Formation of hydrogen bonding network of methane sulfonic acid at low degree of hydration (MSA)m·(H2O)n (m = 1-2 and n = 1-5).

This study employs ab initio calculations based on density functional theory (DFT) to investigate the structural properties, 1H-NMR spectra, and vibrational spectra of methane sulfonic acid (MSA) at low degree of hydration. The findings reveal that energetically stable structures are formed by small clusters consisting of one or two MSA molecules (m = 1 and 2) and one or two water molecules in (MSA)m·(H2O)n (m = 1-2 and n = 1-5).These stable structures arise from the formation of strong cyclic hydrogen bonds between the proton of the hydroxyl (OH) group in MSA and the water molecules. However, clusters containing three or more water molecules (n > 2) exhibit proton transfer from MSA to water, resulting in the formation of ion-pairs composed of CH3SO3- and H3O+species. The measured 1H-NMR spectra demonstrate the presence of hydrogen-bonded interactions between MSA and water, with a single MSA molecule interacting with water molecules. This interaction model accurately represents the hydrogen bonding network, as supported by the agreement between the experimental and calculated NMR chemical shift results.

Green, non-toxic and efficient adsorbent from hazardous ash waste for the recovery of valuable metals and heavy metal removal from waste streams.

As compared to alkali-activated geopolymers with phosphoric acid which may be used in high concentrations resulting in disposal concerns, acid-based geopolymers may have superior properties. A novel green method of converting waste ash to a geopolymer for use in adsorption applications such as water treatment is presented here. We use methanesulfonic acid, a green chemical with high acid strength and biodegradability to form geopolymers from coal and wood fly ashes. The geopolymer is characterized for its physico-chemical properties and tested for heavy metal adsorption. The material specifically adsorbs iron and lead. The geopolymer is coupled to activated carbon forming a composite, which adsorbs silver (precious metal) and manganese (hazardous metal) significantly. The adsorption pattern complies with pseudo-second order kinetics and Langmuir isotherm. Toxicity studies show while activated carbon is highly toxic, the geopolymer and the carbon-geopolymer composite have relatively less toxicity concerns.

Effects of natural and anthropogenic emissions on the composition and toxicity of aerosols in the marine atmosphere.

The impacts of natural dimethyl sulfide (DMS) and ship emissions on marine environments and particulate matter (PM) over the western and southern sea areas around South Korea were studied based on field campaigns from August-September 2017 and May-June 2018 using the Community Multi-scale Air Quality v5.3.2 modeling system. DMS oxidation enhanced the concentrations of both sulfur dioxide (SO2) and sulfate (SO42-) in PM2.5 by 6.2-6.4% and 2.9-3.6%, respectively, in the marine atmosphere during the study period, whereas it slightly decreased nitrate (NO3-) concentrations (by -1.3%), compared to the simulation without DMS oxidation chemistry. Furthermore, ship emissions increased the concentrations of SO42-, NO3-, and NH4+ by 4.5%, 23%, and 7.3%, respectively. Methane sulfonic acid concentration was 0.17 µg m-3, suggesting the importance of the addition channel in the DMS oxidation pathway. The model simulation indicated that ship emissions in the target area contributed dominantly to non-sea-salt SO42-, and the marine DMS emission source was non-negligible. The geographical distribution of PM toxicity (aerosol oxidative potential) was assessed in the marine atmosphere during the study period.

Biogenic aerosol in central East Antarctic Plateau as a proxy for the ocean-atmosphere interaction in the Southern Ocean.

Ten years of data of biogenic aerosol (methane sulfonic acid, MSA, and non-sea salt sulfate, nssSO42-) collected at Concordia Station in the East Antarctic plateau (75° 06' S, 123° 20' E) are interpreted as a function of the Southern Annular Mode (SAM), Chlorophyll-a concentration (Chl-a; a proxy for phytoplankton biomass), sea ice extent and area. It is possible to draw three different scenarios that link these parameters in early, middle, and late summer. In early summer, the biogenic aerosol is significantly correlated to sea ice retreats through the phytoplankton biomass increases. Chl-a shows a significant correlation with nssSO42- in the finest fraction (< 1 µm). In contrast, only Chl-a in West Pacific and Indian Ocean sectors correlates with MSA in the coarse fraction. The transport routes towards the inner Antarctic plateau and aerosol formation processes could explain the different correlation patterns of the two compounds both resulting from the DMS oxidation. In mid-summer, Chl-a concentrations are at the maximum and are not related to sea ice melting. Due to the complexity of transport processes of air masses towards the Antarctic plateau, the MSA concentrations are low and not related to Chl-a concentration. In late summer, MSA and nssSO42- present the highest concentrations in their submicrometric aerosol fraction, and both are significantly correlated with Chl-a but not with the sea ice. In early and mid-summer, the enhanced efficiency of transport processes from all the surrounding oceanic sectors with air masses traveling at low elevation can explain the highest concentrations of nssSO42- and especially MSA. Finally, considering the entire time series, MSA shows significant year-to-year variability. This variability is significantly correlated with SAM but with a different time lag in early (0-month lag) and late summer (4-months lag). This correlation likely occurs through the effect of the SAM on phytoplankton blooms.

