Pub Date : 2026-02-09DOI: 10.1021/acs.jpcb.5c08562
Mengyan Wang, Carlos Bueno, Peter G Wolynes
Huntingtin exon-1 (HTTex1) aggregation at cellular membranes contributes to the propagation of toxic protein assemblies in Huntington's disease. We explore the thermodynamic and structural mechanisms linking membrane binding, curvature sensing, and nucleation of the aggregates. Here, we use the OpenAWSEM coarse-grained force field code with an effective membrane potential to quantify the folding and surface aggregation behavior of three HTTex1 constructs on both flat lipid bilayers and spherical vesicles. The computed free energy profiles reveal a strong α-helical NT17-mediated affinity (ΔGbind = -9 kcal/mol) and a curvature-dependent enhancement of this binding, with effective enrichments of protein concentration at the membrane surface of approximately 1000-fold for the NT17 by itself, compared to 18-fold for the polyQ-extended constructs NT17-polyQ and 36-fold for NT17-polyQ-polyP. The free-energy aggregation landscapes demonstrate that membrane proximity also enhances the formation of larger oligomers and promotes early oligomerization through N-terminal anchoring. Analyzing curvature-sensation analyses across vesicle radii shows deeper insertion on highly curved surfaces along with stronger binders, consistent with experimental vesicle-binding assays. Our results establish a mechanistic framework for understanding how membranes can act as two-dimensional platforms that both concentrate HTTex1 and template the formation of aggregation nuclei.
{"title":"Aggregation of Huntingtin Exon 1 Proteins at Flat and Curved Membrane Surfaces.","authors":"Mengyan Wang, Carlos Bueno, Peter G Wolynes","doi":"10.1021/acs.jpcb.5c08562","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c08562","url":null,"abstract":"<p><p>Huntingtin exon-1 (HTTex1) aggregation at cellular membranes contributes to the propagation of toxic protein assemblies in Huntington's disease. We explore the thermodynamic and structural mechanisms linking membrane binding, curvature sensing, and nucleation of the aggregates. Here, we use the OpenAWSEM coarse-grained force field code with an effective membrane potential to quantify the folding and surface aggregation behavior of three HTTex1 constructs on both flat lipid bilayers and spherical vesicles. The computed free energy profiles reveal a strong α-helical <i>NT</i><sub>17</sub>-mediated affinity (Δ<i>G</i><sub>bind</sub> = -9 kcal/mol) and a curvature-dependent enhancement of this binding, with effective enrichments of protein concentration at the membrane surface of approximately 1000-fold for the <i>NT</i><sub>17</sub> by itself, compared to 18-fold for the polyQ-extended constructs <i>NT</i><sub>17</sub>-polyQ and 36-fold for <i>NT</i><sub>17</sub>-polyQ-polyP. The free-energy aggregation landscapes demonstrate that membrane proximity also enhances the formation of larger oligomers and promotes early oligomerization through N-terminal anchoring. Analyzing curvature-sensation analyses across vesicle radii shows deeper insertion on highly curved surfaces along with stronger binders, consistent with experimental vesicle-binding assays. Our results establish a mechanistic framework for understanding how membranes can act as two-dimensional platforms that both concentrate HTTex1 and template the formation of aggregation nuclei.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146140297","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 : 2026-02-09DOI: 10.1021/acs.jpclett.5c03082
Frédéric Caupin,Robert E. Grisenti
The fate of a metastable substance is governed by rare nucleation events, whose full microscopic details still remain elusive despite over 150 years of study. Experimental nucleation rates often differ by many orders of magnitude from theory and simulations, limiting predictive power. In this Perspective, after a general overview on nucleation, we focus on crystallization in three representative systems: metastable water, colloidal suspensions, and Lennard-Jones liquids. The latter, which are well realized by rare-gas liquids, provide a touchstone for nucleation theory. Recent femtosecond X-ray diffraction experiments on supercooled argon and krypton deliver accurate crystal nucleation statistics and direct insight into structural defects such as stacking faults. These advances establish rare-gas liquids as uniquely well-controlled systems bridging experiment, simulation, and theory, and pave the way toward a more complete microscopic understanding of nucleation.
