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1.
Chemosphere ; 364: 143309, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39265733

RESUMO

Herein, coupling of noble metal-free plasmonic copper nanoparticles with tungsten suboxide and supporting on zeolite nanoclay (Cu/WO3-x@ZNC) composite will be introduced for bi-functional photocatalytic ciprofloxacin (CIP) degradation and water photothermal evaporation under visible/infrared (Vis/IR) exposure. Reduced band-gap of WO3-x via oxygen vacancies creation and localized surface plasmon resonance (LSPR) formation by Cu nanoparticles contributed significantly the extension and intensification of composite's photo-absorption range. Furthermore, small mesoporous structure of ZNC enhanced CIP adsorption and charge carriers separation where the reported photocatalytic efficiencies were 88.3 and 81.7% upon IR and Vis light exposure respectively. It was evidenced that plasmonic hot electrons (e-.s) and hydroxyl radicals (OH•-) performed the basic functions of the photocatalytic process. At the other side, oxygen vacancies existence, plasmonic effect, and confining thermal characteristics of WO3-x, Cu, and ZNC correspondingly induced water photothermal evaporation with efficiencies up to 97.5 and 72.8% under IR and Vis illumination respectively. This work introduces synthesis of a novel bi-functional photocatalytic-photothermal composite by metal sub-oxide and non-noble metal plasmonic coupling and supporting on naturally-derived carrier for water restoration under broad spectral exposure.


Assuntos
Ciprofloxacina , Cobre , Tungstênio , Ciprofloxacina/química , Cobre/química , Tungstênio/química , Catálise , Poluentes Químicos da Água/química , Óxidos/química , Nanopartículas Metálicas/química , Água/química , Zeolitas/química , Raios Infravermelhos , Fotólise , Processos Fotoquímicos , Ressonância de Plasmônio de Superfície , Adsorção
2.
Chem Commun (Camb) ; 60(78): 10966-10969, 2024 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-39263697

RESUMO

Bioactive NAD+ mediated multiple biocatalytic pathways in metabolic networks. Refining the structure of NADH oxidase-like (NOX) mimics to efficiently replenish NAD+ has been promising but challenging in NAD+-dependent dehydrogenase electrochemical cascade biosensing. Herein, we discovered that PtOx structures, formed via lattice oxygen translocation from WO3 to Pt NPs at the interface, potentially activate and modulate the NOX-like functionality in Pt@WO3 nanosheets. Incorporating PtOx leads to a more positive valence of Pt species within Pt/PtOx@WO3-x, where the PtO2 species serve as preeminent reaction sites for NADH coordination, activation, and dehydrogenation. Consequently, such nanozymes display enhanced NOX-like activity towards NADH oxidation in comparison to Pt@WO3. Ultimately, the 650-Pt/PtOx@WO3-x nanozyme is employed in an electrochemical cascade biosensor for ß-hydroxybutyrate (HB) detection, achieving a calculated detection limit of 25 µM. This study offers insights into PtOx activation in Pt-based NOX mimics and supports the future development of NAD+/NADH-dependent electrochemical biosensors.


Assuntos
Técnicas Biossensoriais , Técnicas Eletroquímicas , NAD , Óxidos , Platina , Tungstênio , NAD/química , Tungstênio/química , Platina/química , Óxidos/química , Hidroxibutiratos/química , Oxirredução , Nanopartículas Metálicas/química , Limite de Detecção
3.
Molecules ; 29(17)2024 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-39275012

RESUMO

Pharmaceuticals and personal care products (PPCPs) which include antibiotics such as tetracycline (TC) and ciprofloxacin (CIP), etc., have attracted increasing attention worldwide due to their potential threat to the aquatic environment and human health. In this work, a facile sol-gel method was developed to prepare tungsten-doped TiO2 with tunable W5+/W6+ ratio for the removal of PPCPs. The influence of solvents in the synthesis of the three different tungsten precursors doped TiO2 is also taken into account. WCl6, ammonium metatungstate (AMT), and Na2WO4●2H2O not only acted as the tungsten precursors but also controlled the tungsten ratio. The photocatalyst prepared by WCl6 as the tungsten precursor and ethanol as the solvent showed the highest photodegradation performance for ciprofloxacin (CIP) and tetracycline (TC), and the photodegradation performance for tetracycline (TC) was 2.3, 2.8, and 7.8 times that of AMT, Na2WO4●2H2O as the tungsten precursors and pristine TiO2, respectively. These results were attributed to the influence of the tungsten precursors and solvents on the W5+/W6+ ratio, sample crystallinity and surface properties. This study provides an effective method for the design of tungsten-doped TiO2 with tunable W5+/W6+ ratio, which has a profound impact on future studies in the field of photocatalytic degradation of PPCPs using an environmentally friendly approach.


