Transmembrane Electron Transfer Catalyzed by Porphyrin Derivtives

卟啉衍生物催化的跨膜电子转移

• 批准号: 05680500
• 负责人: NANGO Mamoru
• 金额: $ 1.28万
• 依托单位: NAGOYA INSTITUTE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05680500/
• 关键词: ELECTRON TRANSFER; PORPHYRIN DERIVATIVES; LIPID BILAYERS

1) Poly (ethylene glycol) [PEG] -linked porphyrin derivatives separated by spacer methylene groups (Cn), PEG-Cn-MPFPP (M = H_2, Mn ; n = 0,5,11), PEG-C_<11>-MTTP (M = H_2, Mn), and PEG-C_0-MPFPPBr_8 (M = H_2, Mn) (Scheme 1) were synthesized. The porphyrin portion of poly (ethylene glycol) [PEG] -linked fluorinated porphyrin derivative has been anchored onto a lipid bilayr. PEG-linked fluorinated porphyrins associated easily with phospholipid bilayrs and are chemically stable against oxidant such as H_2O_2. An efficient energy transfer from phospholipid-linked zinc porphyrin, PE-C_0-ZnPFPP (Scheme 1) to externally added PEG-Cn-H_2PFPP (n = 0,5,11) in the lipid bilayr was observed, depending on the length of Cn and the porphyrin structure.Ground state transmembrance electron transfer catalyzed by PEG-Cn-MnPFPP (n = 0,5,11) and PEG-C_<11>-MnTTP revealed that the porphyrin causes a significant accelerated electron transfer especially when n = 11. Comparison of PEG-C_<11>-MnPFPP- and PEG-C_ … More <11>-MnTTP-catalyzed electron transfer is discussed. The electron transfer rate was controlled not only by the separated spacer methylene groups between the porphyrin and PEG moieties but also by the structures of porphyrins.2) Zinc hybrid porpyrin dimer (ZnTTP-C2-H2PFPP,ZnTTP-C2-H2TTP,ZnPFPP-C2-H2PFPP and ZnPFPP-C2-H2TTP) and manganese halogenated porphyrin dimers (MnPFPP-C2-MnPFPP,MnPFPP-C2-MnDCPP,and MnDCPP-C2-MnDCPP) covalently bridged by a dimethylene moiety (Scheme 1) were synthesized and characterized by UV-vis spectra, fluoresecence spectra and cyclic voltammograms. These porphyrin dimers could be embedded into the lipid bilayrs of liposomal membrance. The redox potential of halogenated porphyrin dimers increased with increasing of halogen portions on the porphyrin rings. An efficient energy transfer of the excited singlet state in the covalently-linked zinc hybrid dimers from zinc porphyrin to a free base porphyrin was observed, depending on the porphyrin structure. The manganese halogenated porphyrin dimers showed catalytic activities of transmembrance electron transfer and the hydroxylation of toluene by H2O2, in which these catalytic activities depend on the steric effect of halogen portions on the porphyrin ring and also the presence of imidazole.3) Transmembrane electron transfer across S-cyanoethylated keration (SCEK) and liposomal membranes catalyzed by (1), MnTTP- (CH2) n-MnP (COOMe) 3, n=2,3,12 showed that an enhanced electron transfer wasobserved especially when n=2or3 on (1) in these membranes and imidazole was present. Furthermore, enhanced electron transfer between porphyrins in membranes cast on a glassy carbon electrode was observed especially in hydrophilic keratin membranes containing manganese protoporphyrin dimethyl esters (MnPPDME). An imidazole derivative playd an important role on the electron transfer in hydrophobic S-cyanoethylated keratin membranes containing MnPPDME. Less

