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1.
Proc Natl Acad Sci U S A ; 120(11): e2213910120, 2023 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-36877843

RESUMO

The 2019 to 2020 Australian summer wildfires injected an amount of organic gases and particles into the stratosphere unprecedented in the satellite record since 2002, causing large unexpected changes in HCl and ClONO2. These fires provided a novel opportunity to evaluate heterogeneous reactions on organic aerosols in the context of stratospheric chlorine and ozone depletion chemistry. It has long been known that heterogeneous chlorine (Cl) activation occurs on the polar stratospheric clouds (PSCs; liquid and solid particles containing water, sulfuric acid, and in some cases nitric acid) that are found in the stratosphere, but these are only effective for ozone depletion chemistry at temperatures below about 195 K (i.e., largely in the polar regions during winter). Here, we develop an approach to quantitatively assess atmospheric evidence for these reactions using satellite data for both the polar (65 to 90°S) and the midlatitude (40 to 55°S) regions. We show that heterogeneous reactions apparently even happened at temperatures at 220 K during austral autumn on the organic aerosols present in 2020 in both regions, in contrast to earlier years. Further, increased variability in HCl was also found after the wildfires, suggesting diverse chemical properties among the 2020 aerosols. We also confirm the expectation based upon laboratory studies that heterogeneous Cl activation has a strong dependence upon water vapor partial pressure and hence atmospheric altitude, becoming much faster close to the tropopause. Our analysis improves the understanding of heterogeneous reactions that are important for stratospheric ozone chemistry under both background and wildfire conditions.

2.
Proc Natl Acad Sci U S A ; 120(31): e2303974120, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37487065

RESUMO

Active chlorine in the atmosphere is poorly constrained and so is its role in the oxidation of the potent greenhouse gas methane, causing uncertainty in global methane budgets. We propose a photocatalytic mechanism for chlorine atom production that occurs when Sahara dust mixes with sea spray aerosol. The mechanism is validated by implementation in a global atmospheric model and thereby explaining the episodic, seasonal, and location-dependent 13C depletion in CO in air samples from Barbados [J.E. Mak, G. Kra, T. Sandomenico, P. Bergamaschi, J. Geophys. Res. Atmos. 108 (2003)], which remained unexplained for decades. The production of Cl can also explain the anomaly in the CO:ethane ratio found at Cape Verde [K. A. Read et al., J. Geophys. Res. Atmos. 114 (2009)], in addition to explaining the observation of elevated HOCl [M. J. Lawler et al., Atmos. Chem. Phys. 11, 7617-7628 (2011)]. Our model finds that 3.8 Tg(Cl) y-1 is produced over the North Atlantic, making it the dominant source of chlorine in the region; globally, chlorine production increases by 41%. The shift in the methane sink budget due to the increased role of Cl means that isotope-constrained top-down models fail to allocate 12 Tg y-1 (2% of total methane emissions) to 13C-depleted biological sources such as agriculture and wetlands. Since 2014, an increase in North African dust emissions has increased the 13C isotope of atmospheric CH4, thereby partially masking a much greater decline in this isotope, which has implications for the interpretation of the drivers behind the recent increase of methane in the atmosphere.

