Electron transfer in the type II photoelimination of .alpha.-aminoacetophenones

1971 ◽  
Vol 93 (25) ◽  
pp. 6998-7005 ◽  
Author(s):  
Albert Padwa ◽  
William Eisenhardt ◽  
Robert Gruber ◽  
Deran Pashayan
Keyword(s):  
Pteridines ◽  
2011 ◽  
Vol 22 (1) ◽  
pp. 111-119 ◽  
Author(s):  
Carolina Lorente ◽  
Gabriela Petroselli ◽  
M. Laura Dántola ◽  
Esther Oliveros ◽  
Andrés H. Thomas

Abstract Interest in the photochemistry and photophysics of pterins has increased since the participation of this family of compounds in different photobiological processes has been suggested or demonstrated in recent decades. Pterins participate in relevant biological processes, such as metabolic redox reactions, and can photoinduce the oxidation of biomolecules through both electron transfer mechanisms (Type I) and singlet oxygen production (Type II). This article describes recent findings on electron transfer-initiated reactions photoinduced by the triplet excited state of pterins and connects them in the context of photosensitized processes of biological relevance.


2001 ◽  
Vol 79 (1) ◽  
pp. 63-69
Author(s):  
J A Pincock ◽  
S Rifai ◽  
R Stefanova

Irradiation of trans-2-phenylcyclohexyl 4-cyanobenzoate (4) in methanol results in formation of the 1-phenylcyclohexene and 4-cyanobenzoic acid as the major products. The mechanism proposed for this example of the Norrish Type II-like reaction, normally inefficient for the π,π* state of esters, begins with intramolecular electron transfer in the excited singlet state. The next step, intramolecular proton transfer, is highly exergonic as a result of the increased acidity of the benzylic hydrogen of the radical cation and the increased basicity of the carbonyl oxygen of the radical anion. The final step is cleavage of the 1,4-biradical. This mechanism is proposed on the basis of product studies, absorption spectra, fluorescence spectra, oxidation and reduction potentials, and nanosecond laser flash photolysis spectra. The stereochemical requirements for the process have also been examined using solution NMR, the X-ray structure, and MM3 calculations. The stereoisomer, cis-2-phenylcyclohexyl 4-cyanobenzoate (5), undergoes cis to trans isomerization before photofragmentation. Photolysis of the cis isomer in methanol-OD demonstrated that the cis to trans isomerization occurred by inversion at C1.Key words : Norrish Type II, aromatic esters, intramolecular electron transfer.


1999 ◽  
Vol 121 (15) ◽  
pp. 3785-3786 ◽  
Author(s):  
Dayal P. DeCosta ◽  
Amy K. Bennett ◽  
James A. Pincock

1994 ◽  
Vol 3 (3) ◽  
pp. 429-435 ◽  
Author(s):  
Irma Colombo ◽  
Gaetano Finocchlaro ◽  
Barbara Garavaglia ◽  
Nicoletta Garbugllo ◽  
S. Yamaguchl ◽  
...  

2021 ◽  
Vol 2 ◽  
Author(s):  
Christine M. Latham ◽  
Randi N. Owen ◽  
Emily C. Dickson ◽  
Chloey P. Guy ◽  
Sarah H. White-Springer

In aged humans, low-intensity exercise increases mitochondrial density, function and oxidative capacity, decreases the prevalence of hybrid fibers, and increases lean muscle mass, but these adaptations have not been studied in aged horses. Effects of age and exercise training on muscle fiber type and size, satellite cell abundance, and mitochondrial volume density (citrate synthase activity; CS), function (cytochrome c oxidase activity; CCO), and integrative (per mg tissue) and intrinsic (per unit CS) oxidative capacities were evaluated in skeletal muscle from aged (n = 9; 22 ± 5 yr) and yearling (n = 8; 9.7 ± 0.7 mo) horses. Muscle was collected from the gluteus medius (GM) and triceps brachii at wk 0, 8, and 12 of exercise training. Data were analyzed using linear models with age, training, muscle, and all interactions as fixed effects. At wk 0, aged horses exhibited a lower percentage of type IIx (p = 0.0006) and greater percentage of hybrid IIa/x fibers (p = 0.002) in the GM, less satellite cells per type II fiber (p = 0.03), lesser integrative and intrinsic (p≤ 0.04) CCO activities, lesser integrative oxidative phosphorylation capacity with complex I (PCI; p = 0.02) and maximal electron transfer system capacity (ECI+II; p = 0.06), and greater intrinsic PCI, ECI+II, and electron transfer system capacity with complex II (ECII; p≤ 0.05) than young horses. The percentage of type IIx fibers increased (p < 0.0001) and of type IIa/x fibers decreased (p = 0.001) in the GM, and the number of satellite cells per type II fiber increased (p = 0.0006) in aged horses following exercise training. Conversely, the percentage of type IIa/x fibers increased (p ≤ 0.01) and of type IIx fibers decreased (p ≤ 0.002) in young horses. Integrative maximal oxidative capacity (p ≤ 0.02), ECI+II (p ≤ 0.07), and ECII (p = 0.0003) increased for both age groups from wk 0 to 12. Following exercise training, aged horses had a greater percentage of IIx (p ≤ 0.002) and lesser percentage of IIa/x fibers (p ≤ 0.07), and more satellite cells per type II fiber (p = 0.08) than young horses, but sustained lesser integrative and intrinsic CCO activities (p≤ 0.04) and greater intrinsic PCI, ECI+II, and ECII (p≤ 0.05). Exercise improved mitochondrial measures in young and aged horses; however, aged horses showed impaired mitochondrial function and differences in adaptation to exercise training.


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