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1.
Mikrochim Acta ; 191(6): 303, 2024 05 06.
Artigo em Inglês | MEDLINE | ID: mdl-38709340

RESUMO

A platform was designed based on Fe3O4 and CsPbBr3@SiO2 for integrated magnetic enrichment-fluorescence detection of Salmonella typhimurium, which significantly simplifies the detection process and enhances the working efficiency. Fe3O4 served as a magnetic enrichment unit for the capture of S. typhimurium. CsPbBr3@SiO2 was employed as a fluorescence-sensing unit for quantitative signal output, where SiO2 was introduced to strengthen the stability of CsPbBr3, improve its biomodificability, and prevent lead leakage. More importantly, the SiO2 shell shows neglectable absorption or scattering towards fluorescence, making the CsPbBr3@SiO2 exhibit a high quantum yield of 74.4%. After magnetic enrichment, the decreasing rate of the fluorescence emission intensity of the CsPbBr3@SiO2 supernatant at 527 nm under excitation light at UV 365 nm showed a strong linear correlation with S. typhimurium concentration of 1 × 102~1 × 108 CFU∙mL-1, and the limit of detection (LOD) reached 12.72 CFU∙mL-1. This platform has demonstrated outstanding stability, reproducibility, and resistance to interference, which provides an alternative for convenient and quantitative detection of S. typhimurium.


Assuntos
Corantes Fluorescentes , Limite de Detecção , Salmonella typhimurium , Dióxido de Silício , Salmonella typhimurium/isolamento & purificação , Dióxido de Silício/química , Corantes Fluorescentes/química , Espectrometria de Fluorescência/métodos , Chumbo/química , Sistemas Automatizados de Assistência Junto ao Leito , Sulfetos/química , Nanopartículas de Magnetita/química , Humanos
2.
Sci Rep ; 14(1): 10066, 2024 05 02.
Artigo em Inglês | MEDLINE | ID: mdl-38698009

RESUMO

The global threat of antibiotic resistance has increased the importance of the detection of antibiotics. Conventional methods to detect antibiotics are time-consuming and require expensive specialized equipment. Here, we present a simple and rapid biosensor for detecting ampicillin, a commonly used antibiotic. Our method is based on the fluorescent properties of chitosan-coated Mn-doped ZnS micromaterials combined with the ß-lactamase enzyme. The biosensors exhibited the highest sensitivity in a linear working range of 13.1-72.2 pM with a limit of detection of 8.24 pM in deionized water. In addition, due to the biological specificity of ß-lactamase, the proposed sensors have demonstrated high selectivity over penicillin, tetracycline, and glucose through the enhancing and quenching effects at wavelengths of 510 nm and 614 nm, respectively. These proposed sensors also showed promising results when tested in various matrices, including tap water, bottled water, and milk. Our work reports for the first time the cost-effective (Mn:ZnS)Chitosan micromaterial was used for ampicillin detection. The results will facilitate the monitoring of antibiotics in clinical and environmental contexts.


Assuntos
Ampicilina , Técnicas Biossensoriais , Quitosana , Manganês , Sulfetos , Compostos de Zinco , Ampicilina/análise , Ampicilina/química , Quitosana/química , Técnicas Biossensoriais/métodos , Compostos de Zinco/química , Manganês/química , Sulfetos/química , Antibacterianos/análise , Antibacterianos/química , beta-Lactamases/análise , beta-Lactamases/metabolismo , beta-Lactamases/química , Leite/química , Limite de Detecção , Espectrometria de Fluorescência/métodos , Corantes Fluorescentes/química , Animais
3.
Anal Chim Acta ; 1306: 342585, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38692786

RESUMO

Herein, we developed a convenient and versatile dual-mode electrochemiluminescence (ECL) and photoelectrochemistry (PEC) sensing radar for the detection of Prostate-specific antigen (PSA), which has important implications for detection of low-abundance disease-associated proteins. Cerium-based metal-organic framework (Ce-MOFs) were firstly modified on the electrode, showing well ECL and PEC property. In particular, a unique multifunctional Au@CdS quantum dots (QDs) probe loaded numerous QDs and antibody was fabricated, not only displaying strong ECL and PEC signals, but also having specific recognition to PSA. After the signal probe was linked to the electrode by immune reaction, much amplified signals of ECL and PEC were generated for double-mode detection of PSA. Therefore, this work proposed a multifunctional Au@CdS QDs signal probe with excellent ECL and PEC performance, and developed an ultrasensitive photoelectric biosensing platform for dual-mode detection, which provides an effective method for health monitoring of cancer patients.


