Chemphyschem最新文献

{"title":"Does the Presence of Sigma Holes Affect the Way Neutral Ligands Attach to a Halonium Cation?","authors":"Mariusz Michalczyk","doi":"10.1002/cphc.202500357","DOIUrl":"https://doi.org/10.1002/cphc.202500357","url":null,"abstract":"<p><p>This study explores the fundamental nature of interactions between halonium cations-modeled as fragments of real crystal structures-and Lewis bases, with hydrogen cyanide (HCN) serving as a representative ligand. Two types of halonium cation monomers, namely the iodonium ion of adamantylideneadamantane and ethynyl(phenyl)-λ³-iodane, along with their chlorine and bromine analogues, are examined. Complexes formed with HCN molecules are investigated using quantum chemical calculations and topological analyses of electron density. The findings indicate that the σ-hole plays a decisive role in directing both the geometry and strength of these noncovalent interactions. Systems featuring a single σ-hole exhibit reduced stabilization upon additional ligand coordination, often weakening the primary halogen bond. In contrast, cations with two σ-holes can accommodate up to three or four HCN molecules without compromising the integrity of the original halogen bonds. Nevertheless, the most favorable configuration remains the directional binding of two ligands to two distinct σ-holes.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500357"},"PeriodicalIF":2.2,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144944637","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":"Correlating Metal Spin Electron with CO Adsorption in Single-Atom Catalysts: A Theoretical Investigation.","authors":"Juanjuan Wang, Han Zhang, Xia-Guang Zhang","doi":"10.1002/cphc.202500516","DOIUrl":"https://doi.org/10.1002/cphc.202500516","url":null,"abstract":"<p><p>Electron spin at metal sites plays a critical role in surface/interface reaction activity. Herein, a series of metal (Fe, Co, Ni, Pd, Pt, Cu, Ag, and Au) single-atom catalysts as activity center and CO as a probe molecule, to systematically investigate the role of spin electrons by calculations of structure stability, orbital energy level, and electron transfer. Fe and Pt single-atom structures are most stable in low-spin states, while others are stable in high-spin states. The bond energy of CO influenced by spin state demonstrates the same trend, and the splitting degree of d-σ interaction determines the strength of bond energy. Furthermore, it is found that there is a quasi-linear relationship between frequency shift and bond length of adsorbed CO. This work offers an example of how spin electrons influence orbital interaction of molecular adsorption and helps to understand the role of electron spin at metal sites in reaction.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500516"},"PeriodicalIF":2.2,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144944662","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":"Front Cover: Nanofibrous Interlayers with Ultrafine Decoration of Titanium Oxide to Intercept Lithium Polysulfides in Lithium–Sulfur Batteries (ChemPhysChem 16/2025)","authors":"Ali Ansari Hamedani,&nbsp;Busra Cetiner,&nbsp;Begüm Yarar Kaplan,&nbsp;Selmiye Alkan Gürsel,&nbsp;Alp Yürüm","doi":"10.1002/cphc.70076","DOIUrl":"https://doi.org/10.1002/cphc.70076","url":null,"abstract":"<p><b>The Front Cover</b> demonstrates how a lightweight, electrospun nanofiber “interlayer” packed with nano TiO₂ particles can act as an effective adsorbant, intercepting troublesome lithium polysulfides that normally shuttle back and forth and cause capacity loss. By slipping this interlayer between the sulfur cathode and separator, the cell saw over 50% higher capacity retention after 100 cycles, all with less than a 2 wt% addition to the cell. More information can be found in the Research Article by A. Yürüm and co-workers (DOI: 10.1002/cphc.202401136).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 16","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.70076","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910231","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the Helical Structure of Ethylene Oxides: Beyond Steric and Related Effects.","authors":"Matheus P Freitas","doi":"10.1002/cphc.202500458","DOIUrl":"https://doi.org/10.1002/cphc.202500458","url":null,"abstract":"<p><p>Dimethoxyethane (DME) is the monomer of polyethylene oxide, a polymer widely used in materials science, with its conformation affecting properties such as host-guest interactions with ions. This quantum-chemical study reveals that DME undergoes rotational isomerization among nine rotamers, favoring a zigzag (all-trans) conformation, followed by a conformer with the OCCO fragment in a gauche arrangement. This preference strengthens with increasing chain length but transitions to a gauche configuration resembling a helical structure in polar solvents like DMSO. Unlike expectations based on steric effects or earlier assumptions of a 1,5 CH₃/O nonbonding attraction, the helical structure arises from reduced dipolar repulsion/dipole stabilization and hyperconjugative interactions that surpass Lewis-type interactions. The helical structure of a 21-heavy-atom oligomer further compresses to encapsulate a potassium cation, forming a highly stable complex.