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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.
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66
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33847585883
-
-
note
-
6 L/mol. The binding constant is too large to be determined more precisely by NMR titration.
-
-
-
-
67
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0006565546
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D. Sawyer, R. Kowai, R. McCreey, Experientia 1971, Suppl. 18, 563.
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68
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33847602981
-
-
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.
-
-
-
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69
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0004187703
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Wiley, New York
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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.
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Binding Constants
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Connors, K.A.1
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70
-
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33847604717
-
-
note
-
This assumption is in agreement with the determined binding constant.
-
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71
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0031020439
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A. Niemz, J. Imbriglio, V. M. Rotello, J. Am. Chem. Soc. 1997, 119, 887-892.
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72
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0001132122
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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.
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Holmström, B.1
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73
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84989714159
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J. A. Navarro, M. Roncel, M. A. De la Rosa, Photochem. Photobiol. 1987, 46, 965-970.
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74
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0004777467
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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.
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Traber, R.1
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75
-
-
33847580986
-
-
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
-
-
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.
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0014142138
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A. Ehrenberg, F. Müller, P. Hemmerich, Eur. J. Biochem. 1967, 2, 286.
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Ehrenberg, A.1
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79
-
-
0004797484
-
-
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
-
-
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.
-
-
-
-
81
-
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0034639898
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For a recent study of the role of the N(3)-H hydrogen bonding on the redox properties, see: A. O. Cuello, C. M. McIntosh, V. M. Rotello, J. Am. Chem. Soc. 2000, 122, 3517-3521.
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For some aspects on this topics, see: V. Massey, Biochem. Soc. Trans. 2000, 28, 283-296.
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84945736165
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J. Salbeck, U. Schoeberl, K. M. Rapp, J. Daub, Z. Phys. Chem. (Munich) 1991, 171, 191-212.
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0031767662
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For the synthesis of a similar compound, see: T. Carell, H. Schmid, M. Reinhard, J. Org. Chem. 1998, 63, 8741-8747.
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33847591518
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unpublished results
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M. Sax, B. König, unpublished results.
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Sax, M.1
König, B.2
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89
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0000852154
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M. S. Kionoya, E. Kimura, T. Ikeda, Y. Yamada, J. Am. Chem. Soc. 1992, 114, 10134-10137.
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Kionoya, M.S.1
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90
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0041937629
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For instrumental details, see: M. Büschel, C. Stadler, C. Lambert, M. Beck, J. Daub, J. Electroanal. Chem. 2000, 484, 24-32 and references cited therein.
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Büschel, M.1
Stadler, C.2
Lambert, C.3
Beck, M.4
Daub, J.5
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