BASICITY VISIBLE SPECTRA AND ELECTRON SPIN RESONANCE OF FLAVOSEMIQUINONE ANIONS

BASICITY VISIBLE SPECTRA AND ELECTRON SPIN RESONANCE OF FLAVOSEMIQUINONE ANIONS
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DOI:
10.1111/j.1432-1033.1967.tb00137.x
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发表时间:
1967-01-01
期刊:
EUROPEAN JOURNAL OF BIOCHEMISTRY
影响因子:
--
通讯作者:
HEMMERICH, P
HEMMERICH, P
中科院分区:
其他
文献类型:
--
作者:
EHRENBERG, A;MULLER, F;HEMMERICH, P

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通过ESR [电子自旋共振]研究了黄酮半醌的反硝化作用对pH的依赖性。对于水溶液中的3-烷基化光黄素[R(3)= CH 2COO-],pK(中性黄半醌的解离)为8.4; pKred为6.3。水解环裂解的位置2,8,8 [图像]-二聚体,和10-脱烷基化干扰的形成的黄半醌阴离子。然而,在非水二甲基甲酰胺和化学计量量的强碱(t-BuOK),100%的flavosemiquinone阴离子形成没有干扰的副反应。它的光吸收光谱实际上与红色黄素蛋白自由基的光吸收光谱相同。从ESR谱的个人各向同性超精细耦合常数已被确定。
The dependence on pH of the disproportionation of the flavosemiquinone has been investigated by ESR [electron spin resonance]. For 3-alkylated lumiflavin [R(3) =CH2COO-] in aqueous solution pK (for the dissociation of the neetral flavosemiquinone) is 8.4; pKred is 6.3. Hydrolytic ring cleavage in position 2, 8,8[image]-dimerization, and 10-dealkylation interfere with the formation of the flavosemiquinone anion. However, in non-aqueous dimethylformamide and with stoichiometric amounts of strong base (t-BuOK), 100% flavosemiquinone anion is formed without interfering side reactions. Its light absorption spectrum is practically identical to that of the red flavoprotein radical. From the ESR spectra the individual isotropic hyperfine coupling constants have been determined.