Interactions of low-energy electrons with the DNA and RNA nucleobases are known to form metastable states, known as electronic resonances. In this work, we study electron attachment to solvated uracil, an RNA nucleobase, using the orbital stabilization method at the Equation of Motion-Coupled Cluster for Electron Affinities with Singles and Doubles (EOM-EA-CCSD) level of theory with the Effective Fragment Potential (EFP) solvation method. We benchmarked the approach using multireference methods, as well as by comparing EFP and full quantum calculations. The impact of solvation on the first one particle (1p) shape resonance, formed by electron attachment to the $pi^*$ LUMO orbital, as well as the first two particle one hole (2p1h) resonance, formed by electron attachment to neutral uracil's $pi$-$pi^*$ excited state, was investigated. We used molecular dynamics simulations for solvent configurations and applied charge stabilization technique-based biased sampling to procure configurations adequate to cover the entire range of the electron attachment energy distribution. The electron attachment energy in solution is found to be distributed over a wide range of energies, between 4.6 eV to 6.8 eV for the 2p1h resonance, and between -0.1 eV to 2 eV for the 1p resonance. The solvent effects were similar for the two resonances, indicating that the exact electron density of the state is not as important as the solvent configurations. Multireference calculations extended the findings showing that solvation effects are similar for the lowest four resonances, further indicating that the specific solute electron density is not as important, but rather the water configurations play the most important role in solvation effects. Finally, by comparing bulk solvation to clusters of uracil with a few water molecules around it, we find that the impact of microsolvation is very different from that of bulk solvation.
{"title":"Impact of Solvation on the Electronic Resonances in Uracil","authors":"Divya Tripathi, Maneesh Pyla, Achintya Dutta, Spiridoula Matsika","doi":"10.1039/d4cp04333b","DOIUrl":"https://doi.org/10.1039/d4cp04333b","url":null,"abstract":"Interactions of low-energy electrons with the DNA and RNA nucleobases are known to form metastable states, known as electronic resonances. In this work, we study electron attachment to solvated uracil, an RNA nucleobase, using the orbital stabilization method at the Equation of Motion-Coupled Cluster for Electron Affinities with Singles and Doubles (EOM-EA-CCSD) level of theory with the Effective Fragment Potential (EFP) solvation method. We benchmarked the approach using multireference methods, as well as by comparing EFP and full quantum calculations. The impact of solvation on the first one particle (1p) shape resonance, formed by electron attachment to the $pi^*$ LUMO orbital, as well as the first two particle one hole (2p1h) resonance, formed by electron attachment to neutral uracil's $pi$-$pi^*$ excited state, was investigated. We used molecular dynamics simulations for solvent configurations and applied charge stabilization technique-based biased sampling to procure configurations adequate to cover the entire range of the electron attachment energy distribution. The electron attachment energy in solution is found to be distributed over a wide range of energies, between 4.6 eV to 6.8 eV for the 2p1h resonance, and between -0.1 eV to 2 eV for the 1p resonance. The solvent effects were similar for the two resonances, indicating that the exact electron density of the state is not as important as the solvent configurations. Multireference calculations extended the findings showing that solvation effects are similar for the lowest four resonances, further indicating that the specific solute electron density is not as important, but rather the water configurations play the most important role in solvation effects. Finally, by comparing bulk solvation to clusters of uracil with a few water molecules around it, we find that the impact of microsolvation is very different from that of bulk solvation.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"40 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055457","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}
Fructosyltransferase (FTase) is a key glycosidase with hydrolytic and transglycosylation functions that can utilize sucrose to generate oligofructose (FOS), which is extremely important in the food industry as well as in plants and microorganisms. However, there remain significant gaps in our understanding of the catalytic mechanism of FTase, particularly regarding the regulatory mechanisms of residues on enzyme catalytic activity. In this study, molecular dynamics simulations and immobilized enzyme catalysis experiments were employed to investigate the structural dynamics and catalytic activity of QU10-FTase. The regulations on the structures and activity of QU10-FTase induced by different environments, including the immobilized Fe3O4 interface and solvent temperatures were characterized. The results show that the catalytic activity of QU10-FTase is suppressed by the immobilized Fe3O4. The all-atom MD simulations revealed that the binding sites of QU10-FTase to the Fe3O4 interface are far away from the catalytic triad, but the structures of the catalytic sites are influenced by the interface binding via an allosteric mechanism. The relationship between structure and catalytic activity of QU10-FTase under different temperatures further demonstrated the allosteric regulation in the FTase. Our results not only give the ability to improve the enzyme activity of QU10-FTase to produce FOS but also provide new insights into the allosteric mechanisms of fructosyltransferase.
