A Revisit to the Role of Bridge-adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid at Pt Electrodes

The mechanism and kinetics of electrocatalytic oxidation of formic acid at Pt electrodes is discussed in detail based on previous electrochemical in-situ ATR-FTIRS data [Langmuir 22, 10399 （2006）and Angewa. Chem. Int. Ed. 50, 1159 （2011）]. A kinetic model with formic acid adsorption （and probably the simultaneous C-H bond activation） as the rate determining step, which contributes to the majority of reaction current for formic acid oxi- dation, was proposed for the direct pathway. The model simulates well the IR spectroscopic results obtained under conditions where the poisoning effect of carbon monoxide （CO） is negligible and formic acid concentration is below 0.1 mol/L. The kinetic simulation predicts that in the direct pathway formic acid oxidation probably only needs one Pt atom as active site, formate is the site blocking species instead of being the active intermediate. We review in detail the conclusion that formate pathway （with either 1st or 2nd order reaction kinetics） is the direct pathway, possible origins for the discrepancies are pointed out.

Reaction of Mo(CO)_6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et_4N]_3[Mo_2(CO)_6(μ-OC_6H_4OCH_2C_6H_5)_3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo（0） compound [Et4N]3[Mo2（CO）6（μ-OC6H4OCH2C6H5）3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359（2）, b = 18.378（3）, c = 24.952（2） A, β = 102.268（4）°, V = 6882.3（1 6） A^3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm^3, F（000） = 2832 and μ= 0.424 mm^-1 The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections （I 〉 2σ（I））. I contains a [Mo2O3]^3 core in triangular bi-pyralnidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three ,μ-O atoms from C6H5CH2OC6H4O^- bridging ligands. The Mo…Mo distance is 3.30（8） A, indicating no metalmetal bonding. A formation pathway via forming a di-molybdenum（0） di-bridging OR compound [Mo2（μ-OR）2（CO）8]2 has been figured out and the reaction of Mo（CO）6 with alkoxide has also been discussed.

Seasonal differences in sources and formation processes of PM2.5 nitrate in an urban environment of North China

Nitrate(NO_(3)^(−))has been the dominant ion of secondary inorganic aerosols(SIAs)in PM_(2.5) in North China.Tracking the formation mechanisms and sources of particulate nitrate are vital to mitigate air pollution.In this study,PM_(2.5) samples in winter(January 2020)and in summer(June 2020)were collected in Jiaozuo,China,andwater-soluble ions and(δ_(15)N,δ_(18)O)-NO_(3)^(−)were analyzed.The results showed that the increase of NO_(3)^(−)concentrations was the most remarkable with increasing PM_(2.5) pollution level.δ_(18)O-NO_(3)^(−)values for winter samples(82.7‰ to 103.9‰)were close to calculated δ_(18)O-HNO_(3)(103‰±0.8‰)values by N_(2)O_(5) pathway,while δ_(18)O-NO_(3)^(−)values(67.8‰ to 85.7‰)for summer samples were close to calculated δ_(18)O-HNO_(3) values(61‰±0.8‰)by OH oxidation pathway,suggesting that PM_(2.5) nitrate is largely from N_(2)O_(5) pathway inwinter,while is largely from OH pathway in summer.Averaged fractional contributions of P_(N2O5+H2O) were 70% and 39% in winter and summer sampling periods,respectively,those of POH were 30% and 61%,respectively.Higher δ_(15)N-NO_(3)−values for winter samples(3.0‰to 14.4‰)than those for summer samples(-3.7‰to 8.6‰)might be due to more contributions from coal combustion in winter.Coal combustion(31%±9%,25%±9%in winter and summer,respectively)and biomass burning(30%±12%,36%±12%in winter and summer,respectively)were the main sources using Bayesian mixing model.These results provided clear evidence of particulate nitrate formation and sources under different PM_(2.5) levels,and aided in reducing atmospheric nitrate in urban environments.

Precursor compound enabled formation of aqueous-phase CdSe magic-size clusters at room temperature

The formation pathway of aqueous-phase colloidal semiconductor magic-size clusters(MSCs)remains unrevealed.In the present work,we demonstrate,for the first time,a precursor compound(PC)-enabled formation pathway of aqueous-phase CdSe MSCs exhibiting a sharp absorption peaking at about 420 nm(MSC-420).The CdSe MSC-420 is synthesized with CdCl2 and selenourea as the respective Cd and Se sources,and with 3-mercaptopropionic acid or L-cysteine as a ligand.Absorption featureless CdSe PCs form first in the aqueous reaction batches,which transform to MSC-420 in the presence of primary amines.The coordination between primary amine and Cd^(2+)on PCs may be responsible to the PC-to-MSC transformation.Upon increasing the reactant concentrations or decreasing the CdCl_(2)-ligand feed molar ratios,the Cd precursor self-assembles into large aggregates,which may encapsulate the resulting CdSe PCs and inhibit their transformation to MSC-420.The present study sheds essential light on the syntheses and formation mechanisms of nanocrystals.

Thiolated arsenicals in arsenic metabolism: Occurrence,formation, and biological implications

Arsenic（As） is a notoriously toxic pollutant of health concern worldwide with potential risk of cancer induction, but meanwhile it is used as medicines for the treatment of different conditions including hematological cancers. Arsenic can undergo extensive metabolism in biological systems, and both toxicological and therapeutic effects of arsenic compounds are closely related to their metabolism. Recent studies have identified methylated thioarsenicals as a new class of arsenic metabolites in biological systems after exposure of inorganic and organic arsenicals, including arsenite, dimethylarsinic acid（DMAV）, dimethylarsinous glutathione（DMAIIIGS）, and arsenosugars. The increasing detection of thiolated arsenicals,including monomethylmonothioarsonic acid（MMMTAV）, dimethylmonothioarsinic acid（DMMTAV） and its glutathione conjugate（DMMTAVGS）, and dimethyldithioarsinic acid（DMDTAV） suggests that thioarsenicals may be important metabolites and play important roles in arsenic toxicity and therapeutic effects. Here we summarized the reported occurrence of thioarsenicals in biological systems, the possible formation pathways of thioarsenicals, and their toxicity, and discussed the biological implications of thioarsenicals on arsenic metabolism, toxicity, and therapeutic effects.

Characterization of N-nitrosodimethylamine formation from the ozonation of ranitidine

N-nitrosodimethylamine（NDMA） is an emerging disinfection by-product which is formed during water disinfection in the presence of amine-based precursors. Ranitidine, as one kind of amine-based pharmaceuticals, has been identified as NDMA precursor with high NDMA molar conversion during chloramination. This study focused on the characterization of NDMA formation during ozonation of ranitidine. Influences of operational variables（ozone dose, pH value） and water matrix on NDMA generation as well as ranitidine degradation were evaluated. The results indicate high reactivity of ranitidine with ozone.Dimethylamine（DMA） and NDMA were generated due to ranitidine oxidation. High pH value caused more NDMA accumulation. NDMA formation was inhibited under acid conditions（pH ≤ 5） mainly due to the protonation of amines. Water matrix such as HCO-3and humic acid impacted NDMA generation due to UOH scavenging. Compared with UOH,ozone molecules dominated the productions of DMA and NDMA. However, UOH was a critical factor in NDMA degradation. Transformation products of ranitidine during ozonation were identified using gas chromatography–mass spectrometry. Among these products, just DMA and N,N-dimethylformamide could contribute to NDMA formation due to the DMA group in the molecular structures. The NDMA formation pathway from ranitidine ozonation was also proposed.