The structure of glasses in the aluminoborophosphate glass system with compositions 40Na2O–40P2O5–(20–x)Al2O3–xB2O3 (0 ≤ x ≤ 20) has been studied by single- and double-resonance solid-state nuclear magnetic resonance (NMR) spectroscopy. The principal network forming units (NFUs) were identified and quantified by high-resolution spectra obtained by magic-angle spinning (MAS) NMR. The boron atoms are predominantly four-coordinated, while the Al species occur in four-, five- and six-fold coordination, and their average connectivity increases with increasing boron content. The connectivities between these NFUs were determined by dipolar recoupling experiments such as 11B{31P} and 27Al{31P} rotational echo double resonance (REDOR) and 31P double-quantum filtering experiments. No significant 27Al–11B interaction was detectable. The results indicate a strong preference for Al–O–P and B–O–P heteroatomic connectivities, whereas a random linkage model clearly does not provide an appropriate description. The glass transition temperature shows a characteristic nonlinear compositional dependence on x, with a maximum near x = 10. This behavior can be modeled by considering the average connectivity density of the network, calculated from the NFU distribution as deduced from the quantitative connectivity analysis. 23Na MAS NMR and 23Na{31P} REDOR results indicate that the sodium ions maintain a constant local environment dominated by the phosphate species, explainable by standard bond-valence concepts.
{"title":"Short- and Medium-Range Order of Sodium Aluminoborophosphate Glasses Studied by Dipolar NMR Spectroscopy","authors":"Mojtaba Abbasi,Henrik Bradtmüller,Hellmut Eckert,Scott Kroeker","doi":"10.1021/acs.jpcc.5c07375","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07375","url":null,"abstract":"The structure of glasses in the aluminoborophosphate glass system with compositions 40Na2O–40P2O5–(20–x)Al2O3–xB2O3 (0 ≤ x ≤ 20) has been studied by single- and double-resonance solid-state nuclear magnetic resonance (NMR) spectroscopy. The principal network forming units (NFUs) were identified and quantified by high-resolution spectra obtained by magic-angle spinning (MAS) NMR. The boron atoms are predominantly four-coordinated, while the Al species occur in four-, five- and six-fold coordination, and their average connectivity increases with increasing boron content. The connectivities between these NFUs were determined by dipolar recoupling experiments such as 11B{31P} and 27Al{31P} rotational echo double resonance (REDOR) and 31P double-quantum filtering experiments. No significant 27Al–11B interaction was detectable. The results indicate a strong preference for Al–O–P and B–O–P heteroatomic connectivities, whereas a random linkage model clearly does not provide an appropriate description. The glass transition temperature shows a characteristic nonlinear compositional dependence on x, with a maximum near x = 10. This behavior can be modeled by considering the average connectivity density of the network, calculated from the NFU distribution as deduced from the quantitative connectivity analysis. 23Na MAS NMR and 23Na{31P} REDOR results indicate that the sodium ions maintain a constant local environment dominated by the phosphate species, explainable by standard bond-valence concepts.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"8 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111094","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kai Zhang,Qianyi Wang,Bo Fu,Runmei Ma,Xiangtao Zhang,Le Zhang,Tiantian Li,Bin Wang
{"title":"Toward an AI Foundation Model Integrating Climate Change, Air Pollution, Socioeconomics, and Human Health","authors":"Kai Zhang,Qianyi Wang,Bo Fu,Runmei Ma,Xiangtao Zhang,Le Zhang,Tiantian Li,Bin Wang","doi":"10.1021/acs.est.5c16891","DOIUrl":"https://doi.org/10.1021/acs.est.5c16891","url":null,"abstract":"","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"31 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiwon Park,Eunhye Bae,Hee-Jin Park,Yeonjeong Ha,Beate I. Escher,Jung-Hwan Kwon
Water-soluble polymers (WSPs) represent a key class of polymers widely employed in liquid formulations across diverse industries. We investigated their interactions with synthetic lipid membranes, as well as cytotoxicity triggered by membrane disruption. Zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and negatively charged 1,2-dioleoyl-sn-glycero-3-phosphoglycerol (DOPG) liposomes were utilized as lipid membrane models for assessing fluorescence leakage caused by two positively charged, two negatively charged, and one neutral WSPs. Positively charged WSPs induced substantial leakage in DOPG liposomes with increasing polymer concentrations, whereas the negatively charged WSP caused only minor leakage in DOPC liposomes at high concentrations, and nonionic WSPs did not cause significant disruption. Quantification of in vitro cytotoxicity on one human (MCF7) and one fish (RTgill-W1 from Oncorhynchus mykiss) cell line confirmed the WSP’s ability to disrupt membrane integrity. Cationic WSPs also caused cytotoxicity in both cell lines at similar concentrations, distinguishing them from negatively charged and neutral WSPs. These findings highlight the pivotal role of electrostatic interactions between charge characteristics of WSPs and phospholipid headgroups of biological membranes. Although WSPs are often exempted for toxicity tests in chemicals regulations such as the European Union’s REACH, further evaluation is necessary to understand their toxic potential and modes of toxic action.