{"title":"The allosteric regulation mechanism on the catalytic activity of fructosyltransferase studied by molecular dynamics simulations","authors":"Chaofan Yu, Yanqi Liu, Liang Fu, Zhengyu Shu, Mojie Duan, Yi Zheng","doi":"10.1039/d4cp04131c","DOIUrl":"https://doi.org/10.1039/d4cp04131c","url":null,"abstract":"Fructosyltransferase (FTase) is a key glycosidase with hydrolytic and transglycosylation functions that can utilize sucrose to generate oligofructose (FOS), which is extremely important in the food industry as well as in plants and microorganisms. However, there remain significant gaps in our understanding of the catalytic mechanism of FTase, particularly regarding the regulatory mechanisms of residues on enzyme catalytic activity. In this study, molecular dynamics simulations and immobilized enzyme catalysis experiments were employed to investigate the structural dynamics and catalytic activity of QU10-FTase. The regulations on the structures and activity of QU10-FTase induced by different environments, including the immobilized Fe3O4 interface and solvent temperatures were characterized. The results show that the catalytic activity of QU10-FTase is suppressed by the immobilized Fe3O4. The all-atom MD simulations revealed that the binding sites of QU10-FTase to the Fe3O4 interface are far away from the catalytic triad, but the structures of the catalytic sites are influenced by the interface binding via an allosteric mechanism. The relationship between structure and catalytic activity of QU10-FTase under different temperatures further demonstrated the allosteric regulation in the FTase. Our results not only give the ability to improve the enzyme activity of QU10-FTase to produce FOS but also provide new insights into the allosteric mechanisms of fructosyltransferase.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"39 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050429","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}
The decline in the exploration of new oil sites necessitates the development of efficient strategies to maximize recovery from existing reservoirs. This study employs a Molecular Dynamics (MD) approach to investigate oil detachment from silica surfaces of varying hydrophobicity using a combination of bis-cationic gemini surfactants (GS) and functionalized silica nanoparticles (SNPs). Density profiles and radial distribution function (rdf) plots revealed a multilayered oil adsorption model. A reduction in oil-silica interaction energy was observed with increasing surface hydrophobicity, highlighting the importance of polar interactions. Standard waterflooding studies, involving oil detachment solely with water, were conducted to assess baseline recovery efficiency. All the GS-SNP combinations outperformed standard waterflooding methods. SNPs significantly mitigated GS adsorption on reservoir beds, as evidenced by center-of-mass measurements. However, the effectiveness of the added injectants (GS-SNP) went downhill with increasing surface hydrophobicity, further validating the existence of a potential barrier for oil detachment, as known previously. Finally, supervised Machine Learning (ML) models were generated to predict the GS-SNP combination for a given silica surface, with MD generated descriptors. In most cases, boosting models, viz., XGBoost and AdaBoost yielded best correlation with the observed data. However, for the complex oil model, Ridge regression and Support Vector Regression (SVR) outperformed other ML models in SNP prediction, pointing to the existence of a simpler correlation between the descriptors and the output variable. With these findings, the study attempts to streamline the data-driven design of chemical injectants for Enhanced Oil Recovery purposes.
