ACS Central SciencePub Date : 2024-10-25DOI: 10.1021/acscentsci.4c0116710.1021/acscentsci.4c01167
Fusheng Guo, Fan Xiao, Hao Song, Xiaoyong Li, Yaxin Xiao, Yong Qin* and Xiaoguang Lei*,
{"title":"An Optimized Marinopyrrole A Derivative Targets 6-Phosphoglucosamine Synthetase to Inhibit Methicillin-Resistant Staphylococcus aureus","authors":"Fusheng Guo, Fan Xiao, Hao Song, Xiaoyong Li, Yaxin Xiao, Yong Qin* and Xiaoguang Lei*, ","doi":"10.1021/acscentsci.4c0116710.1021/acscentsci.4c01167","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01167https://doi.org/10.1021/acscentsci.4c01167","url":null,"abstract":"<p >Methicillin-resistant <i>Staphylococcus aureus</i> (MRSA) is a common pathogenic bacterium that causes clinical infection and has become one of the most prominent antibiotic-resistant bacteria in the world. There is a pressing need to develop new antibiotics based on novel modes of action to combat increasingly severe MRSA infection. Marinopyrrole A (MA), a natural product extracted from marine <i>Streptomyces</i> in 2008, has a unique bipyrrole chemical skeleton and shows potent antibacterial activity against MRSA. However, its mode of action is still elusive. Herein, we developed an optimized MA derivative, MA-D1, and applied a chemoproteomic approach to reveal that MA-D1 performs its anti-MRSA activity by directly targeting 6-phosphoglucosamine synthetase (GlmS) to cause the breakdown of bacterial cell wall biosynthesis. Computational and experimental studies showed that MA-D1 interacts with the key R381 and E382 residues of GlmS in a novel binding pocket. Furthermore, MA-D1 showed a low resistance frequency for MRSA treatment and was also sensitive against the linezolid-, vancomycin-, or teicoplanin-resistant MRSA strains. MA-D1 also showed <i>in vivo</i> antibiotic efficacy in multiple animal models. This study demonstrates the promising potential of targeting GlmS to develop a new class of antibiotics to control MRSA pathogen infection.</p><p >Marinopyrrole A derivative MA-D1 shows anti-MRSA activity by targeting GlmS to inhibit cell wall biosynthesis. This discovery provides a novel target and a lead for developing new antibiotics.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 11","pages":"2090–2098 2090–2098"},"PeriodicalIF":12.7,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01167","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719121","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Task-Driven Tailored Covalent Organic Framework for Dynamic Capture of Trace Radioactive CH3131I under High-Flow Rate Conditions","authors":"Linwei He, Baoyu Li, Zhonglin Ma, Fuqiang Zhao, Mingxing Zhang, Junchang Chen, Lingyi Li, Fangdong Tang, Linfeng He, Dongshuai Wu, Yadong Li, Lixi Chen, Long Chen*, Chao Zhao*, Kecheng Cao, Xing Dai, Zhifang Chai and Shuao Wang*, ","doi":"10.1021/acscentsci.4c0131810.1021/acscentsci.4c01318","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01318https://doi.org/10.1021/acscentsci.4c01318","url":null,"abstract":"<p >The removal of radioactive gaseous iodine is crucial for sustainable nuclear energy development, safe spent fuel management, and secure disposal of radioactive waste and radioactive medical waste. However, the efficient capture of gaseous iodine, particularly methyl iodide, under conditions of low concentration and high-flow rate that are representative of real-world scenarios remains underexplored. Herein, we adopted a “theory-first” strategy to design adsorbents with a superior affinity for methyl iodide. The rigorous theoretical calculations for both physisorption and chemisorption have guided us to rationally design a piperazine-based covalent organic framework material (Pip-COF, Pip = piperazine). The pioneering hot-testing under dynamic conditions, featuring low concentrations of 5 ppm radioactive CH<sub>3</sub><sup>131</sup>I and a high-flow rate of 600 mL/min, demonstrated Pip-COF’s exceptional capture performance. Pip-COF exhibits saturated capacities of 39 mg/g at 75 °C and 78 mg/g at 25 °C, significantly outperforming the previously reported best COF (COF-TAPT, 6 mg/g at 25 °C) in this scenario. The gradual process of methylation and the identification of specific high-affinity sites were elucidated by time-resolved FT-IR spectroscopy and density functional theory (DFT) analysis, consistent with the design philosophy. This study exemplifies rational material design in facilitating the separation of trace pollutants in challenging environments.