Current models of the formation and distribution of gold deposits on Earth are based on the long-standing paradigm that hydrogen sulfide and chloride are the ligands responsible for gold mobilization and precipitation by fluids across the lithosphere. Here we challenge this view by demonstrating, using in situ X-ray absorption spectroscopy and solubility measurements, coupled with molecular dynamics and thermodynamic simulations, that sulfur radical species, such as the trisulfur ion S3(-), form very stable and soluble complexes with Au(+) in aqueous solution at elevated temperatures (>250 °C) and pressures (>100 bar). These species enable extraction, transport, and focused precipitation of gold by sulfur-rich fluids 10-100 times more efficiently than sulfide and chloride only. As a result, S3(-) exerts an important control on the source, concentration, and distribution of gold in its major economic deposits from magmatic, hydrothermal, and metamorphic settings. The growth and decay of S3(-) during the fluid generation and evolution is one of the key factors that determine the fate of gold in the lithosphere.
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http://dx.doi.org/10.1073/pnas.1506378112 | DOI Listing |
Nat Commun
January 2025
Department of Dermatology, State Key Laboratory of Biotherapy and Cancer Center, West China Hospital, Sichuan University, Chengdu, China.
Unsymmetric disulfides are prevalent in natural products and are essential in medicinal chemistry and materials science, but their robust synthesis poses significant challenges. In this paper, we report an expeditous transition-metal-free methodology for synthesizing unsymmetric disulfides through the addition of perthiyl radicals to alkenes. This study marks the use of generating perthiyl radicals by reacting SO with unactivated alkyl (pseudo)halides (Cl/Br/I/OTs).
View Article and Find Full Text PDFAnal Chem
January 2025
School of Chemical and Environmental Engineering, Anhui Polytechnic University, 241000 Wuhu, P.R. China.
At present, some progress has been made in developing NIR light-responsive free radical generators. However, the efficacy of theranostics continues to be hindered by tumor-associated inflammatory reactions. Hence, fulfilling the in situ release of free radicals upon NIR light excitation specifically activated by the inflammation microenvironment would be an ideal strategy for efficient inflammation eradication and tumor suppression but remains a challenge.
View Article and Find Full Text PDFEnviron Res
December 2024
Department of Environmental Engineering, Kyungpook National University, 80 Daehak-ro, Buk-gu, Daegu 41566, Republic of Korea. Electronic address:
Peroxydisulfate (PDS) activation is a crucial process for wastewater treatment in complicated water matrices. However, it is frequently limited because of poor selectivity, sluggish kinetics, and short lifetime of radicals. Therefore, in this study, an efficient sulfur-doped CN/DyFeO (SCN/DyF) Z-scheme heterostructure catalyst was rationally developed using a simple wet-chemical strategy to photoactivate PDS, which can effectively degrade norfloxacin (NOR; 96.
View Article and Find Full Text PDFInt J Biol Macromol
December 2024
INFN-Laboratori Nazionali di Frascati, 00044 Frascati, Italy.
This study investigates the synthesis of corn starch nanocrystals (SNCs) via sulfuric acid hydrolysis. Esterification of oleic acid (OA) with SNCs was carried out using Maghnite-H as a catalyst, a non-polluting, eco-friendly proton-exchanged montmorillonite-based green catalyst suitable for various chemical processes. Optimization of synthesis parameters, including reaction temperature, duration, and catalyst quantity, was conducted using response surface methodology (RSM) with a central composite design incorporating three factors and three levels.
View Article and Find Full Text PDFJ Colloid Interface Sci
December 2024
Department of Civil and Environmental Engineering, National University of Singapore, 10 Kent Ridge, Singapore. Electronic address:
Fenton reaction technology has worked well in water and wastewater treatment; however it is often limited by such problems as continuous external supply of HO, slow Fe/Fe cycle rate, high energy requirements, and maintenance of low pH during operation. Herein, a novel self-sufficient heterogeneous Fenton system based on Fe/MoS was designed, fabricated, and optimized to effectively address these problems. The combined presence of Fe and sulfur vacancies sites in MoS played a pivotal role in the generation of HOvia two-step single-electron reduction process without any energy consumption.
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