Chemphyschem最新文献

{"title":"Computational Studies of Enzymes for C-F Bond Degradation and Functionalization.","authors":"Kendra M Cunningham, Wook Shin, Zhongyue J Yang","doi":"10.1002/cphc.202401130","DOIUrl":"10.1002/cphc.202401130","url":null,"abstract":"<p><p>Organofluorine compounds have revolutionized chemical and pharmaceutical industries, serving as essential components in numerous applications and aspects of modern life. However, their bioaccumulation and resistance to degradation have resulted in environmental pollution, posing significant risks to human and animal health. The exceptionally strong C-F bond in these compounds makes their degradation challenging, with current methods often requiring extreme experimental conditions. Therefore, the development of eco-friendly approaches that operate under milder conditions is crucial, with enzyme-mediated C-F bond cleavage strategies emerging as a particularly promising solution. In this review, we present an overview of how computational approaches, including molecular docking, molecular dynamics simulations, quantum mechanics/molecular mechanics calculations, and bioinformatics, have been utilized to investigate the mechanisms underlying enzymatic C-F bond degradation and functionalization. This review highlights how these computational approaches provide critical insights into the atomic-level interactions and energetics underlying enzymatic processes, offering a foundation for the rational design and engineering of enzymes capable of addressing the challenges posed by fluorinated compounds. This review covers several types of enzymes including: fluoroacetate dehalogenases, cysteine dioxygenase, L-2-haloacid dehalogenase, cytochrome P450, fluorinase and tyrosine hydroxylase.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401130"},"PeriodicalIF":2.3,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439996","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: Influence of Atmospheric Gas Species on an Argyrodite-Type Sulfide Solid Electrolyte During Moisture Exposure (ChemPhysChem 4/2025)","authors":"Yusuke Morino,&nbsp;Daisuke Ito,&nbsp;Misae Otoyama,&nbsp;Hikaru Sano","doi":"10.1002/cphc.202580401","DOIUrl":"https://doi.org/10.1002/cphc.202580401","url":null,"abstract":"<p><b>The Front Cover</b> illustrates the effects of various atmospheric gas species on an argyrodite-type sulfide solid electrolyte, Li₆PS₅Cl during moisture exposure, examined by using multiple analytical methods. The electrolyte powder was exposed to different gases: Ar, Ar+CO₂, O₂, and O₂+CO₂, all under a dew point of −20 °C. The generation of H₂S gas was unaffected by the atmospheric gases; however, the conductivity retention of the electrolyte significantly differed. CO₂ exposure promoted the formation of carbonates, whereas O₂ exposure facilitated the formation of phosphates and sulfonates. These reactions led to surface degradation and a consequent reduction in conductivity. More information can be found in the Research Article by Y. Morino, H. Sano and co-workers (DOI: 10.1002/cphc.202400872).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 4","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202580401","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431138","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":"Cover Feature: In Silico Screening of CO2-Dipeptide Interactions for Bioinspired Carbon Capture (ChemPhysChem 4/2025)","authors":"Amarachi G. Sylvanus,&nbsp;Grier M. Jones,&nbsp;Radu Custelcean,&nbsp;Konstantinos D. Vogiatzis","doi":"10.1002/cphc.202580402","DOIUrl":"https://doi.org/10.1002/cphc.202580402","url":null,"abstract":"<p><b>The Cover Feature</b> explores a bioinspired approach to CO₂ capture by using dipeptides. A database of 960 dipeptides was analyzed by automated modeling workflows and quantum chemical methods. Statistical analysis identified amino acid subunits that enhance CO₂ binding through cooperative effects, thus offering insights into designing efficient carbon capture materials. More information can be found in the Research Article by K. D. Vogiatzis and co-workers (DOI: 10.1002/cphc.202400498).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 4","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202580402","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431139","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":"Cover Feature: Microstructure Morphology of Chemical and Structural Phase Separation in Thermally Treated KxFe2-ySe2 Superconductor (ChemPhysChem 4/2025)","authors":"Dr. G. Campi,&nbsp;G. Tomassucci,&nbsp;Dr. M. Tanaka,&nbsp;Dr. H. Takeya,&nbsp;Prof. Y. Takano,&nbsp;Prof. T. Mizokawa,&nbsp;Prof. N. L. Saini","doi":"10.1002/cphc.202580403","DOIUrl":"https://doi.org/10.1002/cphc.202580403","url":null,"abstract":"<p><b>The Cover Feature</b> shows a micro X-ray fluorescence map and spectrum together with a pictorial view of phases characterized by different iron vacancy configurations. In addition to the vacancy-ordered and -disordered phases, an interface configuration appears in the fluorescence map. The microscopic morphology with direct implications on transport can be controlled by heat treatment. More information can be found in the Research Article by G. Campi, N. L. Saini and co-workers (DOI: 10.1002/cphc.202400363).