The recent candidate detection of ∼1 ppb of phosphine in the middle atmosphere of Venus is so unexpected that it requires an exhaustive search for explanations of its origin. Phosphorus-containing species have not been modeled for Venus' atmosphere before, and our work represents the first attempt to model phosphorus species in the venusian atmosphere. We thoroughly explore the potential pathways of formation of phosphine in a venusian environment, including in the planet's atmosphere, cloud and haze layers, surface, and subsurface. We investigate gas reactions, geochemical reactions, photochemistry, and other nonequilibrium processes. None of these potential phosphine production pathways is sufficient to explain the presence of ppb phosphine levels on Venus. If PH's presence in Venus' atmosphere is confirmed, it therefore is highly likely to be the result of a process not previously considered plausible for venusian conditions. The process could be unknown geochemistry, photochemistry, or even aerial microbial life, given that on Earth phosphine is exclusively associated with anthropogenic and biological sources. The detection of phosphine adds to the complexity of chemical processes in the venusian environment and motivates follow-up sampling missions to Venus. Our analysis provides a template for investigation of phosphine as a biosignature on other worlds.
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http://dx.doi.org/10.1089/ast.2020.2352 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland.
Organic redox systems that can undergo oxidative and reductive (ambipolar) electron transfer are elusive yet attractive for applications across synthetic chemistry and energy science. Specifically, the use of ambipolar redox systems in proton-coupled electron transfer (PCET) reactions is largely unexplored but could enable "switchable" reactivity wherein the uptake and release of hydrogen atoms are controlled using a redox stimulus. Here, we describe the synthesis and characterization of an ambipolar functionalized terthiophene (TTH) bearing methyl thioether and phosphine oxide groups that exhibits switchable PCET reactivity.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
TU Dortmund: Technische Universitat Dortmund, Fakultät für Chemie und Chemische Biologie, Otto-Hahn Str.6, 44227, Dortmund, GERMANY.
This study introduces a novel class of carbon-centered diradicals: a monosubstituted C-atom stabilized by a phosphine. The diradical Ph3P→C was photochemically generated from a diazophosphorus ylide precursor (Ph3PCN2) and characterized by EPR and isotope-sensitive ENDOR spectroscopy at low temperatures. Ph3P→C features an axial zero-field splitting parameter D = 0.
View Article and Find Full Text PDFACS Omega
January 2025
Department of Chemistry and Biochemistry, University of Colorado Colorado Springs, 1420 Austin Bluffs Parkway, Colorado Springs, Colorado 80918 United States.
The development of a sensitive and selective silver nanoparticle assay for the quantitation of vitamin C (SNaP-C), as ascorbic acid (AA) and total ascorbic acid (TAA = AA + dehydroascorbic acid, DHAA), is described. Three assay parameters were investigated and optimized: (1) synthesis of silver nanoparticles (AgNPs) to produce a reliable enhanced localized surface plasmon resonance (LSPR) in the presence of specific added antioxidants; (2) ensuring long-term stability of AA and DHAA in aqueous solutions; and (3) SNaP-C assay conditions to allow for rapid analysis of samples (beverages) by monitoring the enhanced LSPR. The synthesis of AgNPs using soluble starch as a capping agent and d-arabinose as a reducing agent was optimized in a CEM Discover SP laboratory microwave.
View Article and Find Full Text PDFPharmaceuticals (Basel)
January 2025
Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3, 1111 Budapest, Hungary.
Methylenebisphosphonic derivatives including hydroxy-methylenebisphosphonic species may be of potential biological activity, and a part of them is used in the treatment of bone diseases. Methylenebisphosphonates may be obtained by the Michaelis-Arbuzov reaction of suitably α-substituted methylphosphonates and trialkyl phosphites or phosphinous esters, while the hydroxy-methylene variations are prepared by the Pudovik reaction of α-oxophosphonates and different >P(O)H reagents, such as diethyl phosphite and diarylphosphine oxides. After converting α-hydroxy-benzylphosphonates and -phosphine oxides to the α-halogeno- and α-sulfonyloxy derivatives, they were utilized in the Michaelis-Arbuzov reaction with trialkyl phosphites and ethyl diphenylphosphinite to afford the corresponding bisphosphonate, bis(phosphine oxide) and phosphonate-phosphine oxide derivatives.
View Article and Find Full Text PDFMolecules
January 2025
Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3, 1111 Budapest, Hungary.
Butyl phenyl--phosphinate that is not available commercially was prepared from phenyl--phosphinic acid by three methods: by alkylating esterification (i), by microwave-assisted direct esterification (ii), and unexpectedly, by thermal esterification (iii). Considering the green aspects, selectivity and scalability, the thermal variation seemed to be optimal. However, there was need for prolonged heating.
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