Assuntos
Compostos de Cádmio , Técnicas Eletroquímicas , Estruturas Metalorgânicas , Antígeno Prostático Específico , Pontos Quânticos , Sulfetos , Pontos Quânticos/química , Compostos de Cádmio/química , Sulfetos/química , Humanos , Antígeno Prostático Específico/análise , Antígeno Prostático Específico/sangue , Estruturas Metalorgânicas/química , Ouro/química , Cério/química , Técnicas Biossensoriais , Processos Fotoquímicos , Limite de Detecção , Eletrodos , Medições Luminescentes
4.
Analyst ; 149(10): 3008-3016, 2024 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-38606455

RESUMO

Fast-scan cyclic voltammetry (FSCV) is a widely used technique for detecting neurotransmitters. However, electrode fouling can negatively impact its accuracy and sensitivity. Fouling refers to the accumulation of unwanted materials on the electrode surface, which can alter its electrochemical properties and reduce its sensitivity and selectivity. Fouling mechanisms can be broad and may include biofouling, the accumulation of biomolecules on the electrode surface, and chemical fouling, the deposition of unwanted chemical species. Despite individual studies discussing fouling effects on either the working electrode or the reference electrode, no comprehensive study has been conducted to compare the overall fouling effects on both electrodes in the context of FSCV. Here, we examined the effects of biofouling and chemical fouling on the carbon fiber micro-electrode (CFME) as the working electrode and the Ag/AgCl reference electrode with FSCV. Both fouling mechanisms significantly decreased the sensitivity and caused peak voltage shifts in the FSCV signal with the CFME, but not with the Ag/AgCl reference electrode. Interestingly, previous studies have reported peak voltage shifts in FSCV signals due to the fouling of Ag/AgCl electrodes after implantation in the brain. We noticed in a previous study that energy-dispersive spectroscopy (EDS) spectra showed increased sulfide ion concentration after implantation. We hypothesized that sulfide ions may be responsible for the peak voltage shift. To test this hypothesis, we added sulfide ions to the buffer solution, which decreased the open circuit potential of the Ag/AgCl electrode and caused a peak voltage shift in the FSCV voltammograms. Also, EDS analysis showed that sulfide ion concentration increased on the surface of the Ag/AgCl electrodes after 3 weeks of chronic implantation, necessitating consideration of sulfide ions as the fouling agent for the reference electrodes. Overall, our study provides important insights into the mechanisms of electrode fouling and its impact on FSCV measurements. These findings could inform the design of FSCV experiments, with the development of new strategies for improving the accuracy and reliability of FSCV measurements in vivo.


Assuntos
Incrustação Biológica , Técnicas Eletroquímicas , Neurotransmissores , Neurotransmissores/análise , Incrustação Biológica/prevenção & controle , Técnicas Eletroquímicas/instrumentação , Técnicas Eletroquímicas/métodos , Animais , Compostos de Prata/química , Fibra de Carbono/química , Microeletrodos , Sulfetos/química , Eletrodos
5.
J Hazard Mater ; 471: 134344, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38678706

RESUMO

More information is needed to fully comprehend how acid mine drainage (AMD) affects the phototransformation of antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs) in karst water and sewage-irrigated farmland soil with abundant carbonate rocks (CaCO3) due to increasing pollution of AMD formed from pyrite (FeS2). The results showed FeS2 accelerated the inactivation of ARB with an inactivation of 8.7 log. Notably, extracellular and intracellular ARGs and mobile genetic elements (MGEs) also experienced rapid degradation. Additionally, the pH of the solution buffered by CaCO3 significantly influenced the photo-inactivation of ARB. The Fe2+ in neutral solution was present in Fe(II) coordination with strong reducing potential and played a crucial role in generating •OH (7.0 µM), which caused severe damage to ARB, ARGs, and MGEs. The •OH induced by photo-Fenton of FeS2 posed pressure to ARB, promoting oxidative stress response and increasing generation of reactive oxygen species (ROS), ultimately damaging cell membranes, proteins and DNA. Moreover, FeS2 contributed to a decrease in MIC of ARB from 24 mg/L to 4 mg/L. These findings highlight the importance of AMD in influencing karst water and sewage-irrigated farmland soil ecosystems. They are also critical in advancing the utilization of FeS2 to inactivate pathogenic bacteria.


