Model Systems for the Primary Photochemical Events of Photosynthesis and Electron Transfer in Bioenergetic Membranes

Electron tunneling in solid-state electron-transfer reactions

“…More recently, this work was extended to study fast ET (nanoseconds) in liquids. 232 In addition, in liquid solution there has been very elegant and exciting recent work by Gray, 233 Isied,234 McLendon,235 and their collaborators on intramolecular ET in biologically-related species (modified cytochromes, peptides, azurin, etc.). These experiments have not yet been extended to solids.…”

Synthesis and characterization of water-soluble/phospholipid bilayer active, polymer-linked porphyrins

“…The yield of the methyl ester of III, 5-[4-(((5-carbomethoxypentyl)amino)-Polymer-Linked Porphyrins 1899 carbonyl)phenyl]-10,15,20-tri-p-tolylporphyrin (IV), was 50% (117 mg). NMR (deuteriochloroform): 9.00-8.75 (m, 8 H, 0-pyrrole), 8.2-7.95 (AB quartet, 4 H, carbomethoxyphenyl-2,3,5,6 and d, 6 H, tolyl-2,6), 7.6-7.4 (d, 6 H, tolyl-3,5), 3.6 (s, 3 H, OCH3), 3.S-3.2 (m, 2 H, CCH2CO), 2.6 (s, 9 H, CH3), 2.5-2.1 (m, 2 H, CCH2NH, 1.7-1.2 (m, 6 H, CCH2C), -2.65 (s, 2 H, pyrrole NH).…”

“…5-[4-(((ll-Carboxyundecyl)amino)carbonyl)phenyl]-10,15,20-tri-p-tolylporphyrin, (TTPP)CONH(CH2)uCOOH (V). This derivative was prepared in a similar way as that described for III; that is, the acid chloride II was reacted with H, tolyl-2,6), 7.75-7.50 (d, 6 H, tolyl-3,5), 3.65 (s, 3 H, OCH3), 3.6-3.4 (m, 2 H, CCH2CO), 2.65 (s, 9 H, CH3), 2.45-2.25 (m, 2 H, NHCH2C), 1.8-1.2 (m, 18 H, CCH2C), -2.8 (s, 2 H, pyrrole NH).…”

“…Our laboratory has been involved in the synthesis of porphyrin complexes both as models for the primary photochemical events of photosynthesis1-6 and also as models for secondary electron transport. 6,7 In pursuit of this goal we have synthesized covalently linked porphyrin dimers and trimers1,2 as well as covalently linked porphyrin-quinone complexes.3-5 One of the limitations of our previously synthesized model complexes, as well as those synthesized by others,8-16 has been their limited solubility in water.…”

Bioinorganic aspects of inorganic photochemistry

“…It was reported that in the liposomes the zinc (II) complex gives a charge-separated product at room temperature that survives up to 1.5 min. (38). These extremely interesting complexes are currently being studied by a number of investigators.…”