An investigation on the detailed kinetics of proton transfer between a set of di- and monofluoro- and chloro- (2,3-, 2,5-, 2,6-, 3,5-, 2-, and 3-) benzoic acids (HA) and Crystal Violet carbinol base in chlorobenzene favors a mechanism in terms of fast equilibrium between HA and D to form a H-bonded complex, D...HA, followed by rate-limiting proton transfer along the H-bond to form the colored ion pair DH+A- under the combined influence of monomer HA catalyst, nonreactive cyclic dimer (HA)2 inhibitor, and hyperacidic homoconjugated complex H(HA2) catalyst through a transition state with nearly 60% charge separation.
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http://dx.doi.org/10.1021/jp709887q | DOI Listing |
Molecules
December 2024
Department of Chemistry, The University of Akron, Akron, OH 44325, USA.
The chalcone derivatives with hydroxy group () have been examined using low-temperature fluorescence spectroscopy. The study aimed to freeze the intramolecular charge transfer (ICT) motion in order to reveal the potential hidden transition(s) that are difficult to observe at room temperature. Although chalcone revealed one emission peak at ~667 nm at room temperature, it exhibited two emission peaks (λ = 580 and 636 nm) in EtOH at liquid N temperatures (77 K).
View Article and Find Full Text PDFMolecules
December 2024
High & New Technology Research Center of Henan Academy of Sciences, No. 56 Hongzhuan Road, Zhengzhou 450002, China.
A series of colorful binuclear Schiff bases derived from the different diamine bridges including 1,2- ethylenediamine (bis-Et-SA, bis-Et-4-NEt, bis-Et-5-NO, bis-Et-Naph), 1,2-phenylenediamine (bis-Ph-SA, bis-Ph-4-NEt, bis-Ph-5-NO, bis-Ph-Naph), dicyano-1,2-ethenediamine (bis-CN-SA, bis-CN-4-NEt, bis-CN-5-NO, bis-CN-Naph) have been designed and prepared. The optical properties of these binuclear Schiff base ligands were fully determined by UV-Vis absorption spectroscopy, fluorescence emission spectroscopy, and time-dependent-density functional theory (TD-DFT) calculations. The inclusion of D-A systems and/or π-extended systems in these binuclear Schiff base ligands not only enables adjustable RGB light absorption and emission spectra (300~700 nm) but also yields high fluorescence quantum efficiencies of up to 0.
View Article and Find Full Text PDFInt J Mol Sci
December 2024
Belozersky Institute of Physico-Chemical Biology, Lomonosov Moscow State University, Leninskie Gory, 119991 Moscow, Russia.
Proton-translocating NADH-ubiquinone oxidoreductase (complex I) catalyzes the oxidation of NADH by ubiquinone accompanied by the transmembrane transfer of four protons, thus contributing to the formation of a proton motive force () across the coupling membranes of mitochondria and bacteria, which drives ATP synthesis in oxidative phosphorylation. In recent years, great progress has been achieved in resolving complex I structure by means of X-ray crystallography and high-resolution cryo-electron microscopy, which has led to the formulation of detailed hypotheses concerning the molecular mechanism of coupling of the redox reaction to vectorial proton translocation. To test and probe proposed mechanisms, a comprehensive study of complex I using other methods including molecular dynamics and a variety of biochemical studies such as kinetic and inhibitory analysis is required.
View Article and Find Full Text PDFInt J Mol Sci
December 2024
Department of Pharmacy and Biotechnology, University of Bologna, Via Irnerio n.42, 40126 Bologna, Italy.
Disaccharide trehalose has been proven in many cases to be particularly effective in preserving the functional and structural integrity of biological macromolecules. In this work, we studied its effect on the electron transfer reactions that occur in the chromatophores of the photosynthetic bacterium . In the presence of a high concentration of trehalose, following the activation of the photochemistry by flashes of light, a slowdown of the electrogenic reactions related to the activity of the photosynthetic reaction center and cytochtome (cyt) complexes is observable.
View Article and Find Full Text PDFEnviron Sci Technol
January 2025
The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou 510006, China.
Electrocatalytic nitrate reduction reaction (NORR) to harmless nitrogen (N) presents a viable approach for purifying NO-contaminated wastewater, yet most current electrocatalysts predominantly produce ammonium/ammonia (NH/NH) due to challenges in facilitating N-N coupling. This study focuses on identifying metal catalysts that preferentially generate N and elucidating the mechanistic origins of their high selectivity. Our evaluation of 16 commercially available metals reveals that only Pb, Sn, and In demonstrated substantial N selectivity (79.
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