Assuntos
Carbonato de Cálcio , Ferro , Mineração , Sulfetos , Carbonato de Cálcio/química , Ferro/química , Sulfetos/química , Sequências Repetitivas Dispersas , Resistência Microbiana a Medicamentos/genética , Bactérias/genética , Bactérias/efeitos dos fármacos , Genes Bacterianos , Farmacorresistência Bacteriana/genética , Antibacterianos/farmacologia
6.
Colloids Surf B Biointerfaces ; 238: 113874, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38581833

RESUMO

The growing resistance of bacteria to antibiotics has posed challenges in treating associated bacterial infections, while the development of multi-model antibacterial strategies could efficient sterilization to prevent drug resistance. High-entropy MXene has emerged as a promising candidate for antibacterial synergy with inherent photothermal and photodynamic properties. Herein, a high-entropy nanomaterial of MXene/CDs was synthesized to amplify oxidative stress under near-infrared laser irradiation. Well-exfoliated MXene nanosheets have proven to show an excellent photothermal effect for sterilization. The incorporation of CDs could provide photo-generated electrons for MXene nanosheets to generate ROS, meanwhile reducing the recombination of electron-hole pairs to further accelerate the generation of photo-generated electrons. The MXene/CDs material demonstrates outstanding synergistic photothermal and photodynamic effects, possesses excellent biocompatibility and successfully eliminates drug-resistant bacteria as well as inhibits biofilm formation. While attaining a remarkable killing efficiency of up to 99.99% against drug-resistant Escherichia coli and Staphylococcus aureus, it also demonstrates outstanding antibacterial effects against four additional bacterial strains. This work not only establishes a synthesis precedent for preparing high-entropy MXene materials with CDs but also provides a potential approach for addressing the issue of drug-resistant bacterial infections.


Assuntos
Antibacterianos , Compostos de Cádmio , Escherichia coli , Testes de Sensibilidade Microbiana , Staphylococcus aureus , Sulfetos , Antibacterianos/farmacologia , Antibacterianos/química , Antibacterianos/síntese química , Escherichia coli/efeitos dos fármacos , Staphylococcus aureus/efeitos dos fármacos , Sulfetos/química , Sulfetos/farmacologia , Compostos de Cádmio/química , Compostos de Cádmio/farmacologia , Farmacorresistência Bacteriana/efeitos dos fármacos , Biofilmes/efeitos dos fármacos , Tamanho da Partícula , Humanos , Propriedades de Superfície , Nanoestruturas/química
7.
Chemosphere ; 356: 141948, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38604521

RESUMO

Surface reaction is a prominent aspect that affects the efficiency of photocatalysis. In this work, acid theory was employed to facilitate the reaction dynamics and enhance the interfacial effect between photocatalysts and target molecules. The photocatalytic removal efficiency of NTP was 66 % for bare CdS in 50 min with apparent rate constants of 0.023 compare to 96 % with apparent rate constants of 0.065 for 5% Ce-CdS. The introduced Ce atom as bifunctional active site reduces the energy barrier of O2 adsorption, strengthens the interfacial effect and accelerates the electrons transfer, which could facilitate surface reaction process and boost the photocatalytic performance.


