The precise manifestations of iron (Fe) imbalance, especially Fe2+ deficiency, are critical for addressing the health effects of ambient fine particulate matter (PM2.5) on human health. This study integrates epidemiological and in vitro and in vivo evidence to elucidate the role of Fe homeostasis in the effects of PM2.5 exposure on lung injury. Serum was collected from 35 women from Hebei Province, North China, and their residential PM2.5 concentrations were monitored from January 2015 to January 2016. We found that the ferritin light chain (FTL) in serum was positively associated with the PM2.5 concentration, suggesting that PM2.5 disrupts Fe homeostasis in the human body. Intratracheal instillation of naphthalene-1,4-dione-coated black carbon (1,4-NQ-BC), a PM2.5 analogue, increased FTL, but impaired the autophagy flux in rat lungs. 1,4-NQ-BC reduced Fe2+, but increased total Fe in RAW264.7 cells, when there was unimpaired Fe transportation through cell membranes. Likewise, 1,4-NQ-BC activated autophagy, but impaired lysosomal function, consequently inhibiting the autophagic flux in RAW264.7 cells. The role of lysosome dysfunction in PM-induced Fe2+ deficiency was revealed for the first time, via overexpression of transcription factor EB in a RAW264.7 cell model. We concluded that lysosomal damage-evoked Fe2+ deficiency provided sensitive biomarkers and potential therapeutic targets in pulmonary injury associated with ambient PM2.5 exposure.
{"title":"Integrated Evidence for Lysosomal Dysfunction-Mediated Iron Dysregulation induced by PM2.5 Exposure","authors":"Qiong Zhang,Yuese Yuan,Yuetong Liu,Jiawei Yang,Tao Zhou,Haichen Zhang,Lening Chen,Yuan Cui,Yang Wang,Ran Zhao,Qianqian Xiao,Qinghe Meng,Jianjun Jiang,Weidong Hao,Bin Wang,Xuetao Wei","doi":"10.1021/acs.est.5c14185","DOIUrl":"https://doi.org/10.1021/acs.est.5c14185","url":null,"abstract":"The precise manifestations of iron (Fe) imbalance, especially Fe2+ deficiency, are critical for addressing the health effects of ambient fine particulate matter (PM2.5) on human health. This study integrates epidemiological and in vitro and in vivo evidence to elucidate the role of Fe homeostasis in the effects of PM2.5 exposure on lung injury. Serum was collected from 35 women from Hebei Province, North China, and their residential PM2.5 concentrations were monitored from January 2015 to January 2016. We found that the ferritin light chain (FTL) in serum was positively associated with the PM2.5 concentration, suggesting that PM2.5 disrupts Fe homeostasis in the human body. Intratracheal instillation of naphthalene-1,4-dione-coated black carbon (1,4-NQ-BC), a PM2.5 analogue, increased FTL, but impaired the autophagy flux in rat lungs. 1,4-NQ-BC reduced Fe2+, but increased total Fe in RAW264.7 cells, when there was unimpaired Fe transportation through cell membranes. Likewise, 1,4-NQ-BC activated autophagy, but impaired lysosomal function, consequently inhibiting the autophagic flux in RAW264.7 cells. The role of lysosome dysfunction in PM-induced Fe2+ deficiency was revealed for the first time, via overexpression of transcription factor EB in a RAW264.7 cell model. We concluded that lysosomal damage-evoked Fe2+ deficiency provided sensitive biomarkers and potential therapeutic targets in pulmonary injury associated with ambient PM2.5 exposure.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"314 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138890","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}
Pub Date : 2026-02-09DOI: 10.1021/acs.jpclett.5c03913
Rafał Szabla, Cristina A. Barboza
Photoinduced electron transfer (PET) lies at the heart of energy conversion from light into chemical reactions. It governs a variety of biological processes including DNA damage and repair and biological photosynthesis. Quantifying PET rates and optimizing them is also crucial for selective photoredox catalysis. However, commonly used rate theories break down for PET operating in the strong coupling and nonequilibrium regimes, while excited-state dynamics simulations are computationally demanding and require complex analysis to extract PET times. Here, we employed surface-hopping nonadiabatic excited-state dynamics simulations and statistical rate theories to characterize ultrafast PET in a dimer of stacked adenine nucleobases. We show that the widely used classical Marcus Theory and Fermi’s Golden Rule fail to describe ultrafast PET or even reproduce qualitative rate trends. Instead, we propose a chromophore-localized variant of nonadiabatic Rice–Rampsperger–Kassel–Marcus (NA-RRKM) theory, which yields PET timescales that are in excellent agreement with excited-state dynamics simulations.
