Pub Date : 2025-04-21DOI: 10.1021/acs.jpcc.5c00874
Eui-Cheol Shin, Youngho Kang, Sang Ho Jeon
This study presents a fundamental investigation into nitrogen complex in group-III nitrides using first-principles calculations, revealing the thermodynamic mechanisms governing vacancy cluster formation under different charge states. We find that nitrogen complexes drive agglomeration of vacancies in (Al, Ga)N through hole compensation and structural reconfiguration, while in n-type conditions and antibonding interactions introduce instability. InN exhibits a distinct behavior, maintaining robust VCs across doping conditions due to the unique role of metal–metal bonding, particularly indium trimer states, which suppress defect-driven instabilities. Our results highlight the intricate interplay between charge states, nitrogen complex, and bonding nature in shaping defect stability, offering new insights into defect engineering for nitride-based semiconductor applications.
{"title":"Thermodynamic Role of Nitrogen Complex in Vacancy Cluster of Group-III Nitrides","authors":"Eui-Cheol Shin, Youngho Kang, Sang Ho Jeon","doi":"10.1021/acs.jpcc.5c00874","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00874","url":null,"abstract":"This study presents a fundamental investigation into nitrogen complex in group-III nitrides using first-principles calculations, revealing the thermodynamic mechanisms governing vacancy cluster formation under different charge states. We find that nitrogen complexes drive agglomeration of vacancies in (Al, Ga)N through hole compensation and structural reconfiguration, while in <i>n</i>-type conditions and antibonding interactions introduce instability. InN exhibits a distinct behavior, maintaining robust VCs across doping conditions due to the unique role of metal–metal bonding, particularly indium trimer states, which suppress defect-driven instabilities. Our results highlight the intricate interplay between charge states, nitrogen complex, and bonding nature in shaping defect stability, offering new insights into defect engineering for nitride-based semiconductor applications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"28 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853386","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}
Xudong Wang, Mingzhu Lin, Jörn Peckmann, Germain Bayon, Qianyong Liang, Harry H. Roberts, Dong Feng
The long-term carbon sequestration capacity of black carbon (BC) is among the factors controlling climate change dynamics. Culture experiments have revealed that anaerobic methanotrophic archaea (ANME) can produce BC, but their impact on the marine BC cycle has not been thoroughly investigated. This study examined the geochemical properties of BC preserved in seep carbonates from the South China Sea and the Gulf of Mexico. δ13CBC values as low as −45.2‰ were observed in seep carbonates, representing the first documented case of ANME-derived BC in natural settings. With the observed range of BC isotope compositions and further calculations with a Bayesian mixing model, microbially produced BC may account for 2–33% of the total BC enclosed in the studied seep carbonates. By integrating data from various empirical studies, the analyses of radiocarbon (Δ14C) compositions suggests that BC in the deep sea is generally older than the associated organic carbon. Given that the organic carbon found at seeps is typically older than the organic carbon in the surrounding sediment not affected by seepage, BC originating from seeps could serve as a plausible source of aged dissolved BC in the deep sea.
