Gas-phase intrinsic structures of intact neutral and anionic glutathione (GSH) have been determined by means of a combination of negative ion photo-electron spectroscopy and quantum chemistry calculations. The inferred structures of the neutral parents of those peptide anions are canonical (non-zwitterionic). These intrinsic structures are compared to those already known in aqueous solution or determined by crystallography in binding sites of enzymes.
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http://dx.doi.org/10.1002/cphc.200900537 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Freie Universitat Berlin, Chemistry and Biochemistry, Fabeckstraße 34-36, 14195, Berlin, GERMANY.
Neutral mesoionic carbenes (MICs) based on a 1,2,3-triazole core have had a strong impact on various branches of chemistry such as homogeneous catalysis, electrocatalysis, and photochemistry/photophysics. We present here the first general synthesis of anionic mesoionic carbenes (anMICs) based on a 1,2,3-triazole core and a borate backbone. The free anMIC is stable in solution under an inert atmosphere at low temperatures, and can be stored for several weeks.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Brown University, Department of Chemistry, UNITED STATES OF AMERICA.
Despite major progress in the investigation of boron cluster anions, direct experimental study of neutral boron clusters remains a significant challenge because of the difficulty in size selection. Here we report a size-specific study of the neutral B9 cluster using threshold photoionization with a tunable vacuum ultraviolet free electron laser. The ionization potential of B9 is measured to be 8.
View Article and Find Full Text PDFSmall
January 2025
Polymer Science & Engineering Department, Conte Center for Polymer Research, University of Massachusetts, 120 Governors Drive, Amherst, MA, 01003, USA.
J Comput Chem
January 2025
Departament de Farmàcia i Tecnologia Farmacèutica, i Fisicoquímica, Facultat de Farmàcia i Ciències de l'Alimentació, Universitat de Barcelona (UB), Barcelona, Spain.
Continuum solvation models such as the polarizable continuum model and the conductor-like screening model are widely used in quantum chemistry, but their application to large biosystems is hampered by their computational cost. Here, we report the parametrization of the Miertus-Scrocco-Tomasi (MST) model for the prediction of hydration free energies of neutral and ionic molecules based on the domain decomposition formulation of COSMO (ddCOSMO), which allows a drastic reduction of the computational cost by several orders of magnitude. We also introduce several novelties in MST, like a new definition of atom types based on hybridization and an automatic setup of the cavity for charged regions.
View Article and Find Full Text PDFInt J Mol Sci
December 2024
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia.
In this work, a series of boronated amidines based on the -dodecaborate anion and amino acids containing an amino group in the side chain of the general formula [BHNHC(NH(CH)CH(NH)COOH)CH], where n = 2, 3, 4, were synthesized. These derivatives contain conserved α-amino and α-carboxyl groups recognized by the binding centers of the large neutral amino acid transporter (LAT) system, which serves as a target for the clinically applied BNCT agent para-boronophenylalanine (BPA). The paper describes several approaches to synthesizing the target compounds, their acute toxicity studies, and tumor uptake studies in vivo in two tumor models.
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