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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 314: 124207, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38554691

RESUMO

In the current work, sulfur and nitrogen co-doped carbon dots (S,N-CDs) as simple, sensitive, and selective turn-off fluorescent nanosensors were utilized for analysis of three phenothiazine derivatives, including acetophenazine (APZ), chlorpromazine (CPH), and promethazine (PZH). S,N-CDs were synthesized through a green one-pot microwave-assisted technique using widely available precursors (thiourea and ascorbic acid). HRTEM, EDX, FTIR spectroscopy, UV-Vis absorption spectroscopy, and fluorescence spectroscopy were used to characterize the as-synthesized CDs. When excited at 330 nm, the carbon dots produced a maximum emission peak at 410 nm. The cited drugs statically quenched the S,N-CDs fluorescence as revealed by the Stern-Volmer equation. The current method represents the first spectrofluorimetric approach for the determination of the studied drugs without the need for chemical derivatization or harsh reaction conditions. The importance of the proposed work is magnified as the cited drugs do not have any fluorescent properties. The fluorescence of the developed sensor exhibited a linear response to APZ, CPH, and PZH in the concentration ranges of 5.0-100.0, 10.0-100.0, and 10.0-200.0 µM with detection limits of 1.53, 1.66, and 2.47 µM, respectively. The developed fluorescent probes have the advantages of rapidity and selectivity for APZ, CPH, and PZH analysis in tablets with acceptable % recoveries of (98.06-101.66 %). Evaluation of the method's greenness was performed using the Complementary Green Analytical Procedure Index (ComplexGAPI) and Analytical GREEnness metric (AGREE) metrics, indicating that the method is environmentally friendly. Validation of the proposed method was performed according to ICHQ2 (R1) guidelines.


Assuntos
Antipsicóticos , Pontos Quânticos , Corantes Fluorescentes/química , Pontos Quânticos/química , Fenotiazinas , Carbono/química , Nitrogênio/química , Enxofre/química
2.
Spectrochim Acta A Mol Biomol Spectrosc ; 313: 124126, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38490122

RESUMO

Large amount of sulphur is released by the combustion of fossil fuels in the form of SoX which affects human health and leads to acid rain. To overcome this issue, it is essential to eliminate sulphur moieties from heterocyclic organo-sulphur compounds like Dibenzothiophene (DBT) present in the petrol. In this study Surface enhanced Raman scattering (SERS) spectroscopy is used to analyze the desulfurizing activity of Tsukamurella paurometabola bacterial strain. The most prominent SERS peaks observed at 791, 837, 944 and 1032 cm-1, associated to C-S stretching, are solely observed in dibenzothiophene and its metabolite-I (DBTS) but absent in 2-Hydroxybiphenyl (metabolite-II) and extraction sample of supernatant as a result of biodesulfurization. Moreover, the SERS peaks observed at 974 (characteristic peak of benzene ring) and 1015 cm-1 is associated to C-C ring breathing while 1642 and 1655 cm-1 assigned to CC bonds of aromatic ring. These peaks are only observed in 2-Hydroxybiphenyl (metabolite-II) and extraction sample of supernatant as a result of biodesulfurization. Notably, these peaks are absent in the Dibenzothiophene and its metabolite-I which indicate that aromatic ring is carrying sulfur in this fraction. Moreover, multivariate data analytical tools like principal component analysis (PCA) and PCA-loadings are applied to further differentiate between dibenzothiophene and its metabolites that are Dibenzothiophene sulphone (metabolite-I) and 2-Hydroxybiphenyl (metabolite-II).


Assuntos
Actinobacteria , Compostos de Bifenilo , Análise Espectral Raman , Enxofre , Tiofenos , Humanos , Enxofre/química , Biodegradação Ambiental
3.
J Phys Chem Lett ; 15(13): 3478-3485, 2024 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-38513124

RESUMO

We propose a novel approach for detecting the binding between proteins making use of the anomalous diffraction of natively present heavy elements, e.g., sulfurs, inside molecular three-dimensional structures. In particular, we analytically and numerically show that the diffraction patterns produced by the anomalous scattering of the sulfur atoms in a given direction depend additively on the relative distances between all couples of sulfur atoms. Thus, the differences in the patterns produced by bound proteins with respect to their nonbonded states can be exploited to rapidly assess protein complex formation. On the basis of our results, we suggest a possible experimental procedure for detecting protein-protein binding. Overall, the completely label-free and rapid method we propose may be readily extended to probe interactions on a large scale, thus paving the way for the development of a novel field of research based on a synchrotron light source.