{"title":"Nucleation Statistics from Experiments as a Benchmark for Theory and Simulations","authors":"Frédéric Caupin,Robert E. Grisenti","doi":"10.1021/acs.jpclett.5c03082","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03082","url":null,"abstract":"The fate of a metastable substance is governed by rare nucleation events, whose full microscopic details still remain elusive despite over 150 years of study. Experimental nucleation rates often differ by many orders of magnitude from theory and simulations, limiting predictive power. In this Perspective, after a general overview on nucleation, we focus on crystallization in three representative systems: metastable water, colloidal suspensions, and Lennard-Jones liquids. The latter, which are well realized by rare-gas liquids, provide a touchstone for nucleation theory. Recent femtosecond X-ray diffraction experiments on supercooled argon and krypton deliver accurate crystal nucleation statistics and direct insight into structural defects such as stacking faults. These advances establish rare-gas liquids as uniquely well-controlled systems bridging experiment, simulation, and theory, and pave the way toward a more complete microscopic understanding of nucleation.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"24 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138790","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 : 2026-02-09DOI: 10.1021/acs.jpcc.5c06383
Weihua Wu,Robbert W. E. van de Kruijs,Dirk J. Gravesteijn,Z. Silvester Houweling,Giorgio Colombi,Alexey Y. Kovalgin
In this work, we develop and validate a spectroscopic ellipsometry (SE) approach to first monitor the performance of a thin-film palladium/hafnium (Pd/Hf) hydrogen detection sensor suitable for applications up to a temperature of 450 °C and second to quantify the hydrogen permeation through thin capping layers. A 2.5 nm aluminum oxide (Al2O3) thin film is tested as a potential protective hydrogen barrier under hydrogen radical (H*) flux conditions found in extreme ultraviolet lithography scanners. To this end, the interaction between molecular and atomic hydrogen and a Pd/Hf stack was studied at temperatures from 120 to 670 °C. Optical and structural changes during hydrogen exposures were investigated using in situ SE and ex situ X-ray diffraction. The stack is confirmed to remain stable in the respective metallic phases during vacuum annealing up to 450 °C without forming any crystalline HfO2 by reaction with trace oxidative species. Upon molecular H2 exposure, the formation of hafnium hydride (HfHx) can be observed for temperatures up to 350 °C, while Hf oxidation occurs at higher temperatures. Upon exposure to H*, HfHx formation is observed for temperatures up to 450 °C, again followed by oxidation at higher temperatures. Capping the stack with a 2.5 nm Al2O3 layer fabricated by atomic layer deposition led to a retardation of 70 times for hydrogenation upon H* exposure at 450 °C accompanied by little oxidation. An analytical SE model was developed for analyzing the H-content incorporated into this stack through the Al2O3 capping layer, showing a decent match with that from absolute quantification by elastic recoil detection analysis.
{"title":"Sensing of Hydrogen Diffusion through Protective Caps: An Ellipsometric Approach to Estimate Hydrogen Content in Pd/Hf Stacks with an Al2O3 Cap","authors":"Weihua Wu,Robbert W. E. van de Kruijs,Dirk J. Gravesteijn,Z. Silvester Houweling,Giorgio Colombi,Alexey Y. Kovalgin","doi":"10.1021/acs.jpcc.5c06383","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c06383","url":null,"abstract":"In this work, we develop and validate a spectroscopic ellipsometry (SE) approach to first monitor the performance of a thin-film palladium/hafnium (Pd/Hf) hydrogen detection sensor suitable for applications up to a temperature of 450 °C and second to quantify the hydrogen permeation through thin capping layers. A 2.5 nm aluminum oxide (Al2O3) thin film is tested as a potential protective hydrogen barrier under hydrogen radical (H*) flux conditions found in extreme ultraviolet lithography scanners. To this end, the interaction between molecular and atomic hydrogen and a Pd/Hf stack was studied at temperatures from 120 to 670 °C. Optical and structural changes during hydrogen exposures were investigated using in situ SE and ex situ X-ray diffraction. The stack is confirmed to remain stable in the respective metallic phases during vacuum annealing up to 450 °C without forming any crystalline HfO2 by reaction with trace oxidative species. Upon molecular H2 exposure, the formation of hafnium hydride (HfHx) can be observed for temperatures up to 350 °C, while Hf oxidation occurs at higher temperatures. Upon exposure to H*, HfHx formation is observed for temperatures up to 450 °C, again followed by oxidation at higher temperatures. Capping the stack with a 2.5 nm Al2O3 layer fabricated by atomic layer deposition led to a retardation of 70 times for hydrogenation upon H* exposure at 450 °C accompanied by little oxidation. An analytical SE model was developed for analyzing the H-content incorporated into this stack through the Al2O3 capping layer, showing a decent match with that from absolute quantification by elastic recoil detection analysis.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"241 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138799","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}
