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1.
J Environ Sci (China) ; 149: 149-163, 2025 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-39181630

RESUMO

Developing heterojunction photocatalyst with well-matched interfaces and multiple charge transfer paths is vital to boost carrier separation efficiency for photocatalytic antibiotics removal, but still remains a great challenge. In present work, a new strategy of chloride anion intercalation in Bi2O3 via one-pot hydrothermal process is proposed. The as-prepared Ta-BiOCl/Bi24O31Cl10 (TBB) heterojunctions are featured with Ta-Bi24O31Cl10 and Ta-BiOCl lined shoulder-by-shouleder via semi-coherent interfaces. In this TBB heterojunctions, the well-matched semi-coherent interfaces and shoulder-by-shoulder structures provide fast electron transfer and multiple transfer paths, respectively, leading to enhanced visible light response and improved photogenerated charge separation. Meanwhile, a type-II heterojunction for photocharge separation has been obtained, in which photogenerated electrons are drove from the CB (conduction band) of Ta-Bi24O31Cl10 to the both of bilateral empty CB of Ta-BiOCl and gathered on the CB of Ta-BiOCl, while the photogenerated holes are left on the VB (valence band) of Ta-Bi24O31Cl10, effectively hindering the recombination of photogenerated electron-hole pairs. Furthermore, the separated electrons can effectively activate dissolved oxygen for the generation of reactive oxygen species (·O2-). Such TBB heterojunctions exhibit remarkably superior photocatalytic degradation activity for tetracycline hydrochloride (TCH) solution to Bi2O3, Ta-BiOCl and Ta-Bi24O31Cl10. This work not only proposes a Ta-BiOCl/Bi24O31Cl10 shoulder-by-shoulder micro-ribbon architectures with semi-coherent interfaces and successive type-II heterojunction for highly efficient photocatalytic activity, but offers a new insight into the design of highly efficient heterojunction through phase-structure synergistic transformation strategy.


Assuntos
Antibacterianos , Bismuto , Poluentes Químicos da Água , Bismuto/química , Antibacterianos/química , Poluentes Químicos da Água/química , Catálise , Processos Fotoquímicos
2.
J Environ Sci (China) ; 149: 164-176, 2025 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-39181631

RESUMO

Cerium and cobalt loaded Co-Ce/TiO2 catalyst prepared by impregnation method was investigated for photothermal catalytic toluene oxidation. Based on catalyst characterizations (XPS, EPR and H2-TPR), redox cycle between Co and TiO2 (Co2+ + Ti4+ ↔ Co3+ + Ti3+) results in the formation of Co3+, Ti3+ and oxygen vacancies, which play important roles in toluene catalytic oxidation reaction. The introduction of Ce brings in the dual redox cycles (Co2+ + Ti4+ ↔ Co3+ + Ti3+, Co2+ + Ce4+ ↔ Co3+ + Ce3+), further promoting the elevation of reaction sites amount. Under full spectrum irradiation with light intensity of 580 mW/cm2, Co-Ce/TiO2 catalyst achieved 96% of toluene conversion and 73% of CO2 yield, obviously higher than Co/P25 and Co/TiO2. Co-Ce/TiO2 efficiently maintains 10-hour stability test under water vapor conditions and exhibits better photothermal catalytic performance than counterparts under different wavelengths illumination. Photothermal catalytic reaction displays improved activities compared with thermal catalysis, which is attributed to the promotional effect of light including photocatalysis and light activation of reactive oxygen species.