3.
Am J Physiol Lung Cell Mol Physiol ; 326(4): L482-L495, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38318664

RESUMO

Chlorine gas (Cl2) has been repeatedly used as a chemical weapon, first in World War I and most recently in Syria. Life-threatening Cl2 exposures frequently occur in domestic and occupational environments, and in transportation accidents. Modeling the human etiology of Cl2-induced acute lung injury (ALI), forensic biomarkers, and targeted countermeasures development have been hampered by inadequate large animal models. The objective of this study was to develop a translational model of Cl2-induced ALI in swine to understand toxico-pathophysiology and evaluate whether it is suitable for screening potential medical countermeasures and to identify biomarkers useful for forensic analysis. Specific pathogen-free Yorkshire swine (30-40 kg) of either sex were exposed to Cl2 (≤240 ppm for 1 h) or filtered air under anesthesia and controlled mechanical ventilation. Exposure to Cl2 resulted in severe hypoxia and hypoxemia, increased airway resistance and peak inspiratory pressure, and decreased dynamic lung compliance. Cl2 exposure resulted in increased total leucocyte and neutrophil counts in bronchoalveolar lavage fluid, vascular leakage, and pulmonary edema compared with the air-exposed group. The model recapitulated all three key histopathological features of human ALI, such as neutrophilic alveolitis, deposition of hyaline membranes, and formation of microthrombi. Free and lipid-bound 2-chlorofatty acids and chlorotyrosine-modified proteins (3-chloro-l-tyrosine and 3,5-dichloro-l-tyrosine) were detected in plasma and lung tissue after Cl2 exposure. In this study, we developed a translational swine model that recapitulates key features of human Cl2 inhalation injury and is suitable for testing medical countermeasures, and validated chlorinated fatty acids and protein adducts as biomarkers of Cl2 inhalation.NEW & NOTEWORTHY We established a swine model of chlorine gas-induced acute lung injury that exhibits several features of human acute lung injury and is suitable for screening potential medical countermeasures. We validated chlorinated fatty acids and protein adducts in plasma and lung samples as forensic biomarkers of chlorine inhalation.


Assuntos
Lesão Pulmonar Aguda , Cloro , Humanos , Animais , Suínos , Cloro/toxicidade , Cloro/metabolismo , Pulmão/metabolismo , Líquido da Lavagem Broncoalveolar , Lesão Pulmonar Aguda/induzido quimicamente , Lesão Pulmonar Aguda/patologia , Biomarcadores/metabolismo , Ácidos Graxos/metabolismo
4.
J Comput Chem ; 2024 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-39016463

RESUMO

Chlorine is an important chemical which has long been produced in chlor-alkali process using dimensionally stable anodes (DSA). However, some serious drawbacks of DSA inspire the development of alternative anodes for chlorine evolution reaction (CER). In this study, we focused on the graphene- and carbon nanotube-supported platinum tetra-phenyl porphyrins as electrocatalysts for CER, which have been theoretically investigated based on density functional theory. Our results reveal that the supported substrates possess potential CER electrocatalytic activity with very low thermodynamic overpotentials (0.012-0.028 V) via Cl* pathway instead of ClO*. The electronic structures analyses showed that electron transfer from the support to the adsorbed chlorine via the Pt center leads to strong Pt-Cl interactions. Furthermore, the supported electrocatalysts exhibited excellent selectivity toward CER because of high overpotentials and reaction barriers of oxygen evolution process. Therefore, our results may pave the way for designing CER electrocatalyst utilizing emerging carbon nanomaterials.

5.
Small ; : e2402250, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38837856

RESUMO

The development of energy- and time-saving synthetic methods to prepare bifunctional and high stability catalysts are vital for overall water splitting. Here, V-doped nickel-iron hydroxide precursor by etching NiFe foam (NFF) at room temperature with dual chloride solution ("NaCl-VCl3"), is obtained then phosphating to obtain V-Ni2P-FeP/NFF as efficient bifunctional (oxygen/hydrogen exchange reaction, OER/HER) electrocatalysts, denoted as NFF(V, Na)-P. The NFF(V, Na)-P requires only 185 and 117 mV overpotentials to reach 10 mA cm-2 for OER and HER. When used as a catalyst for water splitting in a full cell, it can be stably sustained for more than 1000 h in alkaline brine electrolysis at both current densities of 100 and 500 mA cm-2. In situ Raman analyses and density functional theory (DFT) show that the V-doping-induced surface remodeling generates hydroxyl oxides as the true catalytic active centers, which not only enhances the reaction kinetics, but also reduces the free energy change in the rate-determining step. This work provides a cost-effective substrate self-derivation method to convert commercial NFF into a powerful catalyst for electrolytic brine, offering a unique route to the development of efficient electrocatalysts for saline water splitting.

