scholarly journals On the Role of Pre- and Post-Electron-Transfer Steps in the SmI2/Amine/H2O-Mediated Reduction of Esters: New Mechanistic Insights and Kinetic Studies

2014 ◽  
Vol 20 (15) ◽  
pp. 4222-4226 ◽  
Author(s):  
Michal Szostak ◽  
Malcolm Spain ◽  
David J. Procter
2004 ◽  
Vol 71 ◽  
pp. 1-14
Author(s):  
David Leys ◽  
Jaswir Basran ◽  
François Talfournier ◽  
Kamaldeep K. Chohan ◽  
Andrew W. Munro ◽  
...  

TMADH (trimethylamine dehydrogenase) is a complex iron-sulphur flavoprotein that forms a soluble electron-transfer complex with ETF (electron-transferring flavoprotein). The mechanism of electron transfer between TMADH and ETF has been studied using stopped-flow kinetic and mutagenesis methods, and more recently by X-ray crystallography. Potentiometric methods have also been used to identify key residues involved in the stabilization of the flavin radical semiquinone species in ETF. These studies have demonstrated a key role for 'conformational sampling' in the electron-transfer complex, facilitated by two-site contact of ETF with TMADH. Exploration of three-dimensional space in the complex allows the FAD of ETF to find conformations compatible with enhanced electronic coupling with the 4Fe-4S centre of TMADH. This mechanism of electron transfer provides for a more robust and accessible design principle for interprotein electron transfer compared with simpler models that invoke the collision of redox partners followed by electron transfer. The structure of the TMADH-ETF complex confirms the role of key residues in electron transfer and molecular assembly, originally suggested from detailed kinetic studies in wild-type and mutant complexes, and from molecular modelling.


Biochemistry ◽  
2005 ◽  
Vol 44 (18) ◽  
pp. 6929-6937 ◽  
Author(s):  
Siddegowda Bhavani ◽  
V. Trivedi ◽  
V. R. Jala ◽  
H. S. Subramanya ◽  
Purnima Kaul ◽  
...  

Author(s):  
Lars Mohrhusen ◽  
Jessica Kräuter ◽  
Katharina Al-Shamery

The photochemical conversion of organic compounds on tailored transition metal oxide surfaces by (UV) irradiation has found wide applications ranging from the production of chemicals to the degradation of organic...


Author(s):  
Jingwen Pan ◽  
Baoyu Gao ◽  
Pijun Duan ◽  
Kangying Guo ◽  
Muhammad Akram ◽  
...  

Nonradical pathway-based persulfate oxidation technology is considered to be a promising method for high-salinity organic wastewater treatment.


2020 ◽  
Vol 153 (18) ◽  
pp. 185101
Author(s):  
Nirmalendu Acharyya ◽  
Roman Ovcharenko ◽  
Benjamin P. Fingerhut

Molecules ◽  
2021 ◽  
Vol 26 (10) ◽  
pp. 2911
Author(s):  
Miriam Navarrete-Miguel ◽  
Antonio Francés-Monerris ◽  
Miguel A. Miranda ◽  
Virginie Lhiaubet-Vallet ◽  
Daniel Roca-Sanjuán

Photocycloreversion plays a central role in the study of the repair of DNA lesions, reverting them into the original pyrimidine nucleobases. Particularly, among the proposed mechanisms for the repair of DNA (6-4) photoproducts by photolyases, it has been suggested that it takes place through an intermediate characterized by a four-membered heterocyclic oxetane or azetidine ring, whose opening requires the reduction of the fused nucleobases. The specific role of this electron transfer step and its impact on the ring opening energetics remain to be understood. These processes are studied herein by means of quantum-chemical calculations on the two azetidine stereoisomers obtained from photocycloaddition between 6-azauracil and cyclohexene. First, we analyze the efficiency of the electron-transfer processes by computing the redox properties of the azetidine isomers as well as those of a series of aromatic photosensitizers acting as photoreductants and photo-oxidants. We find certain stereodifferentiation favoring oxidation of the cis-isomer, in agreement with previous experimental data. Second, we determine the reaction profiles of the ring-opening mechanism of the cationic, neutral, and anionic systems and assess their feasibility based on their energy barrier heights and the stability of the reactants and products. Results show that oxidation largely decreases the ring-opening energy barrier for both stereoisomers, even though the process is forecast as too slow to be competitive. Conversely, one-electron reduction dramatically facilitates the ring opening of the azetidine heterocycle. Considering the overall quantum-chemistry findings, N,N-dimethylaniline is proposed as an efficient photosensitizer to trigger the photoinduced cycloreversion of the DNA lesion model.


Biochemistry ◽  
2005 ◽  
Vol 44 (42) ◽  
pp. 13970-13980 ◽  
Author(s):  
Barbara Cellini ◽  
Mariarita Bertoldi ◽  
Riccardo Montioli ◽  
Carla Borri Voltattorni

Sign in / Sign up

Export Citation Format

Share Document