A hydrogen bond formed between the superoxide anion and the ammonium ion (NH4+) accelerates electron transfer from the C60 radical anion to oxygen significantly, whereas the tetra-n-butylammonium ion has no ability to form a hydrogen bond with the superoxidie anion, exhibiting no acceleration of the electron-transfer reduction of oxygen. The second-order rate constant of electron transfer from C60*- to O2 increases linearly with increasing concentration of NH4+. This indicates that O2*- produced in the electron transfer from C60 to O2 is stabilized by 1:1 complex formation between O2*- and NH4+. The 1:1 complex formed between O2*- and NH4+ was detected by ESR. The binding of O2*- with NH4+ results in a positive shift of the reduction potential of O2 with increasing concentration of NH4+, leading to the acceleration of electron transfer from C60*- to O2.
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http://dx.doi.org/10.1021/jp064115m | DOI Listing |
ACS Nano
January 2025
Department of Chemistry, University of California Berkeley, Berkeley, California 94720, United States.
Understanding charge transport in semiconductor quantum dot (QD) assemblies is important for developing the next generation of solar cells and light-harvesting devices based on QD technology. One of the key factors that governs the transport in such systems is related to the hybridization between the QDs. Recent experiments have successfully synthesized QD molecules, arrays, and assemblies by directly fusing the QDs, with enhanced hybridization leading to high carrier mobilities and coherent band-like electronic transport.
View Article and Find Full Text PDFScience
January 2025
Redox and Metalloprotein Research Group, Max Planck Institute of Biophysics, Frankfurt am Main, Germany.
In the ancient microbial Wood-Ljungdahl pathway, carbon dioxide (CO) is fixed in a multistep process that ends with acetyl-coenzyme A (acetyl-CoA) synthesis at the bifunctional carbon monoxide dehydrogenase/acetyl-CoA synthase complex (CODH/ACS). In this work, we present structural snapshots of the CODH/ACS from the gas-converting acetogen , characterizing the molecular choreography of the overall reaction, including electron transfer to the CODH for CO reduction, methyl transfer from the corrinoid iron-sulfur protein (CoFeSP) partner to the ACS active site, and acetyl-CoA production. Unlike CODH, the multidomain ACS undergoes large conformational changes to form an internal connection to the CODH active site, accommodate the CoFeSP for methyl transfer, and protect the reaction intermediates.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Chemistry Division, Brookhaven National Laboratory, Upton, NY 11973-5000, USA.
This review discusses the properties of strongly oxidizing radicals in organic and aqueous media and highlights the challenges in obtaining accurate values of their reduction potentials. Transient redox equilibrium methods based on the use of strong photooxidants or initiated by pulse radiolysis are shown to provide versatile approaches for decoupling electron transfer reactions from follow-up reactivity of unstable radical species, resulting in accurate values of reduction potentials of very positive couples, including some solvent radical cations. We also show that correlations of reduction potentials with Hammett ∑+p parameters, as well as gas phase ionization potentials, can be used to estimate the redox properties of unknown couples within a homologous series of compounds.
View Article and Find Full Text PDFAppl Microbiol Biotechnol
January 2025
Marine Biological Section, Department of Biology, University of Copenhagen, Helsingør, Denmark.
One strategy for CO mitigation is using photosynthetic microorganisms to sequester CO under high concentrations, such as in flue gases. While elevated CO levels generally promote growth, excessively high levels inhibit growth through uncertain mechanisms. This study investigated the physiology of the cyanobacterium Synechocystis sp.
View Article and Find Full Text PDFRev Sci Instrum
January 2025
Institute for Physical Chemistry, University of Göttingen, 37077 Göttingen, Germany.
Surface science instruments require excellent vacuum to ensure surface cleanliness; they also require control of sample temperature, both to clean the surface of contaminants and to control reaction rates at the surface, for example, for molecular beam epitaxy and studies of heterogeneous catalysis. Standard approaches to sample heating within high vacuum chambers involve passing current through filaments of refractory metals, which then heat the sample by convective, radiative, or electron bombardment induced heat transfer. Such hot filament methods lead to outgassing of molecules from neighboring materials that are inadvertently heated; they also produce electrons and ions that may interfere with other aspects of the surface science experiment.
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