Assuntos
Cério , Cobalto , Oxirredução , Titânio , Tolueno , Titânio/química , Cobalto/química , Catálise , Tolueno/química , Cério/química , Modelos Químicos , Processos Fotoquímicos
3.
J Environ Sci (China) ; 149: 500-511, 2025 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-39181662

RESUMO

Formic and acetic acids are the most abundant gaseous organic acids and play the key role in the atmospheric chemistry. In iodine-adduct chemical ionization mass spectrometry (CIMS), the low utilization efficiency of methyl iodide and humidity interference are two major issues of the vacuum ultraviolet (VUV) lamp initiated CIMS for on-line gaseous formic and acetic acids analysis. In this work, we present a new CIMS based on VUV lamp, and the ion-molecular reactor is separated into photoionization and chemical ionization zones by a reducer electrode. Acetone was added to the photoionization zone, and the VUV photoionization acetone provided low-energy electrons for methyl iodide to generate I-, and the addition of acetone reduced the amount of methyl iodide by 2/3. In the chemical ionization zone, a headspace vial containing ultrapure water was added for humidity calibration, and the vial changes the sensitivity as a function of humidity from ambiguity to well linear correlation (R2 > 0.95). With humidity calibration, the CIMS can quantitatively measure formic and acetic acids in the humidity range of 0%-88% RH. In this mode, limits of detection of 10 and 50 pptv are obtained for formic and acetic acids, respectively. And the relative standard deviation (RSD) of quantitation stability for 6 days were less than 10.5%. This CIMS was successfully used to determine the formic and acetic acids in the underground parking and ambient environment of the Shandong University campus (Qingdao, China). In addition, we developed a simple model based formic acid concentration to assess vehicular emissions.


Assuntos
Espectrometria de Massas , Espectrometria de Massas/métodos , Poluentes Atmosféricos/análise , Iodetos/análise , Iodetos/química , Raios Ultravioleta , Formiatos/análise , Formiatos/química , Atmosfera/química , Monitoramento Ambiental/métodos , Processos Fotoquímicos , Ácido Acético/análise , Ácido Acético/química , Hidrocarbonetos Iodados/análise , Hidrocarbonetos Iodados/química
4.
Food Chem ; 462: 140693, 2025 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-39208722

RESUMO

A rapid photoelectrochemical (PEC) sensor was constructed for nitrite detection in food based on the one-step chemical etching strategy of BiOCl/Zn0.5Cd0.5S (BOC/ZCS) nanocomposites by nitrite. BOC/ZCS heterojunction was prepared by a simple coprecipitation method, and it was found that BOC/ZCS showed significant photoelectrochemical (PEC) activity. The results of this study confirmed that the decrease in the photocurrent of the sensor was linked to the etching of ZCS by nitrite under acidic conditions. Under optimized conditions, the BOC/ZCS-based PEC sensor showed good analytical properties for detecting nitrite, with linear ranges of 1-100 µM and 100-600 µM. The detection limit of the sensor was 0.41 µM (S/N = 3). Excellent repeatability, reproducibility, low background noise, and immunity to interference were demonstrated using the proposed system, and satisfactory results were achieved for the nitrite assay using real samples. These results demonstrate a new method for nitrite detection developed using the proposed PEC sensor.


Assuntos
Técnicas Eletroquímicas , Limite de Detecção , Nitritos , Nitritos/análise , Técnicas Eletroquímicas/instrumentação , Bismuto/química , Zinco/química , Zinco/análise , Nanocompostos/química , Processos Fotoquímicos , Contaminação de Alimentos/análise
5.
J Environ Sci (China) ; 148: 283-297, 2025 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-39095165

RESUMO

In the quest for effective solutions to address Environ. Pollut. and meet the escalating energy demands, heterojunction photocatalysts have emerged as a captivating and versatile technology. These photocatalysts have garnered significant interest due to their wide-ranging applications, including wastewater treatment, air purification, CO2 capture, and hydrogen generation via water splitting. This technique harnesses the power of semiconductors, which are activated under light illumination, providing the necessary energy for catalytic reactions. With visible light constituting a substantial portion (46%) of the solar spectrum, the development of visible-light-driven semiconductors has become imperative. Heterojunction photocatalysts offer a promising strategy to overcome the limitations associated with activating semiconductors under visible light. In this comprehensive review, we present the recent advancements in the field of photocatalytic degradation of contaminants across diverse media, as well as the remarkable progress made in renewable energy production. Moreover, we delve into the crucial role played by various operating parameters in influencing the photocatalytic performance of heterojunction systems. Finally, we address emerging challenges and propose novel perspectives to provide valuable insights for future advancements in this dynamic research domain. By unraveling the potential of heterojunction photocatalysts, this review contributes to the broader understanding of their applications and paves the way for exciting avenues of exploration and innovation.


