Pub Date : 2025-04-22DOI: 10.1021/acs.jpcc.4c08621
Yves A. Mantz, Yinkai Lei, Wissam A. Saidi, Harry W. Abernathy, Youhai Wen
The coarsening of the Ni particles in the hydrogen electrode of solid oxide cells (SOCs) is an important degradation mechanism. In this paper, density-functional theory and kinetic Monte Carlo methods are used to explore our recent hypothesis that the surface diffusion of NiH may cause faster Ni coarsening in electrolysis cell mode under an overpotential. Using both methods, the diffusion constant or diffusivity of NiH on Ni (111) is determined as the product of the surface coverage and single-molecule diffusivity for the first time considering all possible diffusion paths. It is then determined versus overpotential at the triple-phase boundary of the hydrogen electrode assuming a typical operating temperature of the SOC. Under a significant overpotential, the diffusivity of NiH is found to be sufficiently large to support the above hypothesis that NiH may promote Ni coarsening. However, based on the adsorption configurations identified, the dissociation and reformation of NiH on Ni (111) could occur. Thus, more work is needed to develop a model of Ni coarsening considering both molecular and dissociated forms of NiH.
{"title":"Toward a Better Understanding of Ni Coarsening in Solid Oxide Cells: NiH on Ni (111) Examined Using a Combined Theoretical Approach","authors":"Yves A. Mantz, Yinkai Lei, Wissam A. Saidi, Harry W. Abernathy, Youhai Wen","doi":"10.1021/acs.jpcc.4c08621","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08621","url":null,"abstract":"The coarsening of the Ni particles in the hydrogen electrode of solid oxide cells (SOCs) is an important degradation mechanism. In this paper, density-functional theory and kinetic Monte Carlo methods are used to explore our recent hypothesis that the surface diffusion of NiH may cause faster Ni coarsening in electrolysis cell mode under an overpotential. Using both methods, the diffusion constant or diffusivity of NiH on Ni (111) is determined as the product of the surface coverage and single-molecule diffusivity for the first time considering all possible diffusion paths. It is then determined versus overpotential at the triple-phase boundary of the hydrogen electrode assuming a typical operating temperature of the SOC. Under a significant overpotential, the diffusivity of NiH is found to be sufficiently large to support the above hypothesis that NiH may promote Ni coarsening. However, based on the adsorption configurations identified, the dissociation and reformation of NiH on Ni (111) could occur. Thus, more work is needed to develop a model of Ni coarsening considering both molecular and dissociated forms of NiH.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"4 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862317","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}
Pub Date : 2025-04-22DOI: 10.1021/acs.jpcc.5c00161
Alison Arissa, Thomas Rose, Noémi Leick, Stefan Grimme, Justin C. Johnson, Jenny V. Lockard
Porphyrin-based metal–organic frameworks (MOFs) offer a unique platform for building porous donor–acceptor networks that exhibit long-lived charge separation and transport upon incorporation of electron acceptor guest species. Here, porphyrin-based MOFs, PCN-222(H2) and PCN-222(Zn), synthesized as nanoparticle suspensions, are successfully infiltrated with fullerene acceptor molecules, C60 or PC61BM, in both polar and nonpolar solvent environments. The location and relative binding strength of these guest species are evaluated through a combination of N2 physisorption measurements, photoluminescence quenching, and UV–vis absorption titration experiments. Semiempirical tight binding calculations are used to screen potential locations of the fullerene guest within the MOF pores, and hybrid density functional theory (DFT)-computed interaction energies confirm the energetically favorable positions. The fundamental photophysics of these donor–acceptor host–guest combinations are probed using ultrafast transient absorption spectroscopy. Sub-picosecond electron transfer involving initial exciplex population is observed, with slow charge recombination lifetimes on the order of τ ∼1 ns for all systems in both dimethylformamide and 1,4-dioxane. Charge recombination occurs through population of fullerene and/or framework porphyrin triplet states depending on the porphyrin metalation status. The photophysics of the fullerene-loaded MOFs are discussed in the context of relevant porphyrin–fullerene donor–acceptor molecules to highlight the unique role of the framework environment in dictating photoinduced electron transfer and decay pathways.