</p><p >Inspired by a “theory-first” paradigm, a piperazine-based covalent organic framework (Pip-COF) was designed to capture low-concentration CH<sub>3</sub><sup>131</sup>I under high-flow rate.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 11","pages":"2072–2081 2072–2081"},"PeriodicalIF":12.7,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01318","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719120","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Central SciencePub Date : 2024-10-24DOI: 10.1021/acs.est.4c0559910.1021/acs.est.4c05599
Susana Barros*, Ana M. Coimbra, Lihini Athapaththu Herath, Nélson Alves, Marlene Pinheiro, Marta Ribeiro, Hugo Morais, Ricardo Branco, Olga Martinez, Hugo G. Santos, Rosa Montes, Rosario Rodil, José Benito Quintana, Miguel M. Santos and Teresa Neuparth*,
{"title":"Are Environmental Levels of Nonsteroidal Anti-Inflammatory Drugs a Reason for Concern? Chronic Life-Cycle Effects of Naproxen in Zebrafish","authors":"Susana Barros*, Ana M. Coimbra, Lihini Athapaththu Herath, Nélson Alves, Marlene Pinheiro, Marta Ribeiro, Hugo Morais, Ricardo Branco, Olga Martinez, Hugo G. Santos, Rosa Montes, Rosario Rodil, José Benito Quintana, Miguel M. Santos and Teresa Neuparth*, ","doi":"10.1021/acs.est.4c0559910.1021/acs.est.4c05599","DOIUrl":"https://doi.org/10.1021/acs.est.4c05599https://doi.org/10.1021/acs.est.4c05599","url":null,"abstract":"<p >The nonsteroidal anti-inflammatory drug naproxen (NPX) is among the most consumed pharmaceuticals worldwide, being detected in surface waters within the ng to μg/L range. Considering the limited chronic ecotoxicity data available for NPX in aquatic ecosystems, the present study aimed at evaluating its impact in the model organism <i>Danio rerio</i>, following a full life-cycle exposure to environmentally relevant concentrations (0.1 to 5.0 μg/L). An integration of apical endpoints, i.e., survival, growth, and reproduction, with gonad histopathology and gene transcription (RNA-seq) was performed to provide additional insights into the mode of action (MoA) of NPX. NPX decreased zebrafish growth and reproduction and led to histopathological alterations in gonads at concentrations as low as 0.1 μg/L. At the molecular level, 0.7 μg/L of NPX led to a disruption in gonads transcription of genes involved in several biological processes associated with reproduction, mainly involving steroid hormone biosynthesis and epigenetic/epitranscriptomic machineries. Collectively, these results show that environmentally realistic concentrations of NPX affect zebrafish reproduction and associated signaling pathways, indicating that current hazard and risk assessment data for NPX underestimate the environmental risk of this pharmaceutical.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"58 44","pages":"19627–19638 19627–19638"},"PeriodicalIF":10.8,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Seed Priming with Dynamically Transformed Selenium Nanoparticles to Enhance Salt Tolerance in Rice","authors":"Rong-Xiang Xing, Xiao-Dong Sun*, Yue Wang, Xiao-Min Xie, Miao-Miao Tan, Meng-Xin Xu, Xiao-Yu Liu, Yu-Qian Jiang, Mei-Yan Liu, Jian-Lu Duan, Jing-Ya Ma, Yu-Chen Sun, Ge Meng and Xian-Zheng Yuan, ","doi":"10.1021/acs.est.4c0712110.1021/acs.est.4c07121","DOIUrl":"https://doi.org/10.1021/acs.est.4c07121https://doi.org/10.1021/acs.est.4c07121","url":null,"abstract":"<p >Seed priming with nanomaterials is an emerging approach for improving plant stress tolerance. Here, we demonstrated a mechanism for enhancing salt tolerance in rice under salt stress via priming with nonstimulatory nanoparticles such as selenium nanoparticles (SeNPs), distinct from stimulatory nanomaterials. Due to the dynamic transformation ability of SeNPs, SeNP priming could enhance rice salt tolerance by mediating the