Assuntos
Recuperação e Remediação Ambiental , Recuperação e Remediação Ambiental/métodos , Catálise , Energia Solar , Luz Solar , Semicondutores , Energia Renovável , Processos Fotoquímicos
6.
J Environ Sci (China) ; 147: 561-570, 2025 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-39003071

RESUMO

In the present study, we investigated the influence of surface fluorine (F) on TiO2 for the photocatalytic oxidation (PCO) of toluene. TiO2 modified with different F content was prepared and tested. It was found that with the increasing of F content, the toluene conversion rate first increased and then decreased. However, CO2 mineralization efficiency showed the opposite trend. Based on the characterizations, we revealed that F substitutes the surface hydroxyl of TiO2 to form the structure of Ti-F. The presence of the appropriate amount of surface Ti-F on TiO2 greatly enhanced the separation of photogenerated carriers, which facilitated the generation of ·OH and promoted the activity for the PCO of toluene. It was further revealed that the increase of only ·OH promoted the conversion of toluene to ring-containing intermediates, causing the accumulation of intermediates and then conversely inhibited the ·OH generation, which led to the decrease of the CO2 mineralization efficiency. The above results could provide guidance for the rational design of photocatalysts for toluene oxidation.


Assuntos
Fluoretos , Oxirredução , Titânio , Tolueno , Tolueno/química , Titânio/química , Catálise , Fluoretos/química , Processos Fotoquímicos , Modelos Químicos
7.
Anal Chim Acta ; 1325: 343114, 2024 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-39244302

RESUMO

BACKGROUND: Temperature sensing is commonly used in point-of-care (POC) detection technologies, yet the portability and convenience of use are frequently compromised by the complexity of thermosensitive processes and signal transduction. Especially, multi-step target recognition reactions and temperature measurement in the reaction vessel present challenges in terms of stability and integration of detection devices. To further combine photothermal reaction and signal readout in one assay, these two processes enable to be integrated into miniaturized microfluidic chips, thereby facilitating photothermal sensing and achieving a simple visual temperature sensing as POC detection. RESULTS: A copper ion (Cu2+)-catalyzed photothermal sensing system integrated onto a microfluidic distance-based analytical device (µDAD), enabling the visual, portable, and sensitive quantitative detection of multiple targets, including ascorbic acid, glutathione, and alkaline phosphatase (ALP). The polydopamine nanoparticles (PDA NPs) were synthesized by the regulation of free Cu2+ through redox or coordination reactions, facilitating the transduction of distinct photothermal response signals and providing the versatile Cu2+-responsive sensing systems. Promoted by integration with a photothermal µDAD, the system combines PDA's photothermal responsiveness and thermosensitive gas production of ammonium bicarbonate for improved sensitivity of ALP detection, reaching the detection limit of 9.1 mU/L. The system has successfully achieved on-chip detection of ALP with superior anti-interference capability and recoveries ranging from 96.8 % to 104.7 %, alongside relative standard deviations below 8.0 %. SIGNIFICANCE AND NOVELTY: The µDAD design accommodated both the photothermal reaction of PDA NPs and thermosensitive gas production reaction, achieving the rapid sensing of visual distance signals. The µDAD-based Cu2+-catalyzed photothermal sensing system holds substantial potential for applications in biochemical analysis and clinical diagnostics, underscored by the versatile Cu2+ regulation mechanism for a broad spectrum of biomarkers.


