Chemphyschem最新文献_第8页

Quantum Chemical Insights Into Glycine-Mediated Stepwise Transformation of Halobenzoquinones 甘氨酸介导的卤苯醌逐步转化的量子化学研究

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-19 DOI: 10.1002/cphc.70541

Ping Li, Yuqian Yang, Yuhua Wang, Wenling Feng, Cong Jia, Weihua Wang

{"title":"Quantum Chemical Insights Into Glycine-Mediated Stepwise Transformation of Halobenzoquinones","authors":"Ping Li, Yuqian Yang, Yuhua Wang, Wenling Feng, Cong Jia, Weihua Wang","doi":"10.1002/cphc.70541","DOIUrl":"https://doi.org/10.1002/cphc.70541","url":null,"abstract":"Halobenzoquinones (HBQs) are emerging toxic disinfection byproducts widely present in drinking water. Although their reactions with amino acids have been reported, the detailed stepwise mechanisms remain unclear. Herein, density functional theory (DFT) was employed to systematically explore the transformation of HBQs by the anion of glycine (Gly−), the dominant species at environmental pH. Quantitative thermodynamic and kinetic parameters were obtained for the complete transformation pathway from parent HBQs to poly-Gly-derivatized products. Two major pathways, 1,4-addition (Michael addition) and SN2 substitution, were identified. 1,4-Addition dominates the initial reaction for mono-, di-, and trihalogenated HBQs, while SN2 is crucial for perhalogenated HBQs. Water exerts a dual catalytic effect on key proton-transfer steps. A regioselectivity rule was established, with the para-carbon showing the highest reactivity toward subsequent nucleophilic attack, rationalized by the lowest unoccupied molecular orbital (LUMO) distributions and steric effects. Condensed Fukui functions alone are insufficient for regioselectivity prediction. This work provides molecular-level insights into the transformation and detoxification of HBQs by Gly−, supporting their mass spectrometric identification and the design of amino acid-based water treatment strategies.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 16","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148783897","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}

引用次数: 0

Methyllithium and Its Oligomers as Lewis Bases for Hydrogen and Halogen Bonding 甲基锂及其低聚物作为氢和卤素键的路易斯碱

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-18 DOI: 10.1002/cphc.70512

Zhaohui Jia, Qingzhong Li, Steve Scheiner

引用次数: 0

Multiplexed Detection of Cancer Protein Biomarkers via Surface-Enhanced Raman Scattering Immunoassays on Natural Diatomite Strips 天然硅藻土条带表面增强拉曼散射免疫法检测肿瘤蛋白生物标志物

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-18 DOI: 10.1002/cphc.70540

Ayse Mine Saridag, Isik Didem Karagoz, Sebastian Wachsmann-Hogiu, Mehmet Kahraman

引用次数: 0

Demonstration of Proton Conduction in Electrolyte-Supported Cesium Borophosphate Membrane Electrode Assemblies 质子传导在电解质支持的硼磷酸铯膜电极组件中的演示

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-15 DOI: 10.1002/cphc.70532

J. August Ridenour, Brian L. Chaloux, Michelle D. Johannes, Christopher A. Klug, Noam Bernstein, Eric A. Patterson, Sara C. Mills, Jennifer L. Dysart, Yasmi Chibber, Matthew T. Finn, Albert Epshteyn

{"title":"Demonstration of Proton Conduction in Electrolyte-Supported Cesium Borophosphate Membrane Electrode Assemblies","authors":"J. August Ridenour, Brian L. Chaloux, Michelle D. Johannes, Christopher A. Klug, Noam Bernstein, Eric A. Patterson, Sara C. Mills, Jennifer L. Dysart, Yasmi Chibber, Matthew T. Finn, Albert Epshteyn","doi":"10.1002/cphc.70532","DOIUrl":"https://doi.org/10.1002/cphc.70532","url":null,"abstract":"Electrolyte-supported membrane electrode assemblies (MEAs) were fabricated using Cs3H2[BOB(PO4)3] (affectionately dubbed CsBOB) as the electrolyte and membrane separator and tested for proton conduction and power generation at temperatures up to 250 °C. The devices reached steady state ionic conductivities of 0.8–1.8 × 10−5 S cm−1 and produced commensurate power at nominal steady-state power densities of 0.6–1.2 × 10−2 mW cm−2 over the course of 160-h tests, thereby experimentally demonstrating that the CsBOB electrolyte does, in fact, conduct protons and is chemically stable under fuel cell operating conditions on the order of days. Machine-learned interatomic potentials (MLIP) trained on density functional theory calculations were used for molecular dynamics (MD) simulations, providing computational evidence confirming proton motion through bulk CsBOB. Importantly, the MLIP MD, bolstered by solid-state nuclear magnetic resonance (SS-NMR), also revealed that interstitial water plays a significant role in the CsBOB proton conduction mechanism under the operating conditions that were tested, helping provide high proton mobility. However, at these conductivities, electrochemistry is electrolyte limited; a 2–3 order-of-magnitude increase in proton conductivity is necessary for MEAs utilizing CsBOB electrolyte to achieve sufficiently high power densities for use in commercially competitive fuel cells. Future work will focus on improving CsBOB proton conductivity by increasing carrier density.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 16","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148753762","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}