glutathione cycle to eliminate excess reactive oxygen species (ROS). During priming, SeNPs penetrated rice seeds and transitioned into a soluble form (99.9%) within the embryo endosperm. Subsequently, the soluble selenium (Se) was transported to rice roots and metabolized into various Se-related derivatives, including selenomethionine (SeMet), Na<sub>2</sub>SeO<sub>3</sub> (Se IV), selenocysteine (SeCys<sub>2</sub>), and methylselenocysteine (MeSeCys). These derivatives significantly enhanced the root activities of key enzymes such as glutathione peroxidase (GSH-PX), glutathione reductase (GR), catalase (CAT), peroxidase (POD), and superoxide dismutase (SOD) by 24.97%, 47.98%, 16.23%, 16.81%, and 14.82%, respectively, thus reinforcing the glutathione cycle and ROS scavenging pathways. Moreover, these alterations induced transcriptional changes in rice seedlings, with genes involved in signal transduction, transcription factors (TFs), ROS scavenging, and protein folding being upregulated, activating signal perception and self-repair mechanisms. These findings offer valuable insights for the agricultural application of nanomaterials.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"58 44","pages":"19725–19735 19725–19735"},"PeriodicalIF":10.8,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Central SciencePub Date : 2024-10-24DOI: 10.1021/acs.est.4c0674410.1021/acs.est.4c06744
Yang Li, Xuefei Ma*, Keding Lu*, Yue Gao, Weiguang Xu, Xinping Yang and Yuanhang Zhang*,
{"title":"Investigation of the Cyclohexene Oxidation Mechanism Through the Direct Measurement of Organic Peroxy Radicals","authors":"Yang Li, Xuefei Ma*, Keding Lu*, Yue Gao, Weiguang Xu, Xinping Yang and Yuanhang Zhang*, ","doi":"10.1021/acs.est.4c0674410.1021/acs.est.4c06744","DOIUrl":"https://doi.org/10.1021/acs.est.4c06744https://doi.org/10.1021/acs.est.4c06744","url":null,"abstract":"<p >Monoterpenes, the second most abundant biogenic volatile organic compounds globally, are crucial in forming secondary organic aerosols, making their oxidation mechanisms vital for addressing climate change and air pollution. This study utilized cyclohexene as a surrogate to explore first-generation products from its ozonolysis through laboratory experiments and mechanistic modeling. We employed proton transfer reaction mass spectrometry with NH<sub>4</sub><sup>+</sup> ion sources (NH<sub>4</sub><sup>+</sup>-CIMS) and a custom-built OH calibration source to quantify organic peroxy radicals (RO<sub>2</sub>) and closed-shell species. Under near-real atmospheric conditions in a Potential Aerosol Mass-Oxidation Flow Reactor, we identified 30 ozonolysis products, expanding previous data sets of low-oxygen compounds. Combined with simulations based on the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere and relevant literature, our results revealed that OH dominates over ozone in cyclohexene oxidation at typical atmospheric oxidant levels with H-abstraction contributing 30% of initial RO<sub>2</sub> radicals. Highly oxidized molecules primarily arise from RO<sub>2</sub> autoxidation initiated by ozone, and at least 15% of ozone oxidation products follow the overlooked nonvinyl hydroperoxides pathway. Gaps remain especially in understanding RO<sub>2</sub> cross-reactions, and the structural complexity of monoterpenes further complicates research. As emissions decrease and afforestation increases, understanding these mechanisms becomes increasingly critical.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"58 44","pages":"19807–19817 19807–19817"},"PeriodicalIF":10.8,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577692","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Central SciencePub Date : 2024-10-24DOI: 10.1021/acs.est.4c0576010.1021/acs.est.4c05760
Wenxin Wu, Sophie A. Comer-Warner, Mike Peacock, Xingxing Han, Si-Liang Li, Xiaotang Ju, Cong-Qiang Liu, Pete Smith and Zhifeng Yan*,