Assuntos
Cosméticos , Solventes , Titânio , Tungstênio , Titânio/química , Tungstênio/química , Catálise , Solventes/química , Cosméticos/química , Fotólise , Ciprofloxacina/química , Preparações Farmacêuticas/química , Tetraciclina/química , Processos Fotoquímicos , Poluentes Químicos da Água/química
4.
Chemosphere ; 364: 143008, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39098346

RESUMO

Water pollution has been made worse by the widespread use of organic dyes and their discharge, which has coincided with the industry's rapid development. Piezoelectric catalysis, as an effective wastewater purification method with promising applications, can enhance the catalyst activity by collecting tiny vibrations in nature and is not limited by sunlight. In this work, we designed and synthesized intriguing WS2/Bi2WO6 heterojunction nanocomposites, investigated their shape, structure, and piezoelectric characteristics using a range of characterization techniques, and used ultrasound to accelerate the organic dye Rhodamine B (RhB) degradation in wastewater. In comparison to the pristine monomaterials, the results demonstrated that the heterojunction composites demonstrated excellent degradation and stability of RhB under ultrasonic circumstances. The existence of heterojunctions and the internal piezoelectric field created by ultrasonic driving work in concert to boost catalytic performance, and the organic dye's rate of degradation is further accelerated by the carriers that are mutually transferred between the composites.


Assuntos
Rodaminas , Poluentes Químicos da Água , Catálise , Rodaminas/química , Poluentes Químicos da Água/química , Águas Residuárias/química , Nanocompostos/química , Bismuto/química , Ondas Ultrassônicas , Purificação da Água/métodos , Compostos de Tungstênio/química , Ultrassom , Tungstênio/química
5.
Chemosphere ; 364: 143028, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39111672

RESUMO

The widespread usage of levofloxacin (LVF) intake is executed for several urinary and respiratory systems infections in human. But, its over intake leads to severe damage to humans and the environment by its exposure. Hence the detection of LVF is concerned and we herein developed an electrocatalyst, strontium tungsten oxide nanospheres and later decorated onto the functionalized multiwall carbon nanotubes (SrWO4/f-MWCNT) to perform effective electrochemical recognition of LVF in aquatic and biological samples. Binary metal oxide with carbon composite SrWO4/f-MWCNT was developed due to its specific features as nanostructures. Various methods of investigation have been examined to identify the physiochemical characteristics like X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and morphological characteristics including field emission scanning electron microscopy, and transmission electron microscopy. The synthesized SrWO4/f-MWCNT sample crystalline size was around 32.9 nm. The SrWO4/f-MWCNT modified glassy carbon electrode (GCE) has been subjected to electrochemical investigation with a wide linear range of 0.049 µM-574.73 µM with good sensitivity 2.86 µA µM-1 cm2, the limit of detection at 14.9 nM for LVF sensing. Furthermore, the designed LVF detection exhibited excellent anti-interference, stability, reproducibility, and repeatability. The as-developed sensor's electrochemical outcomes indicate the superior performance inherent in the developed composite.


Assuntos
Técnicas Eletroquímicas , Levofloxacino , Nanotubos de Carbono , Compostos de Tungstênio , Nanotubos de Carbono/química , Levofloxacino/química , Levofloxacino/análise , Levofloxacino/urina , Compostos de Tungstênio/química , Técnicas Eletroquímicas/métodos , Catálise , Eletrodos , Limite de Detecção , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química , Óxidos/química , Tungstênio/química
6.
Environ Geochem Health ; 46(10): 376, 2024 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-39167294