{"title":"Accurate Prediction of Photoinduced Electron Transfer Timescales with Nonadiabatic Microcanonical Rate Theory","authors":"Rafał Szabla, Cristina A. Barboza","doi":"10.1021/acs.jpclett.5c03913","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03913","url":null,"abstract":"Photoinduced electron transfer (PET) lies at the heart of energy conversion from light into chemical reactions. It governs a variety of biological processes including DNA damage and repair and biological photosynthesis. Quantifying PET rates and optimizing them is also crucial for selective photoredox catalysis. However, commonly used rate theories break down for PET operating in the strong coupling and nonequilibrium regimes, while excited-state dynamics simulations are computationally demanding and require complex analysis to extract PET times. Here, we employed surface-hopping nonadiabatic excited-state dynamics simulations and statistical rate theories to characterize ultrafast PET in a dimer of stacked adenine nucleobases. We show that the widely used classical Marcus Theory and Fermi’s Golden Rule fail to describe ultrafast PET or even reproduce qualitative rate trends. Instead, we propose a chromophore-localized variant of nonadiabatic Rice–Rampsperger–Kassel–Marcus (NA-RRKM) theory, which yields PET timescales that are in excellent agreement with excited-state dynamics simulations.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"315 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146476","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}
Zhiwei Wang,Sunxinyi Wang,Xiaoming Xu,Yuxuan Chen,Yuhan Wang,Xuesong Yi,Zihui Wang,Langming Bai,Fuqiang Liu
The development of green and high-performance nanofiltration membranes is of great significance in mitigating the global water crisis. However, conventional nanofiltration membranes are generally constrained by the trade-off between permeability and selectivity, which limits their practical application. In this study, we designed a reactive interlayer based on piperazine-grafted carboxylated cellulose nanofibers, which participates in the interfacial polymerization process to form a mixed nascent layer (MNL) with smaller pore sizes. This intermediate structure further regulated the formation of an ultrathin polyamide layer featuring uniform pore size distribution and a crumpled morphology. Combined with molecular dynamics (MD) simulations, we systematically elucidated the influence of different nascent interlayer structures on the final morphology and chemical composition of the polyamide layer. The resulting membrane exhibits exceptional ion sieving performance, with a Cl–/SO42– selectivity of up to 155.4, and maintains a high water permeance of 43.9 L m–2 h–1 bar–1 while demonstrating effective removal of various micropollutants. This work not only deepens the understanding of the structural evolution mechanism during interfacial polymerization but also provides a new strategy for developing high-performance nanofiltration membranes toward efficient water treatment.