Assuntos
Proteínas , Síncrotrons , Cristalografia por Raios X , Modelos Moleculares , Proteínas/química , Enxofre/química
4.
Bioresour Technol ; 396: 130418, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38325611

RESUMO

A sulfur-based biofilter enhanced by phosphate modified activated carbon as particle electrodes was constructed to simultaneously remove total nitrogen (TN) and estrogen from low carbon-to-nitrogen ratio (C/N) wastewater containing 1 mg/L 17-alpha-ethinylestradiol (EE2). Results showed that the enhanced biofilter achieved outstanding performance in EE2 removal (93.2 %) and TN reduction (effluent < 5 mg/L), demonstrating robustness against C/N fluctuations. It was noteworthy that it successfully reduced both acute toxicity (59.5 %) and estrogenic activity (88.6 %). Comprehensive characterization investigations and microbial community structure analysis revealed that enhanced electron transfer and increased microbial abundance likely contributed to improved biofilter performance. Core microorganisms, such as Pseudomonas and Chryseobacterium were identified as key contributors to synergistic estrogen degradation and denitrification. This study presented a feasible and promising strategy of combined process with three-dimensional electrodes and sulfur-based biofilter, highlighting substantial potential for advanced purification and safe reuse of wastewater.


Assuntos
Desnitrificação , Águas Residuárias , Nitrogênio , Reatores Biológicos , Enxofre/química , Eletrólise , Nitratos
5.
Int J Biol Macromol ; 262(Pt 2): 130106, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38346628

RESUMO

An eco-friendly antimicrobial sulfur quantum dot scale inhibitor (CMC-SQDs) synthesized using carboxymethyl cellulose (CMC) showed strong inhibition of calcium sulfate (CaSO4) at a concentration just below 1 mg/L, with an inhibition efficiency exceeding 99 %. However, the precise interaction process between CMC-SQDs and CaSO4 remains unclear. This article investigates the effectiveness of SQDs in inhibiting the formation of CaSO4 and calcium carbonate (CaCO3) scales. Through static scale inhibition tests, molecular dynamics simulations, and quantum chemical calculations, the study aims to elucidate the different impacts of CMC-SQDs on CaSO4 and CaCO3 scale formation. The research focuses on understanding the relationship between the structural activity of CMC-SQDs and their scale-inhibiting performance and delving into the underlying mechanisms of scale inhibition. The findings describe the role of SQDs in a water-based solution, acting as persistent "nanodusts" that interact with calcium (Ca2+) ions and sulfate ions. CMC forms complexes with Ca2+ ions, and the presence of SQDs enhances the van der Waals force, indirectly increasing the resistance of associated ions and the binding energy on the surface of precipitated gypsum. Conversely, SQDs exhibit weak surface stability and have minimal binding energy when interacting with calcite, leading to limited occupation of available adsorption sites.


Assuntos
Carbonato de Cálcio , Pontos Quânticos , Carbonato de Cálcio/química , Sulfato de Cálcio/química , Carboximetilcelulose Sódica/química , Íons , Enxofre/química
6.
Molecules ; 29(3)2024 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-38338446