{"title":"Disruption of Lipid Membrane Integrity by Synthetic Water-Soluble Polymers: Effects of Lipid Headgroup","authors":"Jiwon Park,Eunhye Bae,Hee-Jin Park,Yeonjeong Ha,Beate I. Escher,Jung-Hwan Kwon","doi":"10.1021/acs.est.5c15107","DOIUrl":"https://doi.org/10.1021/acs.est.5c15107","url":null,"abstract":"Water-soluble polymers (WSPs) represent a key class of polymers widely employed in liquid formulations across diverse industries. We investigated their interactions with synthetic lipid membranes, as well as cytotoxicity triggered by membrane disruption. Zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and negatively charged 1,2-dioleoyl-sn-glycero-3-phosphoglycerol (DOPG) liposomes were utilized as lipid membrane models for assessing fluorescence leakage caused by two positively charged, two negatively charged, and one neutral WSPs. Positively charged WSPs induced substantial leakage in DOPG liposomes with increasing polymer concentrations, whereas the negatively charged WSP caused only minor leakage in DOPC liposomes at high concentrations, and nonionic WSPs did not cause significant disruption. Quantification of in vitro cytotoxicity on one human (MCF7) and one fish (RTgill-W1 from Oncorhynchus mykiss) cell line confirmed the WSP’s ability to disrupt membrane integrity. Cationic WSPs also caused cytotoxicity in both cell lines at similar concentrations, distinguishing them from negatively charged and neutral WSPs. These findings highlight the pivotal role of electrostatic interactions between charge characteristics of WSPs and phospholipid headgroups of biological membranes. Although WSPs are often exempted for toxicity tests in chemicals regulations such as the European Union’s REACH, further evaluation is necessary to understand their toxic potential and modes of toxic action.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"105 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sergio Ibarra-Espinosa,Edmilson Dias de Freitas,Benjamin Gaubert,Pablo Lichtig,Karl Ropkins,Iara da Silva,Guilherme Martins Pereira,Daniel Schuch,Janaina Nascimento,Leonardo Hoinaski,Leila Droprinchinski Martins,Mario Gavidia-Calderón,Angel Vara-Vela,Taciana Toledo de Almeida Albuquerque,Rita Yuri Ynoue,Sebastian Diez,Zamir Mera,Alejandro Casallas,Fidel Vallejo,Valeria Diaz,Rizzieri Pedruzzi,Rosana Abrutzky,Marco A. Franco,Nicolas Huneeus,Hector Jorquera,Luis Carlos Belalcázar-Cerón,Néstor Y. Rojas,Maria de Fatima Andrade,Louisa Emmons,Guy Brasseur
Global emission inventories often fail to capture the complexities of vehicular pollution in regions with unique fuel mixes, such as Brazil’s extensive biofuel use, leading to significant uncertainties in atmospheric modeling. This study presents a century-long (1960–2100) bottom-up vehicular emission inventory for Brazil, leveraging locally derived emission factors. Our estimates reveal substantial discrepancies in magnitude, timing, and speciation of non-CO2 pollutants (CO, NMHC, PM2.5) compared to leading global inventories (EDGAR, CEDS, CAMS), highlighting critical inaccuracies in widely used data sets. More critically, future projections under Shared Socioeconomic Pathways (SSPs) uncover a novel positive feedback mechanism: rising temperatures significantly enhance vehicular evaporative nonmethane hydrocarbon (NMHC) emissions. This temperature-dependent increase and subsequent NMHC oxidation to CO2 suggest an overlooked pathway that could amplify climate warming and air pollution globally, particularly after a breakpoint around 2050 (p < 0.05). While historical emissions peaked in the 1990s–2000s, nonexhaust PM becomes increasingly important. Air quality simulations using our inventory in the MUSICA model show good regional PM2.5 agreement but highlight challenges in resolving local primary pollutant peaks. This comprehensive inventory provides crucial data for Brazil and uncovers globally relevant climate–chemistry interactions, urging a re-evaluation of regional specificities in global emission assessments.
