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Chemosphere Oct 2021Most metal-organic frameworks (MOFs) are synthesized from carboxylate and metal precursors by hydrothermal process, which will consume a large amount of solvent and...
Most metal-organic frameworks (MOFs) are synthesized from carboxylate and metal precursors by hydrothermal process, which will consume a large amount of solvent and carboxylate. To address this issue, a new strategy for Cu-based MOFs was developed, in which the Cu-based MOFs was obtained by using abundant natural polymer (tannic acid) as one of the precursors and using high-energy ball milling to achieve a self-assembly of tannic acid and copper sulfate. Based on this strategy, a novel Cu-based MOFs derivative (CuO@C composite) was synthesized by high-temperature sintering of Cu-based MOFs and used for sulfamerazine (SMR) removal via O activation. The BET specific surface area and average pore size of CuO@C composite were 110.34 m g and 21.06 nm, respectively, which made CuO@C composite had the maximum adsorption capacity (Q) for SMR of 104.65 mg g and favored the subsequent degradation of SMR. The results from XRD and XPS indicated that CuO@C composite contained a lot of Cu and CuO with the sizes of 76.6 nm and 9.8 nm, respectively, which led to its high performance of O activation. The removal efficiency of SMR and 90.2% TOC achieved 100% and 90.2%, respectively in the CuO@C/air system at initial pH of 4.0, air flow rate of 100 mL min, CuO@C dosage of 1 g L and reaction time of 30 min. Reactive species, including HO, OH and O radicals were detected in the CuO@C/air system, and OH and O were mainly responsible for the degradation of SMR.
Topics: Adsorption; Hydrogen Peroxide; Metal-Organic Frameworks; Sulfamerazine
PubMed: 33971422
DOI: 10.1016/j.chemosphere.2021.130678 -
Journal of Hazardous Materials Mar 2023Sulfate radical (SO)-based heterogonous advanced oxidation processes (AOPs) show promising potential to degrade emerging contaminants, however, regulating the electron...
Modulating the electron structure of Co-3d in CoO/WO for boosting peroxymonosulfate activation and degradation of sulfamerazine: Roles of high-valence W and rich oxygen vacancies.
Sulfate radical (SO)-based heterogonous advanced oxidation processes (AOPs) show promising potential to degrade emerging contaminants, however, regulating the electron structure of a catalyst to promote its catalytic activity is challenging. Herein, a hybrid that consists of CoO nanocrystals decorated on urchin-like WO (CoO/WO) with high-valence W and rich oxygen vacancies (OVs) used to modulate the electronic structure of Co-3d was prepared. The CoO/WO that developed exhibited high catalytic activity, activating peroxymonosulfate (PMS), and degrading sulfamerazine (SMR). With the use of CoO/WO, 100 % degradation of SMR was achieved within 2 min, at a pH of 7, with the reaction rate constant k = 3.09 min. Both characterizations and density functional theory (DFT) calculations confirmed the formation of OVs and the promotion of catalytic activity. The introduction of WO greatly regulated the electronic structure of CoO. Specifically, the introduction of high-valence W enabled the Co-3d band centre to be closer to the Fermi level and enhanced electrons (e) transfer ability, while the introduction of OVs-Co in CoO promoted the activity of electrons in the Co-3d orbital and the subsequent catalytic reaction. The reactive oxygen species (ROS) were identified as •OH, SO, and singlet oxygen (O) by quenching experiments and electron spin resonance (EPR) analysis. The DFT calculation using the Fukui index indicated the reactive sites in SMR were available for an electrophilic attack, and three degradation pathways were proposed.
PubMed: 37055981
DOI: 10.1016/j.jhazmat.2022.130576 -
Journal of Materials Chemistry. B Nov 2018A significant research focus in the pharmaceutical industry is on methods to improve drug uptake into the body by increased dissolution of poorly water soluble active...
A significant research focus in the pharmaceutical industry is on methods to improve drug uptake into the body by increased dissolution of poorly water soluble active pharmaceutical ingredients (APIs) or sustained drug release behavior, which results in higher overall uptake. Production of higher energy, higher solubility polymorphs is one approach to address this problem. Here we utilize natural materials, cellulose nanocrystals (CNCs), that have a high surface area covered with readily-modified hydroxyl groups to form organogels that promote API crystallization into polymorphs that differ from the as-received materials. We form the gels by oxidizing the CNCs and mixing them with an amine-containing surfactant, octadecylamine (ODA) in dimethylsulfoxide (DMSO) and we optimize the composition and preparation conditions for these gels. The APIs, sulfamethoxazole, sulfapyridine, and sulfamerazine, are added to the mixture prior to the gelation step and are expected to localize in the solvophobic regions of the physical gel and crystallize. We found that sulfamethoxazle recovered from the gels is in the amorphous state, while sulfapyridine crystallizes into a mixture of forms I, III and IV, and sulfamerazine crystallizes into forms I and II, which are different from the as-received materials. This system shows promise for rational design of nanocellulose organogel supports for heterogeneous crystallization of pharmaceutical materials with desired polymorphs.