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 4","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202580403","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431140","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":"Wolfium Bonds with π Systems as Electron Donors.","authors":"Heting Wang, Qingzhong Li, Shaoli Liu, Sean A C McDowell","doi":"10.1002/cphc.202401095","DOIUrl":"10.1002/cphc.202401095","url":null,"abstract":"<p><p>The term \"wolfium bond\" is employed to denote attractive interactions between group 6 elements and electron-rich moieties. A theoretical investigation of the wolfium bond involving the compounds WnF₄O or WnF₂O, where Wn represents Cr, Mo or W, and π systems such as C₂H₂, C₂H₄ and C₆H₆, was conducted using density functional theory (DFT) at the ωB97XD/aug-cc-pVTZ level of theory. Interaction energies range from -3.74 to -10.86 kcal/mol upon formation of the π-Wn bond. The electrostatic contributions to the interaction energy were found to be dominant. Notably, the WnF₄O system exhibits greater stability than its WnF₂O counterpart, with the exception of the CrF_xO system. The charge transfer between the interacting molecules lies between 0.0114 and 0.0946e in magnitude. The predominant type of orbital interaction is π_C-C→BD*_Wn-O. Our theoretical investigation revealed the presence of weak, but significant, wolfium bonds between group 6 elements and electron-rich π systems.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401095"},"PeriodicalIF":2.3,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143425019","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":"Intermolecular Interaction, Electronic Structure and Aromaticity of Possible Dimers of Cyclo[18]Carbon (C₁₈).","authors":"Chengli Pan, Zhirong Liu","doi":"10.1002/cphc.202400912","DOIUrl":"10.1002/cphc.202400912","url":null,"abstract":"<p><p>The optimized structures in the configuration space of cyclo[18]carbon (C₁₈) dimers, most of which haven't been studied in detail or even discovered yet, were explored here, and their electronic structure, aromaticity and intermolecular interaction between monomers were thoroughly investigated based on quantum chemistry and various electronic wavefunction analyses. For the dimers bound by weak interaction, their dimerization interactions are contributed mainly by dispersion and less significantly by electrostatic attraction. For those bound by covalent bonds, the symmetry of their geometric structures and hence the degeneracy of out-of-plane and in-plane <math><semantics><mi>π</mi> <annotation>${pi }$</annotation> </semantics> </math> orbitals ( <math> <semantics><msub><mi>π</mi> <mrow><mi>o</mi> <mi>u</mi> <mi>t</mi></mrow> </msub> <annotation>${{pi }_{out}}$</annotation> </semantics> </math> and <math> <semantics><msub><mi>π</mi> <mrow><mi>i</mi> <mi>n</mi></mrow> </msub> <annotation>${{pi }_{in}}$</annotation> </semantics> </math> ) are broken after dimerization. Also predicted are the interesting phenomena including their aromaticity or anti-aromaticity, as well as the spin polarization of their singlet ground states as a result of the distortion of their carbon rings.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400912"},"PeriodicalIF":2.3,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143413521","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":"Synthesis and Modeling of Alloy Nanoparticles","authors":"Daniel Forrer,&nbsp;Tatiana Itina,&nbsp;Vincenzo Amendola","doi":"10.1002/cphc.202500033","DOIUrl":"10.1002/cphc.202500033","url":null,"abstract":"<p>Nanoalloys occupy a focal point of research across many fields as, for instance, catalysis, optics, magnetism, quantum technologies and biomedical materials. This special collection provides a panorama of the research ongoing about their synthesis, modelling and applications.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 8","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202500033","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143413566","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":"Understanding Nanoparticle Electronic Spin-State Dynamics and Properties Using Variable-Temperature, Variable-Field Magnetic Circular Photoluminescence.","authors":"Jane A Knappenberger, Kenneth L Knappenberger","doi":"10.1002/cphc.202401139","DOIUrl":"10.1002/cphc.202401139","url":null,"abstract":"<p><p>Attainment of quantum-confined materials with remarkable stoichiometric, geometric, and structural control has been made possible by advances in colloidal nanoparticle synthesis. The quantum states of these systems can be tailored by selective spatial confinement in one, two, or three dimensions. As a result, a multitude of prospects for controlling nanoscale energy transfer have emerged. An understanding of the electronic relaxation dynamics for quantum states of specific nanostructures is required to develop predictive models for controlling energy on the nanoscale. Variable-temperature, variable-magnetic field ( <math> <semantics><mrow><mi>V</mi> <mi>T</mi> <mi>V</mi> <mover><mi>H</mi> <mo>→</mo></mover> </mrow> <annotation>${{rm V}{rm T}{rm