Chemphyschem最新文献

{"title":"Recent Advances in Covalent Organic Frameworks for Lithium-Sulfur Batteries: Applications in Cathodes and Separators.","authors":"Yang-Jie Wang, Hai-Xin Li, Jun-Jie Zhang, Jin-Liang Zhuang","doi":"10.1002/cphc.202500315","DOIUrl":"https://doi.org/10.1002/cphc.202500315","url":null,"abstract":"<p><p>Lithium-sulfur batteries (LSBs) have attracted significant attention due to their high theoretical energy density and cost-effectiveness. However, their practical application is hindered by issues such as the shuttle effect of lithium polysulfides (LiPSs), sluggish redox kinetics, and the insulating nature of sulfur. Covalent organic frameworks (COFs) have emerged as a promising class of porous crystalline materials for enhancing the performance of LSBs due to their tunable structures, high surface areas, and well-defined pore environments. This review systematically summarizes the latest progress in COF-based materials for LSBs, focusing on their applications in cathodes and functional separators. For cathodes, COFs and their derived composites serve as sulfur hosts, leveraging their high surface area and functionalized pore structures to immobilize LiPSs and facilitate sulfur utilization. In separators, COFs and COF-based composites enable efficient suppression of LiPSs migration through physical confinement, chemical adsorption, and catalytic acceleration of sulfur species transformation. Despite these advancements, the practical application of COFs either as host or functional separators faces challenges such as intrinsic low conductivity, structural stability, and large-scale synthesis. Finally, the challenges and perspectives are provided regarding the future design of COF-based cathodes and functional separators for high-performance LSBs.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500315"},"PeriodicalIF":2.2,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144728318","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}

{"title":"Probing Self-Association of (+)-Catechin Coupled with Hydrogen-Deuterium Exchange by Solution NMR Spectroscopy.","authors":"Giacomo Zuccon, Edoardo Longo, Vitali Tugarinov, Emanuele Boselli, Alberto Ceccon","doi":"10.1002/cphc.202500325","DOIUrl":"https://doi.org/10.1002/cphc.202500325","url":null,"abstract":"<p><p>Flavan-3-ols, a subclass of flavonoids found in tea, wine, and other plant-derived foods, exhibit potent antioxidant activity and contribute to various health benefits. Their ability to self-associate into supramolecular structures influences their stability, bioavailability, and function in complex matrices. In this study, we investigate the hydrogen-deuterium (H/D) exchange kinetics at the C6 and C8 positions on the A-ring of (+)-catechin, a widely occurring flavan-3-ol, using ¹H nuclear magnetic resonance spectroscopy. At low concentrations, the exchange follows a two-step pseudo-first-order mechanism, with slightly faster deuteration at C6 than at C8 under physiological conditions (298 K, pD 6). Unexpectedly, higher catechin concentrations lead to accelerated exchange rates, not attributable to pD variation but rather to reversible self-association. Through analysis of exchange-induced chemical shift changes ( <math> <semantics> <mrow><msub><mo>δ</mo> <mrow><mtext>ex</mtext></mrow> </msub> <mo>)</mo></mrow> <annotation>$left(deltaright)_{text{ex}} left.right)$</annotation></semantics> </math> , Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion data, and peak intensity time courses, this study characterizes a weak, transient monomer-dimer equilibrium (lifetime ≈ milliseconds). Importantly, the deuteration rate within the dimer is up to 170-fold faster than in the monomer. These findings uncover a previously unrecognized role of transient self-assembly in modulating the reactivity of polyphenols in solution and underscore the relevance of H/D exchange at carbon centers as a sensitive probe for supramolecular dynamics in polyphenolic systems.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500325"},"PeriodicalIF":2.2,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144728317","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}