Assuntos
Ácido Ascórbico , Cobre , Indóis , Testes Imediatos , Polímeros , Cobre/química , Indóis/química , Polímeros/química , Catálise , Ácido Ascórbico/análise , Ácido Ascórbico/química , Limite de Detecção , Fosfatase Alcalina/metabolismo , Fosfatase Alcalina/análise , Fosfatase Alcalina/química , Temperatura , Humanos , Glutationa/análise , Glutationa/química , Nanopartículas/química , Processos Fotoquímicos , Dispositivos Lab-On-A-Chip , Técnicas Biossensoriais
8.
Luminescence ; 39(9): e4872, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39245989

RESUMO

A highly water-soluble and fluorescent N,S-doped carbon dots/europium (N,S-CDs/Eu) was successfully synthesized via a secondary hydrothermal method. This involved surface modification of N,S-CDs derived from sunflower stem pith (SSP) with europium ions (Eu3+) doping. When excited within the range of 400-470 nm, N,S-CDs/Eu exhibited a stable and broad optimal emission wavelength ranging from 505 to 540 nm. Notably, the photoluminescence quantum yield (PLQY) of N,S-CDs/Eu is 31.4%, significantly higher than the 19.5% observed for N,S-CDs. Additionally, by dissolving N,S-CDs/Eu into polyvinyl alcohol (PVA), a uniform fluorescent anti-counterfeiting ink can be prepared. The N,S-CDs/Eu/TiO2 composite demonstrates excellent photocatalytic degradation ability towards the organic dye methylene blue (MB). N,S-CDs/Eu has potential in the field of fluorescent inks and photocatalysis due to its simple and efficient preparation and excellent properties.


Assuntos
Carbono , Európio , Helianthus , Tinta , Pontos Quânticos , Európio/química , Carbono/química , Catálise , Pontos Quânticos/química , Helianthus/química , Processos Fotoquímicos , Corantes Fluorescentes/química , Corantes Fluorescentes/síntese química , Azul de Metileno/química , Fluorescência
9.
Luminescence ; 39(9): e4903, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39268692

RESUMO

Smart photochromic and fluorescent textile refers to garments that alter their colorimetric properties in response to external light stimulus. Cotton fibers have been reported as a main resource for many textile and non-textile industries, such as automobiles, medical devices, and furniture applications. Cotton is a natural fiber that is distinguished with breathability, softness, cheapness, and highly absorbent. However, there have been growing demands to find other resources for cotton textiles at high quality and low cost for various applications, such as sensor for harmful ultraviolet radiation. Herein, we present a novel method toward luminescent and photochromic nonwoven textiles from recycled cotton waste. Using the screen-printing technology, a cotton fabric that is both photochromic and fluorescent was developed using aqueous inorganic phosphor nanoparticles (10-18 nm)-containing printing paste. Both CIE Lab color coordinates and photoluminescence spectra showed that the transparent film printed on the nonwoven fabric develops a reversible green emission (519 nm) under ultraviolet light (365 nm), even at low pigment concentration (2%) in the printing paste. Colorfastness of printed fabrics showed high durability and photostability.


Assuntos
Celulose , Fibra de Algodão , Estrôncio , Fibra de Algodão/análise , Celulose/química , Estrôncio/química , Têxteis , Raios Ultravioleta , Dispositivos Eletrônicos Vestíveis , Luminescência , Óxido de Alumínio/química , Impressão , Processos Fotoquímicos , Reciclagem
10.
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
11.
J Am Chem Soc ; 146(37): 25416-25421, 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39248674

RESUMO

Calicheamicin γ1 and related natural products are renowned for their potency in DNA cleavage, serving as the warheads in commercial ADCs used for treating leukemia. Their mechanism of action involves the formation of aryl radicals, which abstract hydrogen atoms from nucleic acids. However, the complex strained enediyne structure of calicheamicin γ1 presents significant challenges in synthesis, resulting in high production costs and limited structural and activity modularity for tuning the therapeutic window. This report describes the development of simple molecular mimics based on diazonium salts, synthesized in fewer than 3 steps, capable of generating aryl radicals upon green or red light irradiation. SAR studies conducted on over 30 analogues reveal a wide range of potencies in DNA cleavage, with EC50 values ranging from low nanomolar to micromolar. Forming benzenoid diradicals does not appear to be necessary for potent DNA cleavage; instead, DNA cleavage can be achieved with radicals distributed among different arenes when connected with proper linkages. The potency is influenced by electronic effects, stereochemistry, orbital orientations, the distance between multiradicals, and the number of diazonium motifs within the molecule. In addition to providing a more cost-effective, efficient, and modular alternative to calicheamicin γ1, this technology offers the potential for enhanced specificity through spatiotemporal control.