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500458"},"PeriodicalIF":2.2,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144944605","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":"Impact of Intrinsic Hydrophobicity of Bile Salts on the Inhibition of Temperature-Induced Aggregation of Bovine Serum Albumin.","authors":"Rahul Yadav, Atanu Nandy, Dwaipayan Biswas, Saptarshi Mukherjee","doi":"10.1002/cphc.202500460","DOIUrl":"https://doi.org/10.1002/cphc.202500460","url":null,"abstract":"<p><p>Bile salts are highly hydrophobic biosurfactants known for their unconventional structure and abnormal micellization properties, which aid in several biological processes. The intrinsic hydrophobicity of bile salts plays a pivotal role during the binding interactions of these molecules with other biomolecules. The inhibition effects of three bile salts, sodium taurocholate (NaTC), sodium cholate (NaC), and sodium deoxycholate (NaDC), on the temperature-induced aggregation of BSA are explored. The results acquired from the Thioflavin T (ThT) assay and circular dichroism (CD) experiments demonstrate that all three bile salts can inhibit the BSA aggregation. Additionally, NaDC can have a prominent aggregation inhibition propensity for BSA compared to the other two bile salts. The inhibitory action of three bile salts toward BSA aggregation followed a particular order, complementing their intrinsic hydrophobicity. Further, binding interactions of native BSA with bile salts are characterized by tryptophan fluorescence emission, fluorescence lifetime studies, site marker studies, isothermal titration calorimetry, and thermal melting experiments. The results of these studies substantiate that bile salts bind to the native protein through strong hydrophobic forces and provide significant stabilization to the native conformation of the protein, which subsequently impedes the protein from aggregating.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500460"},"PeriodicalIF":2.2,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144944399","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":"Cover Feature: Porphyrin–Peptide Conjugates: Functional Self-Assembled Nanomaterials for Biomedical and Energy Conversion Applications (ChemPhysChem 16/2025)","authors":"Sowbhick Patra,&nbsp;Rakesh Gowdihalli Nagaraj,&nbsp;Sourav Moyra,&nbsp;Goutam Ghosh","doi":"10.1002/cphc.70077","DOIUrl":"https://doi.org/10.1002/cphc.70077","url":null,"abstract":"<p><b>The Cover Feature</b> shows sunlight as a symbol of the energy conversion capabilities of the porphyrin–peptide system and its versatile applications in energy transformation, artificial photosynthesis, and biomedical fields. The illustration offers a systematic graphical overview, highlighting molecular design and its broader significance in the scientific community. More information can be found in the Review by G. Ghosh and co-workers (DOI: 10.1002/cphc.202500150).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 16","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.70077","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910232","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular Dynamics Analysis of Adhesion and Debonding Properties of Water-Bearing and Non-Water-Bearing Shale Minerals.","authors":"Mengru Hou, Weiji Sun, Bing Liang, Jianfeng Hao, Yaqian Sui","doi":"10.1002/cphc.202500456","DOIUrl":"https://doi.org/10.1002/cphc.202500456","url":null,"abstract":"<p><p>This study aims to investigate the effects of mineral type and water on the adhesion performance and debonding behavior of shale mineral interface systems. Three representative minerals-quartz, illite, and calcite-were selected to establish mineral interface systems and water/mineral interface systems in molecular dynamics (MD) models. A molecular dynamics (MD) method based on classical Newtonian mechanics was employed to calculate the binding energy, free volume, adhesion work, and debonding work of different interface systems, thereby quantifying the adhesion and debonding properties of various mineral interfaces. Simulation results indicate that the magnitude of the binding energy is correlated with the atomic density of the mineral interface; a higher atomic density results in a larger binding energy. The diffusion capabilities of the three mineral interface systems all increase under humid conditions. Under both dry and humid conditions, the relationship between the adhesion work and desorption work of the three mineral interface systems is as follows: quartz/calcite > calcite/illite > quartz/illite. For the quartz/illite, calcite/illite, and quartz/calcite interface systems, moisture increases the adhesion force of the mineral interface systems by 39.79%, 32.50%, and 15.41%, respectively. This work provides a fundamental understanding of the adhesion and de-adhesion behavior of shale mineral interfaces.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500456"},"PeriodicalIF":2.2,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144944419","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":"Unraveling Ratiometric Chemiluminescence Probe: Theoretical Insights into pH Modulation, Luminescence Dynamics, and Energy Transfer Mechanisms.","authors":"Shuangqi Pi, Ya-Jun Liu","doi":"10.1002/cphc.202500437","DOIUrl":"https://doi.org/10.1002/cphc.202500437","url":null,"abstract":"<p><p>Maintaining a stable physiological pH is essential for the normal functioning of both whole organisms and individual cells. Ratiometric chemiluminescence probes have been widely employed to monitor pH in cells and living organisms due to their high sensitivity, resistance to external interferences, and noninvasiveness. In this study, the working mechanism of a specific ratiometric chemiluminescent probe, Ratio-pHCL-1, is investigated using (time-dependent) density functional theory. The mechanism can be divided into three