RESUMO

Currently, one of the primary challenges that human society must overcome is the task of decreasing the amount of energy used and the adverse effects that it has on the environment. The daily increase in liquid waste (comprising organic pollutants) is a direct result of the creation and expansion of new companies, causing significant environmental disruption. Water contamination is attributed to several industries such as textile, chemical, poultry, dairy, and pharmaceutical. In this study, we present the successful degradation of methylene blue dye using g-C3N4 (GCN) mixed with WO3 and V2O5 composites (GCN/WO3/V2O5 ternary composite) as a photocatalyst, prepared by a simple mechanochemistry method. The GCN/WO3/V2O5 ternary composite revealed a notable enhancement in photocatalytic performance, achieving around 97% degradation of aqueous methylene blue (MB). This performance surpasses that of the individual photocatalysts, namely pure GCN, GCN/WO3, and GCN/V2O5 composites. Furthermore, the GCN/WO3/V2O5 ternary composite exhibited exceptional stability even after undergoing five consecutive cycles. The exceptional photocatalytic activity of the GCN/WO3/V2O5 ternary composite can be ascribed to the synergistic effect of metal-free GCN and metal oxides, resulting in the alteration of the band gap and suppression of charge recombination in the ternary photocatalyst. This study offers a better platform for understanding the characteristics of materials and their photocatalytic performance under visible light conditions.


Assuntos
Azul de Metileno , Óxidos , Tungstênio , Poluentes Químicos da Água , Tungstênio/química , Óxidos/química , Catálise , Poluentes Químicos da Água/química , Concentração de Íons de Hidrogênio , Azul de Metileno/química , Grafite/química , Purificação da Água/métodos , Processos Fotoquímicos , Fotólise , Compostos de Nitrogênio
7.
ACS Sens ; 9(8): 4196-4206, 2024 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-39096304

RESUMO

Reliable and real-time monitoring of seafood decay is attracting growing interest for food safety and human health, while it is still a great challenge to accurately identify the released triethylamine (TEA) from the complex volatilome. Herein, defect-engineered WO3-x architectures are presented to design advanced TEA sensors for seafood quality assessment. Benefiting from abundant oxygen vacancies, the obtained WO2.91 sensor exhibits remarkable TEA-sensing performance in terms of higher response (1.9 times), faster response time (2.1 times), lower detection limit (3.2 times), and higher TEA/NH3 selectivity (2.8 times) compared with the air-annealed WO2.96 sensor. Furthermore, the definite WO2.91 sensor demonstrates long-term stability and anti-interference in complex gases, enabling the accurate recognition of TEA during halibut decay (0-48 h). Coupled with the random forest algorithm with 70 estimators, the WO2.91 sensor enables accurate prediction of halibut storage with an accuracy of 95%. This work not only provides deep insights into improving gas-sensing performance by defect engineering but also offers a rational solution for reliably assessing seafood quality.


Assuntos
Algoritmos , Óxidos , Alimentos Marinhos , Tungstênio , Alimentos Marinhos/análise , Tungstênio/química , Óxidos/química , Qualidade dos Alimentos , Algoritmo Florestas Aleatórias
8.
Nanotechnology ; 35(45)2024 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-39127053

RESUMO

In pursuing advanced neuromorphic applications, this study introduces the successful engineering of a flexible electronic synapse based on WO3-x, structured as W/WO3-x/Pt/Muscovite-Mica. This artificial synapse is designed to emulate crucial learning behaviors fundamental to in-memory computing. We systematically explore synaptic plasticity dynamics by implementing pulse measurements capturing potentiation and depression traits akin to biological synapses under flat and different bending conditions, thereby highlighting its potential suitability for flexible electronic applications. The findings demonstrate that the memristor accurately replicates essential properties of biological synapses, including short-term plasticity (STP), long-term plasticity (LTP), and the intriguing transition from STP to LTP. Furthermore, other variables are investigated, such as paired-pulse facilitation, spike rate-dependent plasticity, spike time-dependent plasticity, pulse duration-dependent plasticity, and pulse amplitude-dependent plasticity. Utilizing data from flat and differently bent synapses, neural network simulations for pattern recognition tasks using the Modified National Institute of Standards and Technology dataset reveal a high recognition accuracy of ∼95% with a fast learning speed that requires only 15 epochs to reach saturation.


Assuntos
Redes Neurais de Computação , Plasticidade Neuronal , Óxidos , Tungstênio , Tungstênio/química , Plasticidade Neuronal/fisiologia , Óxidos/química , Sinapses Elétricas/fisiologia , Titânio/química , Aprendizagem , Sinapses/fisiologia
9.
ACS Nano ; 18(35): 24469-24483, 2024 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-39172806