Assuntos
Processos Fotoquímicos , Catálise , Adsorção , Compostos de Cádmio/química , Poluentes Químicos da Água/química , Sulfetos/química , Cério/química
8.
Chem Biodivers ; 21(5): e202400027, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38602839

RESUMO

Garlic oil has a wide range of biological activities, and its broad-spectrum activity against phytopathogenic fungi still has the potential to be explored. In this study, enzymatic treatment of garlic resulted in an increase of approximately 50 % in the yield of essential oil, a feasible GC-MS analytical program for garlic oil was provided. Vacuum fractionation of the volatile oil and determination of its inhibitory activity against 10 fungi demonstrated that garlic oil has good antifungal activity. The antifungal activity levels were ranked as diallyl trisulfide (S-3)>diallyl disulfide (S-2)>diallyl monosulfide (S-1), with an EC50 value of S-3 against Botrytis cinerea reached 8.16 mg/L. Following the structural modification of compound S-3, a series of derivatives, including compounds S-4~7, were synthesized and screened for their antifungal activity. The findings unequivocally demonstrated that the compound dimethyl trisulfide (S-4) exhibited exceptional antifungal activity. The EC50 of S-4 against Sclerotinia sclerotiorum reached 6.83 mg/L. SEM, In vivo experiments, and changes in mycelial nucleic acids, soluble proteins and soluble sugar leakage further confirmed its antifungal activity. The study indicated that the trisulfide bond structure was the key to good antifungal activity, which can be developed into a new type of green plant-derived fungicide for plant protection.


Assuntos
Compostos Alílicos , Antifúngicos , Alho , Testes de Sensibilidade Microbiana , Óleos Voláteis , Sulfetos , Óleos Voláteis/farmacologia , Óleos Voláteis/química , Óleos Voláteis/isolamento & purificação , Óleos Voláteis/síntese química , Sulfetos/farmacologia , Sulfetos/química , Alho/química , Antifúngicos/farmacologia , Antifúngicos/síntese química , Antifúngicos/química , Antifúngicos/isolamento & purificação , Compostos Alílicos/farmacologia , Compostos Alílicos/química , Compostos Alílicos/isolamento & purificação , Compostos Alílicos/síntese química , Destilação , Desenho de Fármacos , Botrytis/efeitos dos fármacos , Relação Estrutura-Atividade , Ascomicetos/efeitos dos fármacos , Estrutura Molecular
9.
Ultrason Sonochem ; 105: 106858, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38564910

RESUMO

Zinc sulfide/graphitic Carbon Nitride binary nanosheets were synthesized by using a novel sonochemical pathway with high electrocatalytic ability. The as- obtained samples were characterized by various analytical methods such as Transmission Electron Microscopy (TEM), Field emission scanning electron microscopy (FESEM), Energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS) to evaluate the properties of ZnS@CNS synthesized by this new route. Subsequently, the electrical and electrochemical performance of the proposed electrodes were characterized by using EIS and CV to establish an electroactive ability of the nanocomposites. The complete properties like structural and physical of ZnS@CNS were analyzed. As-prepared binary nanocomposite was applied towards the detection of anticancer drug (flutamide) by various electrochemical methods such as cyclic voltammetry (CV), differential pulse voltammetry (DPV) and amperometry. The glassy carbon electrode modified with a ZnS@CNS composite demonstrates a remarkable electrocatalytic efficiency for detecting flutamide in a pH 7.0 (PBS). The composite modified electrode shows synergistic effect of ZnS and CNS catalyst. The electrochemical sensing performance of the linear range was improved significantly due to high electroactive sites and rapid electron transport pathways. Crucially, the electrochemical method was successfully demonstrated in biological fluids which reveals its potential real-time applicability in the analysis of drug.


Assuntos
Antineoplásicos , Eletrodos , Grafite , Compostos de Nitrogênio , Sulfetos , Ondas Ultrassônicas , Compostos de Zinco , Compostos de Zinco/química , Sulfetos/química , Antineoplásicos/química , Grafite/química , Flutamida/análise , Flutamida/química , Técnicas Eletroquímicas/métodos , Técnicas de Química Sintética , Eletroquímica , Limite de Detecção , Catálise , Nanocompostos/química , Nanoestruturas/química
10.
J Hazard Mater ; 470: 134193, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38569341