{"title":"Black Carbon Formation at Cold Seeps and Its Potential Contribution to the Marine Black Carbon Budget","authors":"Xudong Wang, Mingzhu Lin, Jörn Peckmann, Germain Bayon, Qianyong Liang, Harry H. Roberts, Dong Feng","doi":"10.1021/acs.est.4c12940","DOIUrl":"https://doi.org/10.1021/acs.est.4c12940","url":null,"abstract":"The long-term carbon sequestration capacity of black carbon (BC) is among the factors controlling climate change dynamics. Culture experiments have revealed that anaerobic methanotrophic archaea (ANME) can produce BC, but their impact on the marine BC cycle has not been thoroughly investigated. This study examined the geochemical properties of BC preserved in seep carbonates from the South China Sea and the Gulf of Mexico. δ<sup>13</sup>C<sub>BC</sub> values as low as −45.2‰ were observed in seep carbonates, representing the first documented case of ANME-derived BC in natural settings. With the observed range of BC isotope compositions and further calculations with a Bayesian mixing model, microbially produced BC may account for 2–33% of the total BC enclosed in the studied seep carbonates. By integrating data from various empirical studies, the analyses of radiocarbon (Δ<sup>14</sup>C) compositions suggests that BC in the deep sea is generally older than the associated organic carbon. Given that the organic carbon found at seeps is typically older than the organic carbon in the surrounding sediment not affected by seepage, BC originating from seeps could serve as a plausible source of aged dissolved BC in the deep sea.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"66 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853651","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}
Little is known about the electron shuttle ability of dissolved organic matter (DOM) and its effects on arsenic (As) mobilization, which makes the underlying mechanism of groundwater As enrichment elusive. In this study, both the electrochemical properties and molecular compositions of DOM in high As groundwater were quantified in the Hetao Basin, China. We found that, along the flow path, the average electron-transferring capacity (ETC) of DOM, including the capacities of electron-accepting and electron-donating, continuously increased from 2.85 to 3.59 mmole-/gC along with As concentrations. The increasing ETC reflected an increase in electron shuttle ability of DOM. Furthermore, the increasing electron shuttle ability was mainly attributed to the recalcitrant compounds in DOM, especially CHOS and CHONS formulas in highly unsaturated structures with high oxygen (HUSHO) and CHO and CHON formulas in aromatic structures (AS). The significantly positive correlation between As concentration and ETC indicated that recalcitrant DOM promoted groundwater As enrichment through electron shuttling for inducing the reductive dissolution of As-containing Fe(III) oxide minerals, which was further supported by our culture experiments showing that goethite was more reduced [133 μM Fe(II)] in the presence of DOM with a higher ETC (3.35 mmole-/gC) as electron shuttling than that [65.2 μM Fe(II)] with a relatively lower ETC (2.41 mmole-/gC). Our study highlights that recalcitrant DOM compounds with unsaturated and AS have high electron shuttle ability, promoting As enrichment in groundwater.
人们对溶解有机物（DOM）的电子穿梭能力及其对砷（As）迁移的影响知之甚少，这使得地下水砷富集的内在机制难以捉摸。本研究对中国河套盆地高砷地下水中 DOM 的电化学性质和分子组成进行了量化。我们发现，沿水流路径，DOM的平均电子传递能力（ETC），包括电子接受能力和电子供能能力，随着As浓度的增加而从2.85 mmole-/gC持续上升到3.59 mmole-/gC。ETC的增加反映了DOM电子穿梭能力的增加。此外，电子穿梭能力的提高主要归因于 DOM 中的难溶化合物，尤其是高氧（HUSHO）高度不饱和结构中的 CHOS 和 CHONS 型以及芳香结构（AS）中的 CHO 和 CHON 型。砷浓度与 ETC 之间的显着正相关表明，难降解 DOM 通过电子穿梭诱导含砷氧化铁（III）矿物的还原溶解，促进了地下水中砷的富集，我们的培养实验进一步证实了这一点，实验结果表明，在 ETC 较高的 DOM（3.35 mmole-/gC）比 ETC 相对较低（2.41 mmole-/gC）的[65.2 μM Fe(II)]更容易被还原为电子穿梭。我们的研究结果表明，具有不饱和和AS的难降解DOM化合物具有很强的电子穿梭能力，可促进地下水中砷的富集。
{"title":"Electrochemistry and Molecular Compositions Reflect Electron Shuttling of Dissolved Organic Matter in High Arsenic Groundwater","authors":"Xiaojun Feng, Yao Li, Jianyi Jin, Wen Qiao, Zhipeng Gao, Huaming Guo","doi":"10.1021/acs.est.4c13575","DOIUrl":"https://doi.org/10.1021/acs.est.4c13575","url":null,"abstract":"Little is known about the electron shuttle ability of dissolved organic matter (DOM) and its effects on arsenic (As) mobilization, which makes the underlying mechanism of groundwater As enrichment elusive. In this study, both the electrochemical properties and molecular compositions of DOM in high As groundwater were quantified in the Hetao Basin, China. We found that, along the flow path, the average electron-transferring capacity (ETC) of DOM, including the capacities of electron-accepting and electron-donating, continuously increased from 2.85 to 3.59 mmol<sub>e-</sub>/gC along with As concentrations. The increasing ETC reflected an increase in electron shuttle ability of DOM. Furthermore, the increasing electron shuttle ability was mainly attributed to the recalcitrant compounds in DOM, especially CHOS and CHONS formulas in highly unsaturated structures with high oxygen (HUSHO) and CHO and CHON formulas in aromatic structures (AS). The significantly positive correlation between As concentration and ETC indicated that recalcitrant DOM promoted groundwater As enrichment through electron shuttling for inducing the reductive dissolution of As-containing Fe(III) oxide minerals, which was further supported by our culture experiments showing that goethite was more reduced [133 μM Fe(II)] in the presence of DOM with a higher ETC (3.35 mmol<sub>e-</sub>/gC) as electron shuttling than that [65.2 μM Fe(II)] with a relatively lower ETC (2.41 mmol<sub>e-</sub>/gC). Our study highlights that recalcitrant DOM compounds with unsaturated and AS have high electron shuttle ability, promoting As enrichment in groundwater.