{"title":"A Century of Vehicular Emissions in Brazil: Unveiling the Impacts of Unique Fuel Mix on Air Quality","authors":"Sergio Ibarra-Espinosa,Edmilson Dias de Freitas,Benjamin Gaubert,Pablo Lichtig,Karl Ropkins,Iara da Silva,Guilherme Martins Pereira,Daniel Schuch,Janaina Nascimento,Leonardo Hoinaski,Leila Droprinchinski Martins,Mario Gavidia-Calderón,Angel Vara-Vela,Taciana Toledo de Almeida Albuquerque,Rita Yuri Ynoue,Sebastian Diez,Zamir Mera,Alejandro Casallas,Fidel Vallejo,Valeria Diaz,Rizzieri Pedruzzi,Rosana Abrutzky,Marco A. Franco,Nicolas Huneeus,Hector Jorquera,Luis Carlos Belalcázar-Cerón,Néstor Y. Rojas,Maria de Fatima Andrade,Louisa Emmons,Guy Brasseur","doi":"10.1021/acs.est.5c08400","DOIUrl":"https://doi.org/10.1021/acs.est.5c08400","url":null,"abstract":"Global emission inventories often fail to capture the complexities of vehicular pollution in regions with unique fuel mixes, such as Brazil’s extensive biofuel use, leading to significant uncertainties in atmospheric modeling. This study presents a century-long (1960–2100) bottom-up vehicular emission inventory for Brazil, leveraging locally derived emission factors. Our estimates reveal substantial discrepancies in magnitude, timing, and speciation of non-CO2 pollutants (CO, NMHC, PM2.5) compared to leading global inventories (EDGAR, CEDS, CAMS), highlighting critical inaccuracies in widely used data sets. More critically, future projections under Shared Socioeconomic Pathways (SSPs) uncover a novel positive feedback mechanism: rising temperatures significantly enhance vehicular evaporative nonmethane hydrocarbon (NMHC) emissions. This temperature-dependent increase and subsequent NMHC oxidation to CO2 suggest an overlooked pathway that could amplify climate warming and air pollution globally, particularly after a breakpoint around 2050 (p < 0.05). While historical emissions peaked in the 1990s–2000s, nonexhaust PM becomes increasingly important. Air quality simulations using our inventory in the MUSICA model show good regional PM2.5 agreement but highlight challenges in resolving local primary pollutant peaks. This comprehensive inventory provides crucial data for Brazil and uncovers globally relevant climate–chemistry interactions, urging a re-evaluation of regional specificities in global emission assessments.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"41 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111204","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yang Chen, Shirui Yan, Yaliang Hou, Yongxiang Lin, Kexin Liu, Dingfan Cao, Yuxuan Xing, Daizhou Zhang, Wei Pu, Xin Wang
Black carbon in seasonal snow (BCS) critically influences the Earth system by reducing surface albedo (snow darkening), perturbing radiative balance, and accelerating snowmelt. However, its climatic and hydrological impacts remain poorly quantified because high-quality data sets are scarce. This study introduces a novel Dual Random Forest (DRF) framework that synergistically constrains BCS concentration estimates through both physical mechanisms and observational fidelity. By pretraining with six spatiotemporally complete Earth System Model (ESM) simulations, driven by multisource reanalysis data, and fine-tuning against global field observations, the DRF generates a 44-year (1981-2024) global monthly BCS data set at 0.5° × 0.625° resolution. This data set achieves higher accuracy in BCS patterns and concentrations compared with observations (spatial correlation R = 0.92; normalized mean error NME = 31%), outperforming both single-constrained machine learning approaches (ESM- or observation-only) and traditional methods (CMIP5, CMIP6, and MODIS; R = 0.07-0.82, NME = 51%-1951%). It also excels in capturing seasonal variations and long-term annual trends, better reproducing increasing trends driven by anthropogenic forcing and decadal variability modulated by natural climate variability. This data set is hence valuable for robust quantification of BCS-induced radiative forcing and attribution of snowmelt acceleration to snow darkening versus climate warming on a global scale.
