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1.
Int J Biol Macromol ; : 132942, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38848841

RESUMO

Grafting thermo-responsive polymers onto cellulose nanocrystals (CNCs) and achieving critical temperature regulation has drawn significant research interest. The thermal transition behavior of CNCs can be controlled by adjusting the polymer molecular brushes on the CNCs surface. We synthesized poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA) grafted CNCs via surface-initiated reversible addition-fragmentation chain transfer, followed by modifying PDMAEMA brushes into poly-3-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate (PDMAPS) brushes via quaternization. The critical temperature was regulated by modifying and grafting of poly (ethylene glycol) methacrylate. Found the thermal stimulus-responsive type and transition point of CNCs can be controlled by adjusting the surface molecular brushes. Ultraviolet-visible spectroscopy and dynamic light scattering analyses indicated that CNC-PDMAEMA aggregated above 70 °C, whereas CNC-PDMAPS aggregated below 31 °C. The thermo-responsive materials based on CNCs exhibited a conversion from a lower critical aggregation temperature to an upper critical aggregation temperature (UCAT) type. CNC-PDMAPS-mPEG was obtained by modifying and grafting for UCAT to be regulated to approximately 37 °C, which is close to the human body temperature. CNC-PDMAPS and CNC-PDMAPS-mPEG exhibited only microscopic alterations and could encapsulate and release substances. Therefore, they demonstrate considerable potential for biomedical applications.

2.
Environ Sci Technol ; 58(21): 9370-9380, 2024 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-38743251

RESUMO

Utilizing solar light and water matrix components in situ to reduce the chemical and energy demands would make treatment technologies more sustainable for micropollutant abatement in wastewater effluents. We herein propose a new strategy for micropollutant abatement through dissolved organic matter (DOM)-mediated photosensitized activation of monochloramine (NH2Cl). Exposing the chlorinated wastewater effluent with residual NH2Cl to solar irradiation (solar/DOM/NH2Cl process) degrades six structurally diverse micropollutants at rate constants 1.26-34.2 times of those by the solar photolysis of the dechlorinated effluent (solar/DOM process). Notably, among the six micropollutants, the degradation rate constants of estradiol, acetaminophen, bisphenol A, and atenolol by the solar/DOM/NH2Cl process are 1.13-4.32 times the summation of those by the solar/DOM and solar/NH2Cl processes. The synergism in micropollutant degradation is attributed to the generation of reactive nitrogen species (RNS) and hydroxyl radicals (HO·) from the photosensitized activation of NH2Cl. Triplet state-excited DOM (3DOM*) dominates the activation of NH2Cl, leading to the generation of RNS, while HO· is produced from the interactions between RNS and other photochemically produced reactive intermediates (e.g., O2·- and DOM·+/·-). The findings advance the knowledge of DOM-mediated photosensitization and offer a sustainable method for micropollutant abatement in wastewater effluents containing residual NH2Cl.


Assuntos
Águas Residuárias , Poluentes Químicos da Água , Águas Residuárias/química , Poluentes Químicos da Água/química , Fotólise , Luz Solar
3.
Chem Biol Interact ; 397: 111062, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38763349

RESUMO

Acute lung injury is the leading cause of paraquat (PQ) poisoning-related mortality. The mechanism by which macrophages are involved in PQ-induced acute lung injury remains unclear. In recent years, the role of metabolic reprogramming in macrophage functional transformation has received significant attention. The current study aimed to identify the role of altered macrophage glucose metabolism and molecular mechanisms in PQ poisoning-induced acute lung injury. We established a model of acute lung injury in PQ-intoxicated mice via the intraperitoneal injection of PQ. PQ exposure induces macrophage M1 polarization and promotes the release of inflammatory factors, which causes the development of acute lung injury in mice. In vitro analysis revealed that PQ altered glucose metabolism, which could be reversed by siRNA transfection to silence the expression of HK1, a key enzyme in glucose metabolism. RNA sequencing revealed that the ERK/MAPK pathway was the crucial molecular mechanism of PQ pathogenesis. Further, U0126, an ERK inhibitor, could inhibit PQ-induced HK1 activation and macrophage M1 polarization. These findings provide novel insights into the previously unrecognized mechanism of ERK/MAPK-HK1 activation in PQ poisoning.


