The benzene radical anion is a molecular ion pertinent to several organic reactions, including the Birch reduction of benzene in liquid ammonia. The species exhibits a dynamic Jahn-Teller effect due to its open-shell nature and undergoes pseudorotation of its geometry. Here, we characterize the complex electronic structure of this condensed-phase system based on ab initio molecular dynamics simulations and GW calculations of the benzene radical anion solvated in liquid ammonia. Using detailed analysis of the molecular and electronic structure, we find that the spatial character of the excess electron of the solvated radical anion follows the underlying Jahn-Teller distortions of the molecular geometry. We decompose the electronic density of states to isolate the contribution of the solute and to examine the response of the solvent to its presence. Our findings show the correspondence between instantaneous molecular structure and spin density; provide important insights into the electronic stability of the species, revealing that it is, indeed, a bound state in the condensed phase; and offer electronic densities of states that aid in the interpretation of experimental photoelectron spectra.
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http://dx.doi.org/10.1063/5.0076115 | DOI Listing |
Chem Soc Rev
January 2025
The Institute for Advanced Studies, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, Wuhan University, 299 Bayi Road, Wuhan, 430072, China.
The Brook rearrangement has emerged as one of the most pivotal transformations in organic chemistry, with broad applications spanning organic synthesis, drug design, and materials science. Since its discovery in the 1950s, the anion-mediated Brook rearrangement has been extensively studied, laying the groundwork for the development of numerous innovative reactions. In contrast, the radical Brook rearrangement has garnered comparatively less attention, primarily due to the challenges associated with the controlled generation of alkoxyl radicals under mild conditions.
View Article and Find Full Text PDFSci Rep
January 2025
Department of Nutritional Sciences, Auburn University, Auburn, AL, 36849, USA.
Oxidative stress (OS) refers to the disruption in the balance between free radical generation and antioxidant defenses, leading to potential tissue damage. Reactive oxygen species (ROS) can interact with biological components, triggering processes like protein oxidation, lipid peroxidation, or DNA damage, resulting in the generation of several volatile organic compounds (VOCs). Recently, VOCs provided new insight into cellular metabolism and can serve as potential biomarkers.
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January 2025
Department of Maxillofacial Radiology, Field of Oncology, Kagoshima University Graduate School of Medical and Dental Sciences, Kagoshima, 890-8544, Japan.
Synephrine, a protoalkaloid found in Citrus aurantium (CA) peels, exerts lipolytic, anti-inflammatory, and vasoconstrictive effects; however, its antioxidant activity remains unclear. In this study, electron spin resonance spectroscopy revealed that synephrine scavenged both hydroxyl and superoxide anion radicals. Several external stimuli, such as HO, X-rays, and ultraviolet (UV) radiation, cause stress-induced premature senescence (SIPS).
View Article and Find Full Text PDFJ Am Soc Mass Spectrom
January 2025
Dipartimento di Scienze del Suolo, della Pianta e degli Alimenti, Università degli Studi di Bari Aldo Moro, Via G. Amendola 165/a, 70126 Bari, Italy.
Coenzyme Q (CoQ) and closely related compounds with varying isoprenoid tail lengths (CoQ, = 6-9) are biochemical cofactors involved in many physiological processes, playing important roles in cellular respiration and energy production. Liquid chromatography (LC) coupled with single or tandem mass spectrometry (MS) using electrospray (ESI) or atmospheric pressure chemical ionization (APCI) is considered the gold standard for the identification and quantification of CoQ in food and biological samples. However, the characteristic fragmentation exhibited by the CoQ radical anion ([M], / 862.
View Article and Find Full Text PDFACS Appl Bio Mater
January 2025
Collaborative Innovation Center of Tumor Marker Detection Technology, Equipment and Diagnosis Therapy Integration in Universities of Shandong, Shandong Province Key Laboratory of Detection Technology for Tumor Makers, College of Medicine, Linyi University, Linyi 276005, China.
The multiple enzymatic properties of the Au-modified metal-organic framework (Au-MOFs) have made it a functional catalytic system for antitumor treatment. However, in the face of insufficient catalytic substrates in tumor tissue, it is still impossible to achieve efficient treatment of tumors. Herein, Au-MOFs loaded with hyaluronic acid (HA)-modified calcium peroxide nanoparticles (CaO NPs) were used to construct a nanozyme (Au-MOF/CaO/HA) for substrate self-supplied and parallel catalytic/calcium-overload-mediated therapy of cancer.
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