RESUMO

Arsenopyrite and pyrite often coexist in metal deposits and tailings, thus simultaneous bioleaching of both sulfides has economic (as well as environmental) significance. Important targets in bio-oxidation operations are high solubilization rates and minimized accumulation of Fe(III)/As-bearing secondary products. This study investigated the role of pyrite bioleaching in the enhancement of arsenopyrite dissolution. At a pyrite to arsenopyrite mass ratio of 1:1, 93.6% of As and 93.0% of Fe were solubilized. The results show that pyrite bio-oxidation can promote arsenopyrite dissolution, enhance S0 bio-oxidation, and inhibit the formation of jarosites, tooeleite, and amorphous ferric arsenate. The dry weight of the pyrite & arsenopyrite residue was reduced by 95.1% after bioleaching, compared to the initial load, while only 5% weight loss was observed when pyrite was absent. A biofilm was formed on the arsenopyrite surface in the presence of pyrite, while a dense passivation layer was observed in the absence of pyrite. As(III) (as As2O3) was a dominant As species in the pyrite & arsenopyrite residue. Novel and detailed findings are presented on arsenopyrite bio-dissolution in the presence of pyrite, and the presented approach could contribute to the development of novel cost-effective extractive bioprocesses. ENVIRONMENTAL IMPLICATION: The oxidation of arsenopyrite presents significant environmental hazards, as it can contribute to acid mine drainage generation and arsenic mobilization from sulfidic mine wastes. Bioleaching is a proven cost-effective and environmentally friendly extractive technology, which has been applied for decades in metal recovery from minerals or tailings. In this work, efficient extraction of arsenic from arsenopyrite bioleaching was presented through coupling the process with bio-oxidation of pyrite, resulting in lowered accumulation of hazardous and metastable Fe(III)/As-bearing secondary phases. The results could help improve current biomining operations and/or contribute to the development of novel cost-effective bioprocesses for metal extraction.


Assuntos
Arsenicais , Compostos de Ferro , Ferro , Minerais , Sulfetos , Sulfetos/química , Ferro/química , Arsenicais/química , Cinética , Minerais/química , Compostos de Ferro/química , Oxirredução , Solubilidade , Arsênio/química , Biofilmes , Acidithiobacillus/metabolismo
11.
Chem Commun (Camb) ; 60(34): 4581-4584, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38576349

RESUMO

A study of an integrated OPECT biosensor gate and the EC color-changing region on the same chip was carried out, achieving sensitive detection through bioetching-induced signal changes. Enzymatic bioetching enables specific alkaline phosphatase (ALP) detection by catalyzing the production of CdS, which modulates the channel current and generates a visual signal.


Assuntos
Fosfatase Alcalina , Técnicas Biossensoriais , Técnicas Eletroquímicas , Fosfatase Alcalina/metabolismo , Fosfatase Alcalina/análise , Transistores Eletrônicos , Compostos de Cádmio/química , Sulfetos/química , Processos Fotoquímicos
12.
Int J Mol Sci ; 25(8)2024 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-38673765

RESUMO

Quantum dots (QDs) are a novel type of nanomaterial that has unique optical and physical characteristics. As such, QDs are highly desired because of their potential to be used in both biomedical and industrial applications. However, the mass adoption of QDs usage has raised concerns among the scientific community regarding QDs' toxicity. Although many papers have reported the negative impact of QDs on a cellular level, the exact mechanism of the QDs' toxicity is still unclear. In this investigation, we study the adverse effects of QDs by focusing on one of the most important cellular processes: actin polymerization and depolymerization. Our results showed that QDs act in a biphasic manner where lower concentrations of QDs stimulate the polymerization of actin, while high concentrations of QDs inhibit actin polymerization. Furthermore, we found that QDs can bind to filamentous actin (F-actin) and cause bundling of the filament while also promoting actin depolymerization. Through this study, we found a novel mechanism in which QDs negatively influence cellular processes and exert toxicity.