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"142 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853849","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}
Platinum group metal (PGM)-free and Cr-free automotive three-way catalyst (TWC) was examined using two types of base-metal oxides for hydrocarbon preferential oxidation (HC-PROX) and NO reduction by CO in tandem configuration. MnOx-based binary mixed metal oxides (X1Mn2, X = Ba, Ca, Co, Cu, Fe, Mg, Ni, Zn, Zr) were investigated for the design of HC-PROX catalysts. Mg1Mn2 achieved both high propene oxidation activity and low CO oxidation activity, and the catalyst phase was determined as MgMn2O4 having the spinel structure. A tandem TWC composed of MgMn2O4 for HC-PROX and CuCo2O4 for NO-CO reaction showed comparable NO reduction activity and higher oxidation activity of propene and CO compared to Rh/ZrO2 as a benchmark. In-situ FTIR study clarified that the suppression of CO oxidation over MgMn2O4 is caused by strongly adsorbed acetate and formate on the catalyst surface.
{"title":"Design of platinum group metal-free automotive three-way catalyst: MgMn2O4 and CuCo2O4 in tandem layout","authors":"Keisuke Maruichi , Taichi Yamaguchi , Ryosuke Sakai , Kakuya Ueda , Akira Oda , Atsushi Satsuma","doi":"10.1016/j.apcata.2025.120305","DOIUrl":"10.1016/j.apcata.2025.120305","url":null,"abstract":"<div><div>Platinum group metal (PGM)-free and Cr-free automotive three-way catalyst (TWC) was examined using two types of base-metal oxides for hydrocarbon preferential oxidation (HC-PROX) and NO reduction by CO in tandem configuration. MnOx-based binary mixed metal oxides (X1Mn2, X = Ba, Ca, Co, Cu, Fe, Mg, Ni, Zn, Zr) were investigated for the design of HC-PROX catalysts. Mg1Mn2 achieved both high propene oxidation activity and low CO oxidation activity, and the catalyst phase was determined as MgMn<sub>2</sub>O<sub>4</sub> having the spinel structure. A tandem TWC composed of MgMn<sub>2</sub>O<sub>4</sub> for HC-PROX and CuCo<sub>2</sub>O<sub>4</sub> for NO-CO reaction showed comparable NO reduction activity and higher oxidation activity of propene and CO compared to Rh/ZrO<sub>2</sub> as a benchmark. In-situ FTIR study clarified that the suppression of CO oxidation over MgMn<sub>2</sub>O<sub>4</sub> is caused by strongly adsorbed acetate and formate on the catalyst surface.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"700 ","pages":"Article 120305"},"PeriodicalIF":4.7,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143855003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.jpcc.5c00130
Ashwin Srinivasan, Nadine van Westrenen, Zachary Benmamoun, Matthew Feldman, Dongjin Seo, William A. Ducker
The equilibrium height of a meniscus in a truncated trapezoidal capillary was examined by theory and experiment. Experiments focused on the limit of larger separation between the parallel sides than the sloped sides, where the capillary rise was dominated by the gap between the sloped sides. The capillary was constructed from hydrophilic borosilicate glass slides, and the liquid was pure water or ethanol–water solutions. Theoretical results were obtained by numerical solution of the Young–Laplace equation to obtain the shape of the vapor–liquid interface as a function of the height above the surrounding liquid. We found good agreement between experiment and theory for wall angles, α, in the range 0–30°, a variety of submerged depths of the capillary, and ethanol solutions in the range 0–30% v/v. Experiment and theory showed that the meniscus rose less for greater angles of the trapezoid, and the rise is much more sensitive to α than to the contact angle, θ, for the small angles explored in this work. The rise is particularly sensitive to variation of α in the range 0–4°. In general, the criterion for the meniscus to rise in a capillary with inclined sides is (θ + α)< 90°, which is in contrast to θ < 90° for a capillary with parallel walls. The inclination of the wall provides an additional control variable, and a useful variable because of the high sensitivity to α at small angles. Capillaries with angled walls occur in natural and engineered systems, such as in porous media, where many wall inclinations can be found. In addition to capillary rise, these results have potentially useful applications to wetting of patterned surfaces, and to filtration.
