首页> 外文期刊>Chemistry: A European journal >Electron-transfer reactions through the associated interaction between cytochrome c and self-assembled monolayers of optically active Cobalt(III) complexes: Molecular recognition ability induced by the chirality of the Cobalt(III) units
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Electron-transfer reactions through the associated interaction between cytochrome c and self-assembled monolayers of optically active Cobalt(III) complexes: Molecular recognition ability induced by the chirality of the Cobalt(III) units

机译:通过细胞色素c和光学活性钴(III)配合物的自组装单层之间的关联相互作用进行电子转移反应:由钴(III)单元的手性诱导的分子识别能力

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Self-assembled monolayers (SAMs) of optically active Co-III complexes ((S)-2/(R)-2) that contain (S)- or (R)-phenylalanine derivatives as a molecular recognition site were constructed on Au electrodes ((S)-2-Au/(R)-2Au). Molecular recognition characteristics induced by the S and R configurations were investigated by measurements of electron-transfer reactions with horse heart cytochrome c (cyt c). The electrochemical studies indicate that the maximum current of cyt c reduction is obtained when the Au electrode is modified by 2 with a moderate coverage of approximately 4.0 x 10(-11) mol cm(-2). Since the Au electrode is not densely packed with the Co-III units at this concentration, we conclude that the penetrative association process between cyt c and the Co-III unit plays an important role in this electron-transfer system. The differences in the electron-transfer rates of (S)-2-Au and (R)-2-Au increase with increasing scan rates, a result indicating that the chiral ligand has an influence on the rate of association of the complexes with cyt c. 3-Au has a mixed monolayer composed of 2 and hexanethiol and exhibits electron-transfer behavior comparable to 2-Au. The difference in the association rates of (S)-3-Au and (R)-3-Au is larger than that between (S)-2-Au and (R)-2-Au, which indicates that the molecular recognition ability of 3-Au has been enhanced by filling the gap between molecules of 2 with hexanethiols. The differences in the oxidation rates of cyt c(II) between (S)-2-Au and (R)-2-Au and between (S)-3-Au and (R)-3-Au were larger than the differences in the rates of the reduction of cyt c(III); this suggests that the size of the heme crevice varies according to the oxidation state of cyt c.
机译:在Au电极上构建了包含(S)-或(R)-苯丙氨酸衍生物作为分子识别位点的光学活性Co-III配合物((S)-2 /(R)-2)的自组装单层(SAMs) ((S)-2-Au /(R)-2Au)。通过测量与马心脏细胞色素c(cyt c)进行的电子转移反应,研究了由S和R构型诱导的分子识别特性。电化学研究表明,当Au电极被2修饰时,具有约4.0 x 10(-11)mol cm(-2)的适度覆盖率,可获得cyt c还原的最大电流。由于在该浓度下Au电极没有被Co-III单元紧密地堆积,因此我们得出结论,cyt c和Co-III单元之间的渗透缔合过程在该电子转移系统中起着重要的作用。 (S)-2-Au和(R)-2-Au电子传递速率的差异随扫描速率的增加而增加,结果表明手性配体对复合物与胞嘧啶的缔合速率有影响。 C。 3-Au具有由2和己硫醇组成的混合单层,并具有与2-Au相当的电子转移性能。 (S)-3-Au和(R)-3-Au的缔合速率差异大于(S)-2-Au和(R)-2-Au的缔合速率差异,这表明分子识别能力通过用己硫醇填充2分子之间的间隙,提高了3-Au的原子能级。 (S)-2-Au和(R)-2-Au之间以及(S)-3-Au和(R)-3-Au之间cyt c(II)氧化速率的差异大于差异cyt c(III)的减少率;这表明血红素缝隙的大小根据cyt c的氧化状态而变化。

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