开发绿色高性能纳滤膜对缓解全球水危机具有重要意义。然而，传统的纳滤膜通常受到渗透性和选择性之间权衡的限制，这限制了它们的实际应用。在本研究中，我们设计了一种基于哌嗪接枝羧化纤维素纳米纤维的反应性中间层，参与界面聚合过程，形成孔径较小的混合新生层（MNL）。这种中间结构进一步调节了具有均匀孔径分布和皱褶形态的超薄聚酰胺层的形成。结合分子动力学（MD）模拟，我们系统地阐明了不同的新生层间结构对聚酰胺层最终形态和化学组成的影响。所制得的膜具有优异的离子筛分性能，Cl - /SO42 -选择性高达155.4，并保持43.9 L m-2 h-1 bar-1的高透水性，同时显示出对各种微污染物的有效去除。这项工作不仅加深了对界面聚合过程中结构演化机制的理解，而且为开发高效水处理的高性能纳滤膜提供了新的策略。
{"title":"Mixed Nascent Layer Based on Reactive Nanofiber to Regulate High-Performance Nanofiltration Membranes","authors":"Zhiwei Wang,Sunxinyi Wang,Xiaoming Xu,Yuxuan Chen,Yuhan Wang,Xuesong Yi,Zihui Wang,Langming Bai,Fuqiang Liu","doi":"10.1021/acs.est.5c15464","DOIUrl":"https://doi.org/10.1021/acs.est.5c15464","url":null,"abstract":"The development of green and high-performance nanofiltration membranes is of great significance in mitigating the global water crisis. However, conventional nanofiltration membranes are generally constrained by the trade-off between permeability and selectivity, which limits their practical application. In this study, we designed a reactive interlayer based on piperazine-grafted carboxylated cellulose nanofibers, which participates in the interfacial polymerization process to form a mixed nascent layer (MNL) with smaller pore sizes. This intermediate structure further regulated the formation of an ultrathin polyamide layer featuring uniform pore size distribution and a crumpled morphology. Combined with molecular dynamics (MD) simulations, we systematically elucidated the influence of different nascent interlayer structures on the final morphology and chemical composition of the polyamide layer. The resulting membrane exhibits exceptional ion sieving performance, with a Cl–/SO42– selectivity of up to 155.4, and maintains a high water permeance of 43.9 L m–2 h–1 bar–1 while demonstrating effective removal of various micropollutants. This work not only deepens the understanding of the structural evolution mechanism during interfacial polymerization but also provides a new strategy for developing high-performance nanofiltration membranes toward efficient water treatment.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"4 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138888","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}
The total synthesis of the complex pentasaccharide repeating unit related to the O-polysaccharide from Aeromonas hydrophila Pt679 is reported. Suitably protected derivatives of the rare β-d-QuiNAc and α-d-Fuc3NAc units are synthesized from d-glucosamine hydrochloride and 1,2;5,6-di-O-isopropylidene-α-l-allofuranose, respectively, and used for stereoselective glycosylation. The 1,2-cis rhamnosidic linkage is successfully accomplished using picoloyl-mediated hydrogen bond-assisted aglycon delivery (HAD method). The target pentasaccharide in the form of its 2-aminoethyl glycoside is ready for further conjugation through the terminal amine functionality without hampering the reducing end stereochemistry.
报道了与嗜水气单胞菌Pt679 o -多糖相关的复合五糖重复单元的全合成。以盐酸d-氨基葡萄糖和1,2为原料，合成了稀有的β-d-QuiNAc和α-d-Fuc3NAc的适当保护衍生物；分别为5,6-二- o -异丙基-α-l-己呋喃糖，并用于立体选择性糖基化。利用picoloyl介导的氢键辅助糖苷传递（HAD法）成功地完成了1,2-顺式鼠李糖苷的连接。目标五糖以其2-氨基乙基糖苷的形式准备通过末端胺官能进一步偶联，而不妨碍还原端立体化学。
{"title":"Total Synthesis of an Aeromonas hydrophila Pt679 O-Antigen Pentasaccharide Repeat Unit Containing β-l-Rha, β-d-QuiNAc, and α-d-Fuc3NAc","authors":"Subrata Das, Sujan De, Balaram Mukhopadhyay","doi":"10.1021/acs.joc.5c03076","DOIUrl":"https://doi.org/10.1021/acs.joc.5c03076","url":null,"abstract":"The total synthesis of the complex pentasaccharide repeating unit related to the O-polysaccharide from <i>Aeromonas hydrophila</i> Pt679 is reported. Suitably protected derivatives of the rare β-<span>d</span>-QuiNAc and α-<span>d</span>-Fuc3NAc units are synthesized from <span>d</span>-glucosamine hydrochloride and 1,2;5,6-di-<i>O</i>-isopropylidene-α-<span>l</span>-allofuranose, respectively, and used for stereoselective glycosylation. The 1,2-<i>cis</i> rhamnosidic linkage is successfully accomplished using picoloyl-mediated hydrogen bond-assisted aglycon delivery (HAD method). The target pentasaccharide in the form of its 2-aminoethyl glycoside is ready for further conjugation through the terminal amine functionality without hampering the reducing end stereochemistry.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146537","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.5c03753
Juan Carlos Jiménez-García,Nicoll Zeballos,Fernando López-Gallego,Xabier López,David De Sancho