6.
Small ; : e2401347, 2024 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-38716685

RESUMO

A challenge facing the chlor-alkali process is the lack of electrocatalyst with high activity and selectivity for the efficient industrial production of chlorine. Herein the authors report a new electrocatalyst that can generate multi-interface structure by in situ growth of graphdiyne on the surface of cobalt oxides (GDY/Co3O4), which shows great potential in highly selective and efficient chlorine production. This result is due to the strong electron transfer and high density charge transport between GDY and Co3O4 and the interconversion of the mixed valence states of the Co atoms itself. These intrinsic characteristics efficiently enhance the conductivity of the catalyst, facilitate the reaction kinetics, and improve the overall catalytic selectivity and activity. Besides, the protective effect of the formed GDY layer is remarkable endowing the catalyst with excellent stability. The catalyst can selectively produce chlorine in low-concentration of NaCl aqueous solution at room temperature and pressure with the highest Faraday efficiency of 80.67% and an active chlorine yield rate of 184.40 mg h-1 cm-2, as well as superior long-term stability.

7.
Small ; : e2401248, 2024 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-38639029

RESUMO

Chlorine has been supplied by the chlor-alkali process that deploys dimensionally stable anodes (DSAs) for the electrochemical chlorine evolution reaction (ClER). The paramount bottlenecks have been ascribed to an intensive usage of precious elements and inevitable competition with the oxygen evolution reaction. Herein, a unique case of Ru2+-O4 active motifs anchored on Magnéli Ti4O7 (Ru-Ti4O7) via a straightforward wet impregnation and mild annealing is reported. The Ru-Ti4O7 performs radically active ClER with minimal deployment of Ru (0.13 wt%), both in 5 m NaCl (pH 2.3) and 0.1 m NaCl (pH 6.5) electrolytes. Scanning electrochemical microscopy demonstrates superior ClER selectivity on Ru-Ti4O7 compared to the DSA. Operando X-ray absorption spectroscopy and density functional theory calculations reveal a universally active ClER (over a wide range of pH and [Cl-]), through a direct adsorption of Cl- on Ru2+-O4 sites as the most plausible pathway, together with stabilized ClO* at low [Cl-] and high pH.

8.
Small ; : e2400141, 2024 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-38431944

RESUMO

Seawater electrolysis holds tremendous promise for the generation of green hydrogen (H2 ). However, the system of seawater-to-H2 faces significant hurdles, primarily due to the corrosive effects of chlorine compounds, which can cause severe anodic deterioration. Here, a nickel phosphide nanosheet array with amorphous NiMoO4 layer on Ni foam (Ni2 P@NiMoO4 /NF) is reported as a highly efficient and stable electrocatalyst for oxygen evolution reaction (OER) in alkaline seawater. Such Ni2 P@NiMoO4 /NF requires overpotentials of just 343 and 370 mV to achieve industrial-level current densities of 500 and 1000 mA cm-2 , respectively, surpassing that of Ni2 P/NF (470 and 555 mV). Furthermore, it maintains consistent electrolysis for over 500 h, a significant improvement compared to that of Ni2 P/NF (120 h) and Ni(OH)2 /NF (65 h). Electrochemical in situ Raman spectroscopy, stability testing, and chloride extraction analysis reveal that is situ formed MoO4 2- /PO4 3- from Ni2 P@NiMoO4 during the OER test to the electrode surface, thus effectively repelling Cl- and hindering the formation of harmful ClO- .

9.
Chemistry ; 30(24): e202304209, 2024 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-38372165

RESUMO

It is challenging to realize the selective C-C bond cleavage of lignin ß-O-4 linkages for production of high-value aromatic chemicals due to its intrinsic inertness and complex structure. Here we report a light-driven, chlorine-radical-based protocol to realize the oxidative C-C bond cleavage in various lignin model compounds catalyzed by commercially available TPT and CaCl2, achieving high conversion and good to high product yields at room temperature. Mechanistic studies reveal that the preferential activation of Cß-H bond facilitates the oxidation and C-C bond cleavage of lignin ß-O-4 model via chlorine radical. Furthermore, this method is also applicable to the depolymerization of natural lignin extracts, furnishing the aromatic oxygenates from the cleavage of Cα-Cß bonds. This study provides experimental foundations to the depolymerization and valorization of lignin into high value-added aromatic compounds.