Design, synthesis and pharmacological evaluation of 4-(3-chloro-4-(3-cyclopropylthioureido)-2-fluorophenoxy)-7-methoxyquinoline-6-carboxamide (WXFL-152): a novel triple angiokinase inhibitor for cancer therapy.

Angiokinases, such as vascular endothelial-, fibroblast- and platelet-derived growth factor receptors (VEGFRs, FGFRs and PDGFRs) play crucial roles in tumor angiogenesis. Anti-angiogenesis therapy using multi-angiokinase inhibitor has achieved great success in recent years. In this study, we presented the design, synthesis, target identification, molecular mechanism, pharmacodynamics (PD) and pharmacokinetics (PK) research of a novel triple-angiokinase inhibitor WXFL-152. WXFL-152, identified from a series of 4-oxyquinoline derivatives based on a structure-activity relationship study, inhibited the proliferation of vascular endothelial cells (ECs) and pericytes by blocking the angiokinase signals VEGF/VEGFR2, FGF/FGFRs and PDGF/PDGFRß simultaneously in vitro. Significant anticancer effects of WXFL-152 were confirmed in multiple preclinical tumor xenograft models, including a patient-derived tumor xenograft (PDX) model. Pharmacokinetic studies of WXFL-152 demonstrated high favourable bioavailability with single-dose and continuous multi-dose by oral administration in rats and beagles. In conclusion, WXFL-152, which is currently in phase Ib clinical trials, is a novel and effective triple-angiokinase inhibitor with clear PD and PK in tumor therapy.

Effect of sea ice retreat on marine aerosol emissions in the Southern Ocean, Antarctica.

Sea ice retreat in the polar region is expected to increase the emissions of sea salt aerosols and biogenic gases, which may significantly impact the climate by increasing cloud condensation nuclei (CCN) population and changing solar radiation. In this study, aerosol compositions were measured at high-time-resolution (1 h) with an in-situ gas and aerosol composition monitoring system in polynya regions of the Southern Ocean (SO) to access the effects of sea ice concentrations on the sea salt aerosol (SSA) and secondary biogenic aerosol (SBA) in the SO. SSA emissions increased by more than 30% as sea ice concentration decreased from 85% to 29%. However, SSA emissions did not increase monotonically as the sea ice concentration decreased. The highest SSA concentration occurred in drifting sea ice region. Sea ice melting increased SBA concentrations by enhancing the air-sea exchanges of SBA precursor gases and the release of algae from sea ice. Positive correlations between SSA and wind speed were present in different sea ice regions, while SBA didn't reveal an obvious correlation with wind speed in the SO. The impact of wind speed on the SSA emissions were very different, Higher slope value of 41.83 and 35.81 were present in the DSI and SIF region, while the value was only about 16.74 in the SIC region. The results extended the knowledge of the effect of future sea ice retreat on marine aerosol emissions and potential climate changes in the polar region.

Contribution of methane sulfonic acid to new particle formation in the atmosphere.

Methane sulfonic acid (MSA) is present in substantial concentrations in the gas phase over oceans and coastal regions. We present an investigation into the contribution of MSA to new particle formation with the common atmospheric aerosol nucleation precursors including MSA, methanol, formic acid, acetone, dimethylether, formaldehyde, methyl formate, by making use a quantum chemical approach. Density functional theory calculations indicate that these bimolecular complexes are characterized by the presence of strong inter-molecular hydrogen bonds (SOH⋯O) with large binding energies and thermodynamic equilibrium constants. Topological analysis employing quantum theory of atoms in molecules shows that the charge density of the SOH⋯O hydrogen bonds of the MSA complexes falls in the range of hydrogen bonding criteria, but the Laplacian at bond critical points exceeds the range, which is due to the strong hydrogen bonding interactions. In all the studied complexes, the electrostatic interactions are found to be the main attractive force by localized molecular orbital energy decomposition analysis. All these indicate the environmental fate of MSA could play the role of nucleation centers in new particle formation. The effect of the atmospheric heights (0-12 km) was also considered. The Gibbs free energy of formation decreases with the increase of the atmospheric height owing to the decrease of the atmospheric temperature and pressure. The calculated Gibbs free energies of formation within the atmospheric temperature and pressure range could help to understand the atmospheric pollution.

Uncertainty Evaluation in the Determination of Methane Sulfonic Acid in Betahistine Mesylate by Ion Chro-matography / 中国药师

Objective:To establish an ion chromatography method for the determination of methane sulfonic acid in betahistine me-sylate and evaluate the uncertainty in the measurement. Methods: An ion chromatographic column IonPac AS11-HC ( 25 mm × 4. 0 mm,5 μm) was used with 12 mmol·L-1 NaOH as the eluent and an electrical conductivity detector with the suppressor of 30 mV. Results:The results showed that methane sulfonic acid could be detected without any interference. The calibration curve was linear within the range of 10-30 μg·ml-1(r=0.999 9)and the LOQ was 0.116 μg·ml-1. The average recovery was 100.8% (RSD=1. 2%, n=9). Based on the results of experiments, the influencing factors of uncertainty in the measurement were quantitatively eval-uated. The expanded uncertainty was obtained. Conclusion:The method is simple, accurate and selective. It can be used for the de-termination of methane sulfonic acid in betahistine mesylate. Based on the evaluation of uncertainty, the analysis can help reduce the uncertainty in the measurement and improve the accuracy and reliability of the determination.