V}mathrel{mathop{{rm H}}limits^{rightarrow }}}$</annotation> </semantics> </math> ) optical methods have emerged as powerful tools for characterizing transient excited states. For example, <math> <semantics><mrow><mi>V</mi> <mi>T</mi> <mi>V</mi> <mover><mi>H</mi> <mo>→</mo></mover> </mrow> <annotation>${{rm V}{rm T}{rm V}mathrel{mathop{{rm H}}limits^{rightarrow }}}$</annotation> </semantics> </math> magnetic circular photoluminescence (MCPL) spectroscopy can be used to calculate electronic g factors, assign spectroscopic term symbols for transitions within metal nanoclusters, and quantify the energy gaps separating electronic fine-structure states. <math> <semantics><mrow><mi>V</mi> <mi>T</mi> <mi>V</mi> <mover><mi>H</mi> <mo>→</mo></mover> </mrow> <annotation>${{rm V}{rm T}{rm V}mathrel{mathop{{rm H}}limits^{rightarrow }}}$</annotation> </semantics> </math> spectroscopic methods are effective for isolating the carrier dynamics of specific quantum fine-structure states, enabling determination of electronic relaxation mechanisms such as electron-phonon scattering and energy transfer between assembled nanoclusters. In particular <math> <semantics><mrow><mi>V</mi> <mi>T</mi> <mi>V</mi> <mover><mi>H</mi> <mo>→</mo></mover> </mrow> <annotation>${{rm V}{rm T}{rm V}mathrel{mathop{{rm H}}limits^{rightarrow }}}$</annotation> </semantics> </math> -MCPL is especially effective for studying electronic spin-state dynamics and properties. This Review highlights specific examples that emphasize insights obtainable from these methods and discusses prospects for future research directions.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401139"},"PeriodicalIF":2.3,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143413567","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":"No Boundaries and Naturally-Defined Boundaries Obtained via the Electrostatic Potential","authors":"Goedele Roos,&nbsp;Danny E. P. Vanpoucke,&nbsp;Jane S. Murray","doi":"10.1002/cphc.202401065","DOIUrl":"10.1002/cphc.202401065","url":null,"abstract":"<p>This paper discusses the use of the electrostatic potential in both recent and older literature, with an emphasis upon a 2022 <i>Molecular Physics</i> article by Politzer and Murray entitled ”Atoms do exist in molecules: analysis using electrostatic potentials at nuclei”. We discuss electrostatic potentials at nuclei and how they easily lead to atoms in molecules, without physically separating the individual atoms. We further summarize the work by the Politzer group on definitions of atomic radii by means of the electrostatic potential. The earlier studies began in the 1970’s and continued through the 1990’s. Unfortunately, access to these older publications is often limited, <i>cfr</i>. digital libraries often limit the authorized access until a certain publication year, and these papers are often not cited in current publications. Although still being highly interesting and relevant, this older literature is in danger of being lost. Digging into this older literature thus opens up new views. Our feeling is that Peter passed ‘on’ a vision that boundaries do not exist between atoms in molecules, but that some useful and meaningful radii can be obtained using the electrostatic potential between atoms in molecules.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 7","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143413565","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":"Photophysical and Time-resolved Infrared Properties of Long-Lived Rhenium(I) 4,5-Diazafluorene Tricarbonyl Chromophores.","authors":"Reem T Alameh, Michael C Rosko, Evgeny O Danilov, Nicolas Durand, Felix N Castellano","doi":"10.1002/cphc.202500008","DOIUrl":"10.1002/cphc.202500008","url":null,"abstract":"<p><p>This report investigates the synthesis, structural characterization, fundamental molecular photophysics, electrochemistry, UV-Vis spectroelectrochemistry, and time-resolved infrared spectroscopic properties of eight [fac-Re(dafR)(CO)₃L]^0/+ complexes, where R=ethyl [(dedaf); 1, 3, 5, 7] or H [(dafH); 2, 4, 6, 8] and L=Cl^- (1, 2), imidazole [(Im); 3, 4], 4-ethylpyridine [(4-Etpy); 5, 6], or pyridine [(py); 7, 8]. Universally, 1-8 yield higher energy photoluminescence (PL) emission bands and higher PL quantum yields (up to 53 %) than the classic 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) ligated Re(I) tricarbonyl complexes. The excited state lifetimes of 1-8 lie between those corresponding to the bpy and phen derivatives, ranging from 120 and 1300 ns at room temperature. Combinations of reductive UV-Vis spectroelectrochemistry, transient absorption spectroscopy, and time-resolved infrared spectroscopy consistently assigned the lowest excited states in 1-8 being of metal-to-ligand charge transfer (MLCT) character. These new Re^I MLCT chromophores follow classic energy gap law behavior and possess the characteristics necessary for serving as valuable photosensitizers suitable to energize excited state electron and energy transfer photochemistry.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500008"},"PeriodicalIF":2.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143398476","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}