10.
Mol Pharm ; 21(4): 1705-1718, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38466144

RESUMO

Photodynamic therapy (PDT) is often applied in a clinical setting to treat bladder cancer. However, current photosensitizers report drawbacks such as low efficacy, low selectivity, and numerous side effects, which have limited the clinical values of PDT for bladder cancer. Previously, we developed the first bladder cancer-specific aptamer that can selectively bind to and be internalized by bladder tumor cells versus normal uroepithelium cells. Here, we use an aptamer-based drug delivery system to deliver photosensitizer chlorine e6 (Ce6) into bladder tumor cells. In addition to Ce6, we also incorporate catalase into the drug complex to increase local oxygen levels in the tumor tissue. Compared with free Ce6, an aptamer-guided DNA nanotrain (NT) loaded with Ce6 and catalase (NT-Catalase-Ce6) can specifically recognize bladder cancer cells, produce oxygen locally, induce ROS in tumor cells, and cause mitochondrial apoptosis. In an orthotopic mouse model of bladder cancer, the intravesical instillation of NT-Catalase-Ce6 exhibits faster drug internalization and a longer drug retention time in tumor tissue compared with that in normal urothelium. Moreover, our modified PDT significantly inhibits tumor growth with fewer side effects such as cystitis than free Ce6. This aptamer-based photosensitizer delivery system can therefore improve the selectivity and efficacy and reduce the side effects of PDT treatment in mouse models of bladder cancer, bearing a great translational value for bladder cancer intravesical therapy.


Assuntos
Clorofilídeos , Fotoquimioterapia , Porfirinas , Neoplasias da Bexiga Urinária , Animais , Camundongos , Catalase/uso terapêutico , Linhagem Celular Tumoral , Oxigênio , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/uso terapêutico , Neoplasias da Bexiga Urinária/tratamento farmacológico , Humanos
11.
Arch Microbiol ; 206(7): 295, 2024 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-38856934

RESUMO

Microbial community biofilm exists in the household drinking water system and would pose threat to water quality. This paper explored biofilm formation and chlorination resistance of ten dual-species biofilms in three typical household pipes (stainless steel (SS), polypropylene random (PPR), and copper), and investigated the role of interspecific interaction. Biofilm biomass was lowest in copper pipes and highest in PPR pipes. A synergistic or neutralistic relationship between bacteria was evident in most biofilms formed in SS pipes, whereas four groups displayed a competitive relationship in biofilms formed in copper pipe. Chlorine resistance of biofilms was better in SS pipes and worse in copper pipes. It may be helped by interspecific relationships, but was more dependent on bacteria and resistance mechanisms such as more stable extracellular polymeric substance. The corrosion sites may also protect bacteria from chlorination. The findings provide useful insights for microbial control strategies in household drinking water systems.


Assuntos
Bactérias , Biofilmes , Cloro , Água Potável , Biofilmes/efeitos dos fármacos , Biofilmes/crescimento & desenvolvimento , Cloro/farmacologia , Bactérias/efeitos dos fármacos , Bactérias/genética , Bactérias/isolamento & purificação , Bactérias/classificação , Água Potável/microbiologia , Cobre/farmacologia , Microbiologia da Água , Aço Inoxidável , Polipropilenos , Abastecimento de Água , Halogenação , Corrosão , Desinfetantes/farmacologia
12.
Environ Sci Technol ; 58(27): 12260-12271, 2024 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-38923944

RESUMO

Despite the critical importance of virus disinfection by chlorine, our fundamental understanding of the relative susceptibility of different viruses to chlorine and robust quantitative relationships between virus disinfection rate constants and environmental parameters remains limited. We conducted a systematic review of virus inactivation by free chlorine and used the resulting data set to develop a linear mixed model that estimates chlorine inactivation rate constants for viruses based on experimental conditions. 570 data points were collected in our systematic review, representing 82 viruses over a broad range of environmental conditions. The harmonized inactivation rate constants under reference conditions (pH = 7.53, T = 20 °C, [Cl-] < 50 mM) spanned 5 orders of magnitude, ranging from 0.0196 to 1150 L mg-1 min-1, and uncovered important trends between viruses. Whereas common surrogate bacteriophage MS2 does not serve as a conservative chlorine disinfection surrogate for many human viruses, CVB5 was one of the most resistant viruses in the data set. The model quantifies the role of pH, temperature, and chloride levels across viruses, and an online tool allows users to estimate rate constants for viruses and conditions of interest. Results from the model identified potential shortcomings in current U.S. EPA drinking water disinfection requirements.