{"title":"IPCC Emission Factor Overestimates N2O Emissions from Agricultural Ditches","authors":"Wenxin Wu, Sophie A. Comer-Warner, Mike Peacock, Xingxing Han, Si-Liang Li, Xiaotang Ju, Cong-Qiang Liu, Pete Smith and Zhifeng Yan*, ","doi":"10.1021/acs.est.4c0576010.1021/acs.est.4c05760","DOIUrl":"https://doi.org/10.1021/acs.est.4c05760https://doi.org/10.1021/acs.est.4c05760","url":null,"abstract":"<p >Agricultural ditches emit disproportionate amounts of nitrous oxide (N<sub>2</sub>O), but their contributions to regional or global N<sub>2</sub>O emissions remain unclear due to limited data. The Intergovernmental Panel on Climate Change (IPCC) recommends using emission factors (EFs) to estimate indirect N<sub>2</sub>O emission, but the EF for ditches (EF<sub>5g</sub>) is categorized as groundwater, which potentially introduces a significant bias. This study conducted a regional-scale campaign in the North China Plain, one of the world’s most intensive agricultural regions, and calculated the EF<sub>5g</sub> values from agricultural ditches by the concentration method (N<sub>2</sub>O–N/NO<sub>3</sub><sup>–</sup>–N). The results found that the regional-scale mean EF<sub>5g</sub> value (0.0028) was less than half of the IPCC default value (0.006), illustrating that the current IPCC methodology significantly overestimates N<sub>2</sub>O emissions from agricultural ditches. Despite the relatively small EF<sub>5g</sub> values, agricultural ditches exhibited a high mean N<sub>2</sub>O concentration (3.36 μg L<sup>–1</sup>) and a large regional emission (1.14 ± 0.86 Gg N<sub>2</sub>O–N yr<sup>–1</sup>), which is equal to 3.8 ± 2.9% of direct N<sub>2</sub>O emission from the croplands in the North China Plain. Since ditches are ubiquitous in agricultural regions and are likely to expand under climate change, refining EF<sub>5g</sub> is crucial to accurately assess their contribution to global N<sub>2</sub>O budgets.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"58 45","pages":"20019–20029 20019–20029"},"PeriodicalIF":10.8,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608828","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Central SciencePub Date : 2024-10-24DOI: 10.1021/acs.est.4c0741310.1021/acs.est.4c07413
Liu Liu*, Xin Zhang*, Sina Schorn, Tomy Doda, Manchun Kang, Damien Bouffard, Georgiy Kirillin, Jana Milucka, Xiaotao Shi* and Hans-Peter Grossart*,
{"title":"Strong Subseasonal Variability of Oxic Methane Production Challenges Methane Budgeting in Freshwater Lakes","authors":"Liu Liu*, Xin Zhang*, Sina Schorn, Tomy Doda, Manchun Kang, Damien Bouffard, Georgiy Kirillin, Jana Milucka, Xiaotao Shi* and Hans-Peter Grossart*, ","doi":"10.1021/acs.est.4c0741310.1021/acs.est.4c07413","DOIUrl":"https://doi.org/10.1021/acs.est.4c07413https://doi.org/10.1021/acs.est.4c07413","url":null,"abstract":"<p >Methane (CH<sub>4</sub>) accumulation in the well-oxygenated lake epilimnion enhances the diffusive atmospheric CH<sub>4</sub> emission. Both lateral transport and in situ oxic methane production (OMP) have been suggested as potential sources. While the latter has been recently supported by increasing evidence, quantifying the exact contribution of OMP to atmospheric emissions remains challenging. Based on a large high-resolution field data set collected during 2019–2020 in the deep stratified Lake Stechlin and on three-dimensional hydrodynamic modeling, we improved existing CH<sub>4</sub> budgets by resolving each component of the mass balance model at a seasonal scale and therefore better constrained the residual OMP. All terms in our model showed a large temporal variability at scales from intraday to seasonal, and the modeled OMP was most sensitive to the surface CH<sub>4</sub> flux estimates. Future efforts are needed to reduce the uncertainties in estimating OMP rates using the mass balance approach by increasing the frequency of atmospheric CH<sub>4</sub> flux measurements.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"58 44","pages":"19690–19701 19690–19701"},"PeriodicalIF":10.8,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Central SciencePub Date : 2024-10-24DOI: 10.1021/acs.est.4c0406110.1021/acs.est.4c04061
Jiwan Kim, and , Jinhee Choi*,