季节性雪（BCS）中的黑碳通过降低地表反照率（雪变暗）、扰乱辐射平衡和加速融雪对地球系统产生重大影响。然而，由于缺乏高质量的数据集，其气候和水文影响的量化仍然很差。本研究引入了一种新的双随机森林（Dual Random Forest， DRF）框架，该框架通过物理机制和观测保真度协同约束BCS浓度估计。DRF利用6个时空完整的地球系统模型（ESM）模拟进行预训练，在多源再分析数据的驱动下，对全球野外观测数据进行微调，生成了一个44年（1981-2024年）的0.5°× 0.625°分辨率的全球月度BCS数据集。与观测数据相比，该数据集在BCS模式和浓度方面具有更高的精度（空间相关R = 0.92，归一化平均误差NME = 31%），优于单约束机器学习方法（ESM或仅观测）和传统方法（CMIP5， CMIP6和MODIS； R = 0.07-0.82, NME = 51%-1951%）。它还擅长捕捉季节变化和长期年度趋势，更好地再现由人为强迫驱动的增加趋势和由自然气候变率调节的年代际变率。因此，该数据集对于bcs引起的辐射强迫的可靠量化以及全球范围内融雪加速归因于雪变暗与气候变暖的关系具有重要价值。
{"title":"Global Quantification of Black Carbon in Seasonal Snow: A Physically and Observationally Constrained Machine-Learning Framework.","authors":"Yang Chen, Shirui Yan, Yaliang Hou, Yongxiang Lin, Kexin Liu, Dingfan Cao, Yuxuan Xing, Daizhou Zhang, Wei Pu, Xin Wang","doi":"10.1021/acs.est.5c09936","DOIUrl":"https://doi.org/10.1021/acs.est.5c09936","url":null,"abstract":"<p><p>Black carbon in seasonal snow (BCS) critically influences the Earth system by reducing surface albedo (snow darkening), perturbing radiative balance, and accelerating snowmelt. However, its climatic and hydrological impacts remain poorly quantified because high-quality data sets are scarce. This study introduces a novel Dual Random Forest (DRF) framework that synergistically constrains BCS concentration estimates through both physical mechanisms and observational fidelity. By pretraining with six spatiotemporally complete Earth System Model (ESM) simulations, driven by multisource reanalysis data, and fine-tuning against global field observations, the DRF generates a 44-year (1981-2024) global monthly BCS data set at 0.5° × 0.625° resolution. This data set achieves higher accuracy in BCS patterns and concentrations compared with observations (spatial correlation <i>R</i> = 0.92; normalized mean error NME = 31%), outperforming both single-constrained machine learning approaches (ESM- or observation-only) and traditional methods (CMIP5, CMIP6, and MODIS; <i>R</i> = 0.07-0.82, NME = 51%-1951%). It also excels in capturing seasonal variations and long-term annual trends, better reproducing increasing trends driven by anthropogenic forcing and decadal variability modulated by natural climate variability. This data set is hence valuable for robust quantification of BCS-induced radiative forcing and attribution of snowmelt acceleration to snow darkening versus climate warming on a global scale.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":" ","pages":""},"PeriodicalIF":11.3,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146117106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Forming two-dimensional (2D) alloys provides a unique way to tune the structural parameter and the electronic structure of a material in comparison to their pure counterparts. By taking motivation from this fact, we are presenting a detailed analysis based on first-principles density functional theory calculation for 2D BY1–xZx (Y, Z = P, As, and Sb, but Y ≠ Z) alloys. From a synthesis point of view, it would be interesting to predict (a) How the structural parameters and electronic structure of BY1–xZx alloys are going to change with doping concentration (x)? (b) How will x affect the thermodynamical stability of alloys? and (c) What are the growth temperatures of these alloys? Our calculations reveal that an increase in x decreases the lattice constant of BY1–xZx alloys, which is in accordance with Vegard’s law. Electronic structure calculations predict a direct band gap for pristine BP, BAs, and BSb at high symmetry point K, equal to 1.35, 1.18, and 0.60 eV, respectively. We notice that for BY1–xZx alloys, the band gap remains direct and shows bowing at x = 0.33. There is a sharp fluctuation in edge valence bands during the band alignment of alloys (maximum for BSb1–xAsx, ∼1 eV). However, the edge conduction bands show a relatively small fluctuation, which is the lowest for BAs1–xPx alloys (∼0.02 eV) on increasing x. The absorption coefficient of BY1–xZx alloys as a function of x shifts the peak toward blue. Further, BAs1–xPx alloys exhibit positive enthalpy of mixing and thus can grow by obeying an endothermic reaction. However, BSb1–xPx and BSb1–xAsx alloys, with negative mixing enthalpies, can be grown by an exothermic reaction. The binodal and spinodal decomposition curves predict the growth temperature of BAs1–xPx, BSb1–xPx, and BSb1–xAsx alloys to be −208, 3082, and 1801 K, respectively.
