Design and synthesis of ferrocene probe molecules for detection by electrochemical methods.
Design and synthesis of ferrocene probe molecules for detection by electrochemical methods.
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DOI：
10.1021/bc060038m
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发表时间：
2006-08
影响因子：
4.7
通讯作者：
Isabelle Tranchant;Anne-Cécile Hervé;S. Carlisle;P. Lowe;C. Slevin;Camilla Forssten;J. Dilleen;R. Bhalla;David E. Williams;A. Tabor;H. Hailes
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文献类型：
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作者：
Isabelle Tranchant;Anne-Cécile Hervé;S. Carlisle;P. Lowe;C. Slevin;Camilla Forssten;J. Dilleen;R. Bhalla;David E. Williams;A. Tabor;H. Hailes
一系列的二茂铁共轭脂肪酸已被设计和合成，以建立所需的生物分子结合研究中使用的关键性能。寻求在0.3 V（相对于Ag/AgCl）的区域中用于蛋白质/血液溶液中的二茂铁缀合物的安培检测。不同的连接体和增溶部分被并入以产生具有最佳电化学性质的缀合物。在电化学研究中，发现直接连接到二茂铁上的连接基显著影响二茂铁阳离子的E（1/2）值和稳定性。酯连接的二茂铁共轭物的E（1/2）范围为+400至+410 mV，而酰胺连接的化合物范围为+350至+370 mV，胺为+260至+270 mV。折叠的长链取代基周围的二茂铁，也显着影响的选择连接器，被推断为一个次要的影响，增加E（1/2）。二茂铁阳离子的稳定性随E（1/2）的增加而系统地降低。氧化电位分别为+640和+570 mV的二取代二茂铁酯和酰胺共轭物在50 mV/s的循环伏安法中仅显示出几乎不可辨别的还原波。电化学测量鉴定了两种具有酰胺和氨基甲酸酯连接体（化合物17和21）的共同结构特征的先导化合物，所述酰胺和氨基甲酸酯连接体具有连接的C（11）脂肪酸链。设想这样的分子可用于模拟和研究脂肪酸和分子如人血清白蛋白之间的生物分子结合相互作用。
A series of ferrocenyl conjugates to fatty acids have been designed and synthesized to establish the key properties required for use in biomolecular binding studies. Amperometric detection of the ferrocene conjugates was sought in the region of 0.3 V (vs Ag/AgCl) for use in protein/blood solutions. Different linkers and solubilizing moieties were incorporated to produce a conjugate with optimal electrochemical properties. In electrochemical studies, the linker directly attached to the ferrocene was found to affect significantly the E(1/2) value and the stability of the ferrocenium cation. Ester-linked ferrocene conjugates had E(1/2) ranging from +400 to +410 mV, while amide-linked compounds ranged from +350 to +370 mV and the amines +260 to +270 mV. Folding of long-chain substituents around the ferrocene, also significantly affected by the choice of linker, was inferred as a secondary effect that increased E(1/2). The stability of the ferrocenium cation decreased systematically as E(1/2) increased. Disubstituted ferrocene ester and amide conjugates, with oxidation potentials of +640 and +570 mV, respectively, showed only a barely discernible reduction wave in cyclic voltammetry at 50 mV/s. Electrochemical measurements identified two lead compounds with the common structural characteristics of an amide and carbamate linker (compounds 17 and 21) with a C(11) fatty acid chain attached. It is envisaged that such molecules can be used to mimic and study the biomolecular binding interaction between fatty acids and molecules such as human serum albumin.