Although enzyme immobilization is widely used in biotechnology, it still poses challenges as a result of the trade-offs among stability, activity, and surface interactions. Computer simulations offer a promising aid to exploring the effects of different immobilization sites and surface chemistry on both the conformational dynamics and catalytic activity of these biomolecules. Here, we introduce a protocol based on a structure-based version of the Martini coarse-grained simulation model (Go̅Martini) to explore how surface tethering geometry influences the structure and function of immobilized Bacillus stearothermophilus alcohol dehydrogenase (BsADH). We compare traditional His-tag tethering with two engineered histidine cluster variants, analyzing their behavior in both soluble and surface-tethered states. We find that cluster-based immobilization locally restricts flexibility in surface-contacting subunits while preserving the mobility of exposed regions, resulting in an enhanced conformational stability under thermal stress. Functional analyses reveal that the ethanol association rates remain largely unaffected by surface attachment, whereas the dissociation of NADH is significantly slowed, explaining the reduced catalytic efficiency. These trends align with experimental findings and highlight the predictive power of Go̅Martini simulations in capturing key functional trade-offs. Altogether, this work offers mechanistic insight into the rational design of immobilized biocatalysts and outlines a practical framework for in silico exploration of enzyme–surface systems.
{"title":"Mechanistic Determinants of Oriented Enzyme Immobilization from Martini Simulations","authors":"Juan Carlos Jiménez-García,Nicoll Zeballos,Fernando López-Gallego,Xabier López,David De Sancho","doi":"10.1021/acs.jpclett.5c03753","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03753","url":null,"abstract":"Although enzyme immobilization is widely used in biotechnology, it still poses challenges as a result of the trade-offs among stability, activity, and surface interactions. Computer simulations offer a promising aid to exploring the effects of different immobilization sites and surface chemistry on both the conformational dynamics and catalytic activity of these biomolecules. Here, we introduce a protocol based on a structure-based version of the Martini coarse-grained simulation model (Go̅Martini) to explore how surface tethering geometry influences the structure and function of immobilized Bacillus stearothermophilus alcohol dehydrogenase (BsADH). We compare traditional His-tag tethering with two engineered histidine cluster variants, analyzing their behavior in both soluble and surface-tethered states. We find that cluster-based immobilization locally restricts flexibility in surface-contacting subunits while preserving the mobility of exposed regions, resulting in an enhanced conformational stability under thermal stress. Functional analyses reveal that the ethanol association rates remain largely unaffected by surface attachment, whereas the dissociation of NADH is significantly slowed, explaining the reduced catalytic efficiency. These trends align with experimental findings and highlight the predictive power of Go̅Martini simulations in capturing key functional trade-offs. Altogether, this work offers mechanistic insight into the rational design of immobilized biocatalysts and outlines a practical framework for in silico exploration of enzyme–surface systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"132 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138789","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}
Tien Van Do,Andreas Zuend,Na Rae Choi,Taehyoung Lee,Hyejung Shin,Kwangyul Lee,Jongsung Park,Seokjun Seo,Mijung Song
The phase state of fine particles (PM2.5) critically governs gas–particle partitioning and multiphase chemical reactivity, yet remains poorly constrained under real-world conditions. In this study, optical microscopy, poke-and-flow experiments, and thermodynamic modeling were combined to examine the phase behavior of wintertime urban PM2.5 collected in Ansan, South Korea. Morphological analyses revealed humidity- and composition-dependent transitions, with liquid–liquid and liquid–liquid–solid states frequently observed in individual particles. Polluted, nitrate-rich aerosols predominantly exhibited liquid-like morphology and followed near-equilibrium partitioning of nitrate and ammonium. In contrast, cleaner, organic-rich particles likely exhibited higher viscosity and nonliquid characteristics, which may have led to partial deviation from equilibrium predictions. These results provide direct experimental evidence of phase complexity in ambient PM2.5 and demonstrate that the particle phase state, modulated by relative humidity and composition, plays a critical role in determining thermodynamic behavior and atmospheric reactivity of urban aerosols.