{"title":"Self-Organization of 2D and 3D Metamaterials in Nematic Liquid Crystals.","authors":"Anu Koviloor Manian, Jayasri Dontabhaktuni","doi":"10.1002/cphc.202500272","DOIUrl":"https://doi.org/10.1002/cphc.202500272","url":null,"abstract":"<p><p>Liquid crystals (LCs) are a fascinating class of materials with anisotropic optical and dielectric properties making them ideal candidates for forming self-organized 2D and 3D photonic structures. They form a versatile medium to support self-organization of structures into periodic, aperiodic, and quasiperiodic structures in 2D and 3D. Key driving forces behind self-organization in LCs include elastic distortions, surface anchoring, and external fields. External stimuli such as electric or magnetic fields, temperature gradients, or light irradiation can reorient LC molecules, providing dynamic control over the self-assembled structures. Hence, these structures interact with incoming light, enabling applications in tunable photonic devices. These photonic structures, particularly in the subdiffraction limit, called as metamaterials, give rise to unprecedented control of light. Metamaterials and their novel applications as well as self-assembly in LCs are well-reviewed subjects. However, there are very few articles on burgeoning and novel field of LC-integrated metamaterials, which is a subject of interest in the current article. In this article, we provide an extensive review of nematic LC-based metasurfaces giving rise to advanced functionalities of light manipulation such as beam steering, light detection and ranging, holography, sensing, and multifunctional and reconfigurable optoelectronic devices.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500272"},"PeriodicalIF":2.2,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144728319","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}

{"title":"Strain-Tunable Band Alignment and Photoelectric Properties of CaAl₂S₄/InGaSe₂ van der Waals Heterostructure.","authors":"Weiqi Fu, Yicheng Wang, Xing Xu, Yipeng Zhao, Liang Ma, Shiqing Tang","doi":"10.1002/cphc.202500281","DOIUrl":"https://doi.org/10.1002/cphc.202500281","url":null,"abstract":"<p><p>Hexagonal α₁-CaAl₂S₄ and Janus α₁-InGaSe₂, featuring unique physical and chemical attributes, stand out as exceptional contenders for optoelectronic implementations. However, on account of weak absorption of visible and UV light, α₁-CaAl₂S₄ faces limitations in optoelectronic device applications. Constructing a heterojunction with α₁-CaAl₂S₄ and α₁-InGaSe₂ can significantly enhance photon absorption in both the visible and UV domains. This research employs first-principles simulations to scrutinize the optical and electrical properties of α₁-CaAl₂S₄, α₁-InGaSe₂, and the heterojunctions formed by these two materials. The output of the calculations shows that CaAl₂S₄/InGaSe₂ heterojunction demonstrates a remarkable enhancement with respect to light collection efficiency across the visible and UV span. The CaAl₂S₄/InGaSe₂ heterojunctions with different stacking structures exhibit type-I and type-II alignment modes, respectively. Furthermore, the bandgap value and type of heterojunctions can be effectively controlled by modulating the interlayer spacing and applying biaxial strain, resulting in a variety of band alignments and light absorption properties. These findings provide new material options and technological pathways for developing high-efficiency photovoltaic cells, photoresponsive devices, solid-state lighting elements, and novel photocatalytic and integrated optoelectronic devices.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500281"},"PeriodicalIF":2.3,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144706507","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}

{"title":"Corrigendum: Reverse Dual-Ion Battery Enabled by Reversing the Cation/Anion Storage Mechanism in an Aqueous ZnCl₂ Water-in-Salt Electrolyte.","authors":"","doi":"10.1002/cphc.202500449","DOIUrl":"https://doi.org/10.1002/cphc.202500449","url":null,"abstract":"","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500449"},"PeriodicalIF":2.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144697711","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}