Assuntos
Cloro , Desinfecção , Cloro/farmacologia , Inativação de Vírus/efeitos dos fármacos , Vírus/efeitos dos fármacos , Desinfetantes/farmacologia
13.
Environ Sci Technol ; 58(18): 8086-8095, 2024 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-38666813

RESUMO

Secondary pollution remains a critical challenge for the catalytic destruction of chlorinated volatile organic compounds (CVOCs). By employing experimental studies and theoretical calculations, we provide valuable insights into the catalytic behaviors exhibited by ceria rods, cubes, and octahedra for monochloromethane (MCM) destruction, shedding light on the elementary reactions over facet-dependent CeO2. Our findings demonstrate that CeO2 nanorods with the (110) facet exhibit the best performance in MCM destruction, and the role of vacancies is mainly to form a longer distance (4.63 Å) of frustrated Lewis pairs (FLPs) compared to the stoichiometric surface, thereby enhancing the activation of MCM molecules. Subsequent molecular orbital analysis showed that the adsorption of MCM mainly transferred electrons from the 3σ and 4π* orbitals to the Ce 4f orbitals, and the activation was mainly caused by weakening of the 3σ bonding orbitals. Furthermore, isotopic experiments and theoretical calculations demonstrated that the hydrogen chloride generated is mainly derived from methyl in MCM rather than from water, and the primary function of water is to form excess saturated H on the surface, facilitating the desorption of generated hydrogen chloride.


Assuntos
Oxigênio , Catálise , Oxigênio/química , Cério/química , Adsorção , Compostos Orgânicos Voláteis/química
14.
Environ Sci Technol ; 58(28): 12585-12597, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-38956968

RESUMO

Elevated levels of atmospheric molecular chlorine (Cl2) have been observed during the daytime in recent field studies in China but could not be explained by the current chlorine chemistry mechanisms in models. Here, we propose a Cl2 formation mechanism initiated by aerosol iron photochemistry to explain daytime Cl2 formation. We implement this mechanism into the GEOS-Chem chemical transport model and investigate its impacts on the atmospheric composition in wintertime North China where high levels of Cl2 as well as aerosol chloride and iron were observed. The new mechanism accounts for more than 90% of surface air Cl2 production in North China and consequently increases the surface air Cl2 abundances by an order of magnitude, improving the model's agreement with observed Cl2. The presence of high Cl2 significantly alters the oxidative capacity of the atmosphere, with a factor of 20-40 increase in the chlorine radical concentration and a 20-40% increase in the hydroxyl radical concentration in regions with high aerosol chloride and iron loadings. This results in an increase in surface air ozone by about 10%. This new Cl2 formation mechanism will improve the model simulation capability for reactive chlorine abundances in the regions with high emissions of chlorine and iron.


Assuntos
Aerossóis , Atmosfera , Cloro , Ferro , Oxirredução , Cloro/química , China , Ferro/química , Atmosfera/química , Poluentes Atmosféricos/química , Fotoquímica
15.
Environ Sci Technol ; 58(2): 1369-1377, 2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-38048160

RESUMO

An improved fundamental understanding of active site structures can unlock opportunities for catalysis from conceptual design to industrial practice. Herein, we present the computational discovery and experimental demonstration of a highly active surface-phosphorylated ceria catalyst that exhibits robust chlorine tolerance for catalysis. Ab initio molecular dynamics (AIMD) calculations and in situ near-ambient pressure X-ray photoelectron spectroscopy (in situ NAP-XPS) identified a predominantly HPO4 active structure on CeO2(110) and CeO2(111) facets at room temperature. Importantly, further elevating the temperature led to a unique hydrogen (H) atom hopping between coordinatively unsaturated oxygen and the adjacent P═O group of HPO4. Such a mobile H on the catalyst surface can effectively quench the chlorine radicals (Cl•) via an orientated reaction analogous to hydrogen atom transfer (HAT), enabling the surface-phosphorylated CeO2-supported monolithic catalyst to exhibit both expected activity and stability for over 68 days during a pilot test, catalyzing the destruction of a complex chlorinated volatile organic compound industrial off-gas.