Microbial communities in drinking water distribution systems (DWDS) develop primarily as biofilms on pipe surfaces. Despite their impact on water quality, infrastructure maintenance, and biosafety, biofilms are not routinely controlled. In this study, we investigated the bacterial community dynamics and functionality in an urban chlorinated DWDS, dominated by Mycobacterium, through a multiphasic approach which included 16S rRNA gene metabarcoding, metagenomics and microscopy. Our results showed that biofilm communities were more functionally diverse compared to those from water and that the biofilm maturity was positively correlated with the prevalence of potential Mycobacterium emerging pathogens and a broader distribution of antibiotic resistance genes (ARGs) within the microbial community. The reconstruction of metagenome-assembled genomes (MAGs) and the corresponding genomospecies allowed the identification of key microbial taxa involved in the biofilm matrix remodeling, with 22% of them strongly responsible for biofilm formation. A diverse and novel viral community was detected across the system, including new putative Mycobacterium phages that might act against mycolic acids and thus contribute to biofilm destabilization. Our findings enhance our understanding of DWDS microbial composition and biofilm formation dynamics, focusing on “who does what” and then providing a foundation for developing effective biofilm control strategies in water distribution systems.
{"title":"Microbial Biofilms Dynamics and Functionality in an Urban Mycobacterium-Dominated Drinking Water Distribution System","authors":"Valentin Gangloff,Borja Aldeguer-Riquelme,M. Adela Yañez,Gabrielle Potocki-Veronese,Etienne Severac,Josefa Antón,Elena Soria,Fernando Santos","doi":"10.1021/acs.est.5c09194","DOIUrl":"https://doi.org/10.1021/acs.est.5c09194","url":null,"abstract":"Microbial communities in drinking water distribution systems (DWDS) develop primarily as biofilms on pipe surfaces. Despite their impact on water quality, infrastructure maintenance, and biosafety, biofilms are not routinely controlled. In this study, we investigated the bacterial community dynamics and functionality in an urban chlorinated DWDS, dominated by Mycobacterium, through a multiphasic approach which included 16S rRNA gene metabarcoding, metagenomics and microscopy. Our results showed that biofilm communities were more functionally diverse compared to those from water and that the biofilm maturity was positively correlated with the prevalence of potential Mycobacterium emerging pathogens and a broader distribution of antibiotic resistance genes (ARGs) within the microbial community. The reconstruction of metagenome-assembled genomes (MAGs) and the corresponding genomospecies allowed the identification of key microbial taxa involved in the biofilm matrix remodeling, with 22% of them strongly responsible for biofilm formation. A diverse and novel viral community was detected across the system, including new putative Mycobacterium phages that might act against mycolic acids and thus contribute to biofilm destabilization. Our findings enhance our understanding of DWDS microbial composition and biofilm formation dynamics, focusing on “who does what” and then providing a foundation for developing effective biofilm control strategies in water distribution systems.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"9 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138894","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}
We report the first metal-salen-catalyzed switchable ortho-C- and O-alkylation of phenols with spiroepoxides at the tertiary sp3-carbon center of spiroepoxides. Catalyst choice between chiral Cr(III)-salen and chiral Co(III)-salen OTf enables a rare divergence in reactivity: the chiral salen Cr(III)Cl catalyst directs the reaction toward highly enantioselective C3-aryloxylation to afford 3-aryloxy-oxindole-3-methanols (up to 98% ee), whereas salenCo(III)OTf (cat. B) switches the outcome to the complementary C3-ortho-arylation pathway without stereoinduction. The method tolerates various N-protecting groups and aromatic substitution patterns, creating a diverse library of functionalized oxindoles. Mass spectrometric studies reveal catalyst–substrate complexes and (hetero)dimeric assemblies, providing insight into a mechanistic pathway that favors aryloxylation. The method also achieves the first asymmetric synthesis of spiro[benzo[b][1,4]dioxine-2,3′-indolin]-2′-one.
