ChemphyschemPub Date : 2024-11-24DOI: 10.1002/cphc.202400820
Bahareh Taghavi Shahraki, Mazdak Khajehpour
{"title":"Understanding Ion-Specific \"Hofmeister\" Effects in Enzyme Catalysis Through Using RNase A as a Paradigm Model.","authors":"Bahareh Taghavi Shahraki, Mazdak Khajehpour","doi":"10.1002/cphc.202400820","DOIUrl":"https://doi.org/10.1002/cphc.202400820","url":null,"abstract":"<p><p>Biophysical studies in the last two decades demonstrate that salts affect biomolecules in an ion-specific manner. Diverse biological processes such as protein folding, protein precipitation, protein coacervation and phase separation, and protein oligomerization, all show that this ion specificity directly relates to how individual ions interact with biomolecular surfaces. Interestingly, although ion-specific effects upon enzyme catalytic processes are well-known in the literature, a molecular level description of these effects is not yet available. This work addresses this need by investigating ion-specific effects upon the enzymatic activity and stability of RNase A. We have developed a robust framework to analyze and quantify ion-specific effects upon the RNase A catalyzed phosphate ring opening reaction of cCMP. Both the folding thermodynamics and the Michaelis-Menten kinetic parameters of this enzyme show ion-specificity. However, these effects are not necessarily directly related to each other. Ion-specific effects observed in protein folding reflects mostly how an individual ion interacts with the overall protein surface; while alternatively, ion-specific effects on enzyme activity indicate how a given ion interacts with the enzyme active site surface or alternatively, how ions interact with the substrate molecule as represented by changes in the substrate thermodynamic activity coefficient.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400820"},"PeriodicalIF":2.3,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142709173","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}
ChemphyschemPub Date : 2024-11-22DOI: 10.1002/cphc.202400919
Bharat Bhushan Sharma, Anjana Kedare, Girish Muralidharan, Ananth Govind Rajan
{"title":"Understanding the Effects of Surface and Edge Functionalization on the Mechanical Properties of Graphene and Graphene Oxide.","authors":"Bharat Bhushan Sharma, Anjana Kedare, Girish Muralidharan, Ananth Govind Rajan","doi":"10.1002/cphc.202400919","DOIUrl":"https://doi.org/10.1002/cphc.202400919","url":null,"abstract":"<p><p>Graphene oxide (GO) is a widely used 2D material employed in various applications due to its tunable properties. Understanding its mechanical properties is crucial to develop polymeric nanocomposites. We employ reactive molecular dynamics simulations to understand the effects of surface and edge functionalization of carbon atoms on the mechanical strength and fracture morphology of graphene and GO. We vary the extent of functionalization of hydroxyl and epoxy groups between 0.1%-70% on the GO surface and find that the tensile strength decreases with increasing functionalization. Nevertheless, there exists an optimal level of surface functionalization of 15-20% where the tensile strength of pristine graphene is retained. Additionally, we find that functionalization alters the fracture morphology from brittle to mild ductile, which is desirable in engineering applications. We also show that the edge functionalization of finite-size graphene nanosheets transfers the failure nucleation sites from the edges to the bulk, although the tensile strength decreases due to increased buckling. Interestingly, the decrement in tensile strength due to surface functionalization is larger as compared to edge functionalization. Overall, this work highlights the possibility of customizing GO's mechanical properties through targeted surface and edge functionalization, paving the way for its controlled application in nanocomposites.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400919"},"PeriodicalIF":2.3,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142692816","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}
ChemphyschemPub Date : 2024-11-21DOI: 10.1002/cphc.202400887
Johannes Henrichsmeyer, Michael Thelen, Reinhold F Fink