Assuntos
Lesão Pulmonar Aguda , Glucose , Hexoquinase , Sistema de Sinalização das MAP Quinases , Macrófagos , Camundongos Endogâmicos C57BL , Paraquat , Animais , Lesão Pulmonar Aguda/induzido quimicamente , Lesão Pulmonar Aguda/metabolismo , Lesão Pulmonar Aguda/patologia , Paraquat/toxicidade , Camundongos , Glucose/metabolismo , Macrófagos/metabolismo , Macrófagos/efeitos dos fármacos , Hexoquinase/metabolismo , Sistema de Sinalização das MAP Quinases/efeitos dos fármacos , Masculino , Transdução de Sinais/efeitos dos fármacos , Células RAW 264.7
4.
Adv Mater ; : e2402391, 2024 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-38669588

RESUMO

High-entropy alloy nanoparticles (HEAs) show great potential in emerging electrocatalysis due to their combination and optimization of multiple elements. However, synthesized HEAs often exhibit a weak interface with the conductive substrate, hindering their applications in long-term catalysis and energy conversion. Herein, a highly active and durable electrocatalyst composed of quinary HEAs (PtNiCoFeCu) encapsulated inside the activated carbonized wood (ACW) is reported. The self-encapsulation of HEAs is achieved during Joule heating synthesis (2060 K, 2 s) where HEAs naturally nucleate at the defect sites. In the meantime, HEAs catalyze the deposition of mobile carbon atoms to form a protective few-layer carbon shell during the rapid quenching process, thus remarkably strengthening the interface stability between HEAs and ACW. As a result, the HEAs@ACW shows not only favorable activity with an overpotential of 7 mV at 10 mA cm-2 for hydrogen evolution but also negligible attenuation during a 500 h stability test, which is superior to most reported electrocatalysts. The design of self-encapsulated HEAs inside ACW provides a critical strategy to enhance both activity and stability, which is also applicable to many other energy conversion technologies.

5.
Environ Sci Technol ; 58(13): 6030-6038, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38517061

RESUMO

Increasing radical yields to reduce UV fluence requirement for achieving targeted removal of micropollutants in water would make UV-based advanced oxidation processes (AOPs) less energy demanding in the context of United Nations' Sustainable Development Goals and carbon neutrality. We herein demonstrate that, by switching the UV radiation source from conventional low-pressure UV at 254 nm (UV254) to emerging Far-UVC at 222 nm (UV222), the fluence-based concentration of HO• in the UV/peroxydisulfate (UV/PDS) AOP increases by 6.40, 2.89, and 6.00 times in deionized water, tap water, and surface water, respectively, with increases in the fluence-based concentration of SO4•- also by 5.06, 5.81, and 55.47 times, respectively. The enhancement to radical generation is confirmed using a kinetic model. The pseudo-first-order degradation rate constants of 16 micropollutants by the UV222/PDS AOP in surface water are predicted to be 1.94-13.71 times higher than those by the UV254/PDS AOP. Among the tested water matrix components, chloride and nitrate decrease SO4•- but increase HO• concentration in the UV222/PDS AOP. Compared to the UV254/PDS AOP, the UV222/PDS AOP decreases the formation potentials of carbonaceous disinfection byproducts (DBPs) but increases the formation potentials of nitrogenous DBPs.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Água , Fotólise , Poluentes Químicos da Água/análise , Peróxido de Hidrogênio , Oxirredução , Raios Ultravioleta , Desinfecção
6.
Carcinogenesis ; 45(5): 288-299, 2024 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-38466106