{"title":"Cr(III)-Salen-Catalyzed Enantioselective C3-Aryloxylation of Spiroepoxy Oxindoles","authors":"Ananda Shankar Mondal,Arindam Jana,Ayan Chatterjee,Kumaresh Ghosh,Saumen Hajra","doi":"10.1021/acs.joc.5c02576","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02576","url":null,"abstract":"We report the first metal-salen-catalyzed switchable ortho-C- and O-alkylation of phenols with spiroepoxides at the tertiary sp3-carbon center of spiroepoxides. Catalyst choice between chiral Cr(III)-salen and chiral Co(III)-salen OTf enables a rare divergence in reactivity: the chiral salen Cr(III)Cl catalyst directs the reaction toward highly enantioselective C3-aryloxylation to afford 3-aryloxy-oxindole-3-methanols (up to 98% ee), whereas salenCo(III)OTf (cat. B) switches the outcome to the complementary C3-ortho-arylation pathway without stereoinduction. The method tolerates various N-protecting groups and aromatic substitution patterns, creating a diverse library of functionalized oxindoles. Mass spectrometric studies reveal catalyst–substrate complexes and (hetero)dimeric assemblies, providing insight into a mechanistic pathway that favors aryloxylation. The method also achieves the first asymmetric synthesis of spiro[benzo[b][1,4]dioxine-2,3′-indolin]-2′-one.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"59 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139056","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}
Yongxing Ren,Dehua Mao,Mohamed Abdalla,Xiaoyan Li,Xinying Shi,Yanbiao Xi,Xiuxue Chen,Zongming Wang,Pete Smith
Wetland conversion and restoration substantially reshape the terrestrial carbon cycle. However, due to limited large-scale sampling and long-term wetland distribution records, their impacts on soil organic carbon (SOC) remain poorly known. Here, we integrated a nationwide wetland SOC density database, multitemporal wetland maps, and related geospatial environmental data sets and applied a random forest model to map China’s wetland carbon pool and quantified SOC losses and gains associated with conversion and restoration between 1980 and 2020. The results showed that the mean SOC density of top 1 m in China’s wetlands was 23.10 kg C m–2 over the study period, with pronounced spatial heterogeneity. We found that SOC density declined markedly within the first decade after conversion of wetlands to agriculture, with an average reduction of ∼19%. The rate of decline then slowed and gradually stabilized. Over the four decades, conversion to agriculture led to a cumulative loss of ∼574.66 Tg C, equivalent to ∼10.6% of the national wetland carbon pool. By contrast, wetland restoration promoted SOC recovery, although levels remained below preconversion baselines. Conservation and restoration can offset over half of the carbon emissions from wetland conversion. Among them, restoration contributed 186.36 Tg C (∼3.43% of the wetland carbon pool), offsetting ∼32.4% of conversion-induced losses. Overall, from 1980 to 2020, SOC losses from conversion gradually decreased, while restoration-driven gains gradually increased. These results highlight the critical role of wetland conservation and restoration in reversing carbon losses and advancing climate change mitigation toward carbon neutrality.