{"title":"What is the exchange-repulsion energy? Insight by partitioning into physically meaningful contributions.","authors":"Johannes Henrichsmeyer, Michael Thelen, Reinhold F Fink","doi":"10.1002/cphc.202400887","DOIUrl":"https://doi.org/10.1002/cphc.202400887","url":null,"abstract":"<p><p>It is shown that the exchange repulsion energy, Exr, can be rationalized by partitioning the respective energy expression for two systems with Hartree-Fock orbitals into physically meaningful contributions. A division of Exr into a positive kinetic and a negative potential part is possible, but these contributions correlate only poorly with the actual exchange repulsion energy. A more meaningful partitioning is derived, where all kinetic energy contributions are collected in a term that vanishes for exact Hartree-Fock orbitals due to their stationarity conditions. The remaining terms can be distinguished into an exchange integral contribution as well as contributions to the repulsion energy with two, three and four orbital indices. The forms, relationships and absolute sizes of these terms suggest an intuitive partitioning of the exchange repulsion energy into Molecular Orbital Pair Contributions to the Exchange repulsion energy (MOPCE). Insight into the analytic form and quantitative size of these contributions is provided by considering the 3Σ+u (1σg1σu) state of the H2 molecule, the water dimer, as well as an argon atom interacting with Cl2 and N2.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400887"},"PeriodicalIF":2.3,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142686119","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}
ChemphyschemPub Date : 2024-11-21DOI: 10.1002/cphc.202400852
Jacob Dickinson Teeter, Daniel P Miller, Stefan Müllegger
{"title":"Stable π Radical BDPA: Adsorption on Cu(100) and Survival of Spin.","authors":"Jacob Dickinson Teeter, Daniel P Miller, Stefan Müllegger","doi":"10.1002/cphc.202400852","DOIUrl":"https://doi.org/10.1002/cphc.202400852","url":null,"abstract":"<p><p>The adsorption of the radical α,γ-bisdiphenylene-β-phenylallyl (BDPA) molecule to the Cu(100) surface was studied using scanning tunnelling microscopy (STM), scanning tunnelling spectroscopy (STS), and density functional theory (DFT) calculations accounting for dispersion forces. BDPA on Cu(100) was observed to align preferentially along [[EQUATION]] directions due to weak Cu-C chemisorption between fluorenyl carbons with the underlying copper atoms. The curved shape of the BDPA molecule on Cu(100) can be ascribed to the lack of molecular orbital character on the phenyl substituent. A Kondo-like feature from differential conductance (dI/dV) measurements centered close to the Fermi energy ([[EQUATION]]) suggests the retention of an electron spin-½ state, which is corroborated by hybrid DFT calculations that place the SOMO below and SUMO above EF for Cu(100).</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400852"},"PeriodicalIF":2.3,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142680829","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}
ChemphyschemPub Date : 2024-11-21DOI: 10.1002/cphc.202400878
Lars Henrik Andersen, Nikolaj Klinkby, Anne Pilgaard Rasmussen, Anders G S Lauridsen
{"title":"Absorption and Excited-State Coherences of Cryogenically Cold Retinal Protonated Schiff Base in Vacuo.","authors":"Lars Henrik Andersen, Nikolaj Klinkby, Anne Pilgaard Rasmussen, Anders G S Lauridsen","doi":"10.1002/cphc.202400878","DOIUrl":"https://doi.org/10.1002/cphc.202400878","url":null,"abstract":"<p><p>Retinal protonated Schiff base (RPSB), found in its all-trans conformer in Bacteriorhodopsin, undergoes barrier-controlled isomerization upon photoabsorption through polyene- chain torsion. The effects of the protein environment on the active vibrations during photoabsorption and their redistribution are still not understood. This paper reports on femtosecond time-resolved action-absorption measurements of cryogenically cooled gas-phase all-trans RPSB, which exhibit two coherent vibrational oscillations, 167(14) cm-1 and 117(1) cm-1, of the first excited state with dephasing times of ∼ 1 ps. The absence of the high-frequency vibration in solution and the low-frequency vibration in the protein indicates that these vibrations are sensitive to environments. An action-absorption spectrum of cryogenically cold all-trans RPSB, reveals a ∼ 310 cm-1 active vibration when using a hole-burning technique and 1500 cm-1 C=C stretching modes.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400878"},"PeriodicalIF":2.3,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142680828","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}
ChemphyschemPub Date : 2024-11-20DOI: 10.1002/cphc.202400881
Wenhao Sun, Denis Kargin, Zsolt Kelemen, Rudolf Pietschnig, Melanie Schnell