Assuntos
Clivagem do DNA , Clivagem do DNA/efeitos dos fármacos , Aminoglicosídeos/química , Processos Fotoquímicos , Enedi-Inos/química , Enedi-Inos/farmacologia , DNA/química , Relação Estrutura-Atividade , Luz , Compostos de Diazônio/química , Humanos , Estrutura Molecular
12.
J Am Chem Soc ; 146(37): 25397-25402, 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39250821

RESUMO

Phototriggered release of various cargos, including soluble protein factors and small molecules, has the potential to correct aberrant biological events by offering spatiotemporal control over local therapeutic levels. However, the poor penetration depth of light historically limits implementation to subdermal regions, necessitating alternative methods of light delivery to achieve the full potential of photodynamic therapeutic release. Here, we introduce a strategy exploiting bioluminescence resonance energy transfer (BRET)-an energy transfer process between light-emitting Nanoluciferase (NLuc) and a photosensitive acceptor molecule-to drive biomolecule release from hydrogel biomaterials. Through a facile, one-pot, and high-yielding synthesis (60-70%), we synthesized a heterobifunctional ruthenium cross-linker bearing an aldehyde and an azide (CHO-Ru-N3), a compound that we demonstrate undergoes predictable exchange of the azide-bearing ligand under blue-green light irradiation (>550 nm). Following site-specific conjugation to NLuc via sortase-tag enhanced protein ligation (STEPL), the modified protein was covalently attached to a poly(ethylene glycol) (PEG)-based hydrogel via strain-promoted azide-alkyne cycloaddition (SPAAC). Leveraging the high photosensitivity of Ru compounds, we demonstrate rapid and equivalent release of epidermal growth factor (EGF) via either direct illumination or via BRET-based bioluminolysis. As NLuc-originated luminescence can be controlled equivalently throughout the body, we anticipate that this unique protein release strategy will find use for locally triggered drug delivery following systemic administration of a small molecule.


Assuntos
Materiais Biocompatíveis , Materiais Biocompatíveis/química , Azidas/química , Rutênio/química , Processos Fotoquímicos , Hidrogéis/química , Hidrogéis/síntese química , Técnicas de Transferência de Energia por Ressonância de Bioluminescência , Luciferases/metabolismo , Luciferases/química , Luz , Polietilenoglicóis/química
13.
Phys Chem Chem Phys ; 26(36): 24179-24188, 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39254634

RESUMO

Resveratrol is well-known for promoting health benefits due to its antioxidant, anti-aging, anti-carcinogenic, and other beneficial activities. Understanding the photophysics of resveratrol is essential for determining its applicability to pharmaceutical innovations. In the present work, we used an explore-then-assess strategy to map the internal conversion pathways of trans-resveratrol. This strategy consists of exploring the multidimensional configurational space with nonadiabatic dynamics simulations based on a semiempirical multireference method, followed by a feasibility assessment of reduced-dimensionality pathways at a high ab initio theoretical level. The exploration step revealed that internal conversion to the ground state may occur near five distinct conical intersections. The assessment step showed that the main photoisomerization pathway involves a twisted-pyramidalized S1/S0 conical intersection, yielding either trans or cis isomers. However, a secondary path was identified, where cis-trans isomerization happens in the excited state and internal conversion occurs at a cyclic conical intersection, yielding a closed-ring resveratrol derivative. This derivative, which can be formed through this direct path or an indirect photoexcitation, may be connected to the production of oxygen-reactive species previously reported and have implications in photodynamic therapy.


