The atmospherically highly relevant methylsulfinyl radical CH3(O)S˙ was generated thermally under flash pyrolysis conditions and isolated in Ar matrices at 10 K; the allyl radical is a byproduct. CH3(O)S˙ and its D3- and (13)C-isotopologues were characterized through the excellent agreement between experimental and computed IR and UV/Vis spectra.
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http://dx.doi.org/10.1039/c3cc45379k | DOI Listing |
Macromolecules
March 2023
Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.
Over the last decade, photoinduced ATRP techniques have been developed to harness the energy of light to generate radicals. Most of these methods require the use of UV light to initiate polymerization. However, UV light has several disadvantages: it can degrade proteins, damage DNA, cause undesirable side reactions, and has low penetration depth in reaction media.
View Article and Find Full Text PDFACS Macro Lett
September 2022
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.
Water-soluble and biocompatible polymers are of interest in biomedicine as the search for alternatives to PEG-based materials becomes more important. In this work, the synthesis of a new sulfoxide-containing monomer, 2-(methylsulfinyl)ethyl acrylamide (MSEAM), is reported. Well-defined polymers were prepared by photoinduced initiators for continuous activator regeneration atom transfer radical polymerization (PICAR ATRP).
View Article and Find Full Text PDFFood Chem
August 2021
University of Warsaw, Faculty of Chemistry, Pasteura 1, 02-093 Warsaw, Poland. Electronic address:
Sulforaphane(SFN) and erucin(ERN) are isothiocyanates (ITCs) bearing, respectively, methylsulfinyl and methylsulfanyl groups. Their chemopreventive and anticancer activity is attributed to ability to modulate cellular redox status due to induction of Phase 2 cytoprotective enzymes (indirect antioxidant action) but many attempts to connect the bioactivity of ITCs with their radical trapping activity failed. Both ITCs are evolved from their glucosinolates during food processing of Cruciferous vegetables, therefore, we studied antioxidant behaviour of SFN/ERN at elevated temperature in two lipid systems.
View Article and Find Full Text PDFAntioxidants (Basel)
November 2020
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland.
Chemphyschem
June 2020
Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602, USA.
Although integral to remote marine atmospheric sulfur chemistry, the reaction between methylsulfinyl radical (CH SO) and ozone poses challenges to theoretical treatments. The lone theoretical study on this reaction reported an unphysically large barrier of 66 kcal mol for abstraction of an oxygen atom from O by CH SO. Herein, we demonstrate that this result stems from improper use of MP2 with a single-reference, unrestricted Hartree-Fock (UHF) wavefunction.
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