Assuntos
Actinas , Compostos de Cádmio , Pontos Quânticos , Compostos de Selênio , Sulfetos , Compostos de Zinco , Pontos Quânticos/química , Actinas/metabolismo , Compostos de Zinco/química , Sulfetos/química , Compostos de Cádmio/química , Compostos de Selênio/química , Polimerização , Animais , Citoesqueleto de Actina/metabolismo , Citoesqueleto de Actina/efeitos dos fármacos , Humanos
13.
J Agric Food Chem ; 72(17): 9669-9679, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38632108

RESUMO

Soil-borne diseases represent an impediment to the sustainable development of agriculture. A soil-borne disease caused by Ilyonectria destructans severely impacts Panax species, and soil disinfestation has proven to be an effective management approach. Here, diallyl trisulfide (DATS), derived from garlic, exhibited pronounced inhibitory effects on the growth of I. destructans in vitro tests and contributed to the alleviation of soil-borne diseases in the field. A comprehensive analysis demonstrated that DATS inhibits the growth of I. destructans by activating detoxifying enzymes, such as GSTs, disrupting the equilibrium of redox reactions. A series of antioxidant amino acids were suppressed by DATS. Particularly noteworthy is the substantial depletion of glutathione by DATS, resulting in the accumulation of ROS, ultimately culminating in the inhibition of I. destructans growth. Briefly, DATS could effectively suppress soil-borne diseases by inhibiting pathogen growth through the activation of ROS, and it holds promise as a potential environmentally friendly soil disinfestation.


Assuntos
Compostos Alílicos , Doenças das Plantas , Espécies Reativas de Oxigênio , Sulfetos , Compostos Alílicos/farmacologia , Compostos Alílicos/química , Sulfetos/farmacologia , Sulfetos/metabolismo , Sulfetos/química , Espécies Reativas de Oxigênio/metabolismo , Doenças das Plantas/prevenção & controle , Doenças das Plantas/microbiologia , Ascomicetos/efeitos dos fármacos , Ascomicetos/crescimento & desenvolvimento , Ascomicetos/metabolismo , Alho/química , Alho/crescimento & desenvolvimento , Solo/química , Microbiologia do Solo , Fungicidas Industriais/farmacologia , Fungicidas Industriais/química
14.
Anal Chem ; 96(17): 6847-6852, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38639290

RESUMO

Organic photoelectrochemical transistor (OPECT) has shown substantial potential in the development of next-generation bioanalysis yet is limited by the either-or situation between the photoelectrode types and the channel types. Inspired by the dual-photoelectrode systems, we propose a new architecture of dual-engine OPECT for enhanced signal modulation and its biosensing application. Exemplified by incorporating the CdS/Bi2S3 photoanode and Cu2O photocathode within the gate-source circuit of Ag/AgCl-gated poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) channel, the device shows enhanced modulation capability and larger transconductance (gm) against the single-photoelectrode ones. Moreover, the light irritation upon the device effectively shifts the peak value of gm to zero gate voltage without degradation and generates larger current steps that are advantageous for the sensitive bioanalysis. Based on the as-developed dual-photoelectrode OPECT, target-mediated recycling and etching reactions are designed upon the CdS/Bi2S3, which could result in dual signal amplification and realize the sensitive microRNA-155 biodetection with a linear range from 1 fM to 100 pM and a lower detection limit of 0.12 fM.


Assuntos
Cobre , Técnicas Eletroquímicas , Sulfetos , Tiofenos , Técnicas Eletroquímicas/instrumentação , Cobre/química , Sulfetos/química , Compostos de Cádmio/química , Técnicas Biossensoriais/instrumentação , Bismuto/química , Transistores Eletrônicos , Processos Fotoquímicos , Poliestirenos/química , MicroRNAs/análise , Eletrodos , Polímeros/química
15.
J Inorg Biochem ; 256: 112573, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38678913