Assuntos
Resveratrol , Resveratrol/química , Isomerismo , Processos Fotoquímicos , Estereoisomerismo , Simulação de Dinâmica Molecular , Teoria Quântica , Estilbenos/química , Estilbenos/efeitos da radiação
14.
Anal Chem ; 96(37): 14759-14765, 2024 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-39234645

RESUMO

Regulating photocurrent polarity is highly attractive for fabricating photoelectrochemical (PEC) biosensors with improved sensitivity and accuracy in practical samples. Here, a new approach that adopts the in situ generated AgI precipitate and AgNCs to reversal Bi2WO6 polarity with formation of Z-type heterojunction was proposed for the first time, which coupled with a high-efficient target conversion strategy of exonuclease III (Exo III)-assisted triple recycling amplification for sensing miRNA-21. The target-related DNA nanospheres in situ generated on electrode with loading of plentiful AgI and AgNCs not only endowed the photocurrent of Bi2WO6 switching from the anodic to cathodic one due to the changes in the electron transfer pathway but also formed AgI/AgNCs/Au/Bi2WO6 Z-type heterojunction to improve the photoelectric conversion efficiency for acquiring extremely enhanced PEC signal, thereby significantly avoiding the problem of high background signal derived from traditional unidirectional increasing/decreasing response and false-positive/false-negative. Experimental data showed that the PEC biosensor had a low detection limit down to 0.085 fM, providing a new polarity-reversal mechanism and expected application in diverse fields, including biomedical research and clinical diagnosis.


Assuntos
Técnicas Biossensoriais , Técnicas Eletroquímicas , MicroRNAs , Compostos de Prata , MicroRNAs/análise , Compostos de Prata/química , Processos Fotoquímicos , Exodesoxirribonucleases/química , Exodesoxirribonucleases/metabolismo , Limite de Detecção , Humanos , Eletrodos , Iodetos
15.
Langmuir ; 40(37): 19441-19457, 2024 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-39238335

RESUMO

Antibiotic residues have been found in several aquatic ecosystems as a result of the widespread use of antibiotics in recent years, which poses a major risk to both human health and the environment. At present, photocatalytic degradation is the most effective and environmentally friendly method. Titanium silicon molecular sieve (TS-1) has been widely used as an industrial catalyst, but its photocatalytic application in wastewater treatment is limited due to its small pores and few active sites. In this paper, we report a method for preparing multistage porous TS-1 with a high specific surface area by alkali treatment. In the photocatalytic removal of CIP (ciprofloxacin) antibiotic wastewater experiments, the alkali-treated catalyst showed better performance in terms of interfacial charge transfer efficiency, which was 2.3 times higher than that of TS-1 synthesized by the conventional method, and it was found to maintain better catalytic performance in the actual water source. In addition, this research studied the effects of solution pH, contaminant concentration, and catalyst dosage on CIP degradation, while liquid chromatography-mass spectrometry (LC-MS) was used to identify intermediates in the degradation process and infer possible degradation pathways and the toxicity of CIP, and its degradation product was also analyzed using ECOSAR 2.2 software, and most of the intermediates were found to be nontoxic and nonharmful. Finally, a 3:5:1 artificial neural network model was established based on the experiments, and the relative importance of the influence of experimental conditions on the degradation rate was determined. The above results confirmed the feasibility and applicability of photocatalytic treatment of wastewater containing antibiotics using visible light excitation alkali post-treatment TS-1, which provided technical support and a theoretical basis for the photocatalytic treatment of wastewater containing antibiotics.


Assuntos
Redes Neurais de Computação , Titânio , Catálise/efeitos da radiação , Titânio/química , Titânio/efeitos da radiação , Porosidade , Antibacterianos/química , Silício/química , Poluentes Químicos da Água/química , Processos Fotoquímicos , Ciprofloxacina/química , Águas Residuárias/química , Fotólise/efeitos da radiação
16.
ACS Appl Mater Interfaces ; 16(37): 49124-49134, 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39230602