stages. At first, pH influences the protonation state of Ratio-pHCL-1 in physiological pH range of 6.8-8.4. Subsequently, Ratio-pHCL-1 decomposes to generate the light emitter in the first excited state (S₁) via a gradually reversible charge-transfer initiated luminescence mechanism. Finally, at higher pH values, the intramolecular energy transfer (ET) occurs, resulting in a redshift of the emission wavelength. The redshift of the emission wavelength effectively enhances the luminescence intensity and improves the imaging ability. While at lower pH values, the ET process does not occur. This is the first systematic study on the working mechanism of ratiometric chemiluminescent probes at the molecular and electronic-state levels. The findings can also be extended to understand the mechanism of a class of ratiometric chemiluminescent probes.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500437"},"PeriodicalIF":2.2,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144944557","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":"<ArticleTitle xmlns:ns0=\"http://www.w3.org/1998/Math/MathML\">Effect of Microsolvation on Nonstatistical Behavior of <ns0:math> <ns0:semantics> <ns0:mrow><ns0:msubsup><ns0:mtext>HO</ns0:mtext> <ns0:mrow><ns0:mn>3</ns0:mn></ns0:mrow> <ns0:mrow><ns0:mo>•</ns0:mo></ns0:mrow> </ns0:msubsup> </ns0:mrow> <ns0:annotation>$text{HO}_{3}^{cdot}$</ns0:annotation></ns0:semantics></ns0:math>.","authors":"Philips Kumar Rai, Pradeep Kumar","doi":"10.1002/cphc.202500296","DOIUrl":"https://doi.org/10.1002/cphc.202500296","url":null,"abstract":"<p><p>Hydrotrioxyl radical ( <math> <semantics> <mrow><msubsup><mtext>HO</mtext> <mrow><mn>3</mn></mrow> <mrow><mo>•</mo></mrow> </msubsup> </mrow> <annotation>$text{HO}_{3}^{cdot}$</annotation></semantics> </math> ) is proposed as a transient species in various important atmospheric reactions. One factor that can influence the lifetime of <math> <semantics> <mrow><msubsup><mtext>HO</mtext> <mrow><mn>3</mn></mrow> <mrow><mo>•</mo></mrow> </msubsup> </mrow> <annotation>$text{HO}_{3}^{cdot}$</annotation></semantics> </math> in the atmosphere is its ability to form complexes with water monomers and dimers, i.e., microsolvated systems. In addition, a recent study suggests that the lifetime of <math> <semantics> <mrow><msubsup><mtext>HO</mtext> <mrow><mn>3</mn></mrow> <mrow><mo>•</mo></mrow> </msubsup> </mrow> <annotation>$text{HO}_{3}^{cdot}$</annotation></semantics> </math> is greatly influenced by the non-Rice-Ramsperger-Kassel-Marcus (RRKM) effect, and hence, the role of water complexation in determining the lifetime of <math> <semantics> <mrow><msubsup><mtext>HO</mtext> <mrow><mn>3</mn></mrow> <mrow><mo>•</mo></mrow> </msubsup> </mrow> <annotation>$text{HO}_{3}^{cdot}$</annotation></semantics> </math> is incomplete without estimating the nonstatistical effect in HO₃··(H₂O)_n (n = 1 and 2) complexes. Therefore, in the present work, using direct dynamics simulations along with high-level electronic structure theory, the stability of these microsolvated systems is studied. The investigation suggests that the microsolvation of <math> <semantics> <mrow><msubsup><mtext>HO</mtext> <mrow><mn>3</mn></mrow> <mrow><mo>•</mo></mrow> </msubsup> </mrow> <annotation>$text{HO}_{3}^{cdot}$</annotation></semantics> </math> reduces its lifetime, and the non-RRKM effect is negligible as the system approaches the solution-phase.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500296"},"PeriodicalIF":2.2,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144944614","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":"Insights into Halogen Atom Effects on Donor-Acceptor Complexes in Organic Solar Cells: A Density Functional Theory Study on Quinoxylated Donors Family.","authors":"Alessandro Romo-Gutiérrez, Zuriel Natanael Cisneros-García, Carlos Iván Méndez-Barrientos, Jaime Gustavo Rodriguez-Zavala","doi":"10.1002/cphc.202500412","DOIUrl":"https://doi.org/10.1002/cphc.202500412","url":null,"abstract":"<p><p>This study explores the molecular structures and properties of quinoxaline-based donor materials complexed with highly efficient electron-acceptor molecules in organic solar cells. Employing density functional theory calculations, the interaction between PBQX (X = 5-F, 6-F, 5-Cl, 5-Br, 6-Cl, 6-Br) electron donors and two well-known electron acceptors (Y6 and BTP-4Br) is systematically analyzed. Variations in the halogen atoms of donor compounds are examined to assess their impact on the electronic structure of donor-acceptor complexes. Halogen atoms (F, Cl, Br) in quinoxylated donors influence weak interactions, crucial for charge transport. Since dipole moment and intermolecular electric field play a significant role in molecular packing and exciton separation, they are also studied, predicting the best performance of PBQ6-F compared to PBQ5-F. Generally transition density matrix, hole-electron analysis, and charge transfer states in complexes corroborate the better behavior of PBQ6-F over PBQ5-F. Finally, all these findings are reflected in the kinetic study, carried out through Marcus theory for the different donor-acceptor combinations analyzed in this work, which could have implications for future experimental studies. As demonstrated by systematic studies such as the present one, variations in halogen atoms shed light on to propose possible donor-acceptor combinations in organic solar cells.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500412"},"PeriodicalIF":2.2,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144944475","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}