RESUMO

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental carcinogens accountable to developing skin cancers. Recently, we reported that exposure to benzo[a]pyrene (B[a]P), a common PAH, causes epigenetic and metabolic alterations in the initiation, promotion and progression of non-melanoma skin cancer (NMSC). As a follow-up investigation, this study examines how dietary triterpenoid ursolic acid (UA) regulates B[a]P-driven epigenetic and metabolic pathways in SKH-1 hairless mice. Our results show UA intercepts against B[a]P-induced tumorigenesis at different stages of NMSC. Epigenomic cytosines followed by guanine residues (CpG) methyl-seq data showed UA diminished B[a]P-mediated differentially methylated regions (DMRs) profiles. Transcriptomic RNA-seq revealed UA revoked B[a]P-induced differentially expressed genes (DEGs) of skin cancer-related genes, such as leucine-rich repeat LGI family member 2 (Lgi2) and kallikrein-related peptidase 13 (Klk13), indicating UA plays a vital role in B[a]P-mediated gene regulation and its potential consequences in NMSC interception. Association analysis of DEGs and DMRs found that the mRNA expression of KLK13 gene was correlated with the promoter CpG methylation status in the early-stage comparison group, indicating UA could regulate the KLK13 by modulating its promoter methylation at an early stage of NMSC. The metabolomic study showed UA alters B[a]P-regulated cancer-associated metabolisms like thiamin metabolism, ascorbate and aldarate metabolism during the initiation phase; pyruvate, citrate and thiamin metabolism during the promotion phase; and beta-alanine and pathothenate coenzyme A (CoA) biosynthesis during the late progression phase. Taken together, UA reverses B[a]P-driven epigenetic, transcriptomic and metabolic reprogramming, potentially contributing to the overall cancer interception against B[a]P-mediated NMSC.


Assuntos
Benzo(a)pireno , Metilação de DNA , Epigênese Genética , Camundongos Pelados , Neoplasias Cutâneas , Triterpenos , Ácido Ursólico , Animais , Neoplasias Cutâneas/induzido quimicamente , Neoplasias Cutâneas/genética , Neoplasias Cutâneas/patologia , Neoplasias Cutâneas/metabolismo , Benzo(a)pireno/toxicidade , Triterpenos/farmacologia , Camundongos , Epigênese Genética/efeitos dos fármacos , Metilação de DNA/efeitos dos fármacos , Carcinógenos Ambientais/toxicidade , Regulação Neoplásica da Expressão Gênica/efeitos dos fármacos , Carcinogênese/efeitos dos fármacos , Carcinogênese/genética , Carcinogênese/induzido quimicamente
7.
Chemosphere ; 351: 141228, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38237782

RESUMO

Wastewater non-potable reuse involves further processing of secondary effluent to a quality level acceptable for reuse and is a promising solution to combating water scarcity. Recalcitrant chromophores in landfill leachate challenge the water quality for non-potable reuse when leachate is co-treated with municipal wastewater. In this study, we first use multivariate statistical analysis to reveal that leachate is an important source (with a Pearson's coefficient of 0.82) of recalcitrant chromophores in the full-scale membrane bioreactor (MBR) effluent. We then evaluate the removal efficacies of chromophores by chlorination, breakpoint chlorination, and the chlorination-UV/chlorine advanced oxidation treatment. Conventional chlorination and breakpoint chlorination only partially remove chromophores, leaving a colour level exceeding the standards for non-potable reuse (>20 Hazen units). We demonstrate that pre-chlorination (with an initial chlorine dosing of 20 mg/L as Cl2) followed by UV radiation (with a UV fluence of 500 mJ/cm2) effectively degraded recalcitrant chromophores (>90%). By quantifying the electron donating capacity (EDC) and radical scavenging capacity (RSC) of the reclaimed water, we demonstrate that pre-chlorination reduces EDC and RSC by up to 64%, increases UV transmittance by 32%, and increases radical yields from UV photolysis of chlorine by 1.7-2.2 times. The findings advance fundamental understanding of the alteration of dissolved coloured substances by (photo)chlorination treatment and provide implications for applying advanced oxidation processes in treating wastewater effluents towards sustainable non-potable reuse.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Águas Residuárias , Cloro , Halogênios , Oxirredução , Raios Ultravioleta
8.
Sci Total Environ ; 912: 169241, 2024 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-38072271