{"title":"Charge Transfer and Recombination Pathways through Fullerene Guests in Porphyrin-Based MOFs","authors":"Alison Arissa, Thomas Rose, Noémi Leick, Stefan Grimme, Justin C. Johnson, Jenny V. Lockard","doi":"10.1021/acs.jpcc.5c00161","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00161","url":null,"abstract":"Porphyrin-based metal–organic frameworks (MOFs) offer a unique platform for building porous donor–acceptor networks that exhibit long-lived charge separation and transport upon incorporation of electron acceptor guest species. Here, porphyrin-based MOFs, PCN-222(H<sub>2</sub>) and PCN-222(Zn), synthesized as nanoparticle suspensions, are successfully infiltrated with fullerene acceptor molecules, C<sub>60</sub> or PC<sub>61</sub>BM, in both polar and nonpolar solvent environments. The location and relative binding strength of these guest species are evaluated through a combination of N<sub>2</sub> physisorption measurements, photoluminescence quenching, and UV–vis absorption titration experiments. Semiempirical tight binding calculations are used to screen potential locations of the fullerene guest within the MOF pores, and hybrid density functional theory (DFT)-computed interaction energies confirm the energetically favorable positions. The fundamental photophysics of these donor–acceptor host–guest combinations are probed using ultrafast transient absorption spectroscopy. Sub-picosecond electron transfer involving initial exciplex population is observed, with slow charge recombination lifetimes on the order of τ ∼1 ns for all systems in both dimethylformamide and 1,4-dioxane. Charge recombination occurs through population of fullerene and/or framework porphyrin triplet states depending on the porphyrin metalation status. The photophysics of the fullerene-loaded MOFs are discussed in the context of relevant porphyrin–fullerene donor–acceptor molecules to highlight the unique role of the framework environment in dictating photoinduced electron transfer and decay pathways.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"37 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862318","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}
Jiang-Hong Liu, Ze-Yu Tian, Zhen-Ye Wu, Tian-Le Huang, Li Hai, Li Guo, Yong Wu, Zhongzhen Yang
We disclosed an organophotoredox-catalyzed three-component oxidative radical-polar crossover strategy for constructing 1,2-alkylamination products. Cycloketone oxime derivatives were used as cyanoalkyl radical precursors and anilines were used as the nucleophiles. This facile protocol shows a good reaction yield and broad substrate scope.
{"title":"Visible-Light-Induced 4CzIPN-Catalyzed Alkylamination of Alkenes via Cyclobutanone Oxime Esters and Anilines","authors":"Jiang-Hong Liu, Ze-Yu Tian, Zhen-Ye Wu, Tian-Le Huang, Li Hai, Li Guo, Yong Wu, Zhongzhen Yang","doi":"10.1021/acs.joc.4c02172","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02172","url":null,"abstract":"We disclosed an organophotoredox-catalyzed three-component oxidative radical-polar crossover strategy for constructing 1,2-alkylamination products. Cycloketone oxime derivatives were used as cyanoalkyl radical precursors and anilines were used as the nucleophiles. This facile protocol shows a good reaction yield and broad substrate scope.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862516","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}
Bocheng Chen, Lucas Pagès, Cyrille Kouklovsky, Sébastien Prévost, Aurélien de la Torre
A chemoselective double allylic substitution involving two different carbon nucleophiles is described. The reaction relies on a dual catalytic approach, with a Lewis acid promoting the first allylic substitution and Pd promoting the second step. Starting from simple allylic diols, a diversity of polycyclic structures can be obtained, including tetrahydroindole, tetrahydrocarbazole, and tetrahydronaphthalene.