PubMed: 32254641
DOI: 10.1039/c8tb01554f -
Journal of Hazardous Materials Feb 2020Here, TPB (triphenylbenzene) - DMTP (dimethoxyterephthaldehyde) -COF was prepared, characterized and used as effective adsorbent for the removal of sulfamerazine (SMT)...
Here, TPB (triphenylbenzene) - DMTP (dimethoxyterephthaldehyde) -COF was prepared, characterized and used as effective adsorbent for the removal of sulfamerazine (SMT) from aqueous solution. Its adsorption characteristics and mechanism were explored. With large channel (∼3.3 nm), high specific surface area (2115 m/g), and high crystallite, TPB-DMTP-COF showed high adsorption capacity (209 mg/g), fast adsorption equilibrium (80 min), and good reusability. Natural pH condition was optimal for its adsorption capacity, while electrostatic repulsion between TPB-DMTP-COF and SMT accounted for the low adsorption performance at acidic or alkaline conditions. According to the DFT method, SMT molecules adsorbed in the pore-sites of COFs via C-H···π interaction was the predominant and stable adsorption configuration accounting for the efficient removal of SMT in large quantity. This study revealed the great adsorption potential of COFs skeleton itself in the application of environmental remediation.
PubMed: 31505428
DOI: 10.1016/j.jhazmat.2019.121126 -
Angewandte Chemie (International Ed. in... Nov 2020The last decade has witnessed a burgeoning of new methods for the enantioselective vicinal difunctionalization of alkenes initiated by electrophilic sulfenyl group... (Review)
Review
The last decade has witnessed a burgeoning of new methods for the enantioselective vicinal difunctionalization of alkenes initiated by electrophilic sulfenyl group transfer. The addition of sulfenium ions to alkenes results in the generation of chiral, non-racemic thiiranium ions. These highly reactive intermediates are susceptible to attack by a myriad of nucleophiles in a stereospecific ring-opening event to afford anti 1,2-sulfenofunctionalized products. The practical application of sulfenium ion transfer has been enabled by advances in the field of Lewis base catalysis. This Review will chronicle the initial discovery and characterization of thiiranium ion intermediates followed by the determination of their configurational stability and the challenges of developing enantioselective variants. Once the framework for the reactivity and stability of thiiranium ions has been established, a critical analysis of pioneering studies will be presented. Finally, a comprehensive discussion of modern synthetic applications will be categorized around the type of nucleophile employed for sulfenofunctionalization.
Topics: Alkenes; Catalysis; Stereoisomerism; Sulfamerazine
PubMed: 32452077
DOI: 10.1002/anie.202005920 -
Journal of Pharmaceutical Sciences Feb 2022Drug product performance is polymorph specific, and it is imperative that solid phase stability be monitored throughout the manufacturing process to ensure final product...
Drug product performance is polymorph specific, and it is imperative that solid phase stability be monitored throughout the manufacturing process to ensure final product quality and performance. PXRD remains the gold standard for polymorph identification, but due to a growing interest in continuous manufacturing, a need has emerged for alternative process analytical technologies (PATs) that can provide fast, reliable, and non-destructive polymorph discrimination amenable to in situ process monitoring. Herein we demonstrate an original application of powder Brillouin light scattering (p-BLS) for the discrimination of polymorphic molecular solids. We hypothesize that the anisotropic sound velocities directly reflect the strength and orientation of the intermolecular forces in molecular solids. Redistributing these forces upon polymorphic conversion should thus clearly be reflected in the sound frequency distributions obtained by p-BLS. To test this hypothesis, three model compounds - resorcinol, sulfamerazine and furosemide - were selected. Distinct, polymorph-specific, acoustic frequency distributions were observed, and these p-BLS spectra were interpreted using a hydrogen-bond analysis and energy frameworks calculated from CrystalExplorer. In conclusion, this study clearly demonstrates that the sound frequencies measured in p-BLS are sensitive to the interaction forces in molecular solids, and p-BLS is a novel optical technique capable of reliably discriminating polymorphs. Extending this study further, we fully expect that many pharmaceutically relevant processes - e.g., hydrate formation, co-crystallization, or amorphous instability - could potentially be monitored using p-BLS.
