Four new antihypertensive piperidinylmethylphenol compounds were synthesized for their potential antihypertensive and antiarhythmic properties. The pKa values were determined experimentally, with the aid of the program SQUAD, by capillary zone electrophoresis (CZE) at T=298.15 K and 0.015 M ionic strength (I=0.05 M) and by UV spectrophotometry at pseudophysiological conditions (T=310.15 K and I=0.15 M), obtaining good agreement between the values determined with both techniques. A theoretical study was followed in order to propose a deprotonation mechanism for each compound.
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http://dx.doi.org/10.1021/jp904474m | DOI Listing |
ACS Omega
December 2024
Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université libre de Bruxelles (ULB), Avenue F. D. Roosevelt 50, CP160/06, Brussels 1050, Belgium.
An in-depth experimental and computational study to rationalize the mechanism underlying the gold-catalyzed intramolecular hydroalkylation of ynamides to indenes is reported. Evaluating the reactivity of a set of deuterated ynamides and gold complexes allowed to get valuable insights into the mechanism of this reaction, while DFT calculations allowed to determine a plausible reaction pathway for this unprecedented transformation. This pathway involves the activation of the ynamide followed by a [1,5]-hydride shift from the highly reactive, in situ generated keteniminium ion, and a subsequent cyclization before deprotonation followed by a final protodeauration.
View Article and Find Full Text PDFSmall
January 2025
School of Chemistry and Chemical Engineering, University of Surrey, GU2 7XH, Guildford, UK.
Understanding the chemical and physical mechanisms at play in 2D materials growth is critical for effective process development of methods such as chemical vapor deposition (CVD) as a toolbox for processing more complex nanostructures and 2D materials. A combination of density functional theory and microkinetic modeling is employed to comprehensively investigate the reaction mechanism governing the epitaxial growth of hexagonal boron nitride (hBN) on Ru(0001) from borazine. This analysis encompasses four key stages prior to the formation of the complete hBN overlayer: (i) adsorption, diffusion and deprotonation of borazine, (ii) dimerization and microkinetic modeling (iii) stability of larger borazine polymers and (iv) formation of nanoporous intermediates.
View Article and Find Full Text PDFACS Omega
December 2024
State Key Laboratory of Research & Development of Characteristic Qin Medicine Resources (Cultivation), Co-Construction Collaborative Innovation Center for Chinese Medicine Resources Industrialization by Shaanxi & Education Ministry, Shaanxi University of Chinese Medicine, Xianyang 712083, China.
Due to the lower oxidation potential than natural nucleic acid bases, one-electron oxidation of DNA is usually funneled into the direction of intermediates for oxidized DNA damage like 8-oxo-7,8-dihydroadenine (8-oxoA) leading to a radical cation, which may undergo facile deprotonation. However, compared to the sophisticated studies devoted to natural bases, much less is known about the radical cation degradation behavior of an oxidized DNA base. Inspired by this, a comprehensive theoretical investigation is performed to illuminate the deprotonation of 8-oxoA radical cation (8-oxoA) in both free and encumbered context by calculating the p value and mapping the energy profiles.
View Article and Find Full Text PDFProtein Sci
January 2025
Department of Neuroscience, Biomedicine and Movement Sciences, Section of Biochemistry, University of Verona, Verona, Italy.
Human succinic semialdehyde dehydrogenase is a mitochondrial enzyme fundamental in the neurotransmitter γ-aminobutyric acid catabolism. It catalyzes the NAD-dependent oxidative degradation of its derivative, succinic semialdehyde, to succinic acid. Mutations in its gene lead to an inherited neurometabolic rare disease, succinic semialdehyde dehydrogenase deficiency, characterized by mental and developmental delay.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
College of Materials, Institute of Artificial Intelligence, State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, iChEM, Fujian Key Laboratory of Advanced Materials, College of Energy, Xiamen University, Xiamen 361005, China.
Nickel-iron-based catalysts are recognized for their high efficiency in the oxygen evolution reaction (OER) under alkaline conditions, yet the underlying mechanisms that drive their superior performance remain unclear. Herein, we revealed the molecular OER mechanism and the structure-intermediate-performance relationship of OER on a phosphorus-doped nickel-iron nanocatalyst (NiFeP). NiFeP exhibited exceptional activity and stability with an overpotential of only 210 mV at 10 mA cm in 1 M KOH and a cell voltage of 1.
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