{"title":"Capillary Rise for Inclined Walls","authors":"Ashwin Srinivasan, Nadine van Westrenen, Zachary Benmamoun, Matthew Feldman, Dongjin Seo, William A. Ducker","doi":"10.1021/acs.jpcc.5c00130","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00130","url":null,"abstract":"The equilibrium height of a meniscus in a truncated trapezoidal capillary was examined by theory and experiment. Experiments focused on the limit of larger separation between the parallel sides than the sloped sides, where the capillary rise was dominated by the gap between the sloped sides. The capillary was constructed from hydrophilic borosilicate glass slides, and the liquid was pure water or ethanol–water solutions. Theoretical results were obtained by numerical solution of the Young–Laplace equation to obtain the shape of the vapor–liquid interface as a function of the height above the surrounding liquid. We found good agreement between experiment and theory for wall angles, α, in the range 0–30°, a variety of submerged depths of the capillary, and ethanol solutions in the range 0–30% v/v. Experiment and theory showed that the meniscus rose less for greater angles of the trapezoid, and the rise is much more sensitive to α than to the contact angle, θ, for the small angles explored in this work. The rise is particularly sensitive to variation of α in the range 0–4°. In general, the criterion for the meniscus to rise in a capillary with inclined sides is (θ + α)< 90°, which is in contrast to θ < 90° for a capillary with parallel walls. The inclination of the wall provides an additional control variable, and a useful variable because of the high sensitivity to α at small angles. Capillaries with angled walls occur in natural and engineered systems, such as in porous media, where many wall inclinations can be found. In addition to capillary rise, these results have potentially useful applications to wetting of patterned surfaces, and to filtration.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"108 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1016/j.colsurfb.2025.114718
Qi Xu , Fang He , Zhimin Mo , Han Hu , Qianyuan He , Zushun Xu , Shengli Yang , Xiaojuan Qin
Emerging multimodal therapy strategies based on sonodynamic therapy (SDT) are foreseen as foundational in forthcoming tumor theranostics. Nevertheless, the therapeutic effects of SDT are limited by the hypoxic environment of the tumor microenvironment (TME). Based on this, nano-enzymes are envisioned to decompose excess hydrogen peroxide in the tumor microenvironment to generate oxygen. Here, PEG-PLGA-coated CeO2 nanoparticles loaded with the sonosensitizer chlorin e6 (CC@PP) were prepared for cancer therapy based on a nanoprecipitation method. CC@PP possesses highly efficient catalase-like (CAT) properties, which are able to decompose overexpressed H2O2 into O2 and enhance the effect of O2-dependent sonodynamic therapy. In addition, it can act as a peroxidase (POD) at lower pH for chemodynamic therapy. Under the guidance of the US, CC@PP can perform synergistic sonodynamic and chemodynamic cancer therapy and inhibit tumor growth efficiently, CC@PP is biocompatible, has good in vivo fluorescence imaging effect, and has integrated diagnostic and therapeutic properties, which can be effectively aggregated at the tumor area. In this study, the effect of sonodynamic therapy was enhanced by improving the hypoxic environment in the TME, and multimodal synergistic enhancement of cancer therapy was realized.