{"title":"Chemoselective Double Allylic Substitutions with Carbon Nucleophiles: Access to Tetrahydroindoles and Tetrahydrocarbazoles","authors":"Bocheng Chen, Lucas Pagès, Cyrille Kouklovsky, Sébastien Prévost, Aurélien de la Torre","doi":"10.1021/acs.joc.5c00121","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00121","url":null,"abstract":"A chemoselective double allylic substitution involving two different carbon nucleophiles is described. The reaction relies on a dual catalytic approach, with a Lewis acid promoting the first allylic substitution and Pd promoting the second step. Starting from simple allylic diols, a diversity of polycyclic structures can be obtained, including tetrahydroindole, tetrahydrocarbazole, and tetrahydronaphthalene.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"51 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862544","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 : 2025-04-22DOI: 10.1021/acs.jpcc.4c08652
Yongjie Jiang, Hui Guo, Feng Cheng, Zhao-Xu Chen
Conversion of CO2 to ethanol is a potential method for carbon capture and utilization. Among various catalysts for this reaction, Pd2Cu is found to have high activity and selectivity. In this paper, we investigated the reaction mechanism using mean-field microkinetic modeling (MF-MKM) and kinetic Monte Carlo (kMC) simulations. To overcome the stiffness problem caused by the significant difference in time scales of different events in kMC simulation, we employed the ads-kMC algorithm proposed in our previous work, in which the adsorption/desorption/reaction rate constants were reduced under certain requirements and the diffusion process was treated by redistributing surface species each time an event occurs. Both methods show similar surface coverage, i.e., the surface is fully covered by H and CO and exhibits high selectivity for ethanol. This study also compares the effect of species diffusion rates on the kMC simulations. The results show that the diffusion rate changes the reaction mechanism and coverage, and under slow diffusion case the kMC predicted selectivity is higher than that under fast diffusion. The present study sheds light on the mechanism of CO2 hydrogenation to ethanol on Pd2Cu catalyst, deepens the understanding of kMC and MF-MKM simulations, and examines the influence of species diffusion on reaction kinetics.
将二氧化碳转化为乙醇是一种潜在的碳捕获和利用方法。在该反应的各种催化剂中，Pd2Cu 被认为具有较高的活性和选择性。本文采用均场微动力学建模（MF-MKM）和动力学蒙特卡罗（kMC）模拟研究了反应机理。为了克服 kMC 模拟中不同事件的时间尺度差异较大所导致的僵化问题，我们采用了之前工作中提出的 ads-kMC 算法，即在一定要求下降低吸附/解吸/反应速率常数，并在每次事件发生时通过重新分配表面物种来处理扩散过程。两种方法都显示出相似的表面覆盖率，即表面被 H 和 CO 完全覆盖，并对乙醇表现出高选择性。本研究还比较了物种扩散率对 kMC 模拟的影响。结果表明，扩散速率会改变反应机制和覆盖率，在慢扩散情况下，kMC 预测的选择性高于快扩散情况下的选择性。本研究揭示了 Pd2Cu 催化剂上 CO2 加氢制乙醇的机理，加深了对 kMC 和 MF-MKM 模拟的理解，并考察了物种扩散对反应动力学的影响。
{"title":"Kinetic Simulations of CO2 Hydrogenation to Ethanol on Pd2Cu (110)","authors":"Yongjie Jiang, Hui Guo, Feng Cheng, Zhao-Xu Chen","doi":"10.1021/acs.jpcc.4c08652","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08652","url":null,"abstract":"Conversion of CO<sub>2</sub> to ethanol is a potential method for carbon capture and utilization. Among various catalysts for this reaction, Pd<sub>2</sub>Cu is found to have high activity and selectivity. In this paper, we investigated the reaction mechanism using mean-field microkinetic modeling (MF-MKM) and kinetic Monte Carlo (kMC) simulations. To overcome the stiffness problem caused by the significant difference in time scales of different events in kMC simulation, we employed the ads-kMC algorithm proposed in our previous work, in which the adsorption/desorption/reaction rate constants were reduced under certain requirements and the diffusion process was treated by redistributing surface species each time an event occurs. Both methods show similar surface coverage, i.e., the surface is fully covered by H and CO and exhibits high selectivity for ethanol. This study also compares the effect of species diffusion rates on the kMC simulations. The results show that the diffusion rate changes the reaction mechanism and coverage, and under slow diffusion case the kMC predicted selectivity is higher than that under fast diffusion. The present study sheds light on the mechanism of CO<sub>2</sub> hydrogenation to ethanol on Pd<sub>2</sub>Cu catalyst, deepens the understanding of kMC and MF-MKM simulations, and examines the influence of species diffusion on reaction kinetics.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"43 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858234","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}
Pub Date : 2025-04-22DOI: 10.1021/acs.jpclett.5c00096
Jianlong Kang, Li Zhou, Yiduo Wang, Jie Zhang, Quan Long, Xianming Zhong, Xin Li, Yingwei Wang, Si Xiao, Jun He
van der Waals crystal NbOCl2 has attracted considerable interest owing to its spontaneous parametric downconversion properties, but challenges remain due to its degradation and reduced optical nonlinearity under ambient conditions. Here, we show that high-temperature vacuum annealing can recover and even enhance second harmonic generation (SHG) in degraded NbOCl2 via recrystallization. During degradation, the second-order nonlinearity decreases, accompanied by changes in the crystal structure of NbOCl2. However, after annealing, SHG is recovered and even improved as a result of recrystallization of the degraded NbOCl2 nanosheets. This strategy enables the realization of tunable nonlinear optical responses, including harmonic generation and nonlinear absorption. By combining linear absorption spectroscopy, transient absorption, and transmission electron microscopy, we show that recrystallization occurs under specific annealing temperatures, leading to bandgap modulation and altered electronic relaxation. This study offers a new approach to achieving tunable and reversible optical nonlinearity for nonlinear optical device applications.