湿地的转化和恢复实质上重塑了陆地碳循环。然而，由于有限的大尺度采样和长期的湿地分布记录，它们对土壤有机碳（SOC）的影响尚不清楚。在此，我们整合了全国湿地有机碳密度数据库、多时间点湿地地图和相关地理空间环境数据集，应用随机森林模型绘制了1980 - 2020年中国湿地碳库，并量化了与转换和恢复相关的有机碳损益。结果表明：研究期间，中国湿地top 1 m平均有机碳密度为23.10 kg C - m - 2，具有明显的空间异质性；我们发现，在湿地向农业转化后的第一个十年里，有机碳密度显著下降，平均下降了19%。随后下降的速度减慢并逐渐稳定下来。在过去的40年里，向农业的转变导致累计损失了~ 574.66 Tg C，相当于国家湿地碳库的~ 10.6%。相比之下，湿地恢复促进了有机碳的恢复，尽管其水平仍低于转化前的基线。保护和恢复可以抵消湿地转化所产生的一半以上的碳排放。其中，恢复贡献了186.36 Tg C（约占湿地碳库的3.43%），抵消了转换引起的损失的32.4%。总体而言，从1980年到2020年，转换导致的有机碳损失逐渐减少，而恢复驱动的有机碳收益逐渐增加。这些结果突出了湿地保护和恢复在扭转碳损失和推进气候变化减缓以实现碳中和方面的关键作用。
{"title":"Conservation and Restoration Can Offset over Half of the Carbon Emissions from Wetland Conversion in China","authors":"Yongxing Ren,Dehua Mao,Mohamed Abdalla,Xiaoyan Li,Xinying Shi,Yanbiao Xi,Xiuxue Chen,Zongming Wang,Pete Smith","doi":"10.1021/acs.est.5c17132","DOIUrl":"https://doi.org/10.1021/acs.est.5c17132","url":null,"abstract":"Wetland conversion and restoration substantially reshape the terrestrial carbon cycle. However, due to limited large-scale sampling and long-term wetland distribution records, their impacts on soil organic carbon (SOC) remain poorly known. Here, we integrated a nationwide wetland SOC density database, multitemporal wetland maps, and related geospatial environmental data sets and applied a random forest model to map China’s wetland carbon pool and quantified SOC losses and gains associated with conversion and restoration between 1980 and 2020. The results showed that the mean SOC density of top 1 m in China’s wetlands was 23.10 kg C m–2 over the study period, with pronounced spatial heterogeneity. We found that SOC density declined markedly within the first decade after conversion of wetlands to agriculture, with an average reduction of ∼19%. The rate of decline then slowed and gradually stabilized. Over the four decades, conversion to agriculture led to a cumulative loss of ∼574.66 Tg C, equivalent to ∼10.6% of the national wetland carbon pool. By contrast, wetland restoration promoted SOC recovery, although levels remained below preconversion baselines. Conservation and restoration can offset over half of the carbon emissions from wetland conversion. Among them, restoration contributed 186.36 Tg C (∼3.43% of the wetland carbon pool), offsetting ∼32.4% of conversion-induced losses. Overall, from 1980 to 2020, SOC losses from conversion gradually decreased, while restoration-driven gains gradually increased. These results highlight the critical role of wetland conservation and restoration in reversing carbon losses and advancing climate change mitigation toward carbon neutrality.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"90 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138896","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}
Zijian Wang,Peisheng He,Mathew T. Baldwin,April Z. Gu
Polyphosphate (polyP), a condensed linear form of orthophosphate residues, is functionally versatile phosphorus (P) polymer that has persisted since prebiotic Earth. Long treated as a cellular biochemical curiosity, it remains systematically overlooked in global P budgets and Earth system models. In this review, we compile the first global-scale synthesis of environmental occurrence, biological regulation, and ecosystem functions of polyP across terrestrial, freshwater, marine, and engineered systems. Integrating 568 environmental observations and over 3000 microbial genomes, we unveil that polyP is a quantitatively significant and phylogenetically widespread component of global P cycling, often comprising 5–40% of total phosphorus in major ecosystems. We synthesize current understanding of how microbial taxa, including bacterial or archaeal polyP-accumulating organisms and arbuscular mycorrhizal fungi, mediate polyP turnover and interact with carbon/nitrogen cocycling under fluctuating redox, nutrient, and climatic conditions. Our quantitative assessment reveals that global polyP stocks in soils, sediments, and wastewater systems form a substantial, yet previously unaccounted, reservoir of recoverable and climate-sensitive P. The omission of polyP from existing models creates systematic blind spots in understanding P bioavailability, retention, cycling, and sustainability. Integrating polyP into the global P narrative is essential for advancing new frontiers in climate-smart biogeochemical forecasts, circular nutrient management, and long-term water-energy-food ecosystem security under global climate change.