{"title":"A multifunctional nanoplatform based on chlorin e6 for fluorescence imaging-guided sonodynamic and chemodynamic cancer therapy","authors":"Qi Xu , Fang He , Zhimin Mo , Han Hu , Qianyuan He , Zushun Xu , Shengli Yang , Xiaojuan Qin","doi":"10.1016/j.colsurfb.2025.114718","DOIUrl":"10.1016/j.colsurfb.2025.114718","url":null,"abstract":"<div><div>Emerging multimodal therapy strategies based on sonodynamic therapy (SDT) are foreseen as foundational in forthcoming tumor theranostics. Nevertheless, the therapeutic effects of SDT are limited by the hypoxic environment of the tumor microenvironment (TME). Based on this, nano-enzymes are envisioned to decompose excess hydrogen peroxide in the tumor microenvironment to generate oxygen. Here, PEG-PLGA-coated CeO<sub>2</sub> nanoparticles loaded with the sonosensitizer chlorin e6 (CC@PP) were prepared for cancer therapy based on a nanoprecipitation method. CC@PP possesses highly efficient catalase-like (CAT) properties, which are able to decompose overexpressed H<sub>2</sub>O<sub>2</sub> into O<sub>2</sub> and enhance the effect of O<sub>2</sub>-dependent sonodynamic therapy. In addition, it can act as a peroxidase (POD) at lower pH for chemodynamic therapy. Under the guidance of the US, CC@PP can perform synergistic sonodynamic and chemodynamic cancer therapy and inhibit tumor growth efficiently, CC@PP is biocompatible, has good <em>in vivo</em> fluorescence imaging effect, and has integrated diagnostic and therapeutic properties, which can be effectively aggregated at the tumor area. In this study, the effect of sonodynamic therapy was enhanced by improving the hypoxic environment in the TME, and multimodal synergistic enhancement of cancer therapy was realized.</div></div>","PeriodicalId":279,"journal":{"name":"Colloids and Surfaces B: Biointerfaces","volume":"253 ","pages":"Article 114718"},"PeriodicalIF":5.4,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143859859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiangfei Chen, Qi Xue, Shenyu Ren, Yi-Lin Liu, Yang Li, Jin-Heng Li
We here describe a versatile, convenient, and efficient approach to synthesize cyclic nitrone compounds by diamination of alkene, which was catalyzed by simple copper salts under basic conditions with good chemoselectivity. The method utilized γ,δ-unsaturated ketoximes with O-benzoylhydroxylamines as an electrophilic nitrogen source to realize intra-/intermolecular 5-exo-trig cyclization of internal alkenes of unsaturated ketoximes without external oxidants required, and a series of substitution patterns, both donor and withdrawing substituted moieties, are well-tolerated, leading to target products in moderate to good yields.
{"title":"Intra-/Intermolecular 1,2-Diamination of Alkenyl Oximes with O-Benzoylhydroxylamines Enabled by Copper Catalysis","authors":"Jiangfei Chen, Qi Xue, Shenyu Ren, Yi-Lin Liu, Yang Li, Jin-Heng Li","doi":"10.1021/acs.joc.5c00271","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00271","url":null,"abstract":"We here describe a versatile, convenient, and efficient approach to synthesize cyclic nitrone compounds by diamination of alkene, which was catalyzed by simple copper salts under basic conditions with good chemoselectivity. The method utilized γ,δ-unsaturated ketoximes with <i>O</i>-benzoylhydroxylamines as an electrophilic nitrogen source to realize intra-/intermolecular 5-<i>exo</i>-trig cyclization of internal alkenes of unsaturated ketoximes without external oxidants required, and a series of substitution patterns, both donor and withdrawing substituted moieties, are well-tolerated, leading to target products in moderate to good yields.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"64 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.jpclett.5c00746
Victor M. Freixas, Nicolas Oldani, Laura Alfonso-Hernandez, Dianelys Ondarse-Alvarez, Hassiel Negrin-Yuvero, Johan Fabian Galindo, Sergei Tretiak, Sebastian Fernandez-Alberti
The synthesis of novel carbon nanostructures with unique topologies expands the landscape of organic molecules, introducing new chemical properties and potential applications. Carbon nanorings, composed of cyclic paraphenylene (CPP) chains, serve as a versatile scaffold for designing materials with unique molecular architectures that impact their optical properties and photoinduced dynamics. These new topologies alter the balance between competing π-conjugation effects, high bending strain energies, and steric hindrances imposed by the rearrangement of their cyclic structures. Here, we explore the photoinduced dynamics of the all-benzene trefoil knot using nonadiabatic excited-state molecular dynamics. We show how its absorption spectra can be modeled by a particle in a box constrained to the trefoil knot geometry, and we analyze the internal conversion process following photoexcitation. Our findings reveal an exciton intraring migration governed by the winding of the paraphenylene chain, ultimately leading to exciton self-trapping at specific high curvature regions of the knot. This behavior contrasts with the nondeterministic exciton self-trapping in the corresponding CPP, where localization occurs randomly across different phenylene units. Our results highlight the ability of molecular knots to control exciton dynamics through curvature, tension, and planarization effects, positioning these materials as promising candidates for future technological applications. This ability to precisely manipulate optical and electronic characteristics is essential for developing more efficient and versatile devices.
