Polar stratospheric clouds (PSCs), of which the surface is a dynamic liquid water layer and might consist of aqueous HNO and HO, is a well-known key meteorological condition contributing to the ozone hole in the polar stratosphere. PSCs has been considered to provide abundant surface for the heterogeneous reactions causing the formation of the Cl and HOCl, which are further photolyzed into Cl and ClO radicals leading to the ozone destruction. Here we demonstrated that the sunlight drives the massive and stable production of OH radicals in aqueous HNO and its main photo-induced byproduct HNO. We also found that the photo-generated OH radicals in aqueous HNO, HNO and HO have the remarkable capability to react with the dissolved HCl, Cl and Br to form halogen radicals. In addition, we observed that the HO can react with dissolved HCl and Br in darkness to form and release Cl and Br gases, which could further be photolyzed into reactive halogen radicals whenever sunlight is available. All these findings suggest that, except for the well-known heterogeneous reactions, photochemical reactions involving the aqueous HNO and HO on and within PSCs surface might constitute another important halogen activation pathway for ozone destruction. This study may shed deeper insights into the mechanism of halogen radicals resulting in ozone depletion in polar stratosphere.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1016/j.chemosphere.2021.132816 | DOI Listing |
J Am Chem Soc
December 2024
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR 999077, China.
Catalytic enantioselective substitution of the readily available racemic α-halo carbonyl compounds by nitrogen nucleophiles represents one of the most convenient and direct approaches to access enantioenriched α-amino carbonyl compounds. Distinct from the two available strategies involving radicals and enolate ions, herein we have developed a new protocol featuring an electronically opposite way to weaken/cleave the carbon-halogen bond. A suitable chiral anion-based catalyst enables effective asymmetric control over the key positively charged intermediates.
View Article and Find Full Text PDFBeilstein J Org Chem
December 2024
Department of Chemical and Geological Sciences, University of Cagliari, S.S. 554, bivio per Sestu, 09042 Monserrato (CA), Italy.
The rising popularity of bioconjugate therapeutics has led to growing interest in late-stage functionalization (LSF) of peptide scaffolds. α,β-Unsaturated amino acids like dehydroalanine (Dha) derivatives have emerged as particularly useful structures, as the electron-deficient olefin moiety can engage in late-stage functionalization reactions, like a Giese-type reaction. Cheap and widely available building blocks like organohalides can be converted into alkyl radicals by means of photoinduced silane-mediated halogen-atom transfer (XAT) to offer a mild and straightforward methodology of alkylation.
View Article and Find Full Text PDFJ Org Chem
December 2024
Jiangxi Province Key Laboratory of Natural and Biomimetic Drugs Research, College of Chemistry and Materials, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. China.
An efficient visible-light-induced radical carbon oximation of styrenes with 1-nitrosopyrrolidine and organic halides is developed. The reaction proceeds smoothly in the absence of a transition metal and a photocatalyst under mild conditions, producing a wide range of functionalized oximes in moderate to good yields. Mechanistic studies reveal that the reaction involves the generation of nucleophilic α-amino alkyl radicals and subsequent halogen atom transfer (XAT) with organic halides.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Chemistry, Oklahoma State University, 107 Physical Sciences, Stillwater, Oklahoma 74078, United States.
While charge-transfer complexes involving halogen-bonding interactions have emerged as an alternative strategy for the photogeneration of carbon radicals, examples using (fluoro)alkyl bromides are limited. This report describes a dual catalytic approach for radical generation from α-bromodifluoroesters and amides under visible-light irradiation. Mechanistic studies suggest that the reaction proceeds through bromide displacement using a catalytic iodide salt, generating a C-I bond that can be engaged by our halogen-bonding photocatalysis platform.
View Article and Find Full Text PDFACS ES T Water
December 2024
Department of Chemistry, University of California, Irvine, Irvine, California 92697, United States.
Wet chemical oxidation (WCO) methods measure total organic carbon (TOC) in aqueous solutions through the formation and detection of carbon dioxide (CO). Prior research documents chloride (Cl) interference during WCO. However, the mechanism that determines WCO interference is not established.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!