Topics: Anisotropy; Crystallization; Light; Mechanical Phenomena; Powders
PubMed: 34516989
DOI: 10.1016/j.xphs.2021.09.010 -
Environmental Pollution (Barking, Essex... Nov 2023Sulfadiazine and its derivatives (sulfonamides, SAs) could induce distinct biotoxic, metabolic and physiological abnormalities, potentially due to their subtle...
Sulfadiazine and its derivatives (sulfonamides, SAs) could induce distinct biotoxic, metabolic and physiological abnormalities, potentially due to their subtle structural differences. This study conducted an in-depth investigation on the interactions between SA homologues, i.e. sulfadiazine (SD), sulfamerazine (SD1), and sulfamethazine (SD2), and the key metabolic enzyme (glycosyltransferase, GT) in rice (Oryza sativa L.). Untargeted screening of SA metabolites revealed that GT-catalyzed glycosylation was the primary transformation pathway of SAs in rice. Molecular docking identified that the binding sites of SAs on GT (D0TZD6) were responsible for transferring sugar moiety to synthesize polysaccharides and detoxify SAs. Specifically, amino acids in the GT-binding cavity (e.g., GLY487 and CYS486) formed stable hydrogen bonds with SAs (e.g., the sulfonamide group of SD). Molecular dynamics simulations revealed that SAs induced conformational changes in GT ligand binding domain, which was supported by the significantly decreased GT activity and gene expression level. As evidenced by proteomics and metabolomics, SAs inhibited the transfer and synthesis of sugar but stimulated sugar decomposition in rice leaves, leading to the accumulation of mono- and disaccharides in rice leaves. While the differences in the increased sugar content by SD (24.3%, compared with control), SD1 (11.1%), and SD2 (6.24%) can be attributed to their number of methyl groups (0, 1, 2, respectively), which determined the steric hindrance and hydrogen bonds formation with GT. This study suggested that the disturbances on crop sugar metabolism by homologues contaminants are determined by the interaction between the contaminants and the target enzyme, and are greatly dependent on the steric hindrance effects contributed by their side chains. The results are of importance to identify priority pollutants and ensure crop quality in contaminated fields.
Topics: Oryza; Glycosyltransferases; Molecular Docking Simulation; Sulfanilamide; Sulfadiazine; Sulfonamides; Metabolic Diseases; Sugars
PubMed: 37669699
DOI: 10.1016/j.envpol.2023.122486 -
Journal of Environmental Management Nov 2021In this work the presence of different pharmaceuticals at Doñana National Park (Spain) and their main entry sources (input source or entry points) have been stated over...
In this work the presence of different pharmaceuticals at Doñana National Park (Spain) and their main entry sources (input source or entry points) have been stated over the 2011-2016 years period. Twenty-three selected pharmaceuticals (corresponding to eight therapeutic families) were evaluated in crayfish and water samples from Doñana National Park (Spain) (six sampling points selected in order to cover different possible pollution sources into and surrounding the Park). The multiresidue determination was carried out using enzymatic-microwave assisted extraction prior to high performance liquid chromatography mass spectrometry detection. Sulphonamides (sulfadiazine, sulfamerazine, sulfamethazine, and sulfamethoxazole); trimethoprim, an antibiotic that is frequently co-administered with sulfamethoxazole; amphenicols (chloramphenicol, florfenicol and thiamphenicol); fluoroquinolones (ciprofloxacin, enrofloxacin, flumequine, danofloxacin, gatifloxacin, norfloxacin, marbofloxacin and grepafloxacin); penicillins (amoxicillin); tetracyclines (chlortetracycline and oxytetracycline); non-steroidal anti-inflammatory drugs (salicylic acid and ibuprofen); beta-blocker drugs (atenolol); and antiepileptics (carbamazepine) were analysed. Ciprofloxacin, ibuprofen, salicylic acid, flumequine, and carbamazepine were detected and/or quantified at some of the selected sampling points. A clear ecotoxicological risk to the ecosystem was demonstrated from the occurrence of ciprofloxacin in samples obtained after the punctual and massive presence of people inside the Park. Furthermore, flumequine and carbamazepine have been detected in Procambarus clarkii specimens in concentrations around 30 ng g and 14 ng g, respectively, and their occurrence in the specimens could indicate the persistence of the discharge sources. The main source of pharmaceuticals into the Park might be the livestock farming activities, and the influence of urban wastewaters from surrounding villages does not seem to be very important.