RESUMO

Ophiopogonis Radix (OR) is a traditional Chinese medicine. In recent years, in order to achieve the purpose of drying, bleaching, sterilizing and being antiseptic, improving appearance, and easy storage, people often use sulfur fumigation for its processing. However, changes in the chemical composition of medicinal herbs caused by sulfur fumigation can lead to the transformation and loss of potent substances. Therefore, the development of methods to rapidly reveal the chemical transformation of medicinal herbs induced by sulfur fumigation can guarantee the safe clinical use of medicines. In this study, a combined full scan-parent ions list-dynamic exclusion acquisition-diagnostic product ions analysis strategy based on UHPLC-LTQ-Orbitrap MS was proposed for the analysis of steroidal saponins and their transformed components in sulfur-fumigated Ophiopogonis Radix (SF-OR). Based on precise mass measurements, chromatographic behavior, neutral loss ions, and diagnostic product ions, 286 constituents were screened and identified from SF-OR, including 191 steroidal saponins and 95 sulfur-containing derivatives (sulfates or sulfites). The results indicated that the established strategy was a valuable and effective analytical tool for comprehensively characterizing the material basis of SF-OR, and also provided a basis for potential chemical changes in other sulfur-fumigated herbs.


Assuntos
Medicamentos de Ervas Chinesas , Plantas Medicinais , Saponinas , Humanos , Cromatografia Líquida de Alta Pressão/métodos , Enxofre/química , Plantas Medicinais/química , Fumigação/métodos , Sulfitos
7.
J Inorg Biochem ; 253: 112487, 2024 04.
Artigo em Inglês | MEDLINE | ID: mdl-38306887

RESUMO

Metal-dependent, nicotine adenine dinucleotide (NAD+)-dependent formate dehydrogenases (FDHs) are complex metalloenzymes coupling biochemical transformations through intricate electron transfer pathways. Rhodobacter capsulatus FDH is a model enzyme for understanding coupled catalysis, in that reversible CO2 reduction and formate oxidation are linked to a flavin mononuclotide (FMN)-bound diaphorase module via seven iron-sulfur (FeS) clusters as a dimer of heterotetramers. Catalysis occurs at a bis-metal-binding pterin (Mo) binding two molybdopterin guanine dinucleotides (bis-MGD), a protein-based Cys residue and a participatory sulfido ligand. Insights regarding the proposed electron transfer mechanism between the bis-MGD and the FMN have been complicated by the discovery that an alternative pathway might occur via intersubunit electron transfer between two [4Fe4S] clusters within electron transfer distance. To clarify this difference, the redox potentials of the bis-MGD and the FeS clusters were determined via redox titration by EPR spectroscopy. Redox potentials for the bis-MGD cofactor and five of the seven FeS clusters could be assigned. Furthermore, substitution of the active site residue Lys295 with Ala resulted in altered enzyme kinetics, primarily due to a more negative redox potential of the A1 [4Fe4S] cluster. Finally, characterization of the monomeric FdsGBAD heterotetramer exhibited slightly decreased formate oxidation activity and similar iron-sulfur clusters reduced relative to the dimeric heterotetramer. Comparison of the measured redox potentials relative to structurally defined FeS clusters support a mechanism by which electron transfer occurs within a heterotetrameric unit, with the interfacial [4Fe4S] cluster serving as a structural component toward the integrity of the heterodimeric structure to drive efficient catalysis.


Assuntos
Formiato Desidrogenases , NAD , NAD/química , Formiato Desidrogenases/química , Elétrons , Oxirredução , Ferro/química , Enxofre/química , Formiatos
8.
Sci Total Environ ; 914: 169857, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38190912

RESUMO

Flue gases are the gases which are produced from industries related to chemical manufacturing, petrol refineries, power plants and ore processing plants. Along with other pollutants, sulfur present in the flue gas is detrimental to the environment. Therefore, environmentalists are concerned about its removal and recovery of resources from flue gases due to its activation ability in the atmosphere to transform into toxic substances. This review is aimed at a critical assessment of the techniques developed for resource recovery from flue gases. The manuscript discusses various bioreactors used in resource recovery such as hollow fibre membrane reactor, rotating biological contractor, sequential batch reactor, fluidized bed reactor, entrapped cell bioreactor and hybrid reactors. In conclusion, this manuscript provides a comprehensive analysis of the potential of thermotolerant and thermophilic microbes in sulfur removal. Additionally, it evaluates the efficacy of a multi-enzyme engineered bioreactor in this process. Furthermore, the study introduces a groundbreaking sustainable model for elemental sulfur recovery, offering promising prospects for environmentally-friendly and economically viable sulfur removal techniques in various industrial applications.