{"title":"Optimizing Oil Detachment from Silica Surfaces Using Gemini Surfactants and Functionalized Silica Nanoparticles: A Combined Molecular Dynamics and Machine Learning Approach.","authors":"Gourav Chakraborty, Keka Ojha, Ajay Mandal, Niladri Patra","doi":"10.1039/d4cp04724a","DOIUrl":"https://doi.org/10.1039/d4cp04724a","url":null,"abstract":"The decline in the exploration of new oil sites necessitates the development of efficient strategies to maximize recovery from existing reservoirs. This study employs a Molecular Dynamics (MD) approach to investigate oil detachment from silica surfaces of varying hydrophobicity using a combination of bis-cationic gemini surfactants (GS) and functionalized silica nanoparticles (SNPs). Density profiles and radial distribution function (rdf) plots revealed a multilayered oil adsorption model. A reduction in oil-silica interaction energy was observed with increasing surface hydrophobicity, highlighting the importance of polar interactions. Standard waterflooding studies, involving oil detachment solely with water, were conducted to assess baseline recovery efficiency. All the GS-SNP combinations outperformed standard waterflooding methods. SNPs significantly mitigated GS adsorption on reservoir beds, as evidenced by center-of-mass measurements. However, the effectiveness of the added injectants (GS-SNP) went downhill with increasing surface hydrophobicity, further validating the existence of a potential barrier for oil detachment, as known previously. Finally, supervised Machine Learning (ML) models were generated to predict the GS-SNP combination for a given silica surface, with MD generated descriptors. In most cases, boosting models, viz., XGBoost and AdaBoost yielded best correlation with the observed data. However, for the complex oil model, Ridge regression and Support Vector Regression (SVR) outperformed other ML models in SNP prediction, pointing to the existence of a simpler correlation between the descriptors and the output variable. With these findings, the study attempts to streamline the data-driven design of chemical injectants for Enhanced Oil Recovery purposes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"34 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050317","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}
Mechanical interatomic bond formation under ultrahigh pressure induced by laser-driven shock waves has been demonstrated for C–C, C–O, and O–O bonds. In this study, molecules generated in primary amine solutions irradiated with high-intensity lasers were identified. When methylamine or ethylamine was dissolved in methanol or ethanol, molecules likely formed through C–C or O–N bonds between the amine and alcohol were detected. Additionally, molecules thought to be formed through the bonding of amines were confirmed. In mixed solutions of amine and formic acid, the formation of amino acids, such as glycine and alanine, which are presumed to result from C–C bond formation, was also confirmed. The generation of these molecules is attributed to mechanical bond formation due to the ultrahigh pressure generated by laser shock waves. This phenomenon is expected to offer a new perspective on the synthesis of complex organic molecules, particularly in relation to the origins of life in space and on Earth.
{"title":"Synthesis of amino acids in intense laser-irradiated primary amine solutions","authors":"Wakako Ishikawa, Shunichi Sato","doi":"10.1039/d4cp04630g","DOIUrl":"https://doi.org/10.1039/d4cp04630g","url":null,"abstract":"Mechanical interatomic bond formation under ultrahigh pressure induced by laser-driven shock waves has been demonstrated for C–C, C–O, and O–O bonds. In this study, molecules generated in primary amine solutions irradiated with high-intensity lasers were identified. When methylamine or ethylamine was dissolved in methanol or ethanol, molecules likely formed through C–C or O–N bonds between the amine and alcohol were detected. Additionally, molecules thought to be formed through the bonding of amines were confirmed. In mixed solutions of amine and formic acid, the formation of amino acids, such as glycine and alanine, which are presumed to result from C–C bond formation, was also confirmed. The generation of these molecules is attributed to mechanical bond formation due to the ultrahigh pressure generated by laser shock waves. This phenomenon is expected to offer a new perspective on the synthesis of complex organic molecules, particularly in relation to the origins of life in space and on Earth.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050412","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}
Ana-Nicoleta Bondar, Leonid S. Brown, Hideki Kandori, Vladimir Ladizhansky
A graphical abstract is available for this content
{"title":"Festschrift for Judith Herzfeld: spectroscopic and theoretical studies of biomolecules, aqueous solutions, and materials","authors":"Ana-Nicoleta Bondar, Leonid S. Brown, Hideki Kandori, Vladimir Ladizhansky","doi":"10.1039/d4cp90218a","DOIUrl":"https://doi.org/10.1039/d4cp90218a","url":null,"abstract":"A graphical abstract is available for this content","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"22 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050411","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}
Substituted boron-dipyrromethene compounds (BODIPYs) have gained significant attention due to their tunable photophysical properties, including two-photon absorption (2PA), a nonlinear optical process where two photons are absorbed simultaneously. The tuning of BODIPY's photophysical properties has recently led to the synthesis of pnictogen-containing derivatives, such as SBDIPY and BIDIPY, where boron is replaced by antimony (Sb) or bismuth (Bi), respectively, as well as other analogues like GADIPY, which contain gallium (Ga). This study presents a computational investigation into their 2PA properties, exploring the impact of various substitutions across these systems. The 2PA cross-sections (σ2PA), electronic excitation energies (ΔE), and dipole moments (μ00, μ11, μ01, Δμ) were computed for 18 DIPY chromophores in the gas-phase with time-dependent density-functional theory (TD-DFT) using several functionals (CAM-B3LYP, ωB97X, M06-2X, M11, and MN15), and then compared to second-order approximate coupled-cluster with the resolution-of-identity approximation (RI-CC2) results. The computed mean absolute errors were small, with the MN15, CAM-B3LYP, and M06-2X functionals being among the best-performing for the properties analyzed. In general, for the parent (unsubstituted) compounds, replacing the core atom in DIPY chromophores results in negligible changes to their σ2PA. However, extending the conjugation through the addition of phenyl substituents significantly increases σ2PA values, and the nature of the core atom impacts the magnitude of this enhancement.