RESUMO

Bacterial infections claim millions of lives every year, with the escalating menace of microbial antibiotic resistance compounding this global crisis. Nanozymes, poised as prospective substitutes for antibiotics, present a significant frontier in antibacterial therapy, yet their precise enzymatic origins remain elusive. With the continuous development of nanozymes, the applications of elemental N-modulated nanozymes have spanned multiple fields, including sensing and detection, infection therapy, cancer treatment, and pollutant degradation. The introduction of nitrogen into nanozymes not only broadens their application range but also holds significant importance for the design of catalysts in biomedical research. The synergistic interplay between W and N induces pivotal alterations in electronic configurations, endowing tungsten nitride (WN) with a peroxidase-like functionality. Furthermore, the introduction of N vacancies augments the nanozyme activity, thus amplifying the catalytic potential of WN nanostructures. Rigorous theoretical modeling and empirical validation corroborate the genesis of the enzyme activity. The meticulously engineered WN nanoflower architecture exhibits an exceptional ability in traversing bacterial surfaces, exerting potent bactericidal effects through direct physical interactions. Additionally, the topological intricacies of these nanostructures facilitate precise targeting of generated radicals on bacterial surfaces, culminating in exceptional bactericidal efficacy against both Gram-negative and Gram-positive bacterial strains along with notable inhibition of bacterial biofilm formation. Importantly, assessments using a skin infection model underscore the proficiency of WN nanoflowers in effectively clearing bacterial infections and fostering wound healing. This pioneering research illuminates the realm of pseudoenzyme activity and bacterial capture-killing strategies, promising a fertile ground for the development of innovative, high-performance artificial peroxidases.


Assuntos
Antibacterianos , Nitrogênio , Antibacterianos/farmacologia , Antibacterianos/química , Nitrogênio/química , Testes de Sensibilidade Microbiana , Compostos de Tungstênio/química , Compostos de Tungstênio/farmacologia , Peroxidase/metabolismo , Peroxidase/química , Animais , Tungstênio/química , Tungstênio/farmacologia , Materiais Biomiméticos/química , Materiais Biomiméticos/farmacologia , Infecções Bacterianas/tratamento farmacológico , Camundongos , Catálise , Nanoestruturas/química , Escherichia coli/efeitos dos fármacos , Humanos
10.
Talanta ; 279: 126609, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39106647

RESUMO

Acebutolol (ACE) is commonly used to treat hypertension and high blood pressure. Large doses of ACE can have adverse effects with potentially life-threatening consequences. It is, therefore, essential to develop a simple, low-cost, reliable, and reproducible device for detecting ACE in biofluids. This study explores the potential of unique two-dimensional nano-flakes, such as tungsten trioxide (WO3). Graphene oxide (GO) typically exhibits lower electrical conductivity than pristine graphene due to the presence of oxygen-containing functional groups that interfere with the π-conjugated structure. Functionalizing GO with tannic acid (TA) can partially reinstate the π-conjugation and limit the amount of oxygen, resulting in enhanced electrical conductivity. Ultrasonic techniques were utilized to create WO3 NFs@TA-rGO, and a range of spectroscopic and microscopic methods were applied to examine the formation of the resulting WO3 NFs@TA-rGO nanocomposites. Under optimal conditions, modified sensors resulted in lower limits of detection (0.0055 µM) and good sensitivity (0.40 µA µM-1 cm-2). They also exhibited a broad linear range spanning from 0.009 to 568.6 µM. Fabricated sensors have significant anti-interference properties with high specificity and excellent storage stability (RSD = 4.3 %), reproducibility (RSD = 3.9 %), and repeatability (RSD = 3.3 %). Ultimately, the sensor's efficacy was confirmed through the successful detection of ACE in biological samples (with recoveries ranging from 99.1 to 99.6 %). Lastly, this study highlights the substantial potential of ACE detection and extends its applications in biomedical diagnostics and pharmaceutical research.


Assuntos
Grafite , Óxidos , Taninos , Tungstênio , Grafite/química , Tungstênio/química , Óxidos/química , Taninos/química , Limite de Detecção , Humanos , Técnicas Eletroquímicas/métodos , Polifenóis
11.
Mikrochim Acta ; 191(9): 514, 2024 08 06.
Artigo em Inglês | MEDLINE | ID: mdl-39105930