{"title":"Recrystallization-Driven High-Performance Optical Nonlinearity Recovery of Layered van der Waals NbOCl2","authors":"Jianlong Kang, Li Zhou, Yiduo Wang, Jie Zhang, Quan Long, Xianming Zhong, Xin Li, Yingwei Wang, Si Xiao, Jun He","doi":"10.1021/acs.jpclett.5c00096","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00096","url":null,"abstract":"van der Waals crystal NbOCl<sub>2</sub> has attracted considerable interest owing to its spontaneous parametric downconversion properties, but challenges remain due to its degradation and reduced optical nonlinearity under ambient conditions. Here, we show that high-temperature vacuum annealing can recover and even enhance second harmonic generation (SHG) in degraded NbOCl<sub>2</sub> via recrystallization. During degradation, the second-order nonlinearity decreases, accompanied by changes in the crystal structure of NbOCl<sub>2</sub>. However, after annealing, SHG is recovered and even improved as a result of recrystallization of the degraded NbOCl<sub>2</sub> nanosheets. This strategy enables the realization of tunable nonlinear optical responses, including harmonic generation and nonlinear absorption. By combining linear absorption spectroscopy, transient absorption, and transmission electron microscopy, we show that recrystallization occurs under specific annealing temperatures, leading to bandgap modulation and altered electronic relaxation. This study offers a new approach to achieving tunable and reversible optical nonlinearity for nonlinear optical device applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858222","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 : 2025-04-22DOI: 10.1016/j.bios.2025.117504
Amadeo Sena-Torralba , Yulieth D. Banguera-Ordoñez , Javier Carrascosa , Ángel Maquieira , Sergi Morais
Lateral flow immunoassays are globally recognized for their simplicity, cost-effectiveness, and rapid qualitative and semiquantitative analyses, making them indispensable as point-of-care screening tools. However, their limited sensitivity restricts their application in clinical settings, requiring the detection of ultralow analyte concentrations in complex sample matrices. To address these challenges, we present a portable biosensing platform integrating battery-powered electrokinetic-driven microfluidics to enhance sensitivity while preserving point-of-care functionality. Our lightweight (151 g), 3D-printed electrophoretic device (€82) supports the simultaneous analysis of three samples and operates with an ultra-low power consumption of 225 mAh−1, enabling 44 h of operation on a single charge. By optimizing key parameters such as Joule heating, buffer evaporation, and electroosmotic flow, the device enables iterative incubation and washing steps directly on the nitrocellulose strip, capabilities unattainable with conventional capillarity-driven LFIAs. This advanced biosensing platform achieves a detection limit of 70 pg mL−1 for human lactate dehydrogenase (h-LDH), a key cancer biomarker, using gold nanoparticles as signal transducers. This result means a 367-fold improvement in sensitivity. Offering rapid, cost-effective, and ultra-sensitive biomarker quantification, this approach holds significant promise for transforming precision medicine, particularly in monitoring LDH-related cancer therapies.