RESUMO

This paper describes the synthesis, structural analysis, as well as the magnetic and spectroscopic characterizations of three new dicopper(II) complexes with dinucleating phenol-based ligands containing different thioether donor substituents: aromatic (1), aliphatic (2) or thiophene (3). Temperature-dependent magnetometry reveals the presence of antiferromagnetic coupling for 1 and 3 (J = -2.27 cm-1 and -5.01 cm-1, respectively, H = -2JS1S2) and ferromagnetic coupling for 2 (J = 5.72 cm-1). Broken symmetry DFT calculations attribute this behavior to a major contribution from the dz2 orbitals for 1 and 3, and from the dx2-y2 orbitals for 2, along with the p orbitals of the oxygens. The bioinspired catalytic activities of these complexes related to catechol oxidase were studied using 3,5-di-tert-butylcatechol as substrate. The order of catalytic rates for the substrate oxidation follows the trend 1 > 2 > 3 with kcat of (90.79 ± 2.90) × 10-3 for 1, (64.21 ± 0.99) × 10-3 for 2 and (14.20 ± 0.32) × 10-3 s-1 for 3. The complexes also cleave DNA through an oxidative mechanism with minor-groove preference, as indicated by experimental and molecular docking assays. Antimicrobial potential of these highly active complexes has shown that 3 inhibits both Staphylococcus aureus bacterium and Epidermophyton floccosum fungus. Notably, the complexes were found to be nontoxic to normal cells but exhibited cytotoxicity against epidermoid carcinoma cells, surpassing the activity of the metallodrug cisplatin. This research shows the multifaceted properties of these complexes, making them promising candidates for various applications in catalysis, nucleic acids research, and antimicrobial activities.


Assuntos
Antineoplásicos , Complexos de Coordenação , Oxirredução , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Humanos , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/síntese química , Ligantes , Sulfetos/química , Sulfetos/farmacologia , Antibacterianos/farmacologia , Antibacterianos/química , Antibacterianos/síntese química , Platina/química , Platina/farmacologia , Linhagem Celular Tumoral
16.
Water Res ; 256: 121601, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38640566

RESUMO

Thioether compounds, prevalent in pharmaceuticals, are of growing environmental concern due to their prevalence and potential toxicity. Peroxy chemicals, including peroxymonosulfate (PMS) and peroxyacetic acid (PAA), hold promise for selectively attacking specific thioether moieties. Still, it has been unclear how chemical structures affect the interactions between thioethers and peroxy chemicals. This study addresses this knowledge gap by quantitatively assessing the relationship between the structure of thioethers and intrinsic reaction rates. First, the results highlighted the adverse impact of electron-withdrawing groups on reactivity. Theoretical calculations were employed to locate reactive sites and investigate structural characteristics, indicating a close relationship between thioether charge and reaction rate. Additionally, we established a SMILES-based model for rapidly predicting PMS reactivity with thioether compounds. With this model, we identified 147 thioether chemicals within the high production volume (HPV) and Food and Drug Administration (FDA) approved drug lists that PMS could effectively eliminate with the toxicity (-lg LC50) decreasing. These findings underscore the environmental significance of thioether compounds and the potential for their selective removal by peroxides.


Assuntos
Ácido Peracético , Peróxidos , Sulfetos , Sulfetos/química , Peróxidos/química , Ácido Peracético/química , Poluentes Químicos da Água/química
17.
Talanta ; 274: 126024, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38583330

RESUMO

The detection of transmissible gastroenteritis virus (TGEV) is of great significance to reduce the loss of pig industry. A LAMP-visualization/PFC self-powered dual-mode output sensor platform was constructed to detect TGEV by combining a simple and intuitive photoelectrochromic material with a highly sensitive PFC self-powered sensing platform without external power supply. The PFC sensing substrate was constructed using CdS nanoparticles modified ZnO NRs (CdS/ZnO NRs) as the photoanode, which exhibited high photoactivity, and Prussian blue (PB) as the cathode. After LAMP reaction on the optical anode, visual signals caused by PB discolorimetry can be detected semi-quantitatively, or PFC power density electrical signals collected by electrochemical workstation can be used. The output power density value is logarithm of TGEV concentration. The linear relationship was good within the detection range of 0.075 fg/µL-7.5 ng/µL, with a detection limit of 0.025 fg/µL (S/N = 3). This multi-signal output sensing platform provides more choices for quantifying TGEV detection results, and the two methods can be mutually verified, which meets the needs of different scenarios and improves the reliability of detection. It has a good effect in the actual sample detection, without the use of expensive and complex instruments, and has a broad application prospect.