{"title":"Histone Methylation-Mediated Reproductive Toxicity to Consumer Product Chemicals in Caenorhabditis elegans: An Epigenetic Adverse Outcome Pathway (AOP)","authors":"Jiwan Kim, and , Jinhee Choi*, ","doi":"10.1021/acs.est.4c0406110.1021/acs.est.4c04061","DOIUrl":"https://doi.org/10.1021/acs.est.4c04061https://doi.org/10.1021/acs.est.4c04061","url":null,"abstract":"<p >The significance of histone methylation in epigenetic inheritance underscores its relevance to disease and the chronic effects of environmental chemicals. However, limited evidence of the causal relationships between chemically induced epigenetic changes and organismal-level effects hinders the application of epigenetic markers in ecotoxicological assessments. This study explored the contribution of repressive histone marks to reproductive toxicity induced by chemicals in consumer products in <i>Caenorhabditis elegans</i>, applying the adverse outcome pathway (AOP) framework. Triclosan (TCS) and tetrabromobisphenol A (TBBPA) exposures caused reproductive toxicity and altered histone methyltransferase (HMT) and histone demethylase (HDM) activities, increasing the level of trimethylation of H3K9 and H3K27. Notably, treatment with an H3K27-specific HMT inhibitor alleviated reproductive defects and the transcriptional response of genes related to vitellogenin, xenobiotic metabolism, and oxidative stress. Comparison of points of departure (PODs) based on calculated benchmark concentrations (BMCs) revealed the sensitivity of histone-modifying enzyme activities to these chemicals. Our findings suggest that the ‘disturbance of HMT and HDM’ can serve as the molecular initiating event (MIE) leading to reproductive toxicity in the epigenetic AOP for TCS and TBBPA. The study extended the biological applicability of these enzymes by identifying model species with analogous protein sequences and functions. This combined approach enhances the essentiality, empirical support, and taxonomic domain of applicability (tDOA), which are crucial considerations for ecotoxicological AOPs. Given the widespread use and environmental distribution of chemicals in consumer products, this study proposes histone-modifying enzyme activity as an effective screening tool for reproductive toxicants and emphasizes the integration of epigenetic mechanisms into a prospective ERA.</p><p >This study verifies the contribution of epigenetic changes as sensitive markers to the toxicity of environmental chemicals in <i>C. elegans</i> and expands their cross-species applicability.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"58 44","pages":"19604–19616 19604–19616"},"PeriodicalIF":10.8,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.est.4c04061","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Central SciencePub Date : 2024-10-23DOI: 10.1021/acs.est.4c0617010.1021/acs.est.4c06170
Rongrong Ding, Junsheng Song, Guangyu Bi, Guannan Zhou*, Xiaocheng Liu, Dahong Huang and Yang Mu*,
{"title":"Phosphate-Induced Acidic Microenvironment for Improved Contaminant Removal during FeS Oxygenation","authors":"Rongrong Ding, Junsheng Song, Guangyu Bi, Guannan Zhou*, Xiaocheng Liu, Dahong Huang and Yang Mu*, ","doi":"10.1021/acs.est.4c0617010.1021/acs.est.4c06170","DOIUrl":"https://doi.org/10.1021/acs.est.4c06170https://doi.org/10.1021/acs.est.4c06170","url":null,"abstract":"<p >The coexistence of mackinawite (FeS) and phosphate is widely observed in natural systems. However, the underlying mechanism regarding how phosphate influences the environmental behavior of FeS, especially during the FeS oxygenation in aquatic systems, remains in its fancy. This study for the first time reported that the presence of phosphate, even at a low concentration of 0.3 mM, significantly promoted the FeS-mediated O<sub>2</sub> activation and thus the pollutant degradation. The enhancement was attributed to a substantial increase in the generation of •OH, as evidenced by the electron paramagnetic resonance tests and the identification of the probing products. A combination of experiments and theoretical calculations revealed that phosphate adsorbed onto the FeS surface via a monodentate mononuclear configuration, establishing an acidic microenvironment on the FeS surface. Such acidic microenvironment not only increased the utilization efficiency of Fe(II) toward