Assuntos
Cloro , Oxigênio , Catálise , Temperatura , Hidrogênio
16.
Environ Sci Technol ; 58(1): 805-815, 2024 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-38156625

RESUMO

Free available chlorine has been and is being applied in global water treatment and readily reacts with dissolved organic matter (DOM) in aquatic environments, leading to the formation of chlorinated products. Chlorination enhances the photoreactivity of DOM, but the influence of chlorinated compounds on the photogeneration of hydroxyl radicals (•OH) has remained unexplored. In this study, a range of chlorinated carboxylate-substituted phenolic model compounds were employed to assess their •OH photogeneration capabilities. These compounds demonstrated a substantial capacity for •OH production, exhibiting quantum yields of 0.1-5.9 × 10-3 through direct photolysis under 305 nm and 0.2-9.5 × 10-3 through a triplet sensitizer (4-benzoylbenzoic acid)-inducing reaction under 365 nm LED irradiation. Moreover, the chlorinated compounds exhibited higher light absorption and •OH quantum yields compared to those of their unchlorinated counterparts. The •OH photogeneration capacity of these compounds exhibited a positive correlation with their triplet state one-electron oxidation potentials. Molecular-level compositional analysis revealed that aromatic structures rich in hydroxyl and carboxyl groups (e.g., O/C > 0.5 with H/C < 1.5) within DOM serve as crucial sources of •OH, and chlorination of these compounds significantly enhances their capacity to generate •OH upon irradiation. This study provides novel insights into the enhanced photogeneration of •OH from chlorinated DOM, which is helpful for understanding the fate of trace pollutants in chlorinated waters.


Assuntos
Radical Hidroxila , Poluentes Químicos da Água , Radical Hidroxila/análise , Radical Hidroxila/química , Matéria Orgânica Dissolvida , Fotólise , Oxirredução , Ácidos Carboxílicos , Poluentes Químicos da Água/análise
17.
Environ Sci Technol ; 58(17): 7672-7682, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38639327

RESUMO

The development of efficient technologies for the synergistic catalytic elimination of NOx and chlorinated volatile organic compounds (CVOCs) remains challenging. Chlorine species from CVOCs are prone to catalyst poisoning, which increases the degradation temperature of CVOCs and fails to balance the selective catalytic reduction of NOx with the NH3 (NH3-SCR) performance. Herein, synergistic catalytic elimination of NOx and chlorobenzene has been originally demonstrated by using phosphotungstic acid (HPW) as a dechlorination agent to collaborate with CeO2. The conversion of chlorobenzene was over 80% at 270 °C, and the NOx conversion and N2 selectivity reached over 95% at 270-420 °C. HPW not only allowed chlorine species to leave as inorganic chlorine but also enhanced the BroÌ·nsted acidity of CeO2. The NH4+ produced in the NH3-SCR process can effectively promote the dechlorination of chlorobenzene at low temperatures. HPW remained structurally stable in the synergistic reaction, resulting in good water resistance and long-term stability. This work provides a cheaper and more environmentally friendly strategy to address chlorine poisoning in the synergistic reaction and offers new guidance for multipollutant control.


Assuntos
Clorobenzenos , Catálise , Clorobenzenos/química , Compostos Orgânicos Voláteis/química , Cloro/química , Cério/química , Halogenação
18.
Environ Sci Technol ; 58(8): 3838-3848, 2024 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-38351523