1）聚（乙二醇）[PEG]连接的卟啉衍生物，由间隔甲基组（CN），PEG-CN-MPFPP（M = H_2，MN; N = 0,5,11），PEG-C_ <11> -MTTP（M = H_2，M = H_2，MN）和PEG-C_____________________________0288（M = H_2，MN; N = 0,5,11）（M = H__2，MN; n = 0,5,11） 1）合成。聚（乙二醇）[PEG]连接的氟化卟啉衍生物的卟啉部分已锚定在脂质bilayr上。与磷脂双层易于相关的钉偶联卟啉，并且在氧化剂（例如H_2O_2）上具有化学稳定。从脂质bilayr中观察到有效的能量转移从脂质bilayr中的磷脂连接锌卟啉，PE-C_0-ZNPFPP（方案1）到外部添加的PEG-CN-H_2PFPP（n = 0,5,11），在脂质bilayr中观察到了CN和porphyrin结构的长度，并取决于Cn和peg-cn的长度。 PEG-C_ <11> -MNTTP表明卟啉会引起明显的加速电子传输，尤其是当n = 11时。在讨论了PEG-C_ <11> -Mnpfpp-和PEG-C_的比较。电子的转移速率不仅由卟啉和钉子部分之间的分离间隔甲基组，而且由卟啉的结构控制。2）锌杂交猪porpyrin二聚体（ZNTTP-C2-C2-H2PFPP，ZNTTP-C2-C2-C2-H2TTP，ZNP-C2-H2TTP，Znpfpp-C2-C2-C2-H2PFPP-C2-H2PFPPPPFPPPPPFPPPPFPTTTP）卟啉二聚体（MNPFPP-C2-MNPFPP，MNPFPP-C2-MNDCPP和MNDCPP-C2-MNDCPP）通过二甲基烯部分共桥接（方案1），并通过UV-VIS光谱，荧光光谱和环状电视图和环状电效率和环状电视图合成并表征。这些卟啉二聚体可以嵌入脂质体膜的脂质双层中。卤代卟啉二聚体的氧化还原潜力随着卟啉环上卤素部分的增加而增加。根据卟啉结构，观察到了从锌卟啉到自由碱基卟啉的共价连接锌混合二聚体中激发单线的有效能量转移。锰卤素二聚体表现出透射电子转移的催化活性和H2O2对甲苯的羟基化，其中这些催化活性取决于卤素部分对卟啉环对卟啉环的空间作用，以及米达唑的存在。由（1），mnttp-（ch2）n-mnp（coome）3，n = 2,3,12催化，表明存在增强的电子转移，尤其是在这些膜和咪唑中存在（1）上的n = 2or3时。此外，尤其是在含有锰原生磷脂二甲基酯（MNPPDME）的亲水性角蛋白膜中，观察到在玻璃碳电极上施放的卟啉之间的电子转移增强。咪唑衍生物Playd在含有MNPPDME的疏水S-甲基化角蛋白膜中电子转移中的重要作用。较少的

项目成果

K.Iida,M,Nango,M.Hikita,A.Hattori.K.Yamashita,K.Yamauchi.K.Tsuda: "Electron Transfer on Electrode Modified with Keratin membranes Containing Manganese Porphyrins" Chemistry Letters. 753-756 (1994)

K.Iida,M,Nango,M.Hikita,A.Hattori.K.Yamashita,K.Yamauchi.K.Tsuda：“用含有锰卟啉的角蛋白膜修饰的电极上的电子转移”化学快报。

K.Iida, M.Nagao, K.Okada, M.Hikita, M.Matsuura, T.Kurihara, T.Tajima, A.Hattori, S.Ishikawa, K.Yamashita, K.Tsuda, Y.kurono: "Synthesis and Characterization of Hybrid Porphyrin Dimers and Halogenated Porphyrin Dimers" Bull.Chem.Soc.Jpn.68. 1959-1968 (1995

K.Iida、M.Nagao、K.Okada、M.Hikita、M.Matsuura、T.Kurihara、T.Tajima、A.Hattori、S.Ishikawa、K.Yamashita、K.Tsuda、Y.kurono：“综合

K.Iida,M,Nango,K.Okada,M.Hikita,M.Matsuura,T.Kurihara,T.Tajima,A.Hattori,S.Ishikawa,K.Yamashita,K.Tsuda,Y.Kurono: "Synthecsis and Characterization of Hybrid Porphyrin Dimers and Halogenated Porphyrin Dimers" Bull.chem.Soc.Jpn.68. 1959-1968 (1995)

K.Iida、M、Nango、K.Okada、M.Hikita、M.Matsuura、T.Kurihara、T.Tajima、A.Hattori、S.Ishikawa、K.Yamashita、K.Tsuda、Y.Kurono：《合成》

K.Iida: "Transmembrane Electron Transfer across a Keratin Membranes and Lipid Bilayers catalyzed by Maganese Porphyrin Dimers" Chem.Lett.1157-1160 (1994)

K.Iida：“锰卟啉二聚体催化的跨角蛋白膜和脂质双层的跨膜电子转移”Chem.Lett.1157-1160 (1994)

K.Iida, M.Nango, M.Hikita, T.Tajima, T.Kurihara, K.Yamashita, K.Tsuda, T.Dewa, J.Komiyama, M.Nakata, Y.Ohtsuka: "Transmembranes Electron Transfer across a Keratin Membrane and Lipid Bilayrs catalyzed by Manganese Porphyrin Dimers" Chem.Lett.1157-1160 (199

K.Iida、M.Nango、M.Hikita、T.Tajima、T.Kurihara、K.Yamashita、K.Tsuda、T.Dewa、J.Komiyama、M.Nakata、Y.Ohtsuka：“跨膜电子转移