{"title":"Phase Behavior of Polluted and Clean Urban Winter PM2.5 from Optical Observations and Thermodynamic Equilibrium Modeling","authors":"Tien Van Do,Andreas Zuend,Na Rae Choi,Taehyoung Lee,Hyejung Shin,Kwangyul Lee,Jongsung Park,Seokjun Seo,Mijung Song","doi":"10.1021/acs.est.5c16878","DOIUrl":"https://doi.org/10.1021/acs.est.5c16878","url":null,"abstract":"The phase state of fine particles (PM2.5) critically governs gas–particle partitioning and multiphase chemical reactivity, yet remains poorly constrained under real-world conditions. In this study, optical microscopy, poke-and-flow experiments, and thermodynamic modeling were combined to examine the phase behavior of wintertime urban PM2.5 collected in Ansan, South Korea. Morphological analyses revealed humidity- and composition-dependent transitions, with liquid–liquid and liquid–liquid–solid states frequently observed in individual particles. Polluted, nitrate-rich aerosols predominantly exhibited liquid-like morphology and followed near-equilibrium partitioning of nitrate and ammonium. In contrast, cleaner, organic-rich particles likely exhibited higher viscosity and nonliquid characteristics, which may have led to partial deviation from equilibrium predictions. These results provide direct experimental evidence of phase complexity in ambient PM2.5 and demonstrate that the particle phase state, modulated by relative humidity and composition, plays a critical role in determining thermodynamic behavior and atmospheric reactivity of urban aerosols.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"90 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138887","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}
Materials informatics tends to rely on existing structural database searches that constrain exploration by omitting unregistered compositions. In this study, an autoencoder-based anomaly detector was developed using composition-only descriptors as input features. The model was trained on thermodynamically stable phases─defined as those on the convex hull with an energy above hull (ΔEhull) of 0 eV/atom─as well as nearly stable phases with ΔEhull < 0.01 eV/atom, sourced from the Materials Project inorganic database. The reconstruction error (RMSE) was used as the anomaly score. It was shown that the RMSE increased systematically with apparent thermal destabilization─that is, increasing energy above hull. It was also shown that for 50,000 dummy oxides with an intentionally perturbed charge balance, the RMSE increased in proportion to the magnitude of the total charge imbalance, indicating that departures from charge neutrality could be captured even without explicit charge information. Feature-importance analysis suggested that element pairs (two-element combinations) were the principal factors governing the reconstruction RMSE. Accordingly, for 50,000 charge-compensated virtual oxides, we ordinally encoded the valence-shell type as s = 1, p = 2, d = 3, and f = 4 and defined, for each element pair, a coarse indicator given by the product of the two codes (hereafter, the spdf product). For each pair, we evaluated the correspondence between the median RMSE (taken over all compositions containing that pair) and its spdf product and obtained an approximately monotonic relationship─that is, pairs with smaller spdf products tended to have a lower median RMSE, whereas those with larger spdf products tended to have higher values. By contrast, pairs containing Ta consistently deviated downward from this relationship (i.e., exhibited a lower RMSE), suggesting that not only the spdf product but other descriptor information could also influence the assessment of synthesizability.