{"title":"Two-Photon Absorption of BODIPY, BIDIPY, GADIPY, and SBDIPY","authors":"Ismael A. Elayan, Mingmin Zhou, Alex Brown","doi":"10.1039/d4cp03915g","DOIUrl":"https://doi.org/10.1039/d4cp03915g","url":null,"abstract":"Substituted boron-dipyrromethene compounds (BODIPYs) have gained significant attention due to their tunable photophysical properties, including two-photon absorption (2PA), a nonlinear optical process where two photons are absorbed simultaneously. The tuning of BODIPY's photophysical properties has recently led to the synthesis of pnictogen-containing derivatives, such as SBDIPY and BIDIPY, where boron is replaced by antimony (Sb) or bismuth (Bi), respectively, as well as other analogues like GADIPY, which contain gallium (Ga). This study presents a computational investigation into their 2PA properties, exploring the impact of various substitutions across these systems. The 2PA cross-sections (σ<small><sup>2PA</sup></small>), electronic excitation energies (ΔE), and dipole moments (μ<small><sub>00</sub></small>, μ<small><sub>11</sub></small>, μ<small><sub>01</sub></small>, Δμ) were computed for 18 DIPY chromophores in the gas-phase with time-dependent density-functional theory (TD-DFT) using several functionals (CAM-B3LYP, ωB97X, M06-2X, M11, and MN15), and then compared to second-order approximate coupled-cluster with the resolution-of-identity approximation (RI-CC2) results. The computed mean absolute errors were small, with the MN15, CAM-B3LYP, and M06-2X functionals being among the best-performing for the properties analyzed. In general, for the parent (unsubstituted) compounds, replacing the core atom in DIPY chromophores results in negligible changes to their σ<small><sup>2PA</sup></small>. However, extending the conjugation through the addition of phenyl substituents significantly increases σ<small><sup>2PA</sup></small> values, and the nature of the core atom impacts the magnitude of this enhancement.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"148 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050414","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}
On the basis of density functional theory (DFT) calculations and AIMD simulations, a novel Ih-symmetry cage-like molecule N20(C2B2)30 is constructed and characterized computationally. It is found that N20(C2B2)30 is structurally similar to fullerene C20, but it has high thermodynamic and kinetic stability. The designed N20(C2B2)30 exhibits strong chemical reactivities, including the Diels-Alder reaction with butadiene (C4H6) and cyclopentadiene (C5H6), as well as the [3+2] addition reaction with diazomethane (N2CH2). In addition, the presence of the boron site and the inverted C=C bond with the charge-shift (CS) bonding in N20(C2B2)30 makes it quite active not only for cycloaddition reaction but also for capture of small molecules (e.g. H2, CO, NO, and NO2). Once N20(C2B2)30 complexes with a transition metal (TM) ion, the resultant complexes (TM)N20(C2B2)30+ (TM=Cu, Ag, and Au) can bind inactive CO2 and N2O at the TM site. Furthermore, AuN20(C2B2)30+ is able to effectively separate CO2 and N2O. Owing to its unique porous structure and reactivity as well as the high stability, N20(C2B2)30 may further enrich the diversity of highly symmetrical molecular family.