Topics: Animals; Astacoidea; Biota; Ecosystem; Environmental Monitoring; Humans; Parks, Recreational; Pharmaceutical Preparations; Spain; Water Pollutants, Chemical
PubMed: 34298344
DOI: 10.1016/j.jenvman.2021.113314 -
The Science of the Total Environment Aug 2023Sulfamerazine (SM) is a commonly used antibiotic and have been widely used to control various bacterial infectious diseases. The structural composition of colored...
Sulfamerazine (SM) is a commonly used antibiotic and have been widely used to control various bacterial infectious diseases. The structural composition of colored dissolved organic matter (CDOM) is known to be a major factor that influences the indirect photodegradation of SM, yet the influence mechanism remains unknown. In order to understand this mechanism, CDOM from different sources was fractionated using ultrafiltration and XAD resin, and characterized using UV-vis absorption and fluorescence spectroscopy. The indirect photodegradation of SM in these CDOM fractions was then investigated. Humic acid (JKHA) and Suwannee River natural organic matter (SRNOM) were used in this study. The results showed that CDOM could be divided into four components (three humic-like components and one protein-like component), and terrestrial humic-like components C1 and C2 were found to be the main components that promote SM indirect photodegradation due to their high aromaticity. The indirect photodegradation of SM was much faster in low molecular weight (MW) solutions, whose structures were dominated by greater aromaticity and terrestrial fluorophores in JKHA and higher terrestrial fluorophores in SRNOM. The HIA and HIB fractions of SRNOM contained large aromaticity and high fluorescence intensities of C1 and C2, resulting in a greater indirect photodegradation rate of SM. The HOA and HIB fractions of JKHA had abundant terrestrial humic-like components and contributed more to SM indirect photodegradation.
Topics: Sulfamerazine; Dissolved Organic Matter; Organic Chemicals; Photolysis; Anti-Bacterial Agents; Rivers; Spectrometry, Fluorescence; China
PubMed: 37201832
DOI: 10.1016/j.scitotenv.2023.164231 -
Archiv Der Pharmazie Feb 2021The novel compounds with the chemical structure of N-({4-[N'-(substituted)sulfamoyl]phenyl}carbamothioyl)benzamide (1a-g) and...
The novel compounds with the chemical structure of N-({4-[N'-(substituted)sulfamoyl]phenyl}carbamothioyl)benzamide (1a-g) and 4-fluoro-N-({4-[N'-(substituted)sulfamoyl]phenyl}carbamothioyl)benzamide (2a-g) were synthesized as potent and selective human carbonic anhydrase (hCA) I and hCA II candidate inhibitors. The aryl part was changed to sulfacetamide, sulfaguanidine, sulfanilamide, sulfathiazole, sulfadiazine, sulfamerazine, and sulfametazine. The K values of compounds 1a-g were in the range of 20.73 ± 4.32 to 59.55 ± 13.07 nM (hCA I) and 5.69 ± 0.43 to 44.81 ± 1.08 nM (hCA II), whereas the K values of compounds 2a-g were in the range of 13.98 ± 2.57 to 75.74 ± 13.51 nM (hCA I) and 8.15 ± 1.5 to 49.86 ± 6.18 nM (hCA II). Comparing the K values of the final compounds and acetazolamide, compound 1c with the sulfanilamide moiety (K = 5.69 ± 0.43 nM, 8.8 times) and 2f with the sulfamerazine moiety (K = 8.15 ± 1.5 nM, 6.2 times) demonstrated promising and selective inhibitory effects against the hCA II isoenzyme, the main target protein in glaucoma. Furthermore, compounds 1d (K = 20.73 ± 4.32, 4 times) and 2d (K = 13.98 ± 2.57, 5.9 times), which have the sulfathiazole moiety, were found as potent hCA I inhibitors. Compounds 1c and 2f can be considered as the lead compounds determined in the present study, which can be investigated further to alleviate glaucoma symptoms.
Topics: Benzamides; Carbonic Anhydrase I; Carbonic Anhydrase II; Carbonic Anhydrase Inhibitors; Dose-Response Relationship, Drug; Humans; Molecular Structure; Structure-Activity Relationship; Sulfonamides; Thiourea
PubMed: 33043495
DOI: 10.1002/ardp.202000230