材料信息学倾向于依赖现有的结构数据库搜索，通过省略未注册的成分来限制探索。在这项研究中，开发了一个基于自动编码器的异常检测器，使用仅成分描述符作为输入特征。该模型是在热力学稳定相（定义为凸壳上的能量为0 eV/原子（ΔEhull）的相）和接近稳定相（ΔEhull <； 0.01 eV/原子）上进行训练的，这些相来自Materials Project无机数据库。以重建误差（RMSE）作为异常评分。结果表明，随着明显的热失稳（即船体上方能量的增加），RMSE有系统地增加。研究还表明，对于50,000种具有故意干扰电荷平衡的假氧化物，RMSE与总电荷不平衡的大小成比例地增加，这表明即使没有明确的电荷信息，也可以捕获偏离电荷中性的情况。特征重要性分析表明，元素对（两元素组合）是控制重建RMSE的主要因素。因此，对于50,000个电荷补偿的虚拟氧化物，我们通常将价壳类型编码为s = 1, p = 2, d = 3和f = 4，并为每个元素对定义由两个代码的乘积给出的粗指示符（以下称为spdf积）。对于每一对，我们评估了中位数RMSE（包含包含该对的所有组合）与其spdf乘积之间的对应关系，并获得了近似单调关系──即spdf乘积较小的配对往往具有较低的中位数RMSE，而spdf乘积较大的配对往往具有较高的值。相比之下，含有Ta的对始终偏离这一关系（即表现出较低的RMSE），这表明不仅spdf产物，而且其他描述符信息也可能影响可合成性的评估。
{"title":"Anomaly-Detection-Driven Screening of Thermodynamic Stability from Composition Descriptors Alone","authors":"Keisuke Makino, Yudai Yamaguchi, Naoto Tanibata, Hayami Takeda, Ryo Kobayashi, Masayuki Karasuyama, Masanobu Nakayama","doi":"10.1021/acs.jpclett.5c03772","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03772","url":null,"abstract":"Materials informatics tends to rely on existing structural database searches that constrain exploration by omitting unregistered compositions. In this study, an autoencoder-based anomaly detector was developed using composition-only descriptors as input features. The model was trained on thermodynamically stable phases─defined as those on the convex hull with an energy above hull (Δ<i>E</i><sub><i>hull</i></sub>) of 0 eV/atom─as well as nearly stable phases with Δ<i>E</i><sub><i>hull</i></sub> < 0.01 eV/atom, sourced from the Materials Project inorganic database. The reconstruction error (RMSE) was used as the anomaly score. It was shown that the RMSE increased systematically with apparent thermal destabilization─that is, increasing energy above hull. It was also shown that for 50,000 dummy oxides with an intentionally perturbed charge balance, the RMSE increased in proportion to the magnitude of the total charge imbalance, indicating that departures from charge neutrality could be captured even without explicit charge information. Feature-importance analysis suggested that element pairs (two-element combinations) were the principal factors governing the reconstruction RMSE. Accordingly, for 50,000 charge-compensated virtual oxides, we ordinally encoded the valence-shell type as s = 1, p = 2, d = 3, and f = 4 and defined, for each element pair, a coarse indicator given by the product of the two codes (hereafter, the spdf product). For each pair, we evaluated the correspondence between the median RMSE (taken over all compositions containing that pair) and its spdf product and obtained an approximately monotonic relationship─that is, pairs with smaller spdf products tended to have a lower median RMSE, whereas those with larger spdf products tended to have higher values. By contrast, pairs containing Ta consistently deviated downward from this relationship (i.e., exhibited a lower RMSE), suggesting that not only the spdf product but other descriptor information could also influence the assessment of synthesizability.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"93 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146448","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}
To address the spectral deficiencies in the red region of commercial white LEDs, developing red-emitting phosphors with reduced dependence on rare-earth elements with limited availability is crucial for spectral compensation. Herein, microstructures and optical characteristics of Mn4+-activated Mg2GeO4 phosphors are presented. While the phosphor exhibits a single orthorhombic phase, its cryogenic micro-Raman and photoluminescence (PL) spectra comprises 19 peaks and three groups of vibronic emissions with wealthy fine structures, respectively. Following the split zero-phonon lines, nine pairs of vibronic lines with an energy separation of 3.5 meV are identified. Furthermore, the overall line shape of the three groups of phonon sidebands can be reproduced by the fully symmetric electron–phonon coupling model, enabling determination of the total density of phonon states. The study sheds light on complicated luminescence fine structures in Mn4+-activated oxide phosphors, offering valuable insights into the design of red-emitting phosphors.