{"title":"Unraveling the stereoisomer configurations of 1,1'-bis(tert-butylphosphino)ferrocene in the gas phase.","authors":"Wenhao Sun, Denis Kargin, Zsolt Kelemen, Rudolf Pietschnig, Melanie Schnell","doi":"10.1002/cphc.202400881","DOIUrl":"https://doi.org/10.1002/cphc.202400881","url":null,"abstract":"<p><p>The molecular structure of a ferrocene derivative with adjacent centers of chirality, 1,1'-bis(tert - butylphosphino)ferrocene, has been examined in the gas phase using broadband microwave spectroscopy under the isolated and cold conditions of a supersonic jet. The diastereomers of 1,1'-bis(tert-butylphosphino)ferrocene can adopt homo- and hetero-chiral configurations, owing to the P-chiral substituents on the cyclopentadienyl rings. Moreover, the internal ring rotation of each diastereomer gives rise to four conformers with eclipsed ring arrangements, where the two tert-butylphosphino groups were separated by dihedral angles of approximately 72◦, 144◦, 216◦, and 288◦ with respect to the two ring centers. The interconversion barriers between the conformations are below 2 kJ/mol, whereas the pyramidal inversion of the tert-butylphosphino groups is hindered by more than 140 kJ/mol, calculated at the B3LYP-D3(BJ)/def2-QZVP level of theory. In the experimental microwave spectrum, we unambiguously identified the two global-minimum diastereomers with 72◦ conformations. The absence of other conformers can be attributed to the relaxation dynamics in the supersonic jet, which transfers the high-energy conformers to the respective global-minimum geometries. Additionally, we discovered that London dispersion inter- actions between the two tert-butylphosphino groups play a crucial role in stabilizing the structures of this ferrocene complex.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400881"},"PeriodicalIF":2.3,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142680832","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}
ChemphyschemPub Date : 2024-11-20DOI: 10.1002/cphc.202400948
Snežana D Zarić, Sonja S Zrilić, Dragan B Ninković, Mihajlo Etinski
{"title":"Perturbational and variational energy decomposition analysis on hydrogen bonds of coordinated glycine with water molecule.","authors":"Snežana D Zarić, Sonja S Zrilić, Dragan B Ninković, Mihajlo Etinski","doi":"10.1002/cphc.202400948","DOIUrl":"https://doi.org/10.1002/cphc.202400948","url":null,"abstract":"<p><p>Three types of hydrogen bonds of coordinated glycine and water had been investigated: NH/O of α-amino group, O1/HO involving oxygen coordinated to the metal ion (O1), and O2/HO involving α-carbonyl oxygen (O2). Various glycine complexes were investigated: octahedral cobalt(III) and nickel(II), square pyramidal copper(II), and square planar copper(II), palladium(II), and platinum(II) complexes. Nature of these three hydrogen bond types was analysed using symmetry-adapted perturbation theory (SAPT) and variational energy decomposition analysis (EDA) method (TPSS-D3/def2-TZVPP). The results of the EDA decomposition are in good agreement with the reliable SAPT2+3/def2-TZVPP and its total interaction values with CCSD(T)/CBS energies. Electrostatic interaction is generally the dominant attractive energy term in most of the interactions, followed by orbital relaxation, and lastly dispersion as the weakest. We compared EDA results of various complexes to determine the effects of complex charge, metal oxidation, coordination, and atomic number on the energy decomposition terms. The complex charge influences the values of decomposition terms the most, followed by metal oxidation and coordination number, while atomic number effects them the least. All complex and metal changes have a more significant effect on the results of NH/O and O1/HO then O2/HO interactions, due to its location further away from the metal ion.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400948"},"PeriodicalIF":2.3,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674724","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}
ChemphyschemPub Date : 2024-11-20DOI: 10.1002/cphc.202400941
Benjamin Rhodes, Lars Schaaf, Mary Zick, Suzi Pugh, Jordon Hilliard, Shivani Sharma, Casey Wade, Phillip Milner, Gábor Csányi, Alexander Forse