RESUMO

Groundwater has been known as the second largest freshwater storage in the world, following surface water. Over the years, groundwater has already been under overwhelming pressure to satisfy human needs for artificial activities around the world. Meanwhile, the most noticeable footprint of human activities is the impact of climate change. Climate change has the potential to change the physical and chemical properties of groundwater, thereby affecting its ecological functions. This study summarizes existing research affiliated with the possible effects of a changing climate on the quality of groundwater, including changes in water availability, increased salinity and pollution from extreme weather events, and the potentiality of seawater intrusion into coastal aquifers. Previous works dealing with groundwater-induced responses to the climate system and climate impacts on groundwater quality through natural and anthropogenic processes have been reviewed. The climate-induced changes in groundwater quality including pH, dissolved oxygen level, salinity, and concentrations of organic and inorganic compounds were assessed. Some future research directions are proposed, including exploring the potential changes in the occurrences and fate of micropollutants in groundwater, examining the relationship between the increase of microcystin in groundwater and climate change, studying the changes in the stability of metals and metal complexation, and completing studies across different regional climate regions.

9.
J Clin Periodontol ; 51(2): 196-208, 2024 02.
Artigo em Inglês | MEDLINE | ID: mdl-38088448

RESUMO

AIM: To reveal the cellular composition and molecular environment of the periodontal and peri-implant inflammatory infiltrates through a single-cell sequencing technique, which may explain the pathological difference between these two diseases. A special focus was placed on the phenotypes and potential roles of neutrophils and fibroblasts in peri-implant/periodontal tissue immunity. MATERIALS AND METHODS: High-throughput single-cell transcriptomic profiling of peri-implant tissues from patients with peri-implantitis as well as periodontal tissues from patients with periodontitis and healthy donors was performed. Immunofluorescence analysis was carried out to further validate the identified cell subtypes and their involvement in peri-implantitis and periodontitis. RESULTS: Based on our single-cell resolution analysis, a quantified proportional increase of neutrophil (Neu) subtypes was shown in peri-implantitis. Among these, a predominance of Neutro_CXCR2 was revealed. We also found the involvement of inflammation-promoting fibroblasts as well as a predominance of CXCL8+ fibroblast-CXCR2+ neutrophil interaction in peri-implantitis. CONCLUSIONS: Our study indicated that the predominance of CXCL8+ fibroblast-CXCR2+ neutrophil interaction might underline the enhanced host response in peri-implantitis compared with periodontitis. This information offers a molecular basis by which fibroblast and neutrophil subtypes might be diagnostically and therapeutically targeted in peri-implantitis.


Assuntos
Implantes Dentários , Peri-Implantite , Periodontite , Humanos , Neutrófilos , Inflamação , Periodontite/patologia , Fibroblastos
10.
Water Res ; 247: 120794, 2023 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-37918199

RESUMO

Understanding the reactivities of chlorine towards micropollutants is crucial for assessing the fate of micropollutants in water chlorination. In this study, we integrated machine learning with kinetic modeling to predict the reaction kinetics between micropollutants and chlorine in deionized water and real surface water. We first established a framework to predict the apparent second-order rate constants for micropollutants with chlorine by combining Morgan molecular fingerprints with machine learning algorithms. The framework was tuned using Bayesian optimization and showed high prediction accuracy. It was validated through experiments and used to predict the unreported apparent second-order rate constants for 103 emerging micropollutants with chlorine. The framework also improved the understanding of the structure-dependence of micropollutants' reactivity with chlorine. We incorporated the predicted apparent second-order rate constants into the Kintecus software to establish a hybrid model to profile the time-dependent changes of micropollutant concentrations by chlorination. The hybrid model was validated by experiments conducted in real surface water in the presence of natural organic matter. The hybrid model could predict how much micropollutants were degraded by chlorination with varied chlorine contact times and/or initial chlorine dosages. This study advances fundamental understanding of the reaction kinetics between chlorine and emerging micropollutants, and also offers a valuable tool to assess the fate of micropollutants during chlorination of drinking water.