{"title":"Optical Properties of Mg2GeO4:Mn4+ Phosphors: From Fine Structures of Vibronic Transitions to the Density of Phonon States","authors":"Hongyi Zhu,Yitong Wang,Wanggui Ye,Tianlong Ruan,Fei Tang,Jiqiang Ning,Shijie Xu","doi":"10.1021/acs.jpcc.5c07885","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07885","url":null,"abstract":"To address the spectral deficiencies in the red region of commercial white LEDs, developing red-emitting phosphors with reduced dependence on rare-earth elements with limited availability is crucial for spectral compensation. Herein, microstructures and optical characteristics of Mn4+-activated Mg2GeO4 phosphors are presented. While the phosphor exhibits a single orthorhombic phase, its cryogenic micro-Raman and photoluminescence (PL) spectra comprises 19 peaks and three groups of vibronic emissions with wealthy fine structures, respectively. Following the split zero-phonon lines, nine pairs of vibronic lines with an energy separation of 3.5 meV are identified. Furthermore, the overall line shape of the three groups of phonon sidebands can be reproduced by the fully symmetric electron–phonon coupling model, enabling determination of the total density of phonon states. The study sheds light on complicated luminescence fine structures in Mn4+-activated oxide phosphors, offering valuable insights into the design of red-emitting phosphors.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"295 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138801","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}
Harry Elliss,Katarina Hricova,Evie Griffiths,Neil Andrew Byrnes,Ben Faill,Eva Hawkins,Kit Proctor,Megan Robertson,John Bagnall,Barbara Kasprzyk-Hordern
Metabolism is a critical bodily function that facilitates the removal of toxic chemical buildup within the body. In wastewater-based epidemiology (WBE), it is crucial to understand the metabolism of biochemical indicators (BCIs) because metabolites are indicative of consumption (e.g., illicit drugs, pharmaceuticals) or unintentional exposure (e.g., pesticides, endocrine disruptors). Phase I metabolites are more widely studied in WBE due to a combination of factors, including, but not limited to, stability and analyte cost. Phase II metabolites are often assumed to deconjugate within the sewer network due to high native concentrations of enzymes. This work deconstructs this assumption and demonstrates how the in-sewer stability of phase II metabolites is dependent on both the parent structure and the conjugate type. In total, 79 BCIs were assessed and compared to urinary metabolism studies via time-variable enzymatic deconjugation using two enzymes, β-glucuronidase and arylsulfatase. The concentrations of free analytes excreted as N-glucuronides, O-glucuronides, and sulfates increased following deconjugation, reinforcing the persistence of these BCIs during transport throughout the sewer network. Conversely, no concentration increase was observed for acylglucuronides, demonstrating complete in-sewer glucuronide cleavage. In-freezer stability of conjugates was also assessed over 6 months, where it was observed that the stability of the parent structure is the driver of stability rather than the conjugates themselves, indicating minimal enzymatic activity upon storage. Overall, this paper presents a framework that can be deployed to gain a more comprehensive understanding of phase II metabolism and improve the accuracy of WBE workflows as well as environmental risk assessment approaches.
{"title":"Understanding the Role of Deconjugation of Phase II Metabolites in Wastewater: Implications for Wastewater-Based Epidemiology","authors":"Harry Elliss,Katarina Hricova,Evie Griffiths,Neil Andrew Byrnes,Ben Faill,Eva Hawkins,Kit Proctor,Megan Robertson,John Bagnall,Barbara Kasprzyk-Hordern","doi":"10.1021/acs.est.5c17466","DOIUrl":"https://doi.org/10.1021/acs.est.5c17466","url":null,"abstract":"Metabolism is a critical bodily function that facilitates the removal of toxic chemical buildup within the body. In wastewater-based epidemiology (WBE), it is crucial to understand the metabolism of biochemical indicators (BCIs) because metabolites are indicative of consumption (e.g., illicit drugs, pharmaceuticals) or unintentional exposure (e.g., pesticides, endocrine disruptors). Phase I metabolites are more widely studied in WBE due to a combination of factors, including, but not limited to, stability and analyte cost. Phase II metabolites are often assumed to deconjugate within the sewer network due to high native concentrations of enzymes. This work deconstructs this assumption and demonstrates how the in-sewer stability of phase II metabolites is dependent on both the parent structure and the conjugate type. In total, 79 BCIs were assessed and compared to urinary metabolism studies via time-variable enzymatic deconjugation using two enzymes, β-glucuronidase and arylsulfatase. The