引用次数: 0

Magnetic Field-Modulated Ion Migration in Electrochemical Cells 电化学电池中的磁场调制离子迁移

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-15 DOI: 10.1002/cphc.70522

Shuokai Xu, Bojun Shi, Baipeng Yin, Chuang Zhang

{"title":"Magnetic Field-Modulated Ion Migration in Electrochemical Cells","authors":"Shuokai Xu, Bojun Shi, Baipeng Yin, Chuang Zhang","doi":"10.1002/cphc.70522","DOIUrl":"https://doi.org/10.1002/cphc.70522","url":null,"abstract":"Ion migration within electrochemical cells fundamentally governs interfacial reaction kinetics, charge transport, and the formation of electric double layers, thereby critically determining the overall performance of electrochemical devices. However, conventional regulation strategies often suffer from limited controllability, high energy consumption, and undesirable side reactions. Magnetic fields have recently emerged as a green, noncontact external stimulus that can precisely manipulate ion migration through magnetohydrodynamic convection and magnetic gradient forces, at both microscopic (ion transport) and macroscopic (electrolyte flow) scales. This review briefly summarizes the core mechanisms of magnetic field‑modulated ion migration and three regulation strategies: external static magnetic field, external dynamic magnetic field, and in situ internal magnetic field constructed by magnetic materials. Recent advances and practical achievements of magnetic field modulated are reviewed across four key areas: electrochemical energy storage, electrochemical synthesis, electrocatalytic conversion, and precise ion separation. Finally, existing challenges and prospective development directions in this field are discussed. This review aims to consolidate the theoretical foundation of magnetic field-assisted electrochemical regulation and promote the theoretical improvement and large-scale practical application of this emerging regulation technology.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 16","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148753939","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}

引用次数: 0

Crystallization of Glasses: A Theoretical Analysis of the Role of Fragility and Polymorphism in Crystals 玻璃的结晶：晶体中脆性和多态性作用的理论分析

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-13 DOI: 10.1002/cphc.70533

Biman Bagchi

{"title":"Crystallization of Glasses: A Theoretical Analysis of the Role of Fragility and Polymorphism in Crystals","authors":"Biman Bagchi","doi":"10.1002/cphc.70533","DOIUrl":"https://doi.org/10.1002/cphc.70533","url":null,"abstract":"Here we develop an elasticity-based theory of crystallization in glasses that incorporates structural heterogeneity, fictive temperature, and polymorph-mediated pathways. In a glass, structural degrees of freedom are effectively frozen, so that the fictive temperature Tf remains higher than the ambient temperature T, rendering the system intrinsically out of equilibrium. A central result is that the crystal–glass interfacial penalty is renormalized in fragile systems by soft, liquid-like regions, leading to a subquadratic mismatch energy scaling as ΣR3/2 rather than the classical R2 form. Applying this framework to ethanol, we show that nucleation proceeds preferentially via a two-step route through a plastic crystalline polymorph. The associated barriers are dramatically reduced: the glass-to-plastic step exhibits barriers of only ∼5 kBT, compared to ∼102 kBT for the direct glass-to-crystal transition. This large separation explains the dominance of the Ostwald pathway and the emergence of a pronounced time–temperature–transformation (TTT) nose. In contrast, silica retains the classical R2 scaling due to its rigid network, leading to very large barriers and suppressed bulk nucleation.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 15","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148753634","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}

引用次数: 0

Elucidating the Role of Aqueous Solvent and Cations in Selectivity of Cobalt–Porphyrin Catalyzed CO2 Reduction Over Hydrogen Evolution 溶剂和阳离子对钴-卟啉催化CO2析氢选择性的影响。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-12 DOI: 10.1002/cphc.202500727

Lingshu Zhuo, Evert Jan Meijer

引用次数: 0

Infrared Photodissociation Spectroscopy of Be(N2)n+ and Be(CO)n+ (n = 3–4): Charge Effects on Bonding and Coordination Be(N2)n +和Be(CO)n + (n = 3-4)的红外光解光谱：电荷对成键和配位的影响