{"title":"Polyphosphate as an Integral Component of Global Phosphorus Cycling through Earth’s History","authors":"Zijian Wang,Peisheng He,Mathew T. Baldwin,April Z. Gu","doi":"10.1021/acs.est.5c08597","DOIUrl":"https://doi.org/10.1021/acs.est.5c08597","url":null,"abstract":"Polyphosphate (polyP), a condensed linear form of orthophosphate residues, is functionally versatile phosphorus (P) polymer that has persisted since prebiotic Earth. Long treated as a cellular biochemical curiosity, it remains systematically overlooked in global P budgets and Earth system models. In this review, we compile the first global-scale synthesis of environmental occurrence, biological regulation, and ecosystem functions of polyP across terrestrial, freshwater, marine, and engineered systems. Integrating 568 environmental observations and over 3000 microbial genomes, we unveil that polyP is a quantitatively significant and phylogenetically widespread component of global P cycling, often comprising 5–40% of total phosphorus in major ecosystems. We synthesize current understanding of how microbial taxa, including bacterial or archaeal polyP-accumulating organisms and arbuscular mycorrhizal fungi, mediate polyP turnover and interact with carbon/nitrogen cocycling under fluctuating redox, nutrient, and climatic conditions. Our quantitative assessment reveals that global polyP stocks in soils, sediments, and wastewater systems form a substantial, yet previously unaccounted, reservoir of recoverable and climate-sensitive P. The omission of polyP from existing models creates systematic blind spots in understanding P bioavailability, retention, cycling, and sustainability. Integrating polyP into the global P narrative is essential for advancing new frontiers in climate-smart biogeochemical forecasts, circular nutrient management, and long-term water-energy-food ecosystem security under global climate change.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"211 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138898","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}
Efficient and durable oxygen evolution reaction (OER) catalysts are crucial for the generation of hydrogen via alkaline seawater electrolysis. Herein, an FeOOH/NiFe-LDH heterostructure with a built-in electric field (BEF) has been synthesized on Ni foam through a one-step cathodic electrodeposition. The formed BEF accelerates the OER kinetics by optimizing the interfacial electronic structure and enhancing the mass transfer and stabilizes the structure of the catalyst by Fe–O–Ni–O–Fe coupling bonds. In addition, the BEF and FeOOH mutually reduce the adsorption of Cl– on the catalyst. Accordingly, FeOOH/NiFe-LDH demonstrates an outstanding OER catalytic performance in alkaline seawater electrolytes. In detail, FeOOH/NiFe-LDH displays small η100 values of 265 and 278 mV in alkaline simulated and natural seawater, respectively, and achieves exceptional durability with smooth operation for ∼150 h at 250 mA cm–2, albeit in a high-salt electrolyte (1 M KOH and 2.5 M NaCl). When FeOOH/NiFe-LDH is used as the anode of the AEM electrolyzer, the cell in alkaline simulated seawater delivers low voltages of 1.59 and 1.92 V at 100 and 500 mA cm–2, respectively. The cell also shows excellent durability after operation over 110 h at 250 mA cm–2 with an insignificant voltage increase of only 27 mV (∼0.25 mV h–1). This work provides insight into the catalytic mechanism of the BEF-based heterostructure as anodic catalysts for alkaline seawater electrolysis.
高效、耐用的析氧反应催化剂是碱性海水电解制氢的关键。本文通过一步阴极电沉积在泡沫镍表面合成了具有内置电场的FeOOH/NiFe-LDH异质结构。形成的BEF通过优化界面电子结构和增强传质加速OER动力学，并通过Fe-O-Ni-O-Fe偶联键稳定催化剂结构。此外，BEF和FeOOH相互减少了Cl -在催化剂上的吸附。因此，FeOOH/NiFe-LDH在碱性海水电解质中表现出优异的OER催化性能。具体来说，FeOOH/NiFe-LDH在碱性模拟海水和自然海水中分别显示出265和278 mV的小η - 100值，并且在250 mA cm-2的高盐电解质（1 M KOH和2.5 M NaCl）中具有优异的耐久性，可以平稳运行约150 h。以FeOOH/NiFe-LDH作为AEM电解槽的阳极时，电解槽在碱性模拟海水中分别在100和500 mA cm-2下提供1.59和1.92 V的低压。在250 mA cm-2下运行110小时后，电池也表现出优异的耐久性，电压仅增加27 mV （~ 0.25 mV h - 1）。本研究揭示了bef基异质结构作为碱性海水电解阳极催化剂的催化机理。
