Legrand Yves-Marie, Gray Mark, Cooke Graeme, Rotello Vincent M
Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003, USA.
J Am Chem Soc. 2003 Dec 24;125(51):15789-95. doi: 10.1021/ja036940b.
A series of flavins were synthesized bearing electron-withdrawing and -donating substituents. The electrochemical properties of these flavins in a nonpolar solvent were determined. The recognition of these flavins by a diamidopyridine (DAP) receptor and the effect this receptor has on flavin redox potential was also quantified. It was found that the DAP-flavin binding affinity and the reduction potentials (E(1/2)) for both the DAP-bound and unbound flavins correlated well with functions derived from linear free energy relationships (LFERs). These results provide insight and predictive capability for the interplay of electronics and redox state-specific interactions for both abiotic and enzymatic systems.
合成了一系列带有吸电子和供电子取代基的黄素。测定了这些黄素在非极性溶剂中的电化学性质。还对二酰胺基吡啶（DAP）受体对这些黄素的识别以及该受体对黄素氧化还原电位的影响进行了量化。结果发现，DAP与黄素的结合亲和力以及DAP结合和未结合黄素的还原电位（E(1/2)）与线性自由能关系（LFERs）衍生的函数具有良好的相关性。这些结果为非生物和酶系统中电子学与氧化还原状态特异性相互作用的相互作用提供了见解和预测能力。