Assuntos
Água Potável , Poluentes Químicos da Água , Purificação da Água , Cloro , Teorema de Bayes , Cinética , Poluentes Químicos da Água/análise , Halogenação
11.
Environ Sci Technol ; 57(51): 21876-21887, 2023 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-37978925

RESUMO

Effective and affordable disinfection technology is one key to achieving Sustainable Development Goal 6. In this work, we develop a process by integrating Far-UVC irradiation at 222 nm with free chlorine (UV222/chlorine) for rapid inactivation of the chlorine-resistant and opportunistic Aspergillus niger spores in drinking water. The UV222/chlorine process achieves a 5.0-log inactivation of the A. niger spores at a chlorine dosage of 3.0 mg L-1 and a UV fluence of 30 mJ cm-2 in deionized water, tap water, and surface water. The inactivation rate constant of the spores by the UV222/chlorine process is 0.55 min-1, which is 4.6-fold, 5.5-fold, and 1.8-fold, respectively, higher than those of the UV222 alone, chlorination alone, and the conventional UV254/chlorine process under comparable conditions. The more efficient inactivation by the UV222/chlorine process is mainly attributed to the enhanced generation of reactive chlorine species (e.g., 6.7 × 10-15 M of Cl•) instead of hydroxyl radicals from UV222 photolysis of chlorine, which is verified through both experiments and a kinetic model. We further demonstrate that UV222 photolysis damages the membrane integrity and benefits the penetration of chlorine and radicals into cells for inactivation. The merits of the UV222/chlorine process over the UV254/chlorine process also include the more effective inhibition of the photoreactivation of the spores after disinfection and the lower formation of chlorinated disinfection byproducts and toxicity.


Assuntos
Água Potável , Purificação da Água , Cloro/farmacologia , Esporos Fúngicos , Fotólise , Desinfecção , Raios Ultravioleta , Cloretos
12.
Environ Sci Technol ; 57(29): 10891-10900, 2023 07 25.
Artigo em Inglês | MEDLINE | ID: mdl-37343195

RESUMO

The dose-response behavior of pathogens and inactivation mechanisms by UV-LEDs and excimer lamps remains unclear. This study used low-pressure (LP) UV lamps, UV-LEDs with different peak wavelengths, and a 222 nm krypton chlorine (KrCl) excimer lamp to inactivate six microorganisms and to investigate their UV sensitivities and electrical energy efficiencies. The 265 nm UV-LED had the highest inactivation rates (0.47-0.61 cm2/mJ) for all tested bacteria. The bacterial sensitivity strongly fitted the absorption curve of nucleic acids at wavelengths of 200-300 nm; however, indirect damage induced by reactive oxygen species (ROS) was the leading cause of bacterial inactivation under 222 nm UV irradiation. In addition, the guanine and cytosine (GC) content and cell wall constituents of bacteria affect inactivation efficiency. The inactivation rate constant of Phi6 (0.13 ± 0.002 cm2/mJ) at 222 nm due to lipid envelope damage was significantly higher than other UVC (0.006-0.035 cm2/mJ). To achieve 2log reduction, the LP UV lamp had the best electrical energy efficiency (required less energy, average 0.02 kWh/m3) followed by 222 nm KrCl excimer lamp (0.14 kWh/m3) and 285 nm UV-LED (0.49 kWh/m3).


Assuntos
Raios Ultravioleta , Purificação da Água , Bactérias , Espécies Reativas de Oxigênio , Cloro , Desinfecção
13.
Water Res ; 241: 120169, 2023 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-37290191