RESUMO

Photocatalytic molecules are considered to be one of the most promising substitutions of antibiotics against multidrug-resistant bacterial infections. However, the strong excitonic effect greatly restricts their efficiency in antibacterial performance. Inspired by the interfacial dipole effect, a Ti3C2 MXene modified photocatalytic molecule (MTTTPyB) is designed and synthesized to enhance the yield of photogenerated carriers under light irradiation. The alignment of the energy level between Ti3C2 and MTTTPyB results in the formation of an interfacial dipole, which can provide an impetus for the separation of carriers. Under the role of a dipole electric field, these photogenerated electrons can rapidly migrate to the side of Ti3C2 for improving the separation efficiency of photogenerated electrons and holes. Thus, more electrons can be utilized to produce reactive oxygen species (ROS) under light irradiation. As a result, over 97.04% killing efficiency can be reached for Staphylococcus aureus (S. aureus) when the concentration of MTTTPyB/Ti3C2 was 50 ppm under 660 nm irradiation for 15 min. A microneedle (MN) patch made from MTTTPyB/Ti3C2 was used to treat the subcutaneous bacterial infection. This design of an organic-inorganic interface provides an effective method to minimize the excitonic effect of molecules, further expanding the platform of inorganic/organic hybrid materials for efficient phototherapy.


Assuntos
Antibacterianos , Staphylococcus aureus , Titânio , Staphylococcus aureus/efeitos dos fármacos , Titânio/química , Titânio/farmacologia , Titânio/efeitos da radiação , Antibacterianos/química , Antibacterianos/farmacologia , Catálise/efeitos da radiação , Luz , Animais , Espécies Reativas de Oxigênio/metabolismo , Espécies Reativas de Oxigênio/química , Camundongos , Testes de Sensibilidade Microbiana , Esterilização/métodos , Processos Fotoquímicos
17.
J Phys Chem B ; 128(37): 8878-8885, 2024 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-39231525

RESUMO

We encounter titanium dioxide nanoparticles (TiO2 NPs) throughout our daily lives in the form of food coloring, cosmetics, and industrial materials. They are used on a massive industrial scale, with over 1 million metric tons in the global market. For the workers who process these materials, inhalation is a major concern. The goal of our current research is to provide a direct comparison of the three major types of TiO2 NPs (P25, E171, R101) in terms of surface characterization, cellular response, and in vivo response following introduction into the lungs of mice. In both cellular and in vivo experiments, we observe a pro-inflammatory response to the P25 TiO2 NPs that is not observed in the E171 or R101 TiO2 NPs at mass-matched concentrations. Cellular experiments measured a cytokine, TNF-α, as a marker of a pro-inflammatory response. In vivo experiments in mice measured the number of immune cells and four pro-inflammatory cytokines (IL-6, MIP-2, IP-10, and MCP-1) present in bronchoalveolar lavage fluid. A detailed physical and chemical characterization of the TiO2 NPs shows that the P25 TiO2 NPs are distinguished by smaller primary particles suggesting that samples matched by mass contain a larger number of P25 TiO2 NPs. Cellular dose-response measurements with the P25, E171, and R101 TiO2 NPs support this hypothesis showing increased TNF-α release by macrophages as a function of TiO2 NP dose. Overall, this direct comparison of the three major types of TiO2 NPs shows that the number of particles in a dose, which is dependent on the particle diameter, is a key parameter in TiO2 NP-induced inflammation.


Assuntos
Titânio , Titânio/química , Titânio/farmacologia , Animais , Camundongos , Catálise , Citocinas/metabolismo , Líquido da Lavagem Broncoalveolar/química , Líquido da Lavagem Broncoalveolar/citologia , Nanopartículas/química , Pulmão/efeitos dos fármacos , Pulmão/metabolismo , Nanopartículas Metálicas/química , Processos Fotoquímicos , Tamanho da Partícula , Fator de Necrose Tumoral alfa/metabolismo
18.
J Phys Chem B ; 128(37): 8956-8965, 2024 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-39240094