RESUMO

A cleanroom free optimized fabrication of a low-cost facile tungsten diselenide (WSe2) combined with chitosan-based hydrogel device is reported for multifunctional applications including tactile sensing, pulse rate monitoring, respiratory rate monitoring, human body movements detection, and human electrophysiological signal detection. Chitosan being a natural biodegradable, non-toxic compound serves as a substrate to the semiconducting WSe2 electrode which is synthesized using a single step hydrothermal technique. Elaborate characterization studies are performed to confirm the morphological, structural, and electrical properties of the fabricated chitosan/WSe2 device. Chitosan/WSe2 sensor with copper contacts on each side is put directly on skin to capture human body motions. The resistivity of the sample was calculated as 26 kΩ m-1. The device behaves as an ultrasensitive pressure sensor for tactile and arterial pulse sensing with response time of 0.9 s and sensitivity of around 0.02 kPa-1. It is also capable for strain sensing with a gauge factor of 54 which is significantly higher than similar other reported electrodes. The human body movements sensing can be attributed to the piezoresistive character of WSe2 that originates from its non-centrosymmetric structure. Further, the sensor is employed for monitoring respiratory rate which measures to 13 counts/min for healthy individual and electrophysiological signals like ECG and EOG which can be used later for detecting numerous pathological conditions in humans. Electrophysiological signal sensing is carried out using a bio-signal amplifier (Bio-Amp EXG Pill) connected to Arduino. The skin-friendly, low toxic WSe2/chitosan dry electrodes pave the way for replacing wet electrodes and find numerous applications in personalized healthcare.


Assuntos
Quitosana , Dispositivos Eletrônicos Vestíveis , Quitosana/química , Humanos , Taxa Respiratória , Selênio/química , Frequência Cardíaca/fisiologia , Movimento , Tungstênio/química , Eletrodos , Monitorização Fisiológica/instrumentação , Monitorização Fisiológica/métodos
12.
Sci Total Environ ; 951: 175472, 2024 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-39142414

RESUMO

Acetaminophen (APAP) is a well-known type of over-the-counter painkillers and is frequently found in surface waterbodies, causing hepatotoxicity and skin irritation. Due to its persistence and chronic effects on the environment, innovative solutions must be provided to decompose APAP, effectively. Innovative catalysts of tungsten-modified iron oxides (TF) were successfully developed via a combustion method and thoroughly characterized using SEM, TEM, XRD, XPS, a porosimetry analysis, Mössbauer spectroscopy, VSM magnetometry, and EPR. With the synthesis method, tungsten was successfully incorporated into iron oxides to form ferrites and other magnetic iron oxides with a high porosity of 19.7 % and a large surface area of 29.5 m2/g. Also, their catalytic activities for APAP degradation by activating peroxymonosulfate (PMS) were evaluated under various conditions. Under optimal conditions, TF 2.0 showed the highest APAP degradation of 95 % removal with a catalyst loading of 2.0 g/L, initial APAP concentration of 5 mg/L, PMS of 6.5 mM, and pH 2.15 at room temperature. No inhibition by solution pHs, alkalinity, and humic acid was observed for APAP degradation in this study. The catalysts also showed chemical and mechanical stability, achieving 100 % degradation of 1 mg/L APAP during reusability tests with three consecutive experiments. These results show that TFs can effectively degrade persistent contaminants of emerging concern in water, offering an impactful contribution to wastewater treatment to protect human health and the ecosystem.


Assuntos
Acetaminofen , Compostos Férricos , Tungstênio , Poluentes Químicos da Água , Tungstênio/química , Acetaminofen/química , Compostos Férricos/química , Poluentes Químicos da Água/química , Peróxidos/química , Catálise
13.
Bioelectrochemistry ; 160: 108780, 2024 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-39018611

RESUMO

To advance cervical cancer diagnostics, we propose a state-of-the-art label-free electrochemical immunosensor designed for the simultaneous detection of multiple biomarker proteins (p16INK4a, p53, and Ki67). This immunosensor is constructed using a polyethyleneimine-coated gold nanoparticles/2D tungsten disulfide/graphene oxide (PEI-AuNPs/2D WS2/GO) composite-modified three-screen-printed carbon electrode (3SPCE) array. The 2D WS2/GO hybrid provides a large specific surface area for supporting well-dispersed PEI-AuNPs and adsorbed redox-active species, enhancing overall performance. The PEI-AuNPs-decorated 2D WS2/GO composite not only improves electrode conductivity but also increases the antibody loading capacity. Redox-active species, including Cd2+ ions, 2,3-diaminophenazine (DAP), and methylene blue (MB), serve as distinct signaling compounds to quantitatively detect the cervical cancer biomarkers p16INK4a, p53, and Ki67, respectively. Additionally, the immunosensor demonstrates the detection with high sensitivity, good storage stability, high selectivity, and acceptable reproducibility. This immunosensor demonstrates a good linear relationship with the logarithm of protein concentrations. Additionally, the immunosensor also demonstrates high sensitivity, good storage stability, high selectivity, and acceptable reproducibility. Our promising results and the successful application of the immunosensor in detecting three tumor markers in human serum highlight its potential for clinical diagnosis of cervical cancer.