RESUMO

Concerns over human health risks associated with chemical contaminants (micropollutants) in drinking waters are rising due to the increased use of reclaimed water or water supplies impacted by upstream wastewater discharges. Ultraviolet (UV)-driven advanced oxidation processes (UV-AOPs) using radiation sources that emit at 254 nm have been developed as advanced treatments to degrade contaminants, while those UV-AOPs can be improved towards higher radical yields and lower byproduct formation. Several previous studies have suggested that Far-UVC radiation (200-230 nm) is a promising radiance source to drive UV-AOPs because the direct photolysis of micropollutants and production of reactive species from oxidant precursors can both be improved. In this study, we summarize from the literature the photodecay rate constants of five micropollutants by direct UV photolysis, which are higher at 222 than 254 nm. We experimentally determine the molar absorption coefficients at 222 and 254 nm of eight oxidants commonly used in water treatment and present the quantum yields of the oxidant photodecay. Our experimental results also show that the concentrations of HO·, Cl·, and ClO· generated in the UV/chlorine AOP can be increased by 5.15-, 15.76-, and 2.86-fold, respectively, by switching the UV wavelength from 254 to 222 nm. We also point out the challenges of applying Far-UVC for micropollutant abatement in water treatment, including the strong light screening effect of matrix components (e.g., carbonate, nitrate, bromide, and dissolved organic matter), the formation of byproducts via new reaction pathways, and the needs to improve the energy efficiency of the Far-UVC radiation sources.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Humanos , Águas Residuárias , Oxirredução , Cloro , Oxidantes , Purificação da Água/métodos , Raios Ultravioleta , Peróxido de Hidrogênio
14.
Environ Sci Technol ; 57(47): 18867-18876, 2023 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-37158565

RESUMO

Increasing the radical yield and reducing energy consumption would enhance the sustainability and competitiveness of advanced oxidation processes (AOPs) for micropollutant degradation in water. We herein report a novel AOP coupling far-UVC radiation at 222 nm with chlorinated cyanurates (termed the UV222/Cl-cyanurates AOP) for radical generation and micropollutant abatement in water. We experimentally determined the concentrations of HO•, Cl•, and ClO• in the UV222/Cl-cyanurates AOP in deionized water and swimming pool water. The radical concentrations are 10-27 times and 4-13 times, respectively, higher than those in the UV254/Cl-cyanurates AOP and the well-documented UV254/chlorine AOP under comparable conditions (e.g., same UV fluence and oxidant dosing). We determined the molar absorption coefficients and innate quantum yields of two chlorine species and two Cl-cyanurates at 222 nm and incorporated these parameters into a kinetic model. The model enables accurate prediction of oxidant photodecay rates as well as the pH impact on radical generation in the UV222/Cl-cyanurates AOP. We predicted the pseudo-first-order degradation rate constants of 25 micropollutants in the UV222/Cl-cyanurates AOP and demonstrated that many micropollutants can be degraded by >80% with a low UV fluence of 25 mJ cm-2. This work advances the fundamental photochemistry of chlorine and Cl-cyanurates at 222 nm and offers a highly effective engineering tool in combating micropollutants in water where Cl-cyanurates are suitable to use.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Água , Cloro , Oxirredução , Raios Ultravioleta , Oxidantes
15.
Environ Sci Technol ; 57(24): 9064-9074, 2023 06 20.
Artigo em Inglês | MEDLINE | ID: mdl-37257188

RESUMO

Far-UVC radiation is an emerging tool for combating pathogenic microorganisms in water, but its vulnerability to water matrix components remains unclear. We herein report the critical impacts of nitrate during Far-UVC disinfection of water. Nitrate at environmentally relevant concentrations (0.5-10.0 mg-N L-1) significantly inhibits Escherichia coli inactivation by Far-UVC radiation at 222 nm, via prolonging the "lag phase" of inactivation and reducing the inactivation rate constants by 1.08-2.74 times, while it shows negligible impact on E. coli inactivation by UVC radiation at 254 nm. The inhibitory impact of nitrate on Far-UVC disinfection is attributed to its strong light-shielding effect. Although hydroxyl radicals and reactive nitrogen species are generated from Far-UVC photolysis of nitrate at high concentrations of 10-13 and ∼10-7 M, respectively, those radicals are unable to compensate for the light-shielding effect of nitrate on E. coli inactivation. Moreover, reactive nitrogen species lead to the formation of nitrogenous byproducts, which increase the genotoxicity of the water. The findings advance the fundamental photochemistry and radical chemistry of nitrate at 222 nm and provide useful insights to guide the operation of Far-UVC in treating nitrate-containing water.