{"title":"First-Principles Insights in Designing Two-Dimensional BY1–xZx (Y, Z = P, As, and Sb, but Y ≠ Z) Alloys: A Potential Candidate for Thin-Film Optoelectronic Devices","authors":"Durgesh Kumar Sharma,Pawan Kumar,Rajeev Ahuja,Sudhir Kumar","doi":"10.1021/acs.jpcc.5c07234","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07234","url":null,"abstract":"Forming two-dimensional (2D) alloys provides a unique way to tune the structural parameter and the electronic structure of a material in comparison to their pure counterparts. By taking motivation from this fact, we are presenting a detailed analysis based on first-principles density functional theory calculation for 2D BY1–xZx (Y, Z = P, As, and Sb, but Y ≠ Z) alloys. From a synthesis point of view, it would be interesting to predict (a) How the structural parameters and electronic structure of BY1–xZx alloys are going to change with doping concentration (x)? (b) How will x affect the thermodynamical stability of alloys? and (c) What are the growth temperatures of these alloys? Our calculations reveal that an increase in x decreases the lattice constant of BY1–xZx alloys, which is in accordance with Vegard’s law. Electronic structure calculations predict a direct band gap for pristine BP, BAs, and BSb at high symmetry point K, equal to 1.35, 1.18, and 0.60 eV, respectively. We notice that for BY1–xZx alloys, the band gap remains direct and shows bowing at x = 0.33. There is a sharp fluctuation in edge valence bands during the band alignment of alloys (maximum for BSb1–xAsx, ∼1 eV). However, the edge conduction bands show a relatively small fluctuation, which is the lowest for BAs1–xPx alloys (∼0.02 eV) on increasing x. The absorption coefficient of BY1–xZx alloys as a function of x shifts the peak toward blue. Further, BAs1–xPx alloys exhibit positive enthalpy of mixing and thus can grow by obeying an endothermic reaction. However, BSb1–xPx and BSb1–xAsx alloys, with negative mixing enthalpies, can be grown by an exothermic reaction. The binodal and spinodal decomposition curves predict the growth temperature of BAs1–xPx, BSb1–xPx, and BSb1–xAsx alloys to be −208, 3082, and 1801 K, respectively.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"75 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111096","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Introducing environmentally benign Zn single-atom catalysts (SACs) in Fenton-like reactions to induce electron transfer processes (ETP) holds great potential in advanced water remediation technologies. However, precise coordination of Zn SACs is highly required to selectively trigger the ETP pathway. Herein, under the guidance of density functional theory (DFT) predictions, we constructed asymmetric Zn–N3Cl sites on N-doped carbon (NC) to unlock the electron-transfer reactivity of redox-inert Zn while maintaining structural robustness. Compared with the symmetric Zn–N4 system, the Zn–N3Cl system achieved a higher sulfamethoxazole (SMX) removal rate and PMS utilization efficiency by 4.4 and 2.3 times, respectively. Mechanism studies revealed that Cl doping significantly altered the electronic structure of Zn sites, thereby promoting their electron transfer capacity. The strongly polarized Zn–N3Cl sites exhibited a notably enhanced interaction with PMS, facilitating the formation of Zn–N3Cl/PMS* with high redox potential and lowering the energy barrier of the rate-determining step (RDS) for ETP. The Zn–N3Cl system demonstrated outstanding catalytic reactivity toward various environmental interferences over a wide pH range. Notably, this system remained effective for the continuous flow-through treatment of pharmaceutical wastewater, coupling high catalytic reactivity and structural robustness. Our rational design of environmentally benign materials offers a blueprint for sustainable water remediation.