Assuntos
Biomarcadores Tumorais , Técnicas Biossensoriais , Dissulfetos , Ouro , Grafite , Nanopartículas Metálicas , Nanocompostos , Oxirredução , Polietilenoimina , Neoplasias do Colo do Útero , Grafite/química , Humanos , Neoplasias do Colo do Útero/diagnóstico , Feminino , Nanopartículas Metálicas/química , Ouro/química , Biomarcadores Tumorais/sangue , Biomarcadores Tumorais/análise , Nanocompostos/química , Polietilenoimina/química , Técnicas Biossensoriais/métodos , Dissulfetos/química , Imunoensaio/métodos , Técnicas Eletroquímicas/métodos , Tungstênio/química , Limite de Detecção
14.
ACS Sens ; 9(7): 3604-3615, 2024 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-39016238

RESUMO

Metal oxides with nanoarray structures have been demonstrated to be prospective materials for the design of gas sensors with high sensitivity. In this work, the WO3 nanoneedle array structures were synthesized by a one-step hydrothermal method and subsequent calcination. It was demonstrated that the calcination of the sample at 400 °C facilitated the construction of lilac-like multiple self-supporting WO3 arrays, with appropriate c/h-WO3 heterophase junction and highly oriented nanoneedles. Sensors with this structure exhibited the highest sensitivity (2305) to 100 ppm ethylene glycol at 160 °C and outstanding selectivity. The enhanced ethylene glycol gas sensing can be attributed to the abundant transport channels and active sites provided by this unique structure. In addition, the more oxygen adsorption caused by the heterophase junction and the aggregation of reaction medium induced by tip effect are both in favor of the improvement on the gas sensing performance.


Assuntos
Etilenoglicol , Nanoestruturas , Óxidos , Tungstênio , Tungstênio/química , Óxidos/química , Etilenoglicol/química , Nanoestruturas/química , Gases/análise , Gases/química
15.
ACS Sens ; 9(8): 4079-4088, 2024 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-39057835

RESUMO

Ambient pressure X-ray photoelectron spectroscopy (APXPS) is combined with simultaneous electrical measurements and supported by density functional theory calculations to investigate the sensing mechanism of tungsten disulfide (WS2)-based gas sensors in an operando dynamic experiment. This approach allows for the direct correlation between changes in the surface potential and the resistivity of the WS2 sensing active layer under realistic operating conditions. Focusing on the toxic gases NO2 and NH3, we concurrently demonstrate the distinct chemical interactions between oxidizing or reducing agents and the WS2 active layer and their effect on the sensor response. The experimental setup mimics standard electrical measurements on chemiresistors, exposing the sample to dry air and introducing the target gas analyte at different concentrations. This methodology applied to NH3 concentrations of 100, 230, and 760 and 14 ppm of NO2 establishes a benchmark for future APXPS studies on sensing devices, providing fast acquisition times and a 1:1 correlation between electrical response and spectroscopy data in operando conditions. Our findings contribute to a deeper understanding of the sensing mechanism in 2D transition metal dichalcogenides, paving the way for optimizing chemiresistor sensors for various industrial applications and wireless platforms with low energy consumption.


Assuntos
Amônia , Espectroscopia Fotoeletrônica , Amônia/análise , Amônia/química , Dióxido de Nitrogênio/análise , Dióxido de Nitrogênio/química , Compostos de Tungstênio/química , Teoria da Densidade Funcional , Pressão , Gases/análise , Gases/química , Tungstênio/química
16.
Int J Biol Macromol ; 277(Pt 1): 134160, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39059538

