Polyoligopeptides functionalized zinc(II)porphyrins. Step towards artificial hemes

作     者：Aly, Shawkat M. Guernon, Hannah Guerin, Brigitte Harvey, Pierre D. 

作者机构：Univ Sherbrooke Dept Chim Sherbrooke PQ J1K 2R1 Canada Univ Sherbrooke Fac Med & Hlth Sci CIMS Sherbrooke PQ J1H 5N4 Canada Univ Sherbrooke Fac Med & Hlth Sci Dept Med Nucl & Radiobiol Sherbrooke PQ J1H 5N4 Canada 

出 版 物：《JOURNAL OF PORPHYRINS AND PHTHALOCYANINES》 (J. Porphyrins Phthalocyanines)

年 卷 期：2011年第15卷第9-10期

页      面：871-882页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：Natural Sciences and Engineering Research Council of Canada (NSERC) Fonds Quebecois de la Recherche sur la Nature et les Technologies (FQRNT) Centre Quebecois sur les Materiaux Fonctionnels (CQMF) Centre d'Excellence sur les Materiaux Optiques et Polymeres de l'Universite de Sherbrooke (CEMOPUS) 

主　　题：porphyrin peptides protein C-60 fluorescence photophysics transient absorption spectra electron transfer 

摘      要：Two new zinc(II)porphyrin oligopeptide conjugates (zinc(II)-5,10,15,20-bis[4-(peptide)phenyl] porphyrin (5) and -tetrakis[3,5-di(peptide) phenyl] porphyrin (9;peptide = -CH2(CO)Gly-Phe-Ala-CNH2) were prepared using the click chemistry with azides and ethynyl-containing precursors. The spectroscopic signature (S-0 - S-1 and transient T-1 - T-n absorption, excitation and emission spectra) are typical for zinc(II)porphyrin and shows no perturbation upon anchoring the oligopeptides, whereas some small decreases in the photophysical parameters (tau(F) and Phi(F)), and larger decrease in T-1 lifetimes are noted, which are attributable to the known loose bolt effect. The structure for 9 in solution was addressed qualitatively using computer modeling and the comparison of the bimolecular fluorescence quenching rate constants between 5 and 9 using C-60 as a photooxidative agent. While 5 exhibits a totally accessible zinc(II)porphyrin unit for a C-60 approach, 9 shows a slower quenching rate constant meaning some steric hindrance must be present.