Assuntos
Escherichia coli , Nitratos , Escherichia coli/efeitos da radiação , Nitratos/farmacologia , Desinfecção , Fotólise , Raios Ultravioleta
16.
Environ Sci Technol ; 57(47): 18735-18743, 2023 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-37126657

RESUMO

Dichloramine (NHCl2) often coexists with monochloramine (NH2Cl) in reverse osmosis (RO) permeate in potable reuse scenarios when NH2Cl is added upstream of RO for membrane fouling control such that UV photolysis of NHCl2 occurs during the downstream UV/chloramine process. However, the formation of reactive nitrogen species (RNS) and their incorporation into byproducts during the UV/NHCl2 process are largely unknown. This study quantitatively evaluated the generation of RNS in the UV/NHCl2 process and investigated the role of RNS in micropollutant transformation. UV photolysis of NHCl2 produced comparable RNS concentration to that of NH2Cl at the same oxidant dosage (100 µM) at pH 5.5. Under the experimental conditions, the RNS contributed greatly (40.6%) to N,N-diethyl-3-methylbenzamide (DEET) degradation. By using 15N-labeling and mass spectrometry methods, seven nitrogenous byproducts of DEET degradation with the incorporation of nitrogen originating from the RNS were detected. Among these seven byproducts, six were identified to contain a nitro group (-NO2). While the UV/NHCl2 process formed comparable intensities of -NO-containing products to those in the UV/NH2Cl process, the later process formed 3-91% higher intensities of -NO2-containing products. These findings are essential in furthering our understanding of the contribution of the UV/NHCl2 process in potable reuse scenarios.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Espécies Reativas de Nitrogênio , Fotólise , Nitrogênio , DEET , Dióxido de Nitrogênio , Oxirredução , Raios Ultravioleta , Cloraminas , Óxido Nítrico , Cloro
17.
Small Methods ; 7(7): e2300192, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37116089

RESUMO

In order to improve the thermal stability of perovskite solar cells (PSCs) and reduce production costs, hole transport layer (HTL)-free carbon-based CsPbI3 PSCs (C-PSCs) have attracted the attention of researchers. However, the power conversion efficiency (PCE) of HTL-free CsPbI3 C-PSCs is still lower than that of PSCs with HTL/ metal electrodes. This is because the direct contact between the carbon electrode and the perovskite layer has a higher requirement on the crystal quality of perovskite layer and matched energy level at perovskite/carbon interface. Herein, the acyl chloride group and its derivative trichloroacetyl chloride are used to passivate CsPbI3 C-PSCs for the first time. The results show that the carbonyl group of trichloroacetyl chloride can effectively passivate the uncoordinated Pb2+ ions in perovskite. At the same time, leaving group Cl- ions can increase the grain size of perovskite and improve the crystallization quality of perovskite layer. In addition, the trichloroacetyl chloride tends to generate cesium chloride acetate, which acts as an electron blocking layer, reduces charge recombination, promotes gradient energy level arrangement, and effectively improves the separation and extraction ability of carriers. The PCE of CsPbI3 HTL-free C-PSCs is successfully increased from 13.40% to 14.82%.

18.
Carcinogenesis ; 44(5): 436-449, 2023 08 10.
Artigo em Inglês | MEDLINE | ID: mdl-37100755

RESUMO

Non-melanoma skin cancer (NMSC) is the most common cancer in the world. Environmental exposure to carcinogens is one of the major causes of NMSC initiation and progression. In the current study, we utilized a two-stage skin carcinogenesis mouse model generated by sequential exposure to cancer-initiating agent benzo[a]pyrene (BaP) and promoting agent 12-O-tetradecanoylphorbol-13-acetate (TPA), to study epigenetic, transcriptomic and metabolic changes at different stages during the development of NMSC. BaP/TPA caused significant alterations in DNA methylation and gene expression profiles in skin carcinogenesis, as evidenced by DNA-seq and RNA-seq analysis. Correlation analysis between differentially expressed genes and differentially methylated regions found that the mRNA expression of oncogenes leucine rich repeat LGI family member 2 (Lgi2), kallikrein-related peptidase 13 (Klk13) and SRY-Box transcription factor (Sox5) are correlated with the promoter CpG methylation status, indicating BaP/TPA regulates these oncogenes through regulating their promoter methylation at different stages of NMSC. Pathway analysis identified that the modulation of macrophage-stimulating protein-recepteur d'origine nantais and high-mobility group box 1 signaling pathways, superpathway of melatonin degradation, melatonin degradation 1, sirtuin signaling and actin cytoskeleton signaling pathways are associated with the development of NMSC. The metabolomic study showed BaP/TPA regulated cancer-associated metabolisms like pyrimidine and amino acid metabolisms/metabolites and epigenetic-associated metabolites, such as S-adenosylmethionine, methionine and 5-methylcytosine, indicating a critical role in carcinogen-mediated metabolic reprogramming and its consequences on cancer development. Altogether, this study provides novel insights integrating methylomic, transcriptomic and metabolic-signaling pathways that could benefit future skin cancer treatment and interception studies.