RESUMO

Substantial natural chlorination processes are a growing concern in diverse terrestrial ecosystems, occurring through abiotic redox reactions or biological enzymatic reactions. Among these, exoenzymatically mediated chlorination is suggested to be an important pathway for producing organochlorines and converting chloride ions (Cl-) to reactive chlorine species (RCS) in the presence of reactive oxygen species like hydrogen peroxide (H2O2). However, the role of natural enzymatic chlorination in antibacterial activity occurring in soil microenvironments remains unexplored. Here, we conceptualized that heme-containing chloroperoxidase (CPO)-catalyzed chlorination functions as a naturally occurring disinfection process in soils. Combining antimicrobial experiments and microfluidic chip-based fluorescence imaging, we showed that the enzymatic chlorination process exhibited significantly enhanced antibacterial activity against Escherichia coli and Bacillus subtilis compared to H2O2. This enhancement was primarily attributed to in situ-formed RCS. Based on semiquantitative imaging of RCS distribution using a fluorescence probe, the effective distance of this antibacterial effect was estimated to be approximately 2 mm. Ultrahigh-resolution mass spectrometry analysis showed over 97% similarity between chlorine-containing formulas from CPO-catalyzed chlorination and abiotic chlorination (by sodium hypochlorite) of model dissolved organic matter, indicating a natural source of disinfection byproduct analogues. Our findings unveil a novel natural disinfection process in soils mediated by indigenous enzymes, which effectively links chlorine-carbon interactions and reactive species dynamics.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Desinfecção , Cloro/química , Cloro/metabolismo , Halogenação , Peróxido de Hidrogênio , Solo , Ecossistema , Antibacterianos , Catálise
19.
J Appl Microbiol ; 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-39013612

RESUMO

AIMS: This study aimed to assess the effects of chlorine dioxide (ClO2) in water on whiteleg shrimp Penaeus vannamei, evaluating its impact on stomach microbiota, gill transcriptome, and pathogens. METHODS AND RESULTS: ClO2 was added to the aquarium tanks containing the shrimp. The application of ClO2 to rearing water was lethal to shrimp at concentrations above 1.2 ppm. On the other hand, most of the shrimp survived at 1.0 ppm of ClO2. Microbiome analysis showed that ClO2 administration at 1.0 ppm significantly reduced the α-diversity of bacterial community composition in the shrimp stomach, and this condition persisted for at least 7 days. Transcriptome analysis of shrimp gill revealed that ClO2 treatment caused massive change of the gene expression profile including stress response genes. However, after 7 days of the treatment, the gene expression profile was similar to that of shrimp in the untreated control group, suggesting a recovery to the normal state. This 1.0-ppm ClO2 significantly reduced shrimp mortality in artificial challenges with an AHPND-causing Vibrio parahaemolyticus and white spot syndrome virus, which were added to rearing water. CONCLUSIONS: The use of ClO2 at appropriate concentrations effectively eliminates a significant portion of the bacteria in the shrimp stomach and pathogens in the water. The results of this study provide fundamental knowledge on the disinfection of pathogens in water using ClO2 and the creation of semi germ-free shrimp, which has significantly decreased microbiome in the stomach.

20.
Environ Res ; 243: 117884, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38072103

RESUMO

Environmental health problems caused by antibiotic-resistant bacteria (ARB) and antibiotic-resistant genes (ARGs) have become a global concern. ARB and ARGs have been continuously detected in various water environments, which pose a new challenge for water quality safety assurance. Disinfection is a key water treatment process to eliminate pathogenic microorganisms in water, and combined chlorine and UV processes (the UV/Cl2 process, the UV-Cl2 process, and the Cl2-UV process) are considered potential disinfection methods to control antibiotic resistance. This review documented the efficacy and mechanism of combined UV and chlorine processes for the control of antibiotic resistance, as well as the effects of chlorine dose, solution pH, UV wavelength, and water matrix on the effectiveness of the processes. There are knowledge gaps in research on the combined chlorine and UV processes for antibiotic resistance control, in particular the UV-Cl2 process and the Cl2-UV process. In addition, changes in the structure of microbial communities and the distribution of ARGs, which are closely related to the spread of antibiotic resistance in the water, induced by combined processes were also addressed. Whether these changes could lead to the re-transmission of antibiotic resistance and harm human health may need to be further evaluated.


Assuntos
Cloro , Purificação da Água , Humanos , Cloro/farmacologia , Antagonistas de Receptores de Angiotensina/farmacologia , Raios Ultravioleta , Inibidores da Enzima Conversora de Angiotensina/farmacologia , Resistência Microbiana a Medicamentos/genética , Desinfecção/métodos , Genes Bacterianos , Purificação da Água/métodos , Antibacterianos/farmacologia
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