RESUMO

In this work, chemical modification of the chitosan with ethyl acetoacetate was performed through a base-catalyzed reaction in which epichlorohydrin facilitated the insertion as well as nucleophilic substitution reaction to graft the 1,3-dioxo moiety across the linear chains of the base biopolymer to establish specificity and selectivity for U(VI) removal. The modified chitosan (EAA-CS) was intercalated into phosphate rich alginate matrix (PASA). Later on, the WO3-doped composites with different WO3 to PASA mass ratio were prepared and characterized using FTIR, XPS, SEM-EDS, XRD, and elemental mapping analysis. WO3 significantly contributed to chemically stable inorganic-organic composites with improved porous texture. Among the prepared composites, MCPS-3 microspherical beads, having mass ratio of 30.0 % w/w, exhibited excellent sorption capacity for U(VI) at an optimal pH 4.5. The successful U(VI) sorption was validated by the existence of two U4f peaks at 392.25 and 381.36 eV due to U4f5/2 and U4f7/2 sub-peaks with an intensity ratio of 3:4, respectively. Batch mode sorption kinetics followed pseudo-second-order rate equation (R2 ≈ 0.99, qe,th ≈ 116.88 mg/g, k2 = 0.86 × 10-4 g/mg.min-1) and equilibrium sorption data aligns with Langmuir (R2 = 0.99, qm = 343.85 mg/g at 310 K and pH = 4.5, KL = 2.00 × 10-2 L/mg) and Temkin models (R2 ≈ 0.99). Thermodynamic parameters ΔHo (30.51 kJ/mol), ΔSo (0.19 kJ/mol.K) and ΔGo (-25.64, -26.89, and - 27.91 kJ/mol) at 298, 305, and 310 K, respectively, suggested that the uptake process is feasible, endothermic and spontaneous. Based on these findings, it is reasonable to conclude that MCPS-3 could be a better hydrogel-based biomaterial for appreciable uranium recovery.


Assuntos
Alginatos , Quitosana , Óxidos , Ácido Fítico , Tungstênio , Urânio , Quitosana/química , Alginatos/química , Adsorção , Tungstênio/química , Óxidos/química , Ácido Fítico/química , Urânio/química , Cinética , Concentração de Íons de Hidrogênio , Purificação da Água/métodos
17.
Environ Sci Pollut Res Int ; 31(34): 47378-47393, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-39002083

RESUMO

In this research, a novel nano-biocomposite material, namely, tungsten trioxide-Butea monosperma leaf powder (WO3@BLP), is an effective and eco-friendly adsorbent used for the mitigation of congo red (CR) and crystal violet (CV) dyes from its aqueous phase. The as-prepared WO3@BLP was characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), DLS analysis, and TGA. Many factors such as solution pH, WO3@BLP dose, temperature, contact time, and initial CR/CV dye concentrations were exploited to monitor the adsorption efficiency of WO3@BLP composites. The biosorption of both CR and CV dyes followed the Langmuir isotherm, with maximum adsorption capacities (qmax) reaching 84.91 mg g-1 for CR at pH 2.3 and 162.75 mg g-1 for CV at pH 8, fitting of kinetics data to the PSO model with closed values of qeexp (mg g-1) and qecal (mg g-1), i.e., 25.69 to 25.38 mg g-1 for CR dye and 29.06 to 29.08 mg g-1 for CV dye. The interaction mechanism behind the adsorption of CR and CV dyes onto the WO3@BLP bionanocomposite includes electrostatic interaction and surface complexation. The synthesized materials were tested for antifungal activity against three different Candida cells, i.e., C. albicans ATCC 90028, C. glabrata ATCC 90030, and C. tropicalis ATCC 750, by using broth dilution method on the minimum inhibiting concentration (MIC). Furthermore, the cytotoxicity of nano-formulated WO3@BLP was studied by in vitro hemolytic assay on a human host. Overall, this research presents a pioneering nano-biocomposite, WO3@BLP, as a sustainable adsorbent for CR and CV dye removal, adhering to Langmuir isotherm and pseudo-second-order kinetics. Its multifaceted approach includes elucidating interaction mechanisms, demonstrating antifungal activity, and assessing cytotoxicity, marking a significant advancement in environmental remediation.


Assuntos
Folhas de Planta , Tungstênio , Purificação da Água , Purificação da Água/métodos , Tungstênio/química , Folhas de Planta/química , Adsorção , Poluentes Químicos da Água/química , Óxidos/química , Vermelho Congo
18.
Food Chem ; 459: 140338, 2024 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-38996633

RESUMO

It is highly desirable to develop a low-cost and rapid detection method for trace levels of carbendazim fungicide residues, which would be beneficial for improving human health and mitigating environmental issues. Herein, isolated single tungsten atoms were implanted onto well-organized metal-organic framework (MOF)-derived N-doped carbons to form W-N-C single-site heterojunctions with ultrahigh electrocatalytic activity. The coupling of W-N-C with Cu3(HHTP)2, an electronically conductive MOF with a large surface area and porous structure, exhibited enhanced electrocatalytic performance for the oxidation of carbendazim (CBZ) when they were used for decorating graphene nanoplatelet flexible electrode arrays fabricated via template-assisted scalable filtration. A wide linear range (3.0 nM-50 µM) with an ultra-low detection limit of 0.97 nM and fast response was achieved for CBZ analysis. Moreover, the sensing platform has been utilised to monitor CBZ levels in vegetable samples with satisfactory recovery rates of 97.2-102% and a low relative standard deviation of 1.9%.