Assuntos
Poluentes Atmosféricos , Poluentes Ambientais , Gases/química , Enxofre/química , Reatores Biológicos
9.
J Am Chem Soc ; 146(3): 1860-1873, 2024 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-38215281

RESUMO

Biotin synthase (BioB) is a member of the Radical SAM superfamily of enzymes that catalyzes the terminal step of biotin (vitamin B7) biosynthesis, in which it inserts a sulfur atom in desthiobiotin to form a thiolane ring. How BioB accomplishes this difficult reaction has been the subject of much controversy, mainly around the source of the sulfur atom. However, it is now widely accepted that the sulfur atom inserted to form biotin stems from the sacrifice of the auxiliary 2Fe-2S cluster of BioB. Here, we bioinformatically explore the diversity of BioBs available in sequence databases and find an unexpected variation in the coordination of the auxiliary iron-sulfur cluster. After in vitro characterization, including the determination of biotin formation and representative crystal structures, we report a new type of BioB utilized by virtually all obligate anaerobic organisms. Instead of a 2Fe-2S cluster, this novel type of BioB utilizes an auxiliary 4Fe-5S cluster. Interestingly, this auxiliary 4Fe-5S cluster contains a ligated sulfide that we propose is used for biotin formation. We have termed this novel type of BioB, Type II BioB, with the E. coli 2Fe-2S cluster sacrificial BioB representing Type I. This surprisingly ubiquitous Type II BioB has implications for our understanding of the function and evolution of Fe-S clusters in enzyme catalysis, highlighting the difference in strategies between the anaerobic and aerobic world.


Assuntos
Proteínas de Escherichia coli , Proteínas Ferro-Enxofre , Escherichia coli/metabolismo , Biotina/química , Proteínas de Escherichia coli/química , Enxofre/química , Sulfurtransferases/metabolismo , Proteínas Ferro-Enxofre/química
10.
J Environ Manage ; 353: 120173, 2024 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-38280249

RESUMO

Morphological regulation and defect engineering are efficient methods for photocatalytic technology by improving photon absorption and electron dissociation. Herein, In2S3-x hollow microtubes with S-vacancies (MIS) were fabricated via a simple solvothermal reaction using In-based metal-organic frameworks (In-MOFs) as a precursor. Experimental results demonstrate that the hollow structure and optimal S-vacancies can jointly accelerate the photocatalytic reaction, attributed to a larger specific surface area, more active sites, and faster electron transfer efficiency. The champion MIS(2) displayed significantly better photocatalytic activity for Cr(VI) reduction and tetracycline (TC) degradation. The Cr(VI) reduction rate by MIS(2) is 3.67 and 2.82 times higher than those of optimal In2S3 template-free (HIS(2)) and MIS(1) with poor S-vacancies, respectively. The removal efficiency of TC by MIS(2) is 1.37 and 1.15 times higher than those of HIS(2) and MIS(1). Further integration of MIS(2) with aerogel simplifies the recovery process significantly.


Assuntos
Cromo , Luz , Cromo/química , Tetraciclina , Antibacterianos , Enxofre/química
11.
Anal Biochem ; 687: 115458, 2024 04.
Artigo em Inglês | MEDLINE | ID: mdl-38182032

RESUMO

In the late 1970s, sulfane sulfur was defined as sulfur atoms covalently bound only to sulfur atoms. However, this definition was not generally accepted, as it was slightly vague and difficult to comprehend. Thus, in the early 1990s, it was defined as "bound sulfur," which easily converts to hydrogen sulfide upon reduction with a thiol-reducing agent. H2S-related bound sulfur species include persulfides (R-SSH), polysulfides (H2Sn, n ≥ 2 or R-S(S)nS-R, n ≥ 1), and protein-bound elemental sulfur (S0). Many of the biological effects currently associated with H2S may be attributed to persulfides and polysulfides. In the 20th century, quantitative determination of "sulfane sulfur" was conventionally performed using a reaction called cyanolysis. Several methods have been developed over the past 30 years. Current methods used for the detection of H2S and polysulfides include colorimetric assays for methylene blue formation, sulfide ion-selective or polarographic electrodes, gas chromatography with flame photometric or sulfur chemiluminescence detection, high-performance liquid chromatography analysis with fluorescent derivatization of sulfides, liquid chromatography with tandem mass spectrometry, the biotin switch technique, and the use of sulfide or polysulfide-sensitive fluorescent probes. In this review, we discuss the methods reported to date for measuring sulfane sulfur and the results obtained using these methods.