{"title":"Portable electrophoretic lateral flow biosensing for ultra-sensitive human lactate dehydrogenase detection in serum samples","authors":"Amadeo Sena-Torralba , Yulieth D. Banguera-Ordoñez , Javier Carrascosa , Ángel Maquieira , Sergi Morais","doi":"10.1016/j.bios.2025.117504","DOIUrl":"10.1016/j.bios.2025.117504","url":null,"abstract":"<div><div>Lateral flow immunoassays are globally recognized for their simplicity, cost-effectiveness, and rapid qualitative and semiquantitative analyses, making them indispensable as point-of-care screening tools. However, their limited sensitivity restricts their application in clinical settings, requiring the detection of ultralow analyte concentrations in complex sample matrices. To address these challenges, we present a portable biosensing platform integrating battery-powered electrokinetic-driven microfluidics to enhance sensitivity while preserving point-of-care functionality. Our lightweight (151 g), 3D-printed electrophoretic device (€82) supports the simultaneous analysis of three samples and operates with an ultra-low power consumption of 225 mAh<sup>−1</sup>, enabling 44 h of operation on a single charge. By optimizing key parameters such as Joule heating, buffer evaporation, and electroosmotic flow, the device enables iterative incubation and washing steps directly on the nitrocellulose strip, capabilities unattainable with conventional capillarity-driven LFIAs. This advanced biosensing platform achieves a detection limit of 70 pg mL<sup>−1</sup> for human lactate dehydrogenase (h-LDH), a key cancer biomarker, using gold nanoparticles as signal transducers. This result means a 367-fold improvement in sensitivity. Offering rapid, cost-effective, and ultra-sensitive biomarker quantification, this approach holds significant promise for transforming precision medicine, particularly in monitoring LDH-related cancer therapies.</div></div>","PeriodicalId":259,"journal":{"name":"Biosensors and Bioelectronics","volume":"282 ","pages":"Article 117504"},"PeriodicalIF":10.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143859335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Historically, environmental protection by governmental agencies has focused on controlling point-source discharges, in many cases emphasizing wastewaters laden with nutrients, pathogens, metals, and/or synthetic organics. Most non-United States countries do not focus effluent limits much beyond nutrients and dissolved oxygen and do not put limits on metals and synthetic organics. Water quality standards were established to regulate dischargers and drinking water and protect aquatic biota from impairment associated with point-source pollution. Nevertheless, widespread causes of ecosystem impairments from non-point-source (diffuse) pollution, habitat degradation, and invasive species had not been a focus of regulatory enforcement internationally. The U.S. Clean Water Act (sections 303(d), 305(b), and 314) requires each state to submit a biennial report on the quality of its water resources to the U.S. EPA. These reports identify monitored parameters causing failure of a water body to meet its “designated use”. In these reports, the overwhelming causes of impairments are single contaminants, such as chemicals, nutrients, or <i>Escherichia coli</i>, rather than the suite of stressors to which organisms are exposed. These stressors are certainly similar to those in other human-dominated watersheds of the world. Many international and national organizations, e.g., UNEP, WHO, IUCN, Council of Biological Diversity, JPI Oceans Knowledge Hub, Australia State of the Environment, Joint Nature Conservation Committee (UK), and U.S. EPA Office of Research & Development, and scientific authors have stated in recent years that cumulative effect assessments (CEAs) must be adopted to better protect ecosystems from physical, chemical, and biological stressors. Santos et al. (1) reviewed CEAs in terms of improving the European Water Framework Directive and highlighted the need for climate stressor inclusion. Nevertheless, most of the CEAs have failed to emphasize how climate stress and other chemical, physical, and biological stressors should be integrated (Figure 1). Figure 1. Climate-related stressors interact with traditionally managed stressors with known consequences. Cumulative stressor risk assessments are necessary for effective management. Environmental management and regulations can no longer take this overly simplistic focus. The increasing frequency and magnitude of climate change (CC)-related disasters and their interactions with these “traditional” parameters (stressors) mandate a more realistic assessment of ecosystem quality for protection, management, and restoration. Most areas of the planet have already been altered by CC, with large areas experiencing widespread devastation to ecosystems and human systems. To make matters worse, there are far more studies examining single stressors than the interaction of CC-related stressors (i.e., warming temperatures, wildfire, drought, and flooding) and stressors of traditional regulatory focus. Additional