H<sub>2</sub>O<sub>2</sub> generation (i.e., <i></i><math><msub><mrow><mi>O</mi></mrow><mrow><mn>2</mn></mrow></msub><mo>+</mo><mn>2</mn><msup><mrow><mi>H</mi></mrow><mrow><mo>+</mo></mrow></msup><mo>+</mo><mn>2</mn><mi>F</mi><mi>e</mi><mrow><mo>(</mo><mi>I</mi><mi>I</mi><mo>)</mo></mrow><mo>→</mo><msub><mrow><mi>H</mi></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mi>O</mi></mrow><mrow><mn>2</mn></mrow></msub><mo>+</mo><mn>2</mn><mi>F</mi><mi>e</mi><mrow><mo>(</mo><mi>I</mi><mi>I</mi><mi>I</mi><mo>)</mo></mrow></math>), but also prevented the subsequent side reaction of H<sub>2</sub>O<sub>2</sub> self-decomposition (i.e., <i></i><math><msub><mrow><mi>H</mi></mrow><mrow><mn>2</mn></mrow></msub><msub><mrow><mi>O</mi></mrow><mrow><mn>2</mn></mrow></msub><mo>+</mo><mi>O</mi><msup><mrow><mi>H</mi></mrow><mrow><mo>−</mo></mrow></msup><mo>→</mo><mi>H</mi><msubsup><mrow><mi>O</mi></mrow><mrow><mn>2</mn></mrow><mrow><mo>−</mo></mrow></msubsup><mo>+</mo><msub><mrow><mi>H</mi></mrow><mrow><mn>2</mn></mrow></msub><mi>O</mi></math>). The results highlight the beneficial role of commonly encountered phosphate in FeS-based systems, which has profound implications for the degradation of waterborne contaminants.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"58 44","pages":"19883–19892 19883–19892"},"PeriodicalIF":10.8,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577547","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Central SciencePub Date : 2024-10-23DOI: 10.1021/acs.est.4c0449510.1021/acs.est.4c04495
Ségolène Humann-Guilleminot*, Pierre Blévin, Geir Wing Gabrielsen, Dorte Herzke, Vladimir A. Nikiforov, William Jouanneau, Børge Moe, Charline Parenteau, Fabrice Helfenstein and Olivier Chastel,
{"title":"PFAS Exposure is Associated with a Lower Spermatic Quality in an Arctic Seabird","authors":"Ségolène Humann-Guilleminot*, Pierre Blévin, Geir Wing Gabrielsen, Dorte Herzke, Vladimir A. Nikiforov, William Jouanneau, Børge Moe, Charline Parenteau, Fabrice Helfenstein and Olivier Chastel, ","doi":"10.1021/acs.est.4c0449510.1021/acs.est.4c04495","DOIUrl":"https://doi.org/10.1021/acs.est.4c04495https://doi.org/10.1021/acs.est.4c04495","url":null,"abstract":"<p >Several studies have reported an increasing occurrence of poly- and perfluorinated alkyl substances (PFASs) in Arctic wildlife tissues, raising concerns due to their resistance to degradation. While some research has explored PFAS’s physiological effects on birds, their impact on reproductive functions, particularly sperm quality, remains underexplored. This study aims to assess (1) potential association between PFAS concentrations in blood and sperm quality in black-legged kittiwakes (<i>Rissa tridactyla</i>), focusing on the percentage of abnormal spermatozoa, sperm velocity, percentage of sperm motility, and morphology; and (2) examine the association of plasma levels of testosterone, corticosterone, and luteinizing hormone with both PFAS concentrations and sperm quality parameters to assess possible endocrine disrupting pathways. Our findings reveal a positive correlation between the concentration of longer-chain perfluoroalkyl carboxylates (PFCA; C11–C14) in blood and the percentage of abnormal sperm in kittiwakes. Additionally, we observed that two other PFAS (i.e., PFOSlin and PFNA), distinct from those associated with sperm abnormalities, were positively correlated with the stress hormone corticosterone. These findings emphasize the potentially harmful substance-specific effects of long-chain PFCAs on seabirds and the need for further research into the impact of pollutants on sperm quality as a potential additional detrimental effect on birds.</p><p >This research investigates, for the first time, the correlation between PFAS concentrations in blood and sperm quality in Arctic black-legged kittiwakes, revealing an increase in the percentage of abnormal spermatozoa as PFAS blood concentrations rise.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"58 44","pages":"19617–19626 19617–19626"},"PeriodicalIF":10.8,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.est.4c04495","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}