嗜热自养甲烷杆菌辅因子F430的五烷基酰胺衍生物的镍（II）和镍（I）形式。

Ni(II) and Ni(I) forms of pentaalkylamide derivatives of cofactor F430 of Methanobacterium thermoautotrophicum.

作者信息

Hamilton C L, Ma L, Renner M W, Scott R A

机构信息

Department of Chemistry, University of Georgia, Athens 30602.

出版信息

Biochim Biophys Acta. 1991 Jul 8;1074(2):312-9. doi: 10.1016/0304-4165(91)90169-h.

DOI:10.1016/0304-4165(91)90169-h

PMID:1648401

Abstract

A series of pentaalkylamide forms of F430 and of its 12,13-diepimer have been generated and characterized. Carbodiimide-assisted N-hydroxysulfosuccinimide activation of all five peripheral carboxylates of the F430 macrocycle allows nucleophilic attack by a number of primary amines (RNH2, R- = CH3-, CH3CH2-, CF3CH2-, CH3(CH2)3-) generating the pentaalkylamide derivatives. The identity of each derivative has been verified by fast-atom bombardment mass spectrometry (FAB-MS). The solubility of these derivatives in aprotic organic solvents varies as the amine alkyl substituent (R-) is changed. Electrochemical measurements have shown that the Ni(II/I) reduction potentials in N,N-dimethylformamide (DMF) are approximately -1 V (Ag/AgCl). Reduction by sodium amalgam in THF generates the Ni(I) form of the F430 diepimer pentabutylamide. The visible and EPR spectra of this Ni(I) species are very similar to the corresponding spectra of Ni(I) F430M (Jaun, B. and Pfaltz, A. (1986) J. Chem. Soc. Chem. Commun. 1327-1329.).

摘要

已生成并表征了一系列F430及其12,13 - 二差向异构体的五烷基酰胺形式。F430大环的所有五个外围羧酸盐通过碳二亚胺辅助的N - 羟基磺基琥珀酰亚胺活化，使得许多伯胺（RNH₂，R⁻ = CH₃⁻、CH₃CH₂⁻、CF₃CH₂⁻、CH₃(CH₂)₃⁻）进行亲核进攻，生成五烷基酰胺衍生物。每种衍生物的身份已通过快原子轰击质谱法（FAB - MS）验证。随着胺烷基取代基（R⁻）的变化，这些衍生物在非质子有机溶剂中的溶解度也有所不同。电化学测量表明，在N，N - 二甲基甲酰胺（DMF）中，Ni(II/I)还原电位约为 - 1 V（Ag/AgCl）。在四氢呋喃中用钠汞齐还原生成F430二差向异构体五丁基酰胺的Ni(I)形式。该Ni(I)物种的可见光谱和电子顺磁共振光谱与Ni(I) F430M的相应光谱非常相似（Jaun, B.和Pfaltz, A.（1986年）《化学学会化学通讯》1327 - 1329页）。