{"title":"Pinning Excited State Self-Trapping with All-Benzene Trefoil Knot","authors":"Victor M. Freixas, Nicolas Oldani, Laura Alfonso-Hernandez, Dianelys Ondarse-Alvarez, Hassiel Negrin-Yuvero, Johan Fabian Galindo, Sergei Tretiak, Sebastian Fernandez-Alberti","doi":"10.1021/acs.jpclett.5c00746","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00746","url":null,"abstract":"The synthesis of novel carbon nanostructures with unique topologies expands the landscape of organic molecules, introducing new chemical properties and potential applications. Carbon nanorings, composed of cyclic paraphenylene (CPP) chains, serve as a versatile scaffold for designing materials with unique molecular architectures that impact their optical properties and photoinduced dynamics. These new topologies alter the balance between competing π-conjugation effects, high bending strain energies, and steric hindrances imposed by the rearrangement of their cyclic structures. Here, we explore the photoinduced dynamics of the all-benzene trefoil knot using nonadiabatic excited-state molecular dynamics. We show how its absorption spectra can be modeled by a particle in a box constrained to the trefoil knot geometry, and we analyze the internal conversion process following photoexcitation. Our findings reveal an exciton intraring migration governed by the winding of the paraphenylene chain, ultimately leading to exciton self-trapping at specific high curvature regions of the knot. This behavior contrasts with the nondeterministic exciton self-trapping in the corresponding CPP, where localization occurs randomly across different phenylene units. Our results highlight the ability of molecular knots to control exciton dynamics through curvature, tension, and planarization effects, positioning these materials as promising candidates for future technological applications. This ability to precisely manipulate optical and electronic characteristics is essential for developing more efficient and versatile devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"13 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853378","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}
Energy conservation has become a priority in transitioning nations from non-renewable energy to renewable and sustainable energy sources. This study aims to provide a comparative analysis by investigating locals' and foreigners’ energy conservation intentions (ECI) and behavior in China. The study combines the theory of Karma and the theory of planned behavior with energy consumption habits in the assessment. A total of 1046 sample data of locals and foreigners were collected across Shanghai in China and analyzed using partial least squares structural equation modeling. The results reveal several significant findings. First, the duty of orientation was found to have a strong influence on equanimity, which in turn significantly affects foreigners' intentions. The duty of orientation also significantly influences indifference to rewards for both local and foreign participants. However, indifference to rewards does not influence locals' intentions but does impact foreigners' ECI. It was found that attitude does not significantly influence locals' ECI but has a substantial impact on foreigners' ECI. Perceived behavioral control was identified as a critical factor, significantly influencing ECI for both locals and foreigners. Intention was found to positively influence behavior for both groups, highlighting the importance of intention in driving actual energy conservation actions. Additionally, habit was shown to play a pivotal role, significantly influencing attitudes, the duty of orientation, intentions, and behaviors for both locals and foreigners. These findings provide a comprehensive understanding of the distinct drivers of energy conservation behaviors across different demographic groups, offering insights for targeted interventions to promote sustainable energy use.