Assuntos
Polímeros de Fluorcarboneto , Técnicas de Diagnóstico Molecular , Técnicas de Amplificação de Ácido Nucleico , Vírus da Gastroenterite Transmissível , Óxido de Zinco , Vírus da Gastroenterite Transmissível/isolamento & purificação , Óxido de Zinco/química , Animais , Suínos , Limite de Detecção , Compostos de Cádmio/química , Técnicas Eletroquímicas/métodos , Técnicas Eletroquímicas/instrumentação , Nanopartículas/química , Sulfetos/química
18.
Chem Commun (Camb) ; 60(37): 4958-4961, 2024 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-38629343

RESUMO

Potential-selective electrochemiluminescence (ECL) with tunable maximum-emission-potential ranging from 0.95 to 0.30 V is achieved using AgInS2/ZnS nanocrystals, which is promising in the design of multiplexed bioassay on commercialized ECL setups. The model system AgInS2/ZnS/N2H4 exhibits efficient ECL around 0.30 V and can be exploited for sensitive immunoassays with less electrochemical interference and crosstalk.


Assuntos
Técnicas Eletroquímicas , Medições Luminescentes , Nanopartículas , Sulfetos , Compostos de Zinco , Sulfetos/química , Compostos de Zinco/química , Imunoensaio/métodos , Nanopartículas/química , Índio/química , Prata/química , Compostos de Prata/química , Humanos , Nanopartículas Metálicas/química
19.
Environ Sci Pollut Res Int ; 31(20): 29264-29279, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38573576

RESUMO

Guided by efficient utilization of natural plant oil and sulfur as low-cost sorbents, it is desired to tailor the porosity and composition of polysulfides to achieve their optimal applications in the management of aquatic heavy metal pollution. In this study, polysulfides derived from soybean oil and sulfur (PSSs) with improved porosity (10.2-22.9 m2/g) and surface oxygen content (3.1-7.0 wt.%) were prepared with respect to reaction time of 60 min, reaction temperature of 170 °C, and mass ratios of sulfur/soybean oil/NaCl/sodium citrate of 1:1:3:2. The sorption behaviors of PSSs under various hydrochemical conditions such as contact time, pH, ionic strength, coexisting cations and anions, temperature were systematically investigated. PSSs presented a fast sorption kinetic (5.0 h) and obviously improved maximum sorption capacities for Pb(II) (180.5 mg/g), Cu(II) (49.4 mg/g), and Cr(III) (37.0 mg/g) at pH 5.0 and T 298 K, in comparison with polymers made without NaCl/sodium citrate. This study provided a valuable reference for the facile preparation of functional polysulfides as well as a meaningful option for the removal of aquatic heavy metals.


Assuntos
Cobre , Chumbo , Metais Pesados , Óleo de Soja , Sulfetos , Poluentes Químicos da Água , Adsorção , Chumbo/química , Óleo de Soja/química , Cobre/química , Sulfetos/química , Porosidade , Poluentes Químicos da Água/química , Metais Pesados/química , Cromo/química , Cinética , Concentração de Íons de Hidrogênio
20.
Environ Sci Pollut Res Int ; 31(16): 24163-24179, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38436860

RESUMO

Coastal sedimentary systems are affected by continental and marine metal pollutant inputs associated with different hydrodynamic characteristics and geochemical processes. These include the formation of acid-volatile sulfides (AVS) within sediments, which affects metal bioavailability and associated aquatic biota toxicity risks. Physicochemical changes in these environments in the face of extreme natural or man-made environmental influences can dramatically alter metal bioavailability and toxicity through metal binding and immobilization as insoluble sulfides. Surface sediments from Guanabara Bay, river mouths, and two mangrove areas were collected, and AVS and simultaneously extracted metals Cd, Cu, Fe, Mn, Ni, Pb, and Zn and ΣSEM were determined to assess sediment quality. A severe eutrophication history favored AVS concentrations exceeding or close to the sum-SEM concentrations, demonstrating that AVS play an important role in making trace metals unavailable for assimilation by living organisms, mitigating the risks of contamination for the local biota. This eutrophication-driven sulfide accumulation may attenuate the sediment toxicity in sites heavily polluted by metals, while some fewer eutrophic sites became more exposed to metals in excess to AVS.


Assuntos
Metais Pesados , Oligoelementos , Poluentes Químicos da Água , Ácidos , Baías , Monitoramento Ambiental , Sedimentos Geológicos/química , Metais/análise , Metais Pesados/análise , Sulfetos/química , Poluentes Químicos da Água/análise
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