{"title":"High-Symmetry Cage-like Molecule N20(C2B2)30: Computational Insight into Its Bonding and Reactivity","authors":"Miaorun Zhang, Lin Zhang, Zexing Cao, Yi Zhao","doi":"10.1039/d4cp04653f","DOIUrl":"https://doi.org/10.1039/d4cp04653f","url":null,"abstract":"On the basis of density functional theory (DFT) calculations and AIMD simulations, a novel Ih-symmetry cage-like molecule N20(C2B2)30 is constructed and characterized computationally. It is found that N20(C2B2)30 is structurally similar to fullerene C20, but it has high thermodynamic and kinetic stability. The designed N20(C2B2)30 exhibits strong chemical reactivities, including the Diels-Alder reaction with butadiene (C4H6) and cyclopentadiene (C5H6), as well as the [3+2] addition reaction with diazomethane (N2CH2). In addition, the presence of the boron site and the inverted C=C bond with the charge-shift (CS) bonding in N20(C2B2)30 makes it quite active not only for cycloaddition reaction but also for capture of small molecules (e.g. H2, CO, NO, and NO2). Once N20(C2B2)30 complexes with a transition metal (TM) ion, the resultant complexes (TM)N20(C2B2)30+ (TM=Cu, Ag, and Au) can bind inactive CO2 and N2O at the TM site. Furthermore, AuN20(C2B2)30+ is able to effectively separate CO2 and N2O. Owing to its unique porous structure and reactivity as well as the high stability, N20(C2B2)30 may further enrich the diversity of highly symmetrical molecular family.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"26 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055456","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}
Chow-shing Lam, Xi-Guang Wei, Yi PAN, Kai Chung Lau
The energetics of ionization and dissociation of benzylperoxy radical have been investigated using explicitly correlated coupled-cluster methods. The theoretical values for adiabatic ionization energy, 9.331 eV and cationic dissociation barrier, 0.155 eV, harmoniously predict the elusiveness of benzylperoxy radical in the contexts of photoionization and ion-molecule reaction. These properties make it stand out as an exception among unsaturated alkyl peroxy radicals, which typically undergo dissociative ionization. An in-depth scrutiny into the underlying electronic effects resulting in its elusiveness - predictably spanning photoionization mass spectrometry and ion-molecule reaction preparation - has profound implications, calling for a revised view of valence bond perspective. By employing localized intrinsic bond orbital (IBO) methods in the study of benzylperoxy radical cation, we present a case for re-introducing the Linnett double-quartet theory as the missing link between theoretical basis and intuitive mechanisms involving triplet species such as molecular oxygen.
{"title":"Benzylperoxy radical cation: an exceptionally stable and bound species","authors":"Chow-shing Lam, Xi-Guang Wei, Yi PAN, Kai Chung Lau","doi":"10.1039/d4cp03905j","DOIUrl":"https://doi.org/10.1039/d4cp03905j","url":null,"abstract":"The energetics of ionization and dissociation of benzylperoxy radical have been investigated using explicitly correlated coupled-cluster methods. The theoretical values for adiabatic ionization energy, 9.331 eV and cationic dissociation barrier, 0.155 eV, harmoniously predict the elusiveness of benzylperoxy radical in the contexts of photoionization and ion-molecule reaction. These properties make it stand out as an exception among unsaturated alkyl peroxy radicals, which typically undergo dissociative ionization. An in-depth scrutiny into the underlying electronic effects resulting in its elusiveness - predictably spanning photoionization mass spectrometry and ion-molecule reaction preparation - has profound implications, calling for a revised view of valence bond perspective. By employing localized intrinsic bond orbital (IBO) methods in the study of benzylperoxy radical cation, we present a case for re-introducing the Linnett double-quartet theory as the missing link between theoretical basis and intuitive mechanisms involving triplet species such as molecular oxygen.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"21 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044496","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}
Chiara Nania, Francesco Ferrante, Marco Bertini, Laura Gueci, Dario Duca
The use of biomass as renewable feedstock for commodity chemicals may largely benefit from the successful development and application of heterogeneous catalysts for decomposition processes. The present investigation combines density functional theory and Christiansen-like microkinetic analysis to describe, at the atomistic level, the mechanisms related to the conversion of oxygenated biomass compounds to deoxygenated and semi-satured hydrocarbons on a subnanometric Pt10 cluster. The DFT calculations and the kinetic analysis based on the evaluated free energy variations, associated both to elementary steps barriers and to rearrangement/desorption processes occurring on the cluster, suggest that benzene is the preferred product, together with a compound still bearing oxygen, cyclopentadienone, which would form as minor product only at high temperature. Other than highlighting the role of the peculiar interaction between carbon and platinum, the reported investigation underlines the importance of cluster fluxionality and reorganization ability in promoting catalyzed reactions.DFT, biomass, catalytic reaction mechanisms, decomposition.