Assuntos
Sulfetos , Enxofre , Cromatografia Gasosa-Espectrometria de Massas , Sulfetos/química , Enxofre/química
12.
Talanta ; 269: 125461, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38056416

RESUMO

Gastrodia elata Bl. is a widely used traditional Chinese medicine known for its medicinal properties. However, during the drying process, G. elata is often fumigated with sulfur to prevent corrosion and improve its appearance. Sulfur-fumigation can result in a reduction in the effective components of the herb and can also be hazardous to human health due to the remaining sulfur dioxide. Sulfur-fumigation of G. elata poses a significant challenge to both end-users and researchers. The detection of p-hydroxybenzyl hydrogen sulfite (p-HS) is a useful tool in determining whether G. elata has been fumigated with sulfur. Unfortunately, the current method for detecting p-HS is costly and requires sophisticated instruments. Therefore, there is a need to develop a more cost-effective and user-friendly method for the detection of p-HS. This study utilized the Capture-SELEX technique to screen high-affinity aptamers for p-HS, which were subsequently characterized by isothermal titration calorimetry (ITC). An aptamer sequence (seq 6) with a high affinity of Kd = 26.5 µM was obtained following 8 rounds of selection against p-HS. With the aptamer serving as the recognition element and gold nanoparticles as the colorimetric indicator, a simple and efficient colorimetric sensor was developed for the specific detection of p-HS. This detection method exhibited a limit of detection of 1 µg/ml, while the p-HS recoveries demonstrated a range of between 88.5 % and 105 % for samples of G. elata obtained in the market. In summary, the aptamer exhibited a high affinity for p-HS, and the sensor developed through the use of a colloidal gold detector based on nucleic acid aptamer can be utilized for rapid detection of sulfur-fumigated G. elata. With these findings, this research paper provides valuable scientific insights and highlights significant potential for future studies in this area.


Assuntos
Medicamentos de Ervas Chinesas , Gastrodia , Nanopartículas Metálicas , Humanos , Gastrodia/química , Medicamentos de Ervas Chinesas/química , Ouro , Enxofre/química
13.
Water Res ; 249: 120898, 2024 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-38086206

RESUMO

Biological sulfide production processes mediated by sulfate/sulfur reduction have gained attention for metal removal from industrial wastewater (e.g., mine water (MW) and metallurgical wastewater) via forming insoluble metal sulfides. However, these processes often necessitate the addition of external organic compounds as electron donors, which poses a constraint on the broad application of this technology. A recent proof of concept study reported that microbial sulfur disproportionation (SD) produced sulfide with no demand for organics, which could achieve more cost-benefit MW treatment against the above-mentioned processes. However, the resistance of SD bioprocess to different metals and high sulfate content in MW remains mysterious, which may substantially affect the practical applicability of such process. In this study, the sulfur-disproportionating bacteria (SDB)-dominated consortium was enriched from a previously established SD-driven bioreactor, in which Dissulfurimicrobium sp. with a relative abundance of 39.9 % was the predominated SDB. When exposed to the real pretreated acidic MW after the pretreatment process of pH amelioration, the sulfur-disproportionating activity remained active, and metals were effectively removed from the MW. Metal tolerance assays further demonstrated that the consortium had a good tolerance to different metal ions (i.e., Pb2+, Cu2+, Ni2+, Mn2+, Zn2+), especially for Mn2+ with a concentration of approximately 20 mg/L. It suggested the robustness of Dissulfurimicrobium sp. likely due to the presence of genes encoding for the enzymes associated with metal(loid) resistance/uptake. Additionally, although high sulfate content resulted in a slight inhibition on the sulfur-disproportionating activity, the consortium still achieved sulfide production rates of 27.3 mg S/g VSS-d on average under an environmentally relevant sulfate level (i.e., 1100 mg S/L), which is comparable to those reported in sulfate reduction. Taken together, these findings imply that SDB could ensure sustainable MW treatment in a more cost-effective and organic-free way.