{"title":"Kinetic and Thermodynamic Study of Proton Transfer Reactions of 1-Hydroxy-2,2-Dinitroethane: Establishing a Predictive Relationship between Tautomeric and Acidity Constants in Water.","authors":"Rania Khaldi, Amel Hedhli, Taoufik Boubaker","doi":"10.1002/cphc.202500219","DOIUrl":"https://doi.org/10.1002/cphc.202500219","url":null,"abstract":"<p><p>The proton transfer reactions of the nitronate anion derived from 1-hydroxy-2,2-dinitroethane 1 with HCl and carboxylic acid buffers in aqueous solution at 25 °C are investigated through a comprehensive kinetic and thermodynamic analysis. The reaction mechanism is elucidated, allowing the determination of acidity constants for both O-protonation ( <math> <semantics><mrow><mi>p</mi> <msubsup><mi>K</mi> <mi>a</mi> <mrow> <msub><mrow><mtext>NO</mtext></mrow> <mn>2</mn></msub> <mi>H</mi></mrow> </msubsup> </mrow> <annotation>$p K_{text{a}}^{left(text{NO}right)_{2} text{H}}$</annotation></semantics> </math>  = 1.67) and C-protonation ( <math> <semantics><mrow><mi>p</mi> <msubsup><mi>K</mi> <mi>a</mi> <mrow><mtext>CH</mtext></mrow> </msubsup> </mrow> <annotation>$p K_{text{a}}^{text{CH}}$</annotation></semantics> </math>  = 3.78), which are among the weakest reported for nitroalkanes in water to date. The intrinsic rate constant (log k_o = 1.60), determined using the Marcus approach, is markedly lower than typical values reported for nitrile protonation, reflecting the exceptional resonance stabilization of the conjugate base by the strongly electron-withdrawing NO₂ groups. Most importantly, by combining reported data from the literature with the results obtained in this study, a fundamental and predictive relationship between the tautomeric equilibrium constants (pK_N =  <math> <semantics><mrow><mi>p</mi> <msubsup><mi>K</mi> <mi>a</mi> <mrow><mtext>CH</mtext></mrow> </msubsup> </mrow> <annotation>$p K_{text{a}}^{text{CH}}$</annotation></semantics> </math> - <math> <semantics><mrow><mi>p</mi> <msubsup><mi>K</mi> <mi>a</mi> <mrow> <msub><mrow><mtext>NO</mtext></mrow> <mn>2</mn></msub> <mi>H</mi></mrow> </msubsup> </mrow> <annotation>$p K_{text{a}}^{left(text{NO}right)_{2} text{H}}$</annotation></semantics> </math> ) and the acidity constants ( <math> <semantics><mrow><mi>p</mi> <msubsup><mi>K</mi> <mi>a</mi> <mrow><mtext>CH</mtext></mrow> </msubsup> </mrow> <annotation>$p K_{text{a}}^{text{CH}}$</annotation></semantics> </math> ) of nitroalkanes in water has been established. This unprecedented linear correlation allows to estimate the acidity constants of the nitronic acids of four nitroalkanes in water, which were previously experimentally inaccessible. To the best of knowledge, this work is among the first to exploit such an approach, representing a significant advancement in understanding the structure-reactivity relationships governing the protonation of carbon and oxygen sites in nitroalkanes.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500219"},"PeriodicalIF":2.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144688993","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}

{"title":"Exploring Pillar[6]quinone as Cathode Material for Aqueous Zinc-Ion Batteries.","authors":"Serkan Yeşilot, Nazmiye Kılıç, Selin Sariyer, Yasemin Solmaz, Merve Güner, Rezan Demir-Cakan","doi":"10.1002/cphc.202500422","DOIUrl":"https://doi.org/10.1002/cphc.202500422","url":null,"abstract":"<p><p>Quinone cathodes have wide application prospects in aqueous zinc-ion batteries (AZIBs) due to their high performance, structural diversity, sustainability, high specific capacity, and fast reaction kinetics. Herein, pillar[6]quinone (P6Q), a member of the quinone group, is used as a cathode in AZIBs for the first time. The P6Q structure consisting of six benzoquinone units with a higher cavity than the quinone structures with small molecule structures is found to greatly improve the cycling stability of the cathode. The P6Q electrode exhibits remarkable electrochemical stability and a long-term cycle life (discharge capacity of 118 mAh g^-1 and capacity retention of 83% after 10 000 cycles at current density of 50C). In addition, density functional theory calculations and ex situ characterization methods such as ultraviolet-visible spectroscopy, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy are used to clarify the possible coordination mechanism between P6Q and Zn²⁺/H⁺ ions.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500422"},"PeriodicalIF":2.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144697712","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}