{"title":"Tailoring the Interfacial Microenvironment of Atomically Dispersed Zinc to Boost Electron Transfer Process for Water Purification","authors":"Zhiyuan Huang,Qi Hao,Songru Xie,Chaoyi Huang,Li Jin,Rui Li,Linxuan Xie,Qi Tang,Jiang Xu,Kai Liu","doi":"10.1021/acs.est.5c18038","DOIUrl":"https://doi.org/10.1021/acs.est.5c18038","url":null,"abstract":"Introducing environmentally benign Zn single-atom catalysts (SACs) in Fenton-like reactions to induce electron transfer processes (ETP) holds great potential in advanced water remediation technologies. However, precise coordination of Zn SACs is highly required to selectively trigger the ETP pathway. Herein, under the guidance of density functional theory (DFT) predictions, we constructed asymmetric Zn–N3Cl sites on N-doped carbon (NC) to unlock the electron-transfer reactivity of redox-inert Zn while maintaining structural robustness. Compared with the symmetric Zn–N4 system, the Zn–N3Cl system achieved a higher sulfamethoxazole (SMX) removal rate and PMS utilization efficiency by 4.4 and 2.3 times, respectively. Mechanism studies revealed that Cl doping significantly altered the electronic structure of Zn sites, thereby promoting their electron transfer capacity. The strongly polarized Zn–N3Cl sites exhibited a notably enhanced interaction with PMS, facilitating the formation of Zn–N3Cl/PMS* with high redox potential and lowering the energy barrier of the rate-determining step (RDS) for ETP. The Zn–N3Cl system demonstrated outstanding catalytic reactivity toward various environmental interferences over a wide pH range. Notably, this system remained effective for the continuous flow-through treatment of pharmaceutical wastewater, coupling high catalytic reactivity and structural robustness. Our rational design of environmentally benign materials offers a blueprint for sustainable water remediation.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"41 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sustainable generation of ferrous iron (Fe(II)) through engineered zero-valent iron (ZVI, Fe(0)) offers an innovative strategy for efficient pollutant reduction. This study presents a wet ball milling-surface engineering strategy for synthesizing low-molecular-weight organic acid (LMWOA)-modified ZVI, which enables a novel dual redox activation mechanism for Fe(II)─a functionality that cannot be achieved by conventional wet ball milling or external LMWOA addition. X-ray absorption fine structure spectroscopy and density functional theory calculations demonstrate that α-hydroxy carboxylic acids (e.g., citric, tartaric, and malic acids) form five-membered chelate rings via hydrogen bonding, thereby significantly enhancing electron transfer kinetics from Fe(0) to Fe(II). Meanwhile, non-α-hydroxy carboxylic acids (e.g., succinic/acetic/formic acids) promote Fe(III) adsorption–reduction cycles, thus sustaining Fe(II) regeneration. Notably, ZVI modified with oxalic acid or ascorbic acid exhibited a synergistic effect of both pathways, resulting in the highest Cr(VI) removal capacities, with 19.7- and 22.6-fold increases in Cr(VI) removal and Fe(III) recovery rates of 81.7% and 108.9% relative to unmodified ZVI, respectively. This enhanced performance can be attributed to the improved dissolution of Fe(II) and the elevated levels of structurally bound Fe(II), which collectively promote sustained electron generation and effective transfer to Cr(VI). These findings indicate that LMWOA-modified ZVI establishes a tunable Fe(II) activation system, thereby positioning LMWOA as a promising strategic platform for groundwater remediation.