Assuntos
Metais Pesados , Águas Residuárias , Sulfatos/química , Água/química , Oxirredução , Bactérias/genética , Enxofre/química , Reatores Biológicos/microbiologia , Sulfetos/química
14.
J Biol Chem ; 300(2): 105612, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38159858

RESUMO

NCOA4 is a selective cargo receptor for ferritinophagy, the autophagic turnover of ferritin (FTH), a process critical for regulating intracellular iron bioavailability. However, how ferritinophagy flux is controlled through NCOA4 in iron-dependent processes needs to be better understood. Here, we show that the C-terminal FTH-binding domain of NCOA4 harbors a [3Fe-4S]-binding site with a stoichiometry of approximately one labile [3Fe-4S] cluster per NCOA4 monomer. By analyzing the interaction between NCOA4 and HERC2 ubiquitin ligase or NCOA4 and FTH, we demonstrate that NCOA4 regulates ferritinophagy by sensing the intracellular iron-sulfur cluster levels. Under iron-repletion conditions, HERC2 recognizes and recruits holo-NCOA4 as a substrate for polyubiquitination and degradation, favoring ferritin iron storage. Under iron-depletion conditions, NCOA4 exists in the form of apo-protein and binds ferritin to promote the occurrence of ferritinophagy and release iron. Thus, we identify an iron-sulfur cluster [3Fe-4S] as a critical cofactor in determining the fate of NCOA4 in favoring iron storage in ferritin or iron release via ferritinophagy and provide a dual mechanism for selective interaction between HERC2 and [3Fe-4S]-NCOA4 for proteasomal degradation or between ferritin and apo-NCOA4 for ferritinophagy in the control of iron homeostasis.


Assuntos
Homeostase , Ferro , Coativadores de Receptor Nuclear , Autofagia , Ferritinas/metabolismo , Ferro/química , Ferro/metabolismo , Coativadores de Receptor Nuclear/genética , Coativadores de Receptor Nuclear/metabolismo , Enxofre/química , Enxofre/metabolismo , Humanos , Animais , Camundongos , Domínios Proteicos , Linhagem Celular , Células Cultivadas , Ubiquitina-Proteína Ligases/metabolismo , Estabilidade Proteica , Complexo de Endopeptidases do Proteassoma/metabolismo
15.
Chemosphere ; 349: 140922, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38101479

RESUMO

Drinking water treatment residuals (DWTRs) are produced from the coagulation and flocculation processes in conventional drinking water treatment. The abundant metal oxide content of these materials resulting from the use of coagulants, like alum and ferric chloride, has driven strong research interest into the reuse of DWTRs as sorptive materials. Using a suite of aluminum-based DWTRs, we provide new insights into Hg(II) sorption mechanisms. Experiments performed at circum-neutral pH show that sorption capacities are related to the amount of organic carbon/matter present in DWTRs. We found that carbon rich samples can scavenge about 9000 mg/kg of Hg, in contrast to 2000 mg/kg for lime based DWTRs. X-ray absorption spectroscopy (XAS) at the Hg L3 edge further characterizes mercury coordination. X-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) results point to a partial association of mercury with sulfur at low mass loadings, transitioning to a full association with oxygen/carbon at higher concentrations of sorbed Hg(II) and in DWTRs with limited sulfur content. These results suggest that sorption of Hg(II) is primarily controlled by the carbon/organic matter fraction of DWTRs, but not by the coagulants.