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-09 DOI: 10.1002/cphc.70530

Yangyu Zhou, Guanjun Wang, Jiaye Jin, Mingfei Zhou

{"title":"Infrared Photodissociation Spectroscopy of Be(N2)n+ and Be(CO)n+ (n = 3–4): Charge Effects on Bonding and Coordination","authors":"Yangyu Zhou, Guanjun Wang, Jiaye Jin, Mingfei Zhou","doi":"10.1002/cphc.70530","DOIUrl":"10.1002/cphc.70530","url":null,"abstract":"Beryllium dinitrogen and carbonyl cation complexes, Be(N2)n+ and Be(CO)n+ (n = 3–4), were produced in the gas phase by a laser vaporization-supersonic expansion ion source and investigated by infrared photodissociation spectroscopy in conjunction with quantum chemical calculations. Be(N2)3+ is assigned to a planar D3h-symmetric structure with three equivalent end-on coordinated molecular N2 ligands, whereas Be(N2)4+ is characterized as a weakly bound N2 adduct of Be(N2)3+. The corresponding carbonyl complexes exhibit analogous structural motifs. Bonding analyses reveal that the L → Be (L = NN/CO) interactions in these end-on complexes are governed by L → Be σ donation, accompanied by weaker L ← Be π back-donation. In contrast to our previous study on Be(N2)3 (Angew. Chem. Int. Ed. 2020, 59, 10603), where both end-on and side-on coordination motifs coexist, only end-on structures are observed for the cationic species. The absence of side-on coordination is attributed to the positive charge, which significantly weakens π back-donation while only modestly enhancing σ donation, thereby destabilizing side-on binding motifs.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 15","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148700451","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}

引用次数: 0

Polyhalogenated 2,1,3-Benzochalcogenadiazoles: A Small-Molecule Platform for Multicentered Spin–Orbit Coupling Affecting Optical Properties (Chalcogens = S, Se, Te; Halogens = F, Cl, Br, I) 多卤化2,1,3-苯并硫代二唑：影响光学性质的多中心自旋-轨道耦合的小分子平台（卤素= S, Se, Te；卤素= F, Cl, Br， I）。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-07 DOI: 10.1002/cphc.70524

Ekaterina A. Radiush, Taisiya S. Sukhikh, Yulia S. Kosenkova, Ivan S. Golovanov, Elena V. Karpova, Nikolay A. Semenov, Andrey V. Zibarev

{"title":"Polyhalogenated 2,1,3-Benzochalcogenadiazoles: A Small-Molecule Platform for Multicentered Spin–Orbit Coupling Affecting Optical Properties (Chalcogens = S, Se, Te; Halogens = F, Cl, Br, I)","authors":"Ekaterina A. Radiush, Taisiya S. Sukhikh, Yulia S. Kosenkova, Ivan S. Golovanov, Elena V. Karpova, Nikolay A. Semenov, Andrey V. Zibarev","doi":"10.1002/cphc.70524","DOIUrl":"10.1002/cphc.70524","url":null,"abstract":"2,1,3-Benzochalcogenadiazoles and their halogen derivatives (chalcogen = S, Se, Te; halogen = F, Cl, Br, I) are widely employed in organic optoelectronics as chromophoric/fluorophoric electron-acceptor building blocks. In this work they are specified as an advantageous small-molecule platform for multicentered (Se, Te; Cl, Br, I) spin–orbit coupling (SOC) affecting optical properties of π-organics. Electronic absorption and emission/photoluminescence spectra of 4,7-di- and 4,5,6,7-tetrahalogenated 2,1,3-benzochalcogenadiazoles E/X’ and E/X, respectively (E = chalcogen, X = halogen), have been studied in solid-state and THF solutions experimentally and theoretically. It has been found that the nature of E is the key factor controlling the photophysical properties of E/X’ and E/X, such as energy levels, Stokes shifts, and the photoluminescence quantum yields, while X serves for further fine tuning of the properties. Combined E and X variation allows target-oriented design of absorptive and emissive materials for metal-free SOC-controlled optoelectronics and emerging spin–orbitronics.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 15","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148688709","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}

引用次数: 0

Spatially Correlated Flickering of All-Inorganic Perovskite Microrods 全无机钙钛矿微棒的空间相关闪烁。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-06 DOI: 10.1002/cphc.70528

Sasank Pattnaik, Shruti Singh, Arindam Chowdhury

{"title":"Spatially Correlated Flickering of All-Inorganic Perovskite Microrods","authors":"Sasank Pattnaik, Shruti Singh, Arindam Chowdhury","doi":"10.1002/cphc.70528","DOIUrl":"10.1002/cphc.70528","url":null,"abstract":"All-inorganic halide perovskites, especially CsPbBr3 microrods, are often considered to be optically stable and less defect-prone compared to their organometallic counterparts. Nevertheless, reports of photoluminescence (PL) blinking in bulk perovskite systems till date are restricted to organometallic halide perovskite nano-/microrods, leaving it an open question whether similar intermittency behavior can be observed in all-inorganic halide perovskites of comparable dimensions. Intriguingly, we witnessed multilevel PL fluctuations (flickering) in individual green-emitting CsPbBr3 microrods. Wide-field PL microscopy reveals that the intensity fluctuations are nearly identical along the microrod, owing to charge carrier migration and waveguide-assisted propagation. Our measurements on single microrod suggest that the flickering dynamics is strongly influenced by excitation power, excitation energy, and local environmental constituents. Under dry argon environment, a substantial reduction in the PL intensity is observed, indicating the formation of a large number of nonradiative (NR) traps, which quenches all the photogenerated carriers, suppressing overall emission intensity and PL flickering. The exposure of oxygen and moisture passivates these NR traps along with generation of a few photo-induced supertraps. Our findings establish that spatiotemporally correlated intermittency is not limited to organometallic perovskites but extends to all-inorganic perovskite bulk emitters as well, in presence of certain atmospheric constituents.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 15","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148683598","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}

引用次数: 0