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Carbohydrate Polymers May 2021The manifold array of saccharide linkages leads to a great variety of polysaccharide architectures, comprising three conformations in aqueous solution: compact sphere,...
The manifold array of saccharide linkages leads to a great variety of polysaccharide architectures, comprising three conformations in aqueous solution: compact sphere, random coil, and rigid rod. This conformational variation limits the suitability of the commonly applied molecular weight cut-off (MWCO) as selection criteria for polysaccharide ultrafiltration membranes, as it is based on globular marker proteins with narrow M and hydrodynamic volume relation. Here we show the effect of conformation on ultrafiltration performance using randomly coiled pullulan and rigid rod-like scleroglucan as model polysaccharides for membrane rejection and molecular weight distribution. Ultrafiltration with a 10 kDa polyethersulfone membrane yielded significant different recoveries for pullulan and scleroglucan showing 1% and 71%, respectively. We found deviations greater than 77-fold between nominal MWCO and apparent M of pullulan and scleroglucan, while recovering over 90% polysaccharide with unchanged M. We anticipate our work as starting point towards an optimized membrane selection for polysaccharide applications.
Topics: Glucans; Membranes, Artificial; Molecular Conformation; Molecular Weight; Polymers; Polysaccharides; Sulfones; Ultrafiltration
PubMed: 33712169
DOI: 10.1016/j.carbpol.2021.117830 -
Pesticide Biochemistry and Physiology Nov 2020In this study, thirty 1,3,4-oxadiazole sulfone derivatives containing 3,4-dichloroisothiazolamide moiety were designed and synthesized, and their antibacterial...
In this study, thirty 1,3,4-oxadiazole sulfone derivatives containing 3,4-dichloroisothiazolamide moiety were designed and synthesized, and their antibacterial activities were evaluated. Bioassay results showed that some compounds exhibited excellent antibacterial activities against Xanthomonas oryzae pv. oryzae (Xoo) and Xanthomonas oryzae pv. oryzicola (Xoc) in vitro and in vivo. Notably, the EC values of compounds 2 and 3 against Xoo were 0.79 and 0.85 μg/mL, respectively, which were superior to those of the control agents isotianil, bismerthiazol, and thiodiazole copper. In addition, in vivo antibacterial activities revealed that the compound 2 at 50 μg/mL possessed protective and curative activities of 43.99% and 41.06% against Xoo, respectively, which were better than positive controls. Furthermore, the preliminary mechanism study disclosed that compound 2 exhibited effective antibacterial activity against Xoo by inhibiting the formation of extracellular polysaccharides from Xoo, increasing cell permeability, and changing the shape of cells. This study suggested that 1,3,4-oxadiazole sulfone derivatives containing 3,4-dichloroisothiazolamide moiety displayed excellent antibacterial activity and could be further explored and developed as commercial pesticides.
Topics: Anti-Bacterial Agents; Microbial Sensitivity Tests; Oryza; Oxadiazoles; Plant Diseases; Sulfones; Xanthomonas
PubMed: 32980058
DOI: 10.1016/j.pestbp.2020.104695 -
ChemMedChem Oct 2020Based on the previously reported potent and selective sulfone hydroxamate inhibitors SC-76276, SC-78080 (SD-2590), and SC-77964, potent MMP inhibitors have been designed...
Based on the previously reported potent and selective sulfone hydroxamate inhibitors SC-76276, SC-78080 (SD-2590), and SC-77964, potent MMP inhibitors have been designed and synthesized to append a boron-rich carborane cluster by employing click chemistry to target tumor cells that are known to upregulate gelatinases. Docking against MMP-2 suggests binding involving the hydroxamate zinc-binding group, key H-bonds by the sulfone moiety with the peptide backbone residues Leu82 and Leu83, and a hydrophobic interaction with the deep P1' pocket. The more potent of the two triazole regioisomers exhibits an IC of 3.7 nM versus MMP-2 and IC of 46 nM versus MMP-9.