{"title":"Decomposition of Guaiacol on a Subnanometric Platinum Cluster: A DFT Investigation Followed by Microkinetic Analysis","authors":"Chiara Nania, Francesco Ferrante, Marco Bertini, Laura Gueci, Dario Duca","doi":"10.1039/d4cp04504a","DOIUrl":"https://doi.org/10.1039/d4cp04504a","url":null,"abstract":"The use of biomass as renewable feedstock for commodity chemicals may largely benefit from the successful development and application of heterogeneous catalysts for decomposition processes. The present investigation combines density functional theory and Christiansen-like microkinetic analysis to describe, at the atomistic level, the mechanisms related to the conversion of oxygenated biomass compounds to deoxygenated and semi-satured hydrocarbons on a subnanometric Pt10 cluster. The DFT calculations and the kinetic analysis based on the evaluated free energy variations, associated both to elementary steps barriers and to rearrangement/desorption processes occurring on the cluster, suggest that benzene is the preferred product, together with a compound still bearing oxygen, cyclopentadienone, which would form as minor product only at high temperature. Other than highlighting the role of the peculiar interaction between carbon and platinum, the reported investigation underlines the importance of cluster fluxionality and reorganization ability in promoting catalyzed reactions.DFT, biomass, catalytic reaction mechanisms, decomposition.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"120 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044545","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}
Yuanyuan Lin, Hanzhou Liu, Yaqi Hu, Yang Lu, Zongliang Zhang, Yang Liu, Yongle Chen, Kun Zhang, Shuo Yin, Fangyang Liu
The practical applications of all-solid-state batteries (ASSBs) are hindered by poor Li kinetics in electrodes due to the inadequate contact between the cathode active materials (CAMs) and solid-state electrolytes (SSEs). Therefore, improving the contact interface between CAMs and SSEs is necessary to improve the cathodic Li kinetics by increasing the lithium-ion transport sites. To address this issue, sub-micrometer Li6PS5Cl (SU-LPSC) particles of high specific areas were utilized to fabricate cathodes with high mass loading. SU-LPSC powders can provide fruitful ionic transport pathways by suppressing inert voids in the electrodes, forming conformal contacts. The reduced porosity contributed to the decrease of the ion tortuosity from 3.91 to 1.77. Therefore, the apparent lithium-ion diffusion coefficient improved by nearly 65%. The SU-LPSC-based cathode/LPSC/Li-In battery exhibits good capacity and cycle performance with different cathode loading amounts. Those assembled batteries utilizing SU-LPSC cathode deliver comparable initial discharge capacities of 197.5 mA h g−1 and an initial coulombic efficiency of 82.4% when cycled at 0.1C, and maintain 93.4% at 0.5C after 200 cycles at room temperature. In comparison to the IN-LPSC cathode battery, the capacity retention after 200 cycles is enhanced by 8.7%. This study investigated the sub-micrometer particle sizes of SSEs to determine the Li kinetics in the cathode, reflecting the good performance of ASSBs, providing a valuable reference for designing high-energy cathodes and optimizing composite cathode structures.
{"title":"Sub-micrometer Li6PS5Cl regulated cathodic Li kinetics in sulfide based all-solid-state batteries","authors":"Yuanyuan Lin, Hanzhou Liu, Yaqi Hu, Yang Lu, Zongliang Zhang, Yang Liu, Yongle Chen, Kun Zhang, Shuo Yin, Fangyang Liu","doi":"10.1039/d4cp03893b","DOIUrl":"https://doi.org/10.1039/d4cp03893b","url":null,"abstract":"The practical applications of all-solid-state batteries (ASSBs) are hindered by poor Li kinetics in electrodes due to the inadequate contact between the cathode active materials (CAMs) and solid-state electrolytes (SSEs). Therefore, improving the contact interface between CAMs and SSEs is necessary to improve the cathodic Li kinetics by increasing the lithium-ion transport sites. To address this issue, sub-micrometer Li<small><sub>6</sub></small>PS<small><sub>5</sub></small>Cl (SU-LPSC) particles of high specific areas were utilized to fabricate cathodes with high mass loading. SU-LPSC powders can provide fruitful ionic transport pathways by suppressing inert voids in the electrodes, forming conformal contacts. The reduced porosity contributed to the decrease of the ion tortuosity from 3.91 to 1.77. Therefore, the apparent lithium-ion diffusion coefficient improved by nearly 65%. The SU-LPSC-based cathode/LPSC/Li-In battery exhibits good capacity and cycle performance with different cathode loading amounts. Those assembled batteries utilizing SU-LPSC cathode deliver comparable initial discharge capacities of 197.5 mA h g<small><sup>−1</sup></small> and an initial coulombic efficiency of 82.4% when cycled at 0.1C, and maintain 93.4% at 0.5C after 200 cycles at room temperature. In comparison to the IN-LPSC cathode battery, the capacity retention after 200 cycles is enhanced by 8.7%. This study investigated the sub-micrometer particle sizes of SSEs to determine the Li kinetics in the cathode, reflecting the good performance of ASSBs, providing a valuable reference for designing high-energy cathodes and optimizing composite cathode structures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"47 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044546","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}
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