Assuntos
Água Potável , Mercúrio , Espectroscopia por Absorção de Raios X , Adsorção , Mercúrio/química , Carbono , Enxofre/química
16.
Environ Sci Technol ; 58(1): 960-969, 2024 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-38150269

RESUMO

SO2 reduction with CH4 to produce elemental sulfur (S8) or other sulfides is typically challenging due to high energy barriers and catalyst poisoning by SO2. Herein, we report that a comproportionation reaction (CR) induced by H2S recirculating significantly accelerates the reactions, altering reaction pathways and enabling flexible adjustment of the products from S8 to sulfides. Results show that SO2 can be fully reduced to H2S at a lower temperature of 650 °C, compared to the 800 °C required for the direct reduction (DR), effectively eliminating catalyst poisoning. The kinetic rate constant is significantly improved, with CR at 650 °C exhibiting about 3-fold higher value than DR at 750 °C. Additionally, the apparent activation energy decreases from 128 to 37 kJ/mol with H2S, altering the reaction route. This CR resolves the challenges related to robust sulfur-oxygen bond activation and enhances CH4 dissociation. During the process, the well-dispersed lamellar MoS2 crystallites with Co promoters (CoMoS) act as active species. H2S facilitates the comproportionation reaction, reducing SO2 to a nascent sulfur (Sx*). Subsequently, CH4 efficiently activates CoMoS in the absence of SO2, forming H2S. This shifts the mechanism from Mars-van Krevelen (MvK) in DR to sequential Langmuir-Hinshelwood (L-H) and MvK in CR. Additionally, it mitigates sulfation poisoning through this rapid activation reaction pathway. This unique comproportionation reaction provides a novel strategy for efficient sulfur resource utilization.


Assuntos
Metano , Dióxido de Enxofre , Metano/química , Sulfetos/química , Temperatura , Enxofre/química , Oxirredução
17.
Water Res ; 250: 121067, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38150861

RESUMO

We developed a model to predict pH, alkalinity, and the Langelier Saturation Index (LSI) in coupled systems of hydrogen-based autotrophic sulfate reduction and aerobic oxidation of sulfide to elemental sulfur. To neutralize the biologically generated base, the model allows for the addition of CO2 as part of the gas mixture, the independent addition of HCl or CO2, or a combination of the alternatives. The model was evaluated against the results from a laboratory system for the production of elemental sulfur from sulfate present in mine-tailings water, which is characterized by the presence of elevated sulfate and calcium concentrations. Model results were consistent with measurements of pH, alkalinity, and LSI. The model showed how the acid demands of the coupled reactors vary with pH, being approximately equivalent at pH over 8, when ionized sulfide predominates. Also, while the sulfidogenic reactor was well buffered due to the production of ionized sulfide, the sulfidotrophic reactor in the absence of sulfide and carbonate alkalinity was prone to pH declines. Considering that both reactors operated in the positive range of LSI, the model also indicated that addition of CO2 should be minimized due to increase in the bicarbonate concentration and its effect on increasing the LSI. Furthermore, the model also showed that exclusive reliance on HCl for pH control can be incompatible with Cl- effluent standards, which means that a compromise must be reached between CO2 and HCl additions.


Assuntos
Sulfatos , Água , Sulfatos/química , Dióxido de Carbono , Oxirredução , Enxofre/química , Concentração de Íons de Hidrogênio , Sulfetos/química , Reatores Biológicos
18.
Protein Sci ; 33(2): e4874, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38100250

RESUMO

Several essential cellular metabolites, such as enzyme cofactors, contain sulfur atoms and their biosynthesis requires specific thiolation enzymes. LarE is an ATP-dependent sulfur insertase, which catalyzes the sequential conversion of the two carboxylate groups of the precursor of the lactate racemase cofactor into thiocarboxylates. Two types of LarE enzymes are known, one that uses a catalytic cysteine as a sacrificial sulfur donor, and the other one that uses a [4Fe-4S] cluster as a cofactor. Only the crystal structure of LarE from Lactobacillus plantarum (LpLarE) from the first class has been solved. We report here the crystal structure of LarE from Methanococcus maripaludis (MmLarE), belonging to the second class, in the cluster-free (apo-) and cluster-bound (holo-) forms. The structure of holo-MmLarE shows that the [4Fe-4S] cluster is chelated by three cysteines only, leaving an open coordination site on one Fe atom. Moreover, the fourth nonprotein-bonded iron atom was able to bind an anionic ligand such as a phosphate group or a chloride ion. Together with the spectroscopic analysis of holo-MmLarE and the previously reported biochemical investigations of holo-LarE from Thermotoga maritima, these crystal structures support the hypothesis of a reaction mechanism, in which the [4Fe-4S] cluster binds a hydrogenosulfide ligand in place of the chloride anion, thus generating a [4Fe-5S] intermediate, and transfers it to the substrate, as in the case of [4Fe-4S]-dependent tRNA thiolation enzymes.