Topics: Boron Compounds; Click Chemistry; Enzyme Assays; Humans; Hydroxamic Acids; Ligands; Matrix Metalloproteinase 2; Matrix Metalloproteinase 9; Matrix Metalloproteinase Inhibitors; Molecular Docking Simulation; Sulfones; Zinc
PubMed: 32720425
DOI: 10.1002/cmdc.202000470 -
Biomacromolecules Mar 2023This paper reports the polymerization of tall oil lignin (TOL), starch, and 2-methyl-2-propene-1-sulfonic acid sodium salt (MPSA), a sulfonate-containing monomer, in a...
This paper reports the polymerization of tall oil lignin (TOL), starch, and 2-methyl-2-propene-1-sulfonic acid sodium salt (MPSA), a sulfonate-containing monomer, in a three-component system to generate flocculants for colloidal systems. By utilizing the advanced H, COSY, HSQC, HSQC-TOCSY, and HMBC NMR techniques, it was confirmed that the phenolic substructures of TOL and the anhydroglucose unit of starch were covalently polymerized by the monomer to generate the three-block copolymer. The molecular weight, radius of gyration, and shape factor of the copolymers were fundamentally correlated to the structure of lignin and starch, as well as the polymerization outcomes. The deposition behavior of the copolymer, studied by a quartz crystal microbalance with dissipation (QCM-D) analysis, revealed that the copolymer with a larger molecular weight (ALS-5) deposited more and generated more compact adlayer than the copolymer with a smaller molecular weight on a solid surface. Owing to its higher charge density, molecular weight, and extended coil-like structure, ALS-5 produced larger flocs with faster sedimentation in the colloidal systems, regardless of the extent of agitation and gravitational force. The results of this work provide a new approach to preparing a lignin-starch polymer, i.e., a sustainable biomacromolecule with excellent flocculation performance in colloidal systems.
Topics: Humans; Alkanesulfonates; Flocculation; Lignin; Polymers; Starch
PubMed: 36802502
DOI: 10.1021/acs.biomac.2c01437 -
Applied and Environmental Microbiology Jul 2020Bacterial alkane metabolism is associated with a number of cellular stresses, including membrane stress and oxidative stress, and the limited uptake of charged ions such...
Bacterial alkane metabolism is associated with a number of cellular stresses, including membrane stress and oxidative stress, and the limited uptake of charged ions such as sulfate. In the present study, the genes and in DR1 cells, which encode an alkanesulfonate monooxygenase and a taurine dioxygenase, respectively, were found to be responsible for hexadecanesulfonate (CSOH) and taurine metabolism, and Cbl was experimentally identified as a potential regulator of and expression. The expression of and occurred under sulfate-limited conditions generated during -hexadecane degradation. Interestingly, expression analysis and knockout experiments suggested that both genes are required to protect cells against oxidative stress, including that generated by -hexadecane degradation and HO exposure. Measurable levels of intracellular hexadecanesulfonate were also produced during -hexadecane degradation. Phylogenetic analysis suggested that and are mainly present in soil-dwelling aerobes within the and classes, which suggests that they function as controllers of the sulfur cycle and play a protective role against oxidative stress in sulfur-limited conditions. and , which play a role in the degradation of organosulfonate, were expressed during -hexadecane metabolism and oxidative stress conditions in DR1. Our study confirmed that hexadecanesulfonate was accidentally generated during bacterial -hexadecane degradation in sulfate-limited conditions. Removal of this by-product by SsuD and TauD must be necessary for bacterial survival under oxidative stress generated during -hexadecane degradation.
Topics: Acinetobacter; Alkanes; Alkanesulfonates; Bacterial Proteins; Hydrogen Peroxide; Mixed Function Oxygenases; Oxidative Stress
PubMed: 32503904
DOI: 10.1128/AEM.00692-20 -
Bioorganic Chemistry Dec 2023The synthesis of hitherto unreported 3-sulfenylindole derivatives is achieved from 4-hydroxy-2H-chromene-2-thione (1) and indole (2) by employing an oxidative...
Synthesis of 3-sulfenylindole derivatives from 4-hydroxy-2H-chromene-2-thione and indole using oxidative cross-dehydrogenative coupling reaction and anti-proliferative activity study of some of their sulfone derivatives.