{"title":"Tuning the Fe-Oxide Nanoparticle Properties by Playing with Salt Precursors and Camellia sinensis Extract Concentrations.","authors":"Renzo Rueda-Vellasmin, Juan A Ramos-Guivar, Jeferson Marques Santos, Noemi-Raquel Checca-Huaman, Edson C Passamani","doi":"10.1002/cphc.202500226","DOIUrl":"https://doi.org/10.1002/cphc.202500226","url":null,"abstract":"<p><p>By varying salt precursors and precipitating agents, polyphenol-functionalized γ-Fe₂O₃ nanoparticles (NPs) were systematically biosynthesized with controlled particle sizes and varying polyphenol layer thicknesses via two distinct approaches. In the in situ process (ISP), green tea (GT) extract influenced the formation of particles with different sizes during the synthesis, while in the after synthesis process (ASP), it enabled the functionalization of preformed γ-Fe₂O₃ NPs. The use of GT extract significantly reduced the amount of precipitating agent (NH₄OH or NaOH) commonly used in the coprecipitation method. However, even in a polyphenol-rich environment, the Fe₃O₄ phase is detected only a few hours after the ISP. Results from various characterization techniques revealed that altering the GT extract content-expressed as percent weight-to-volume (x = %w/v)-affects the nanocrystallite size, magnetic behavior, and hyperfine properties, particularly in samples biosynthesized via ISP. Functionalization with GT extract enhanced the effective magnetic anisotropy of the γ-Fe₂O₃ NPs compared to bare γ-Fe₂O₃ NPs; however, this anisotropy decreased progressively as the x-value increases. This trend suggests that the thicker organic layer reduced interparticle dipolar interactions by improving the dispersion of the magnetic NPs.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500226"},"PeriodicalIF":2.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144697713","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}

{"title":"Adjustment of the Proton-Accepting Ability of Π-Bonds and Lone Pairs.","authors":"Akhtam Amonov, Steve Scheiner","doi":"10.1002/cphc.202500448","DOIUrl":"https://doi.org/10.1002/cphc.202500448","url":null,"abstract":"<p><p>A hydroxyl group is placed on a series of systems containing CC double bonds, and quantum chemical calculations consider the preferred target of an incoming1 HCl molecule to form an H-bond. The O lone pairs are favored over the π-system in most instances but can be reversed by the presence of electron-donating substituents. This reversal occurs when NH₂ groups are added to a simple alkene or if NMe₂ substituents are placed on a conjugated butadiene derivative. There are a variety of means of favoring the aromatic ring as a proton-accepting site over the phenol O. Dispersion is the primary factor in determining the preferred electron-donor site in the aromatic systems. The particular site and orientation of attachment of HCl to the π system is controlled by a combination of electrostatic potential and HOMO disposition.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500448"},"PeriodicalIF":2.3,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144688992","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}

{"title":"Surface-Enhanced Raman Scattering Properties of Densely-Packed Thin-Films Fabricated using Mixed Gold Nanoparticles with Different Diameters.","authors":"Natsuki Koyama, Hironobu Tahara, Takeo Oku, Tsuyoshi Akiyama","doi":"10.1002/cphc.202500250","DOIUrl":"https://doi.org/10.1002/cphc.202500250","url":null,"abstract":"<p><p>Densely-packed thin films of plasmonic nanoparticles enhance Raman scattering. The effect of size uniformity of plasmonic nanoparticles in such thin films contributes to the development of highly sensitive Raman scattering spectroscopy for practical use. In this research, densely-packed thin films containing a mixture of gold nanoparticles with two different sizes are fabricated and evaluated about their surface-enhanced Raman scattering properties. The enhancement efficiency of gold nanoparticle films with different sizes is lower than that of single-sized gold nanoparticle films. This tendency suggests a relationship between Raman scattering enhancement efficiency and the electric field generated by localized surface plasmon resonance among gold nanoparticles of different sizes.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500250"},"PeriodicalIF":2.3,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144682050","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}