERCETIN; ZINC COMPLEX;

EID: 0034967135     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0690(200106)2001:12<2297::AID-EJOC2297>3.0.CO;2-R     Document Type: Article
Times cited : (28)

References (90)
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    • (Ed.: F. L. Boschke), Springer-Verlag, Berlin
    • F. Müller in Topics Curr. Chem. Vol. 108 (Ed.: F. L. Boschke), Springer-Verlag, Berlin, 1983, 71-107.
    • (1983) Topics Curr. Chem. Vol. 108 , vol.108 , pp. 71-107
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  • 21
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    • Exchange of single amino acids in the environment of the flavin binding site by site specific mutagenesis is used to study binding motifs. A difficulty arises from the fact that most interactions are between the flavin and main chain functionalities of the peptide chain, that are not altered by amino acid exchange. For selected papers on this topic, see: A. L. Shen, C. B. Kasper, Biochemistry 1996, 35, 9451.
    • (1996) Biochemistry , vol.35 , pp. 9451
    • Shen, A.L.1    Kasper, C.B.2
  • 47
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    • For the binding of biologically important imides by zinc(I-I)cyclen, see: M. Shinoya, E. Kimura, M. Shiro, J. Am. Chem. Soc. 1993, 115, 6730-6737.
    • (1993) J. Am. Chem. Soc. , vol.115 , pp. 6730-6737
    • Shinoya, M.1    Kimura, E.2    Shiro, M.3
  • 53
    • 0026726368 scopus 로고
    • A characteristic feature of the zinc(II) effected by the macrocyclic coordination is the promotion of proton dissociation at physiological pH from carboxamides and sulfonamides which is rendered more favorable by the strong interaction of zinc(II) and the anionic ligand. Therefore depending on the structure of the zinc-azamacrocycle, imide coordination is observed to a large extent in weakly basic aqueous solutions, even at neutral pH. T. Koike, E. Kimura, I. Nakamura, Y. Hashimoto, M. Shiro, J. Am. Chem. Soc. 1992, 114, 7338-7345.
    • (1992) J. Am. Chem. Soc. , vol.114 , pp. 7338-7345
    • Koike, T.1    Kimura, E.2    Nakamura, I.3    Hashimoto, Y.4    Shiro, M.5
  • 66
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    • note
    • 6 L/mol. The binding constant is too large to be determined more precisely by NMR titration.
  • 68
    • 33847602981 scopus 로고    scopus 로고
    • note
    • Alternatively function under physiological conditions could be achieved by shielding the binding site from the competing polar solvent. However, this requires complex receptor structures.
  • 69
    • 0004187703 scopus 로고
    • Wiley, New York
    • The binding constant was derived by nonlinear fitting using algorithms provided by the program Sigma plot. K. A. Connors, Binding Constants, Wiley, New York 1987.
    • (1987) Binding Constants
    • Connors, K.A.1
  • 70
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    • note
    • This assumption is in agreement with the determined binding constant.
  • 72
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    • B. Holmström, Arkiv Kemi 1964, 22, 281. This paper is often quoted to justify the monitoring of semireduced radical of flavins at 560 nm.
    • (1964) Arkiv Kemi , vol.22 , pp. 281
    • Holmström, B.1
  • 74
    • 0004777467 scopus 로고
    • For a report of flavin radical anion formation by flash photolysis in buffered water, see: R. Traber, H. E. A. Kramer, P. Hemmerich, Pure Appl. Chem. 1982, 54, 1651-1665. The lifetime of the radical under these conditions is less than 200 μs.
    • (1982) Pure Appl. Chem. , vol.54 , pp. 1651-1665
    • Traber, R.1    Kramer, H.E.A.2    Hemmerich, P.3
  • 75
    • 33847580986 scopus 로고    scopus 로고
    • note
    • As known from earlier investigations, coordination of zinc cyclen complexes to flavins is possible in water at neutral pH. Therefor similar effects on the redox chemistry of flavin cofactors are to be expected under physiological conditions. Due to the restricted electrochemical window of water no spectroelectrochemical investigations of the system under such conditions were possible.
  • 76
    • 0014709323 scopus 로고
    • Flavosemiquinone is not stable in neutral aqueous solution, undergoes spontaneous disproportionation to yield flavohydroquinone and flavoquinone. An EPR study has shown that the stability of the flavosemiquinone is slightly increased in the equilibrium by addition of zinc(II) ions, which supports our observation. F. Müller, L. E. G. Erikson, A. Ehrenberg, Eur. J. Biochem. 1970, 12, 93-108.
    • (1970) Eur. J. Biochem. , vol.12 , pp. 93-108
    • Müller, F.1    Erikson, L.E.G.2    Ehrenberg, A.3
  • 77
  • 79
    • 0004797484 scopus 로고    scopus 로고
    • note
    • Both processes, the formation of the radical anion and the formation of the flavinhydroquinone cannot be fully separated and occur to some extend simultaneously.
  • 80
    • 33847585015 scopus 로고    scopus 로고
    • note
    • With a large excess of added 2a effects become noticeable, but redox waves are very broad and unstructured. Changes are much less pronounced as in the case of 1b.
  • 82
    • 0033851115 scopus 로고    scopus 로고
    • For some aspects on this topics, see: V. Massey, Biochem. Soc. Trans. 2000, 28, 283-296.
    • (2000) Biochem. Soc. Trans. , vol.28 , pp. 283-296
    • Massey, V.1
  • 88
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    • unpublished results
    • M. Sax, B. König, unpublished results.
    • Sax, M.1    König, B.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.