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Two novel methods based on hydride generation atomic fluorescence spectrometry for the accurate screening of total and inorganic arsenic (As) in rice grain digests in 5 and 2 minutes, respectively, are proposed here. Total As determination was achieved using online UV photolysis aided by alkaline potassium persulphate oxidation, which converted all organic As to arsenate and thus allowed quantitative hydride generation. Determination of inorganic As in rice grains was accomplished by selective hydride generation at high acidity (4.8 M HCl), which allowed ∼50 times higher efficiency for hydride generation of arsenite than the prevalent form of organic As in rice, namely dimethylarsonic acid (DMA), after pre-reduction of all inorganic As using potassium iodide/ascorbic acid. The accuracy of the method was verified by (1) excellent agreement with the certified value of total As and the literature values of inorganic As in NIST SRM 1658a; (2) complete recovery of total As in NIST SRM 1568a spiked with additional 2 ng As g of DMA; (3) excellent agreement of total and inorganic As values in 80 samples of different types, origins and treatments (standing for different matrices) compared to ICP-MS and HPLC-ICP-MS measurements; (4) ∼100% recovery of inorganic As in ERM-BC-211 and a round grain rice sample even spiked with DMA up to 200 ng As g. Additionally, the low data dispersion was indicated by the low relative standard deviation (∼4.3%) in the day-to-day precision for quantifying inorganic As in NIST SRM 1568a on 7 different days.
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http://dx.doi.org/10.1039/c4ay00858h | DOI Listing |
Inorg Chem
September 2025
Institute of Inorganic Chemistry of Czech Academy of Sciences, Husinec-Řež 1001, 250 68, Czech Republic.
We report the synthesis and reactivity of phenylpyridine-based boron azides readily accessible via nucleophilic substitution from generated borenium-type precursors. Three azides were obtained: a hydridic species (L)BHN (L = 2-phenylpyridine), a cyclopentyl-substituted analogue (L)B(cyclopentyl)N, and a boron diazide (L)B(N) obtained as a byproduct from the synthesis of (L)BHN. The prepared borane azides exhibit notable thermal and photochemical robustness, with decomposition temperatures around 140 °C in mesitylene solution and above 170 °C in the solid state, as evidenced by DSC/TGA analysis.
View Article and Find Full Text PDFChem Sci
August 2025
Max-Planck-Institut für Kohlenforschung Kaiser-Wilhelm-Platz 1 45470 Mülheim an der Ruhr Germany
What governs the relationship between the reaction rate and thermodynamic driving force? Despite decades of rate theory, no general physically grounded equation exists to relate rate and driving force across all regimes. Classical models, such as the Marcus equation and Leffler equations, either rely on under-realistic assumptions or only capture the local behaviour, failing outside narrow regimes. We derive a general, non-linear equation from microscopic reversibility, arriving at three physically meaningful parameters: a minimum preorganisational barrier ( ), a reaction symmetry offset ( ), and a kinetic curvature factor ().
View Article and Find Full Text PDFPLoS One
September 2025
School of Geography and Resources, Guizhou Education University, Guiyang, China.
Antimony (Sb) is extensively utilized in industrial activities, but most of its compounds exhibit human toxicity and are classified as priority-controlled pollutants. Unlike traditional electrochemical methods that remove metallic pollutants via coagulation or precipitation, electrochemical hydride generation technology converts antimony (Sb) in wastewater into stibine gas (SbH3) for efficient removal. Furthermore, the generated SbH₃ can be decomposed thermally to partially recover metallic antimony.
View Article and Find Full Text PDFBiometals
September 2025
Environmental Health Department, National Institute of Public Health, 62100, Cuernavaca, Morelos, Mexico.
Describe the levels of arsenic, mercury, manganese, and lead in the hair of older Mexican adults and analyze their association with exposure and sociodemographic factors. This cross-sectional study used a random subsample of 2474 adults aged 50 and older from the 2018 Mexican Health and Aging Study. Metal levels in hair were quantified using inductively coupled plasma mass spectrometry and an optical emission spectrometer with a hydride generator.
View Article and Find Full Text PDFbioRxiv
August 2025
Department of Biochemistry and Molecular Biology, Michigan State University, MI, USA.
The nickel pincer nucleotide (NPN) cofactor catalyzes the racemization/epimerization of α-hydroxy acids in enzymes of the LarA family. The established proton-coupled hydride transfer mechanism requires two catalytic histidine residues that alternately act as general acids and general bases. Notably, however, a fraction of LarA homologs (LarAHs) lack one of the active site histidine residues, replacing it with an asparaginyl side chain that cannot participate in acid/base catalysis.
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