{"title":"17O NMR spectroscopy reveals CO2 speciation and dynamics in hydroxide-based carbon capture materials.","authors":"Benjamin Rhodes, Lars Schaaf, Mary Zick, Suzi Pugh, Jordon Hilliard, Shivani Sharma, Casey Wade, Phillip Milner, Gábor Csányi, Alexander Forse","doi":"10.1002/cphc.202400941","DOIUrl":"https://doi.org/10.1002/cphc.202400941","url":null,"abstract":"<p><p>Carbon dioxide capture technologies are set to play a vital role in mitigating the current climate crisis. Solid-state 17O NMR spectroscopy can provide key mechanistic insights that are crucial to effective sorbent development. In this work, we present the fundamental aspects and complexities for the study of hydroxide-based CO2 capture systems by 17O NMR. We perform static density functional theory (DFT) NMR calculations to assign peaks for general hydroxide CO2 capture products, finding that 17O NMR can readily distinguish bicarbonate, carbonate and water species. However, in application to CO2 binding in two test case hydroxide-functionalised metal-organic frameworks (MOFs): MFU-4l and KHCO3-cyclodextrin-MOF, we find that a dynamic treatment is necessary to obtain agreement between computational and experimental spectra. We therefore introduce a workflow that leverages machine-learning forcefields to capture dynamics across multiple chemical exchange regimes, providing a significant improvement on static DFT predictions. In MFU-4l, we parameterise a two-component dynamic motion of the bicarbonate motif involving a rapid carbonyl seesaw motion and intermediate hydroxyl proton hopping. For KHCO3-CD-MOF, we combined experimental and modelling approaches to propose a new mixed carbonate-bicarbonate binding mechanism and thus, we open new avenues for the study and modelling of hydroxide-based CO2 capture materials by 17O NMR.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400941"},"PeriodicalIF":2.3,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674718","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}
ChemphyschemPub Date : 2024-11-19DOI: 10.1002/cphc.202400936
Raoul D Brand, Mareike Maass, Anatoliy G Grebenyuk, Alexander A Golub, Bernd M Smarsly
{"title":"Commercial silica materials functionalized with a versatile organocatalyst for the catalysis of acylation reactions in liquid media.","authors":"Raoul D Brand, Mareike Maass, Anatoliy G Grebenyuk, Alexander A Golub, Bernd M Smarsly","doi":"10.1002/cphc.202400936","DOIUrl":"https://doi.org/10.1002/cphc.202400936","url":null,"abstract":"<p><p>Silica materials represent a promising material for the application in heterogeneous organocatalysis due to their readily modifiable surface and chemical inertness. To achieve high catalyst loadings, usually, porous carriers with high surface areas are used, such as special silica monoliths or spherical particles for backed bed reactors. Yet, their synthesis is elaborate, and thus less complex and cheaper alternatives are of interest, especially considering scaling up. In this work, two commercial silica materials functionalized with the organocatalyst 4-(dimethylamino)pyridine (DMAP) were used in catalytic acylation reactions: a mesoporous silica gel (Siliabond®-DMAP) and non-porous silica nanoparticles (Ludox®). Both were successfully used in the acylation of phenylethanol, but the latter required significantly longer reaction times, presumably due to mass-transfer limitations as a consequence of substantial agglomeration that limits the accessible amount of catalyst. Furthermore, it was shown that the influence of the linker molecule is negligible, since both reaction yields and the activation energy remain largely similar. As main result the commercial material Siliabond-DMAP, despite the non-uniform particles, exhibited significant yield in a flow setup, thus demonstrating the potential as support material for application in heterogeneous organocatalysis.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400936"},"PeriodicalIF":2.3,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674722","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}
ChemphyschemPub Date : 2024-11-19DOI: 10.1002/cphc.202482202
M. Johnsi, V. J. Asha Shalini, M. Azhagulakshmi, B. Kavin Kumar, N. Balasubramanian
{"title":"Cover Feature: Exploration of Optimization Strategies for Locking Sulfur in 2D Layered/Polymer-Enveloped Cathode Composite for High Power Li-S Batteries (ChemPhysChem 22/2024)","authors":"M. Johnsi, V. J. Asha Shalini, M. Azhagulakshmi, B. Kavin Kumar, N. Balasubramanian","doi":"10.1002/cphc.202482202","DOIUrl":"https://doi.org/10.1002/cphc.202482202","url":null,"abstract":"<p><b>Sulfur-locked cathode: gotcha, polysulfides</b>! The Cover Feature illustrates a metal–sulfur battery cathode with polysulfide adsorption active sites enabled by a sulfur-infused, polymer-enveloped cathode that could boost electron conductivity and redox kinetics. More information can be found in the Research Article by N. Balasubramanian and co-workers (DOI: 10.1002/cphc.202400415).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"25 22","pages":""},"PeriodicalIF":2.3,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202482202","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142707734","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}