The Role of Chemical Reactions Placed Between Successive Electron Transfer in the Reduction of 2-Methylthio-4,6-di(alkylamino)-1,3,5-triazines on Mercury Electrodes

2001 ◽  
Vol 148 (10) ◽  
pp. E419 ◽  
Author(s):  
R. Ortiz ◽  
M. J. Higuera ◽  
R. Marı́n Galvı́n ◽  
J. M. Rodrı́guez Mellado
Author(s):  
David R. Veblen

Extended defects and interfaces control many processes in rock-forming minerals, from chemical reactions to rock deformation. In many cases, it is not the average structure of a defect or interface that is most important, but rather the structure of defect terminations or offsets in an interface. One of the major thrusts of high-resolution electron microscopy in the earth sciences has been to identify the role of defect fine structures in reactions and to determine the structures of such features. This paper will review studies using HREM and image simulations to determine the structures of defects in silicate and oxide minerals and present several examples of the role of defects in mineral chemical reactions. In some cases, the geological occurrence can be used to constrain the diffusional properties of defects.The simplest reactions in minerals involve exsolution (precipitation) of one mineral from another with a similar crystal structure, and pyroxenes (single-chain silicates) provide a good example. Although conventional TEM studies have led to a basic understanding of this sort of phase separation in pyroxenes via spinodal decomposition or nucleation and growth, HREM has provided a much more detailed appreciation of the processes involved.


1992 ◽  
Vol 57 (9) ◽  
pp. 1836-1842 ◽  
Author(s):  
Rafael Marín Galvín ◽  
José Miguel Rodríguez Mellado

The electroreduction of niazid on mercury electrodes has been studied in acidic media (pH < 6). Tafel slopes and reaction orders were obtained at potentials corresponding to the foot of the first polarographic wave. On the basis of both polarographic and voltammetric results it has been shown that the waves appearing at more negative potentials correspond to the reduction of nicotinamide. Protonation of niazid plays an essential role in its reduction and pK values of 1.4, 3.2 and 11.5 were obtained by UV spectroscopy. The process corresponding to the first wave is irreversible, being the second one-electron transfer the rate determining step. Above pH 4 the process is complex due to the overlapping of the waves caused by the occurrence of protonation reactions.


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.


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