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Substituent and Heteroatom Effects on π-π Interactions: Evidence That Parallel-Displaced π-Stacking is Not Driven by Quadrupolar Electrostatics.
J Am Chem Soc
January 2025
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Stacking interactions are a recurring motif in supramolecular chemistry and biochemistry, where a persistent theme is a preference for parallel-displaced aromatic rings rather than face-to-face π-stacking. This is typically explained in terms of quadrupole-quadrupole interactions between the arene moieties but that interpretation is inconsistent with accurate calculations, which reveal that the quadrupolar picture is qualitatively wrong. At typical π-stacking distances, quadrupolar electrostatics may differ in sign from an exact calculation based on charge densities of the interacting arenes.
View Article and Find Full Text PDFHydrogen Bond Blueshifts in Nitrile Vibrational Spectra Are Dictated by Hydrogen Bond Geometry and Dynamics.
JACS Au
December 2024
Freie Universität Berlin, Physics Department, Experimental Molecular Biophysics, Arnimallee 14, 14195 Berlin, Germany.
Vibrational Stark effect (VSE) spectroscopy has become one of the most important experimental approaches to determine the strength of noncovalent, electrostatic interactions in chemistry and biology and to quantify their influence on structure and reactivity. Nitriles (C≡N) have been widely used as VSE probes, but their application has been complicated by an anomalous hydrogen bond (HB) blueshift which is not encompassed within the VSE framework. We present an empirical model describing the anomalous HB blueshift in terms of H-bonding geometry, i.
View Article and Find Full Text PDFA Pilot Study: Treatment of High Alcohol Consumption in a Novel Minipig Model of Alcohol Use Disorder.
Alcohol Treat Q
May 2024
Department of Cell Biology & Biochemistry, Texas Tech University Health Sciences Center, Lubbock, Texas, USA.
Three medications are FDA approved in the US for treatment of Alcohol Use Disorder (AUD), and a few others are used off-label. Patient compliance and efficacy in the broader population are major hurdles for current AUD medications. As a consequence, there is an urgent need for improved pharmacotherapeutics to complement behavioral approaches.
View Article and Find Full Text PDFEnsemble Inequivalence in Long-Range Quantum Systems.
Phys Rev Lett
August 2024
SISSA and INFN Sezione di Trieste, Via Bonomea 265, I-34136 Trieste, Italy and Istituto dei Sistemi Complessi, Consiglio Nazionale delle Ricerche, Via Madonna del Piano 10, I-50019 Sesto Fiorentino, Italy.
Ensemble inequivalence, i.e., the possibility of observing different thermodynamic properties depending on the statistical ensemble which describes the system, is one of the hallmarks of long-range physics, which has been demonstrated in numerous classical systems.
View Article and Find Full Text PDFThe role of interleukin-10 in mitigating endoplasmic reticulum stress in aged mice through exercise.
Am J Physiol Endocrinol Metab
September 2024
Postgraduate Program in Rehabilitation and Functional Performance, Ribeirão Preto Medical School, University of São Paulo (USP), São Paulo, Brazil.
Although unfolded protein response (UPR) is essential for cellular protection, its prolonged activation may induce apoptosis, compromising cellular longevity. The aging process increases the endoplasmic reticulum (ER) stress in skeletal muscle. However, whether combined exercise can prevent age-induced ER stress in skeletal muscle remains unknown.
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