Assuntos
Carcinógenos Ambientais , Melatonina , Neoplasias Cutâneas , Camundongos , Animais , Benzo(a)pireno/toxicidade , Benzo(a)pireno/metabolismo , Carcinogênese/genética , Neoplasias Cutâneas/induzido quimicamente , Neoplasias Cutâneas/genética , Acetato de Tetradecanoilforbol , Epigênese Genética
19.
Artigo em Inglês | MEDLINE | ID: mdl-36759344

RESUMO

Due to the advantages of low cost and good thermal stability, all-inorganic CsPbI2Br carbon-based perovskite solar cells (C-PSCs) without a hole transport layer have been rapidly developed in recent years. While the carbon electrode is in direct contact with the CsPbI2Br film, higher requirements are placed on the defects and energy level arrangement of the CsPbI2Br layer, which leads to the relatively low photoelectric conversion efficiency (PCE) of C-PSCs. Herein, propylamine hydrobromide (PABr) and its derivative 3-bromopropylamine hydrobromide (3Br-PABr) were used to passivate the surface defects of CsPbI2Br C-PSCs for the first time. The results show that passivation molecules are modulated by the substituent effect, leading to a stronger interaction between amino groups and uncoordinated Pb2+ ions, which facilitates a better passivation effect of 3Br-PABr. In addition, 3Br-PABr promotes the gradient arrangement of energy levels while passivating surface defects, which accelerates the rapid extraction of holes. After the passivation by PABr and 3Br-PABr, the PCE of HTL-free CsPbI2Br C-PSCs increased from 12.15% for the control device to 13.15 and 14.04%, respectively, which are among the highest reported values of CsPbI2Br C-PSCs.

20.
Water Res ; 233: 119781, 2023 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-36841167

RESUMO

In rural areas where low-temperature groundwater is used as a drinking water source, cost-effective sterilization techniques are needed to prevent groundwater consumers from the disease risks triggered by pathogenic microorganisms like Escherichia coli and fungal spores. In this study, micro/nano bubbles (MNBs) coupled with the tellurium (Te)-based catalysts were used to considerably enhance the solar disinfection (SODIS) efficiency while overcoming the intrinsic defects of SODIS, particularly in low-temperature. Sterilization tests showed that 6.5 log10 cfu/mL of E. coli K-12 and 4.0 log10 cfu/mL of Aspergillus niger spores were completely inactivated within 5 min while applying this novel process for disinfection of raw groundwater, even in low-temperature. The underlying mechanisms of the extraordinary sterilization efficiency were revealed through comprehensive characterization of the catalysts and the physiological changes of the microorganisms. The localized surface plasmon resonance (LSPR) effect of the Te catalysts was identified to take advantage of photothermal synergism to achieve cell death. The integration of MNBs with the facet-engineered Te catalysts improved the photothermal catalytic effect and extracellular electron transfer, which substantially strengthened disinfection efficiency. This study provides a targeted solution into microbial inactivation in groundwater and emphasizes a cost-effective groundwater sterilization process.


Assuntos
Água Subterrânea , Purificação da Água , Telúrio , Escherichia coli , Água Subterrânea/microbiologia , Desinfecção/métodos , Purificação da Água/métodos
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