{"title":"Self-Supporting FeOOH/NiFe-LDH Heterostructures with a Built-In Electric Field for Efficient and Durable Alkaline Seawater Oxidation","authors":"Lin Chen,Fei Ma,Yutong An,Yuning Zhang,Shiqi Yin,Xiaohan Yuan,Kaicai Fan,Lei Wang,Zhiqiang Hu,Tianrong Zhan","doi":"10.1021/acs.jpclett.5c04027","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c04027","url":null,"abstract":"Efficient and durable oxygen evolution reaction (OER) catalysts are crucial for the generation of hydrogen via alkaline seawater electrolysis. Herein, an FeOOH/NiFe-LDH heterostructure with a built-in electric field (BEF) has been synthesized on Ni foam through a one-step cathodic electrodeposition. The formed BEF accelerates the OER kinetics by optimizing the interfacial electronic structure and enhancing the mass transfer and stabilizes the structure of the catalyst by Fe–O–Ni–O–Fe coupling bonds. In addition, the BEF and FeOOH mutually reduce the adsorption of Cl– on the catalyst. Accordingly, FeOOH/NiFe-LDH demonstrates an outstanding OER catalytic performance in alkaline seawater electrolytes. In detail, FeOOH/NiFe-LDH displays small η100 values of 265 and 278 mV in alkaline simulated and natural seawater, respectively, and achieves exceptional durability with smooth operation for ∼150 h at 250 mA cm–2, albeit in a high-salt electrolyte (1 M KOH and 2.5 M NaCl). When FeOOH/NiFe-LDH is used as the anode of the AEM electrolyzer, the cell in alkaline simulated seawater delivers low voltages of 1.59 and 1.92 V at 100 and 500 mA cm–2, respectively. The cell also shows excellent durability after operation over 110 h at 250 mA cm–2 with an insignificant voltage increase of only 27 mV (∼0.25 mV h–1). This work provides insight into the catalytic mechanism of the BEF-based heterostructure as anodic catalysts for alkaline seawater electrolysis.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"10 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138852","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 : 2026-02-08DOI: 10.1021/acs.jpcc.5c05791
Florentino López-Urías,Francisco Sánchez-Ochoa
We investigated the honeycomb lattice using a two-orbital (α and β) Hubbard model and many-body exact calculations. The spin gap (Δs), charge gap (Δc), intrasite (γiiαβ=⟨S→iα·S→iβ⟩), intersite (γijαβ=⟨S→iα·S→jβ⟩), spin–spin correlations, and orbital magnetic moments μiα are analyzed for different band-filling (n), which denotes the number of electrons per site. Special attention was set in one-quarter-filled (n = 1) and half-filled (n = 2) bands. The results are presented by varying Coulomb repulsion (U), Hund’s coupling (JH), external magnetic field (B), and orbital energy splitting (Δϵ). For the one-quarter-filled band, an intrasite magnetic disorder (γiiαβ≈0) begins to form for large values of U/t, which is interpreted as a possible signature of a resonating valence bond state. Full orbital polarization (γiiαβ=0.25) with intersite antiferromagnetic (AFM) order (γijαβ=−0.25) was observed in the half-filled band for U/t ≫ 1, indicating that the two-orbital Hubbard model can be mapped to an AFM Heisenberg model with S = 1. The increase of JH is conductive to insulating and metallic phases for half- and one-quarter-filled bands, respectively. For a fractional n, the honeycomb lattice can exhibit spin-glass-like behavior, predominating as a disordered magnetic system characterized by random values of γijαβ. The magnetic field induced a reduction in Δc, which became zero at the critical external magnetic field. Twisted bilayer graphene (TBG) exhibits approximately flat electronic bands at magic angles and interesting correlated phenomena, such as unconventional superconductivity and correlated insulating states around n = 1 and n = 2, respectively. The dominance of electron–electron interactions in TBG makes the Hubbard model, in various versions (extended or multi-orbital), offer a practical, structure-scale account for investigating many-body effects in large moiré unit cells, where first-principles density-functional theory calculations are computationally challenging.
