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}
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}
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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：