concentrations of free analytes excreted as N-glucuronides, O-glucuronides, and sulfates increased following deconjugation, reinforcing the persistence of these BCIs during transport throughout the sewer network. Conversely, no concentration increase was observed for acylglucuronides, demonstrating complete in-sewer glucuronide cleavage. In-freezer stability of conjugates was also assessed over 6 months, where it was observed that the stability of the parent structure is the driver of stability rather than the conjugates themselves, indicating minimal enzymatic activity upon storage. Overall, this paper presents a framework that can be deployed to gain a more comprehensive understanding of phase II metabolism and improve the accuracy of WBE workflows as well as environmental risk assessment approaches.","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":"146138848","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}
Sara Torbatian,Marc Saleh,Laura Minet,Milad Saeedi,Shayamila Mahagammulla Gamage,Daniel Yazgi,Youngseob Kim,Tufayel Chowdhury,James Vaughan,An Wang,Kianoush Mousavi,Matthew J. Roorda,Marianne Hatzopoulou
Urban trucking poses significant health and environmental risks, particularly diesel-fueled trucks. Off-peak delivery (OPD), which refers to the delivery of goods during evening and overnight hours, provides an opportunity to mitigate traffic congestion and improve delivery efficiency. However, the impacts of this delivery schedule on population exposure to air pollution are not clear. This study investigates the spatial distribution of traffic-related air pollutants under two OPD scenarios and assesses their environmental justice implications, in the Greater Toronto and Hamilton Area (GTHA). Using truck movement information from a regional travel demand model and a chemical transport model, we estimated the diurnal changes in air pollutants. The OPD scenarios entail shifting the shares of delivery trips to the evening and overnight periods and account for induced passenger trips during the daytime, resulting from a reduction in truck traffic. One scenario was designed to reflect the industry sectors that would most likely participate in such a scheme and a realistic participation rate, while the other reflects an aggressive shift to overnight periods. While ambient air quality improves during the daytime, despite increased commuter traffic replacing truck movements, air pollutant concentrations worsen at night due to increased emissions under more stable atmospheric conditions. Under both scenarios, the most disadvantaged communities experience the highest variations in air pollution, as they often live close to highways and major truck routes.
{"title":"Implications of Off-Peak Commercial Deliveries for Air Quality and Environmental Justice","authors":"Sara Torbatian,Marc Saleh,Laura Minet,Milad Saeedi,Shayamila Mahagammulla Gamage,Daniel Yazgi,Youngseob Kim,Tufayel Chowdhury,James Vaughan,An Wang,Kianoush Mousavi,Matthew J. Roorda,Marianne Hatzopoulou","doi":"10.1021/acs.est.5c07138","DOIUrl":"https://doi.org/10.1021/acs.est.5c07138","url":null,"abstract":"Urban trucking poses significant health and environmental risks, particularly diesel-fueled trucks. Off-peak delivery (OPD), which refers to the delivery of goods during evening and overnight hours, provides an opportunity to mitigate traffic congestion and improve delivery efficiency. However, the impacts of this delivery schedule on population exposure to air pollution are not clear. This study investigates the spatial distribution of traffic-related air pollutants under two OPD scenarios and assesses their environmental justice implications, in the Greater Toronto and Hamilton Area (GTHA). Using truck movement information from a regional travel demand model and a chemical transport model, we estimated the diurnal changes in air pollutants. The OPD scenarios entail shifting the shares of delivery trips to the evening and overnight periods and account for induced passenger trips during the daytime, resulting from a reduction in truck traffic. One scenario was designed to reflect the industry sectors that would most likely participate in such a scheme and a realistic participation rate, while the other reflects an aggressive shift to overnight periods. While ambient air quality improves during the daytime, despite increased commuter traffic replacing truck movements, air pollutant concentrations worsen at night due to increased emissions under more stable atmospheric conditions. Under both scenarios, the most disadvantaged communities experience the highest variations in air pollution, as they often live close to highways and major truck routes.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"1 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138928","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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