{"title":"A Plea for Cumulative Stressor Risk Assessments in Light of Climate Change","authors":"G. Allen Burton, Jr., Jason R. Rohr","doi":"10.1021/acs.est.5c02733","DOIUrl":"https://doi.org/10.1021/acs.est.5c02733","url":null,"abstract":"Historically, environmental protection by governmental agencies has focused on controlling point-source discharges, in many cases emphasizing wastewaters laden with nutrients, pathogens, metals, and/or synthetic organics. Most non-United States countries do not focus effluent limits much beyond nutrients and dissolved oxygen and do not put limits on metals and synthetic organics. Water quality standards were established to regulate dischargers and drinking water and protect aquatic biota from impairment associated with point-source pollution. Nevertheless, widespread causes of ecosystem impairments from non-point-source (diffuse) pollution, habitat degradation, and invasive species had not been a focus of regulatory enforcement internationally. The U.S. Clean Water Act (sections 303(d), 305(b), and 314) requires each state to submit a biennial report on the quality of its water resources to the U.S. EPA. These reports identify monitored parameters causing failure of a water body to meet its “designated use”. In these reports, the overwhelming causes of impairments are single contaminants, such as chemicals, nutrients, or <i>Escherichia coli</i>, rather than the suite of stressors to which organisms are exposed. These stressors are certainly similar to those in other human-dominated watersheds of the world. Many international and national organizations, e.g., UNEP, WHO, IUCN, Council of Biological Diversity, JPI Oceans Knowledge Hub, Australia State of the Environment, Joint Nature Conservation Committee (UK), and U.S. EPA Office of Research & Development, and scientific authors have stated in recent years that cumulative effect assessments (CEAs) must be adopted to better protect ecosystems from physical, chemical, and biological stressors. Santos et al. (1) reviewed CEAs in terms of improving the European Water Framework Directive and highlighted the need for climate stressor inclusion. Nevertheless, most of the CEAs have failed to emphasize how climate stress and other chemical, physical, and biological stressors should be integrated (Figure 1). Figure 1. Climate-related stressors interact with traditionally managed stressors with known consequences. Cumulative stressor risk assessments are necessary for effective management. Environmental management and regulations can no longer take this overly simplistic focus. The increasing frequency and magnitude of climate change (CC)-related disasters and their interactions with these “traditional” parameters (stressors) mandate a more realistic assessment of ecosystem quality for protection, management, and restoration. Most areas of the planet have already been altered by CC, with large areas experiencing widespread devastation to ecosystems and human systems. To make matters worse, there are far more studies examining single stressors than the interaction of CC-related stressors (i.e., warming temperatures, wildfire, drought, and flooding) and stressors of traditional regulatory focus. Additional","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"17 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862290","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}
Herein, we described the addition reactions of sulfur-containing reagents (sodium sulfinates, dithiosulfonates) with α-trifluoromethyl alkenes under visible light. A series of trifluoromethyl sulfonates were synthesized via the visible-light-induced radical addition reaction of sodium sulfinates and α-trifluoromethyl alkenes to obtain protons from the solvent. A series of dithiosulfonated derivatives were synthesized via visible-light-induced bifunctionalization reaction of α-trifluoromethyl alkenes with dithiosulfonates.This strategy has the advantages of mild reaction conditions, good substrate universality and high yield up to 99% yield.
{"title":"Visible-Light-Mediated Addition Reactions of Sulfur-Containing Reagents with α-Trifluoromethyl Alkenes","authors":"Yi-Rong Chen, Jia-Hui Han, Weidong Rao, Ping Song, Shu-su Shen, Daopeng Sheng, Shun-Yi Wang","doi":"10.1021/acs.joc.5c00396","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00396","url":null,"abstract":"Herein, we described the addition reactions of sulfur-containing reagents (sodium sulfinates, dithiosulfonates) with α-trifluoromethyl alkenes under visible light. A series of trifluoromethyl sulfonates were synthesized via the visible-light-induced radical addition reaction of sodium sulfinates and α-trifluoromethyl alkenes to obtain protons from the solvent. A series of dithiosulfonated derivatives were synthesized via visible-light-induced bifunctionalization reaction of α-trifluoromethyl alkenes with dithiosulfonates.This strategy has the advantages of mild reaction conditions, good substrate universality and high yield up to 99% yield.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"51 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858115","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}
In March 1972, Assembly Bill 2165 (AB 2165), a product safety-specific bill “relating to furniture and bedding”, was one of 2395 bills introduced in the California State Assembly and one of 896 bills enacted on January 1, 1973. AB 2165 was co-authored by Assemblymembers John Burton and Willie Brown who, from 1965 to 1974, represented the 20th and 18th districts, respectively, within San Francisco County. Based on the public record, it is unclear what compelled Burton and Brown to co-author AB 2165 during the 1972–1973 session. AB 2165 included a 141-word amendment to Section 19161 of the Business and Professions Code (BPC) requiring that “all mattresses manufactured for sale in this state ... shall be fire retardant” and “all upholstered furniture sold or offered for sale by a manufacturer or wholesaler for use in this state ... shall be fire retardant and shall