RESUMO

Photoinduced vitamin D formation occurs 10-15-fold faster in phospholipid bilayers (PLB) than in isotropic solution. It has been hypothesized that amphipatic interactions of the PLB with the rotationally flexible previtamin D (Pre) stabilize its helical conformers, enhancing thermal intramolecular [1,7]-hydrogen transfer, forming vitamin D. To test this hypothesis, we carried out molecular dynamics (MD) simulations of Pre in a PLB composed of dipalmitoylphosphatidylcholine (DPPC). We designed a classical force field capable of accurately describing the equilibrium composition of Pre conformers. Using adaptive biasing force MD simulations, we determined the free energy of Pre conformers in isotropic environments (hexane and gas-phase) and in the anisotropic environment of a DPPC PLB. We find a total increase of 25.5% of the population of both helical conformers (+20.5% g+Zg+ and +5% g-Zg-) in DPPC compared to hexane. In view of ab initio simulations, showing that hydrogen transfer occurs in both helical conformers, our study strongly suggests the validity of the initial hypothesis. Regarding the amphipatic interactions of Pre with the PLB, we find that, similar to cholesterol (Chol) and 7-dehydrocholesterol (7-DHC), Pre entertains hydrogen bonds mainly to the carbonyl groups of DPPC and, to a lesser extent, with phosphate oxygen atoms and rarely to water molecules at the interface. We further report order parameters of the Pre/DPPC system, which are slightly smaller than those for Chol/DPPC and 7-DHC/DPPC, but larger than for pure DPPC. This indicates a loss in membrane viscosity upon photochemical ring-opening of 7-DHC to form Pre.


Assuntos
1,2-Dipalmitoilfosfatidilcolina , Bicamadas Lipídicas , Simulação de Dinâmica Molecular , 1,2-Dipalmitoilfosfatidilcolina/química , Bicamadas Lipídicas/química , Bicamadas Lipídicas/metabolismo , Vitamina D/química , Vitamina D/análogos & derivados , Vitamina D/metabolismo , Processos Fotoquímicos , Conformação Molecular , Termodinâmica
19.
Dalton Trans ; 53(36): 15176-15189, 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39221457

RESUMO

Cyclometalated iridium(III) compounds have been widely explored due to their outstanding photo-physical properties and multiple anticancer activities. In this paper, three cyclometalated iridium(III) compounds [Ir(ppy)2(DBDIP)]PF6 (5a), [Ir(bzq)2(DBDIP)]PF6 (5b), and [Ir(piq)2(DBDIP)]PF6 (5c) (ppy: 2-phenylpyridine; bzq: benzo[h]quinoline; piq: 1-phenylisoquinoline, and DBDIP: 2-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-1H-imidazo[4,5-f][1,10]phenanthroline) were synthesized and the mechanism of antitumor activity was investigated. Compounds photoactivated by visible light show strong cytotoxicity against tumor cells, especially toward A549 cells. Biological experiments such as migration, cellular localization, mitochondrial membrane potential and permeability, reactive oxygen species (ROS) and calcium ion level detection were performed, and they demonstrated that the compounds induced the apoptosis of A549 cells through a mitochondrial pathway. At the same time, oxidative stress caused by ROS production increases the release of damage-related molecules and the expression of porogen gasdermin D (GSDMD), and the content of LDH released from damaged cell membranes also increased. Besides, the content of the lipid peroxidation product, malondialdehyde (MDA), increased and the expression of GPX4 decreased. These indicate that the compounds promote cell death by combining ferroptosis and pyroptosis. The results reveal that cyclometalated iridium(III) compounds 5a-5c may be a potential chemotherapeutic agent for photodynamic therapy of cancers.


Assuntos
Antineoplásicos , Complexos de Coordenação , Ensaios de Seleção de Medicamentos Antitumorais , Irídio , Espécies Reativas de Oxigênio , Humanos , Irídio/química , Irídio/farmacologia , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/síntese química , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Espécies Reativas de Oxigênio/metabolismo , Células A549 , Apoptose/efeitos dos fármacos , Luz , Potencial da Membrana Mitocondrial/efeitos dos fármacos , Proliferação de Células/efeitos dos fármacos , Neoplasias Pulmonares/tratamento farmacológico , Neoplasias Pulmonares/patologia , Neoplasias Pulmonares/metabolismo , Estrutura Molecular , Cálcio/metabolismo , Movimento Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Processos Fotoquímicos , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/síntese química
20.
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
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