Design, synthesis and photophysical properties of C60-modified proteins
Design, synthesis and photophysical properties of C60-modified proteins
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C60 修饰蛋白的设计、合成和光物理性质
DOI：
10.1039/b201145j
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发表时间：
2002
影响因子：
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通讯作者：
N. Nakashima
中科院分区：
文献类型：
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作者：
H. Murakami;R. Matsumoto;Yuko Okusa;T. Sagara;M. Fujitsuka;O. Ito;N. Nakashima
设计并合成了与 Fe 和 Zn 离子（1·Fe 和 1·Zn）配位的富勒烯-卟啉缀合物。化合物1·Fe和1·Zn成功地重构为脱辅基肌红蛋白，分别产生C60修饰的肌红蛋白1·Fe-Mb和1·Zn-Mb。轴向配体交换反应表明，除了自氧化速率常数外，1·Fe-Mb 保持了天然 Mb 的固有特性，表明蛋白质中卟啉部分具有相似的微环境。 1·Fe-Mb-双十二烷基二甲基铵薄膜修饰石墨电极的循环伏安图（CV）
溴化物 (DDAB) 显示出两个具有 E0' 的可逆氧化还原对
=
-206 和 -1048 mV 分别归因于 Fe2+/3+ 和卟啉环的还原。用 1·Fe-Mb-三十二烷基甲基溴化铵 (TDAB) 薄膜修饰的电极在含有 0.5 M 四乙基氯化铵和 10 mM 2,2',2"-次氮基三乙醇的水中的差分脉冲伏安图在 E½,1 处显示三个阴极峰
=
−372，E½,2
=
−555 和 E½,3
=
-1028 mV，分别归因于 Fe2+/3+、C600/1− 和卟啉环的还原。 1·Fe-Mb和1·Zn-Mb修饰的电极
给出阳极光电流与开关光照射。 1·Zn-Mb-DDAB薄膜的光电流作用光谱与1·Zn-Mb的紫外可见吸收光谱一致。 1·Zn 在苯甲腈中和 1·Zn-Mb 在 50 mM 磷酸盐缓冲液中在 532 nm 纳秒激光脉冲照射后 100 ns 的瞬态吸收光谱显示出在 700、830 和 1000 nm 处的三个吸收最大值，这可归因于 C60 的三重激发态
(3C60*)、锌卟啉 (3ZnP*) 的三重激发态和 C60 自由基阴离子 (C60˙−)。表观 C60˙− 的存在表明电荷分离的产生
态，ZnP˙+–C60˙−。根据荧光数据计算出1·Zn和1·Zn-Mb中电荷分离态产生的速率常数分别为8.2 × 108 s−1和6.4 × 108 s−1，相应的量子产率为0.62和0.59。
Fullerene–porphyrin conjugates coordinated with Fe and Zn ions (1·Fe and 1·Zn) were designed and synthesized. Compounds 1·Fe and 1·Zn were reconstituted into apomyoglobin successfully to produce C60-modified myoglobins, 1·Fe-Mb and 1·Zn-Mb, respectively. The axial-ligand exchange reaction revealed that 1·Fe-Mb maintains the intrinsic properties of native Mb, except for the autooxidation rate constant, suggesting similar microenvironment of the porphyrin moieties in the proteins. Cyclic voltammogram (CV) of a graphite electrode modified with a film of 1·Fe-Mb–didodecyldimethylammonium
bromide (DDAB) showed two reversible redox couples with E0′
=
−206 and −1048 mV which are attributable to Fe2+/3+ and the reduction of the porphyrin ring, respectively. Differential pulse voltammogram of an electrode modified with a 1·Fe-Mb–tridodecylmethylammonium bromide (TDAB) film in water containing 0.5 M tetraethylammonium chloride and 10 mM 2,2′,2″-nitrilotriethanol showed three cathodic peaks at E½,1
=
−372, E½,2
=
−555, and E½,3
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−1028 mV which are attributable to Fe2+/3+, C600/1−, and the reduction of the porphyrin ring, respectively. The electrodes modified with 1·Fe-Mb and 1·Zn-Mb
gave anodic photocurrent coupled with on–off light irradiation. The action spectrum of photocurrent for a 1·Zn-Mb–DDAB film was in accord with the UV–vis absorption spectrum of 1·Zn-Mb. Transient absorption spectra of 1·Zn in benzonitrile and 1·Zn-Mb in a 50 mM phosphate buffer at 100 ns after the ns-laser light pulse irradiation at 532 nm showed three absorption maxima at 700, 830, and 1000 nm which are assignable to the triplet excited state of C60
(3C60*), the triplet excited state of the zinc porphyrin (3ZnP*), and C60 radical anion (C60˙−), respectively. Existence of the apparent C60˙− indicates the generation of charge-separation
state, ZnP˙+–C60˙−. The rate constants for the generation of the charge separation states in 1·Zn and 1·Zn-Mb calculated from the fluorescence data were 8.2 × 108 s−1 and 6.4 × 108 s−1, respectively, and the corresponding quantum yields were 0.62 and 0.59.
H. Imahori：“模拟光合作用中光诱导多步电子转移的有机光电化学电池：金电极上卟啉连接的富勒烯自组装单分子层的界面结构和光电化学性能”B
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