The synthesis of hitherto unreported 3-sulfenylindole derivatives is achieved from 4-hydroxy-2H-chromene-2-thione (1) and indole (2) by employing an oxidative cross-dehydrogenative coupling reaction using a combination of 10 mol% of molecular iodine and 1 equivalent of TBHP in DMSO at room temperature. Then, the 3-sulfenylindole derivatives 3a, 3b, 3d, 3f, 3 h, and 3 k were converted into their corresponding sulfone derivatives because of lead likeness properties. Subsequently, a target prediction and docking study of six sulfone derivatives (5a-f) was performed, and four sulfones, namely 5a, 5d, 5e, and 5f, were selected for further in-vitro studies. The four sulfones mentioned above exhibited prominent anti-proliferative activity on breast cancer (MCF7) cell lines. In addition, this reaction was exergonic through quantum chemical analysis of the mechanistic steps. The salient features of this reaction are mild reaction conditions, good yields, and broad substrate scope.
Topics: Humans; Antineoplastic Agents; Cell Line, Tumor; Drug Screening Assays, Antitumor; Indoles; Molecular Structure; Oxidative Stress; Structure-Activity Relationship; Sulfones; Thiones; Benzopyrans
PubMed: 37813073
DOI: 10.1016/j.bioorg.2023.106900 -
Journal of the American Chemical Society Dec 2022The selective introduction of perfluoro--butyl group (PFtB, the bulkier analogue of CF group) into arenes has long been sought after but remains a formidable task. We...
The selective introduction of perfluoro--butyl group (PFtB, the bulkier analogue of CF group) into arenes has long been sought after but remains a formidable task. We herein report the first general synthetic protocol to realize aromatic perfluoro--butylation. The key to the success is the identification of PFtB phenyl sulfone as a new source of PFtB anion, which reacts with arynes in a highly regioselective manner to afford perfluoro--butylated arenes in high yields. The application of the method is demonstrated by the preparation of sensitive F-labeled NMR probes with an extraordinary resolving ability.
Topics: Sulfones
PubMed: 36475403
DOI: 10.1021/jacs.2c10479 -
Journal of Veterinary Pharmacology and... Jan 2024Toltrazuril (TZR) is currently the only registered chemotherapeutic drug in the European Union for the treatment of Cystoisospora suis. This study investigated the...
Toltrazuril (TZR) is currently the only registered chemotherapeutic drug in the European Union for the treatment of Cystoisospora suis. This study investigated the comparative pharmacokinetics and tissue concentration-time profiles of TZR and its active metabolite, toltrazuril sulfone (TZR-SO ), after oral (per os, p.o.) and intramuscular (i.m.) administration to suckling piglets. Following a single administration of TZR orally at 50 mg/piglet or intramuscularly at 45 mg/piglet, higher concentrations of TZR and TZR-SO were observed in all three investigated tissues after p.o. administration. The mean TZR concentration in serum peaked at 14 μg/mL (34.03 h) and 5.36 μg/mL (120 h), while TZR-SO peaked at 14.12 μg/mL (246 h) and 9.92 μg/mL (330 h) after p.o. and i.m. administration, respectively. TZR was undetectable in the liver after p.o. administration (18 days) and in the jejunum (24 days) after i.m. injection, while TZR-SO was still detectable in all three tissues after 36 days regardless of administration routes. This study showed that p.o. formulation exhibited faster absorption and higher serum/tissue TZR/TZR-SO concentrations than i.m. formulation. Both formulations generated sufficient therapeutic concentrations in the serum and jejunum, and sustained enough time to protect against Cystoisospora suis infection in the piglets.
Topics: Animals; Swine; Coccidiostats; Administration, Oral; Triazines; Sulfones; Injections, Intramuscular
PubMed: 37593974
DOI: 10.1111/jvp.13405 -
Molecules (Basel, Switzerland) Jan 2023Eighteen per-and polyfluoroalkyl substances (PFASs) were investigated in surface waters of four river basins in Portugal (Ave, Leça, Antuã, and Cértima) during the...