Assuntos
Benzimidazóis , Carbamatos , Cobre , Eletrodos , Contaminação de Alimentos , Fungicidas Industriais , Grafite , Estruturas Metalorgânicas , Verduras , Carbamatos/análise , Carbamatos/química , Grafite/química , Verduras/química , Catálise , Estruturas Metalorgânicas/química , Benzimidazóis/química , Benzimidazóis/análise , Cobre/química , Fungicidas Industriais/análise , Fungicidas Industriais/química , Contaminação de Alimentos/análise , Técnicas Eletroquímicas/instrumentação , Técnicas Eletroquímicas/métodos , Tungstênio/química , Limite de Detecção , Oxirredução
19.
Chemosphere ; 363: 142767, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38971443

RESUMO

Characterization and evaluation of hazardous spent V2O5-WO3/TiO2 catalysts are critical to determining their treatment or final disposal. This study employs a thermal approach to simulate the preparation of spent catalysts derived from commercial V2O5-WO3/TiO2 catalysts and investigate the structure-activity relationship of the carrier changes during the deactivation process. The results indicate that the catalyst carrier undergoes two processes: an increase in grain size and a transformation in crystal structure. Both structural and catalytic investigations demonstrate that the grain size for catalyst deactivation is 24.62 nm, and the formation of CaWO4 occurs before the crystalline transformation. The specific surface area is susceptible to an increase in grain size. The reactions of selective catalytic reduction involve the participation of both Brønsted acid and Lewis acid sites. The deactivation process of the carrier initially affects Brønsted acid sites, followed by a reduction in Lewis acid sites, resulting in a decline in NH3 adsorption capacity and oxidation. Correlation analysis reveals that changes in the physicochemical properties of the catalyst reduce the NO conversion, with the order being The grain size > Total acid amount > The surface area. It is recommended to recycle the spent catalyst if the carrier grain size is less than 25 nm. The findings of this investigation contribute to expanding the database for evaluating and understanding the physicochemical properties of spent catalysts for disposal.


Assuntos
Óxidos , Titânio , Tungstênio , Titânio/química , Tungstênio/química , Catálise , Óxidos/química , Relação Estrutura-Atividade , Compostos de Vanádio/química , Adsorção , Oxirredução
20.
Chemosphere ; 363: 142785, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38972463

RESUMO

In this study, we investigated the degradation of the flame retardant tetrabromobisphenol A (TBBPA) using platinized tungsten oxide (Pt/WO3), synthesized via a simple photodeposition method, under visible light. The results of degradation experiments show a significant enhancement in TBBPA degradation upon surface platinization of WO3, with the degradation rate increasing by 13.4 times compared to bare WO3. The presence of Pt on the WO3 surface stores conduction band electrons, which facilitates the two-electron reduction of oxygen and enhances the production of valence band holes (hVB+) and hydroxyl radicals (●OH). Both hVB+ and ●OH are significantly involved in the degradation of TBBPA in the visible light-irradiated Pt/WO3 system. This was verified through fluorescence spectroscopy employing coumarin as a chemical probe and oxidizing species-quenching experiments. The analysis of degradation products and their toxicity assessment demonstrate that the toxicity of TBBPA-contaminated water is significantly reduced after Pt/WO3 photocatalysis. The degradation rate of TBBPA increased with increasing Pt/WO3 dosage, reached an optimum at a Pt content of 0.5 wt%, but decreased with increasing TBBPA concentration. The decrease in degradation efficiency of Pt/WO3 was minor, both in the presence of various anions and after repeated use. This study proposes that Pt/WO3 is a viable photocatalyst for the degradation of TBBPA in water under visible light.


Assuntos
Retardadores de Chama , Luz , Óxidos , Bifenil Polibromatos , Tungstênio , Tungstênio/química , Óxidos/química , Bifenil Polibromatos/química , Catálise , Poluentes Químicos da Água/química , Platina/química , Fotólise , Processos Fotoquímicos , Oxirredução
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