{"title":"Electron Correlations Study toward Understanding Twisted Bilayer Graphene: Two-Orbital Hubbard Model and Exact Numerical Calculations","authors":"Florentino López-Urías,Francisco Sánchez-Ochoa","doi":"10.1021/acs.jpcc.5c05791","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c05791","url":null,"abstract":"We investigated the honeycomb lattice using a two-orbital (α and β) Hubbard model and many-body exact calculations. The spin gap (Δs), charge gap (Δc), intrasite (γiiαβ=⟨S→iα·S→iβ⟩), intersite (γijαβ=⟨S→iα·S→jβ⟩), spin–spin correlations, and orbital magnetic moments μiα are analyzed for different band-filling (n), which denotes the number of electrons per site. Special attention was set in one-quarter-filled (n = 1) and half-filled (n = 2) bands. The results are presented by varying Coulomb repulsion (U), Hund’s coupling (JH), external magnetic field (B), and orbital energy splitting (Δϵ). For the one-quarter-filled band, an intrasite magnetic disorder (γiiαβ≈0) begins to form for large values of U/t, which is interpreted as a possible signature of a resonating valence bond state. Full orbital polarization (γiiαβ=0.25) with intersite antiferromagnetic (AFM) order (γijαβ=−0.25) was observed in the half-filled band for U/t ≫ 1, indicating that the two-orbital Hubbard model can be mapped to an AFM Heisenberg model with S = 1. The increase of JH is conductive to insulating and metallic phases for half- and one-quarter-filled bands, respectively. For a fractional n, the honeycomb lattice can exhibit spin-glass-like behavior, predominating as a disordered magnetic system characterized by random values of γijαβ. The magnetic field induced a reduction in Δc, which became zero at the critical external magnetic field. Twisted bilayer graphene (TBG) exhibits approximately flat electronic bands at magic angles and interesting correlated phenomena, such as unconventional superconductivity and correlated insulating states around n = 1 and n = 2, respectively. The dominance of electron–electron interactions in TBG makes the Hubbard model, in various versions (extended or multi-orbital), offer a practical, structure-scale account for investigating many-body effects in large moiré unit cells, where first-principles density-functional theory calculations are computationally challenging.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"244 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138855","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 : 2026-02-08DOI: 10.1021/acs.jpclett.5c03971
Xinyue Xu,Xinyu Ding,Guangming Meng,Jing Lv,Dong Ding,Feng Li,Tao Zhuang,Erkin Zakhidov,Mingliang Sun
Carbazole-based organic room-temperature phosphorescent (RTP) materials have attracted widespread attention, yet their structural diversification has remained limited due to inherent synthetic constraints. In this work, a dual-mechanical strategy integrating mechanochemical synthesis with 3D-printed processing is introduced. A g-configured benzoindole (Bd[g]) skeleton is efficiently obtained through a solvent-free mechanochemical protocol, enabling rapid and scalable access to high-performance RTP molecular frameworks. When dispersed within a poly(vinyl butyral) (PVB) matrix, Bd[g] derivatives display stable RTP emission as a result of suppressed molecular motion and minimized environmental quenching. Benefiting from the excellent processability of PVB-based composites, the RTP materials are further shaped into customizable 3D-printed architectures featuring persistent phosphorescence, mechanical flexibility, and strong resistance to seawater. This fully mechanical “molecule-to-device” methodology establishes a practical route toward durable organic RTP systems and underscores their potential in marine sensing, underwater imaging, and long-term anticorrosion applications.
{"title":"Process-Mechanized Green Approach to Organic Phosphorescence: From Mechanochemistry Synthesis to 3D Printing","authors":"Xinyue Xu,Xinyu Ding,Guangming Meng,Jing Lv,Dong Ding,Feng Li,Tao Zhuang,Erkin Zakhidov,Mingliang Sun","doi":"10.1021/acs.jpclett.5c03971","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03971","url":null,"abstract":"Carbazole-based organic room-temperature phosphorescent (RTP) materials have attracted widespread attention, yet their structural diversification has remained limited due to inherent synthetic constraints. In this work, a dual-mechanical strategy integrating mechanochemical synthesis with 3D-printed processing is introduced. A g-configured benzoindole (Bd[g]) skeleton is efficiently obtained through a solvent-free mechanochemical protocol, enabling rapid and scalable access to high-performance RTP molecular frameworks. When dispersed within a poly(vinyl butyral) (PVB) matrix, Bd[g] derivatives display stable RTP emission as a result of suppressed molecular motion and minimized environmental quenching. Benefiting from the excellent processability of PVB-based composites, the RTP materials are further shaped into customizable 3D-printed architectures featuring persistent phosphorescence, mechanical flexibility, and strong resistance to seawater. This fully mechanical “molecule-to-device” methodology establishes a practical route toward durable organic RTP systems and underscores their potential in marine sensing, underwater imaging, and long-term anticorrosion applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"23 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138851","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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