Eighteen per-and polyfluoroalkyl substances (PFASs) were investigated in surface waters of four river basins in Portugal (Ave, Leça, Antuã, and Cértima) during the dry and wet seasons. All sampling sites showed contamination in at least one of the seasons. In the dry season, perfluorooctanoate acid (PFOA) and perfluoro-octane sulfonate (PFOS), were the most frequent PFASs, while during the wet season these were PFOA and perfluobutane-sulfonic acid (PFBS). Compounds detected at higher concentrations were PFOS (22.6 ng L) and perfluoro-butanoic acid (PFBA) (22.6 ng L) in the dry and wet seasons, respectively. Moreover, the prospective environmental risks of PFASs, detected at higher concentrations, were evaluated based on the Risk Quotient (RQ) classification, which comprises acute and chronic toxicity. The results show that the RQ values of eight out of the nine PFASs were below 0.01, indicating low risk to organisms at different trophic levels in the four rivers in both seasons, wet and dry. Nevertheless, in the specific case of perfluoro-tetradecanoic acid (PFTeA), the RQ values calculated exceeded 1 for fish (96 h) and daphnids (48 h), indicating a high risk for these organisms. Furthermore, the RQ values were higher than 0.1, indicating a medium risk for fish, daphnids and green algae (96 h).
Topics: Animals; Rivers; Alkanesulfonic Acids; Portugal; Prospective Studies; Water Pollutants, Chemical; Environmental Monitoring; Fluorocarbons; Alkanesulfonates; Fishes
PubMed: 36770878
DOI: 10.3390/molecules28031209 -
Environmental Science & Technology Apr 2023Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and...
Uptake of Per- and Polyfluoroalkyl Substances by Fish, Mussel, and Passive Samplers in Mobile-Laboratory Exposures Using Groundwater from a Contamination Plume at a Historical Fire Training Area, Cape Cod, Massachusetts.
Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and polyfluoroalkyl substances (PFAS) groundwater contamination plume. The potential for PFAS bioconcentration from exposure to the contaminated groundwater, which discharges to surface water bodies, was assessed with mobile-laboratory experiments using groundwater from the contamination plume and a nearby reference location. The on-site continuous-flow 21-day exposures used male and female fathead minnows, freshwater mussels, polar organic chemical integrative samplers (POCIS), and polyethylene tube samplers (PETS) to evaluate biotic and abiotic uptake. The composition of the PFAS-contaminated groundwater was complex and 9 PFAS were detected in the reference groundwater and 17 PFAS were detected in the contaminated groundwater. The summed PFAS concentrations ranged from 120 to 140 ng L in reference groundwater and 6100 to 15,000 ng L in contaminated groundwater. Biotic concentration factors (CF) for individual PFAS were species, sex, source, and compound-specific and ranged from 2.9 to 1000 L kg in whole-body male fish exposed to contaminated groundwater for 21 days. The fish and mussel CF generally increased with increasing fluorocarbon chain length and were greater for sulfonates than for carboxylates. The exception was perfluorohexane sulfonate, which deviated from the linear trend and had a 10-fold difference in CF between sites, possibly because of biotransformation of precursors such as perfluorohexane sulfonamide. Uptake for most PFAS in male fish was linear over time, whereas female fish had bilinear uptake indicated by an initial increase in tissue concentrations followed by a decrease. Uptake of PFAS was less for mussels (maximum CF = 200) than for fish, and mussel uptake of most PFAS also was bilinear. Although abiotic concentration factors were greater than CF, and values for POCIS were greater than for PETS, passive samplers were useful for assessing PFAS that potentially bioconcentrate in fish but are present at concentrations below method quantitation limits in water. Passive samplers also accumulate short-chain PFAS that are not bioconcentrated.
Topics: Animals; Male; Female; Water Pollutants, Chemical; Fishes; Water; Fluorocarbons; Groundwater; Alkanesulfonates; Massachusetts; Polyethylene
PubMed: 36972291
DOI: 10.1021/acs.est.2c06500