be labeled in a manner specified by the bureau.” The Bureau of Electronic and Appliance Repair, Home Furnishings, and Thermal Insulation (now Bureau of Household Goods and Services) held jurisdictional authority over the furniture and bedding industries and were responsible for ensuring compliance with this new law. However, this amendment did not specify how mattresses and upholstered furniture “shall be fire retardant”. In 1973, the Federal Mattress Flammability Standard was simultaneously introduced by the U.S. Consumer Product Safety Commission (CPSC), allowing mattress manufacturers to immediately comply with California’s amendment to Section 19161 of the BPC. However, California was the only state that legally required that (1) upholstered furniture be fire retardant and (2) manufacturers affix permanent labels indicating compliance with state-specific flammability standards. As a result, this led to the implementation of an upholstered furniture flammability performance standard (Technical Bulletin 117, or TB117) in 1975, a deadline mandated by AB 2165. TB117 required that interior filling materials (e.g., polyurethane foam) of upholstered furniture be individually evaluated using open flame and cigarette smolder tests. In 2013, TB117 was revised (now TB117-2013) to address the potential ignition of upholstered cover fabric and interactions among different upholstered furniture components following exposure to smoldering ignition sources (i.e., cigarettes). Importantly, as a smolder-specific standard, TB117-2013 provides manufacturers the flexibility to use either flame retardant (FR) chemicals or barrier (interliner) materials to maintain compliance. Since 1975, TB117-compliant furniture has been sold across the entire United States to simplify production and distribution. As a result, TB117 has been the <i>de facto</i> flammability standard across the country since California was the only state that required upholstered furniture to be fire retardant. Moreover, the adoption of TB117 in the United States preceded fire safety regulations for upholstered furniture in the United King
{"title":"A Proposal to Permanently Ban Flame Retardant Chemicals to Meet California’s Flammability Standard for Upholstered Furniture","authors":"David C. Volz","doi":"10.1021/acs.est.5c03121","DOIUrl":"https://doi.org/10.1021/acs.est.5c03121","url":null,"abstract":"In March 1972, Assembly Bill 2165 (AB 2165), a product safety-specific bill “relating to furniture and bedding”, was one of 2395 bills introduced in the California State Assembly and one of 896 bills enacted on January 1, 1973. AB 2165 was co-authored by Assemblymembers John Burton and Willie Brown who, from 1965 to 1974, represented the 20th and 18th districts, respectively, within San Francisco County. Based on the public record, it is unclear what compelled Burton and Brown to co-author AB 2165 during the 1972–1973 session. AB 2165 included a 141-word amendment to Section 19161 of the Business and Professions Code (BPC) requiring that “all mattresses manufactured for sale in this state ... shall be fire retardant” and “all upholstered furniture sold or offered for sale by a manufacturer or wholesaler for use in this state ... shall be fire retardant and shall be labeled in a manner specified by the bureau.” The Bureau of Electronic and Appliance Repair, Home Furnishings, and Thermal Insulation (now Bureau of Household Goods and Services) held jurisdictional authority over the furniture and bedding industries and were responsible for ensuring compliance with this new law. However, this amendment did not specify how mattresses and upholstered furniture “shall be fire retardant”. In 1973, the Federal Mattress Flammability Standard was simultaneously introduced by the U.S. Consumer Product Safety Commission (CPSC), allowing mattress manufacturers to immediately comply with California’s amendment to Section 19161 of the BPC. However, California was the only state that legally required that (1) upholstered furniture be fire retardant and (2) manufacturers affix permanent labels indicating compliance with state-specific flammability standards. As a result, this led to the implementation of an upholstered furniture flammability performance standard (Technical Bulletin 117, or TB117) in 1975, a deadline mandated by AB 2165. TB117 required that interior filling materials (e.g., polyurethane foam) of upholstered furniture be individually evaluated using open flame and cigarette smolder tests. In 2013, TB117 was revised (now TB117-2013) to address the potential ignition of upholstered cover fabric and interactions among different upholstered furniture components following exposure to smoldering ignition sources (i.e., cigarettes). Importantly, as a smolder-specific standard, TB117-2013 provides manufacturers the flexibility to use either flame retardant (FR) chemicals or barrier (interliner) materials to maintain compliance. Since 1975, TB117-compliant furniture has been sold across the entire United States to simplify production and distribution. As a result, TB117 has been the <i>de facto</i> flammability standard across the country since California was the only state that required upholstered furniture to be fire retardant. Moreover, the adoption of TB117 in the United States preceded fire safety regulations for upholstered furniture in the United King","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"69 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857689","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}
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