Assuntos
Cloretos , Proteínas Ferro-Enxofre , Cloretos/metabolismo , Ligantes , Cisteína/química , Catálise , Enxofre/química , Enxofre/metabolismo , Proteínas Ferro-Enxofre/química
19.
Environ Sci Pollut Res Int ; 31(4): 6332-6349, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38147249

RESUMO

This research endeavors to address the pressing challenge of reducing sulfur content in fuels, an environmental imperative. It does so by employing bimetallic catalysts to enhance the efficiency of oxidative desulfurization (ODS) processes. This involves utilizing successive impregnation and co-impregnation methods to prepare a MoO3-V2O5/Al2O3. The catalysts underwent characterization using various techniques including X-ray diffraction (XRD), N2 adsorption-desorption, UV-vis (DRS), temperature-programmed desorption (NH3-TPD), Raman, Fourier-transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), and energy dispersive spectrum (EDS). The catalyst was utilized for the evaluation of the ODS process of dibenzothiophene (DBT). The effects of oxidants, namely H2O2 and t-butyl hydroperoxide (TBHP), were studied in the ODS. The catalyst prepared using the co-impregnation method (5M-15V-co) demonstrated significant acidic sites and exhibited remarkable efficiency in oxidative desulfurization. Remarkably, this catalyst achieved 100% oxidation of sulfur components within 30 min (min). To assess the catalyst's performance further, competitive compounds including nitrogen-containing compounds (NCCs) and saturated and unsaturated hydrocarbon compounds (HCs) were employed in the ODS. Initially, the introduction of NCCs led to a decrease in the sulfur removal rate; however, the catalyst successfully oxidized DBT completely within 60 min. When cyclohexene was present as an olefinic hydrocarbon compound, the catalyst oxidized DBT by approximately 75%, whereas DBT oxidation reached 100% within 20 min when p-xylene was introduced to the catalytic reactor. Additionally, as the O/S ratio increased from 2/5 to 10, the sulfur removal rate improved from 30 to 90%, indicating that HCs and NCCs compete with sulfur in terms of oxidant consumption.


Assuntos
Peróxido de Hidrogênio , Compostos de Nitrogênio , Oxirredução , Temperatura , Estresse Oxidativo , Enxofre/química
20.
Chem Biodivers ; 21(2): e202301738, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38126280

RESUMO

The prevalence of diabetes mellitus is on the rise, which demands the identification of novel antidiabetic drugs. There is a need for safer and more effective alternatives because the therapy methods now available to manage diabetes have limits. Due to their diverse pharmacological characteristics, heterocyclic molecules with nitrogen and Sulfur atoms have become intriguing candidates in medicinal chemistry. These substances have a wide variety of structures that can be customized to target different pathways associated with diabetes and can affect important biological targets involved in glucose homeostasis. This review provides a thorough summary of the most recent studies on heterocyclic analogues of nitrogen and Sulfur as prospective antidiabetic agents. This review examines the variety of their structural forms, their methods of action, and assesses the results of preclinical and clinical investigations on their effectiveness and safety. Additionally, further optimization and development of innovative antidiabetic medications are highlighted, as well as the difficulties and prospects for the future in utilizing the therapeutic potential of these analogues. This study seeks to stimulate additional investigation and cooperation between researchers and medicinal chemists, promoting improvements in the creation of efficient and secure antidiabetic medicines to fulfill the needs in the management of diabetes.


Assuntos
Diabetes Mellitus , Hipoglicemiantes , Humanos , Hipoglicemiantes/farmacologia , Hipoglicemiantes/uso terapêutico , Hipoglicemiantes/química , Nitrogênio , Estudos Prospectivos , Diabetes Mellitus/tratamento farmacológico , Enxofre/química
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