{"title":"Dual Activation of Ferrous Iron via Surface Engineering of Zero-Valent Iron with Low-Molecular-Weight Organic Acids","authors":"Linbo Qian,Zhenyu Kang,Hangyu Li,Zhen Ni,Hongtao Sheng,Yuqing Wang,Xiaoqi Long,Mengfang Chen,Baoliang Chen","doi":"10.1021/acs.est.5c14314","DOIUrl":"https://doi.org/10.1021/acs.est.5c14314","url":null,"abstract":"Sustainable generation of ferrous iron (Fe(II)) through engineered zero-valent iron (ZVI, Fe(0)) offers an innovative strategy for efficient pollutant reduction. This study presents a wet ball milling-surface engineering strategy for synthesizing low-molecular-weight organic acid (LMWOA)-modified ZVI, which enables a novel dual redox activation mechanism for Fe(II)─a functionality that cannot be achieved by conventional wet ball milling or external LMWOA addition. X-ray absorption fine structure spectroscopy and density functional theory calculations demonstrate that α-hydroxy carboxylic acids (e.g., citric, tartaric, and malic acids) form five-membered chelate rings via hydrogen bonding, thereby significantly enhancing electron transfer kinetics from Fe(0) to Fe(II). Meanwhile, non-α-hydroxy carboxylic acids (e.g., succinic/acetic/formic acids) promote Fe(III) adsorption–reduction cycles, thus sustaining Fe(II) regeneration. Notably, ZVI modified with oxalic acid or ascorbic acid exhibited a synergistic effect of both pathways, resulting in the highest Cr(VI) removal capacities, with 19.7- and 22.6-fold increases in Cr(VI) removal and Fe(III) recovery rates of 81.7% and 108.9% relative to unmodified ZVI, respectively. This enhanced performance can be attributed to the improved dissolution of Fe(II) and the elevated levels of structurally bound Fe(II), which collectively promote sustained electron generation and effective transfer to Cr(VI). These findings indicate that LMWOA-modified ZVI establishes a tunable Fe(II) activation system, thereby positioning LMWOA as a promising strategic platform for groundwater remediation.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"20 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A protocol of C–C direct coupling of the C-2 position of 3-acetylaminofuran, derived from biomass, with quinoxalinone was reported for the first time. This study confirmed that the quinoxalinone free radical, generated by acid protonation and illumination, is used to perform C–C dehydrogenation coupling with 3-acetylaminofuran (3AF), in which oxygen participates in the reaction process. On this basis, acid-catalyzed deacetylation was used to obtain the corresponding aminofuran derivatives. Intramolecular dehydration can be realized to form an imine tetracyclic compound.