{"title":"Comparing energy conservation behavior from the perspective of the karma effect","authors":"Bright Obuobi , ChenGuang Liu , Faustina Awuah , Gibbson Adu-Gyamfi , Emmanuel Nketiah","doi":"10.1016/j.rser.2025.115753","DOIUrl":"10.1016/j.rser.2025.115753","url":null,"abstract":"<div><div>Energy conservation has become a priority in transitioning nations from non-renewable energy to renewable and sustainable energy sources. This study aims to provide a comparative analysis by investigating locals' and foreigners’ energy conservation intentions (ECI) and behavior in China. The study combines the theory of Karma and the theory of planned behavior with energy consumption habits in the assessment. A total of 1046 sample data of locals and foreigners were collected across Shanghai in China and analyzed using partial least squares structural equation modeling. The results reveal several significant findings. First, the duty of orientation was found to have a strong influence on equanimity, which in turn significantly affects foreigners' intentions. The duty of orientation also significantly influences indifference to rewards for both local and foreign participants. However, indifference to rewards does not influence locals' intentions but does impact foreigners' ECI. It was found that attitude does not significantly influence locals' ECI but has a substantial impact on foreigners' ECI. Perceived behavioral control was identified as a critical factor, significantly influencing ECI for both locals and foreigners. Intention was found to positively influence behavior for both groups, highlighting the importance of intention in driving actual energy conservation actions. Additionally, habit was shown to play a pivotal role, significantly influencing attitudes, the duty of orientation, intentions, and behaviors for both locals and foreigners. These findings provide a comprehensive understanding of the distinct drivers of energy conservation behaviors across different demographic groups, offering insights for targeted interventions to promote sustainable energy use.</div></div>","PeriodicalId":418,"journal":{"name":"Renewable and Sustainable Energy Reviews","volume":"217 ","pages":"Article 115753"},"PeriodicalIF":16.3,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143851348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.jpcc.5c00183
Edirisuriya M. Dilanga Siriwardane, Rongzhi Dong, Jianjun Hu, Deniz Çakır
Ultralow compressible materials, which have a high bulk modulus (K), are invaluable in extreme conditions due to their ability to undergo significant compression without structural failure. As a large number of borides can be found with high K, this study develops a computational framework to scan the vast chemical space to identify the ultralow compressible borides. Transformer-based networks are helpful to generate new chemical compositions due to their self-attention mechanism, scalability, and ability to capture long-range dependencies. First, we developed a transformer-based network to generate new binary and ternary boride compositions based on the known boride compositions. Next, we trained a hybrid model based on AdaBoost and Gradient Boosting algorithms with a mean absolute error (MAE) of 14.1 GPa to scan the high K borides. The CALYPSO code was used to find the possible structures for those materials. After predicting K for a broad chemical domain, we found that Re–B and W–B systems are promising ultralow compressible materials. We then performed density functional theory (DFT) calculations to investigate the stability of the high K materials. Our computations suggest that W3B2, W2B3, W5VB4, and Re5CrB4 materials exhibit K > 300 GPa with a negative formation energy and energy-above-hull less than 40 meV. These materials are mechanically and dynamically stable based on the elastic constant calculations and the phonon dispersion.
{"title":"Exploiting Transformer-Based Networks and Boosting Algorithms for Ultralow Compressible Boride Design","authors":"Edirisuriya M. Dilanga Siriwardane, Rongzhi Dong, Jianjun Hu, Deniz Çakır","doi":"10.1021/acs.jpcc.5c00183","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00183","url":null,"abstract":"Ultralow compressible materials, which have a high bulk modulus (<i>K</i>), are invaluable in extreme conditions due to their ability to undergo significant compression without structural failure. As a large number of borides can be found with high <i>K</i>, this study develops a computational framework to scan the vast chemical space to identify the ultralow compressible borides. Transformer-based networks are helpful to generate new chemical compositions due to their self-attention mechanism, scalability, and ability to capture long-range dependencies. First, we developed a transformer-based network to generate new binary and ternary boride compositions based on the known boride compositions. Next, we trained a hybrid model based on AdaBoost and Gradient Boosting algorithms with a mean absolute error (MAE) of 14.1 GPa to scan the high <i>K</i> borides. The CALYPSO code was used to find the possible structures for those materials. After predicting <i>K</i> for a broad chemical domain, we found that Re–B and W–B systems are promising ultralow compressible materials. We then performed density functional theory (DFT) calculations to investigate the stability of the high <i>K</i> materials. Our computations suggest that W<sub>3</sub>B<sub>2</sub>, W<sub>2</sub>B<sub>3</sub>, W<sub>5</sub>VB<sub>4</sub>, and Re<sub>5</sub>CrB<sub>4</sub> materials exhibit <i>K</i> > 300 GPa with a negative formation energy and energy-above-hull less than 40 meV. These materials are mechanically and dynamically stable based on the elastic constant calculations and the phonon dispersion.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853384","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}
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