Synthesis, Spectra, and Electron-Transfer Reaction of Aspartic Acid-Functionalized Water-Soluble Perylene Bisimide in Aqueous Solution
Synthesis, Spectra, and Electron-Transfer Reaction of Aspartic Acid-Functionalized Water-Soluble Perylene Bisimide in Aqueous Solution
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DOI：
10.1021/am4004446
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发表时间：
2013-04-24
影响因子：
9.5
通讯作者：
Zhu, Shourong
中科院分区：
文献类型：
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作者：
Zhong, Lina;Xing, Feifei;Zhu, Shourong
合成并表征了天冬氨酸功能化的水溶性苝双酰亚胺N,N'-二(2-琥珀酸)-苝-3,4,9,10-四羧基双酰亚胺(PASP)。它在 pH 7.20 HEPES 缓冲液中分别在 527 nm 和 498 nm 处具有最大吸光度 A(0-0) 和 A(0-1)（ε 大约为 1.7 x 10(4) L cm(-1) mol(-1)）。在 pH 7-12.5 水溶液中，E-1/2 分别在 -0.17 和 -0.71 V（相对于 Ag/AgCl）下发生两个准可逆氧化还原过程。 PASP在纯水溶液中可与Na2S反应，依次形成一价阴离子自由基和二价阴离子自由基。 PASP(-中心点) 在水溶液中具有 g = 1.998 的 EPR 信号，而 PASP(2-) 没有 EPR 信号。单阴离子自由基的形成是一级反应，k = 8.9 x 10(-2) s(-1)。双阴离子物质的形成是零级反应，速率常数为4.3 x 10(-8) mol s(-1)。 H2O2 的存在大大增加了自由基形成速率常数。 PASP作为一种双电子转移试剂有望用于水的光解。
An aspartic acid-functionalized water-soluble perylene bisimide, N,N'-di(2-succinic acid)-perylene-3,4,9,10-tetracarboxylic bisimide (PASP) was synthesized and characterized. It has absorbance maximum A(0-0) and A(0-1) at 527 and 498 nm (epsilon approximate to 1.7 x 10(4) L cm(-1) mol(-1)) respectively in pH 7.20 HEPES buffer. Two quasi-reversible redox processes with E-1/2 at -0.17 and -0.71 V (vs Ag/AgCl) respectively in pH 7-12.5 aqueous solutions. PASP can react with Na2S in pure aqueous solution to form monoanion radical and dianion species consecutively. PASP(-center dot) has EPR signal with g = 1.998 in aqueous solution, whereas PASP(2-) is EPR silent. The monoanion radical formation is a first-order reaction with k = 8.9 x 10(-2) s(-1). Dianion species formation is a zero-order reaction and the rate constant is 4.3 x 10(-8) mol s(-1). The presence of H2O2 greatly increases the radical formation rate constant. PASP as a two-electron transfer reagent is expected to be used in the water photolysis.