{"title":"Synthesis of Aminofuranquinoxalinones from a Two-Step Cascade: Photoinduced TFA-Promoted Coupling of Quinoxalin-2(1H)-ones with 3-Acetamidofuran and Hydrolysis","authors":"Peipei Ma,Guangyu Yang,Yuan Wang,Hongli Wu,Haifeng Gan,Fei Cao,Jianliang Zhu","doi":"10.1021/acs.joc.5c02986","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02986","url":null,"abstract":"A protocol of C–C direct coupling of the C-2 position of 3-acetylaminofuran, derived from biomass, with quinoxalinone was reported for the first time. This study confirmed that the quinoxalinone free radical, generated by acid protonation and illumination, is used to perform C–C dehydrogenation coupling with 3-acetylaminofuran (3AF), in which oxygen participates in the reaction process. On this basis, acid-catalyzed deacetylation was used to obtain the corresponding aminofuran derivatives. Intramolecular dehydration can be realized to form an imine tetracyclic compound.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"108 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111188","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-04DOI: 10.1021/acs.jpca.5c06566
Jason Howard, Garvit Agarwal, John Low, Rajeev S Assary, Larry Curtiss
In this work, we explore the use of constrained density functional theory for the calculation of the charge transfer parameters of 2,1,3-benzothiadiazole (BTZ), a promising redoxmer, in acetonitrile (MeCN) solvent. The BTZ molecule has been studied as an anolyte in redox flow batteries, where charge transfer is a crucial process. It is highly desirable to simulate ab initio charge-transfer parameters, given their accuracy in predicting electron-transfer rates and structure-activity relationships. This work explores the state of the art in charge-transfer simulation for this process. Constrained density functional theory (DFT) calculations are used to predict charge-transfer free energies and electronic couplings, which are crucial for evaluating charge transfer within the Marcus theory. Based on the simulations, we find that electronic coupling fluctuates rapidly with time and also depends on the difference between the donor and acceptor state energies (reaction gap energy). Based on our evaluation of Marcus theory, BTZ has a predicted self-exchange reaction rate constant on the order of 0.5 M-1 s-1 at 1 M concentration in MeCN. Our work demonstrates the utility of constrained DFT for providing physical insight into a charge-transfer process, while also highlighting current limitations in computational and algorithmic capacity in achieving desirable system sizes and levels of ergodicity in molecular dynamics simulations. A significant conclusion of this work is that time-dependent sampling of electronic coupling as a function of the reaction gap energy, as described herein, is essential for future predictions of charge and electron transfer.
{"title":"Dynamic Electronic Coupling in the Self-Exchange Charge Transfer Reaction of Benzothiadiazole Redoxmer in Acetonitrile Calculated with Constrained Density Functional Theory.","authors":"Jason Howard, Garvit Agarwal, John Low, Rajeev S Assary, Larry Curtiss","doi":"10.1021/acs.jpca.5c06566","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c06566","url":null,"abstract":"<p><p>In this work, we explore the use of constrained density functional theory for the calculation of the charge transfer parameters of 2,1,3-benzothiadiazole (BTZ), a promising redoxmer, in acetonitrile (MeCN) solvent. The BTZ molecule has been studied as an anolyte in redox flow batteries, where charge transfer is a crucial process. It is highly desirable to simulate ab initio charge-transfer parameters, given their accuracy in predicting electron-transfer rates and structure-activity relationships. This work explores the state of the art in charge-transfer simulation for this process. Constrained density functional theory (DFT) calculations are used to predict charge-transfer free energies and electronic couplings, which are crucial for evaluating charge transfer within the Marcus theory. Based on the simulations, we find that electronic coupling fluctuates rapidly with time and also depends on the difference between the donor and acceptor state energies (reaction gap energy). Based on our evaluation of Marcus theory, BTZ has a predicted self-exchange reaction rate constant on the order of 0.5 M<sup>-1</sup> s<sup>-1</sup> at 1 M concentration in MeCN. Our work demonstrates the utility of constrained DFT for providing physical insight into a charge-transfer process, while also highlighting current limitations in computational and algorithmic capacity in achieving desirable system sizes and levels of ergodicity in molecular dynamics simulations. A significant conclusion of this work is that time-dependent sampling of electronic coupling as a function of the reaction gap energy, as described herein, is essential for future predictions of charge and electron transfer.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146117174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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