Physical Chemistry Chemical Physics最新文献

{"title":"Construction of metal-organic nanostructures and their structural transformations on metal surfaces","authors":"Rujia Hou, Chi Zhang, Lei Xu, Yuanqi Ding, Wei Xu","doi":"10.1039/d5cp00030k","DOIUrl":"https://doi.org/10.1039/d5cp00030k","url":null,"abstract":"Metal-organic nanostructures, composed of organic molecules as building blocks and metal atoms as linkers, exhibit high reversibility and flexibility and open up new vistas for the creation of novel metal-organic nanomaterials and the fabrication of functional molecule-based nanodevices. With the rapid development of emerging surface science and scanning probe microscopy, various metal-organic nanostructures, ranging from zero to two dimensions, have been prepared with atomic precision on well-defined metal surfaces in a bottom-up manner and further visualized at the submolecular (or even atomic) level. In such processes, the metal-organic interactions involved and the synergy and competition of multiple intermolecular interactions have been clearly discriminated as the cause of the diversity and preference of metal-organic nanostructures. Moreover, structural transformations can be controllably directed by subtly tuning such intermolecular interactions. In this perspective, we review recent exciting progress in the construction of metal-organic nanostructures on metal surfaces ranging from zero to two dimensions, which is mainly in terms of the selection of metal types (including sources), in other words, different metal-organic interactions formed. Subsequently, the corresponding structural transformations in response to internal or external conditions are discussed, providing mechanistic insights into precise structural control, e.g., by means of metal/molecule stoichiometric ratios (including through scanning probe microscopy (SPM) manipulations), thermodynamic control, introduction of extrinsic competing counterparts, etc. In addition, some other regulatory factors, such as the functionalization of organic molecules and the choice of substrates and lattices, which also crucially govern the structural transformations, are briefly mentioned in each part. Finally, some potential perspectives for metal-organic nanostructures are evoked.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"24 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766426","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Self-propulsion of liquid droplet assemblies controlled by the functionalities of their components","authors":"Rony Mallick, Chiho Watanabe, Shinpei Tanaka","doi":"10.1039/d5cp00597c","DOIUrl":"https://doi.org/10.1039/d5cp00597c","url":null,"abstract":"The self-propulsion of droplet assemblies consisting of droplets of 1-decanol and either an ethyl salicylate (ES) or a composite droplet of ES and liquid polydimethylsiloxane (PDMS) is reported. The ES-PDMS composite droplets have an ES core covered by a PDMS layer that stabilizes the assembly significantly. Their self-propulsion exhibits characteristic predator-prey behavior, with a decanol droplet closely chasing the ES or ES-PDMS composite droplet, forming a bound droplet pair. Furthermore, the stability that PDMS gives the system enables us to construct more complex assemblies, such as two, three, and four decanol droplets closely chasing an ES-PDMS droplet, whose motion patterns depend strongly on the symmetry in the structure of the assemblies. Our findings demonstrate that long-lived assemblies composed of droplets with distinct functionalities can serve as a versatile platform for developing self-organizing and adaptive droplet systems, functioning as \"droplet robots\".","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"22 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766378","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":"Decoding the selective mechanism behind a monobody inhibitor to the phosphatase domain of SHP2: insights from molecular dynamics simulations","authors":"Yang Wang, Mingfei Ji, Linxuan Zhou, Quan Zhang, Xun Lu, Ning Liu, Xiaolong Li, Shaoyong Lu","doi":"10.1039/d5cp00211g","DOIUrl":"https://doi.org/10.1039/d5cp00211g","url":null,"abstract":"Src-homology 2 (SH2) domain-containing phosphatase 2 (SHP2), encoded by PTPN11, is essential for various cellular processes, including proliferation, survival, and migration, making it a significant target in cancer therapy. In contrast, SHP1, another member of the SH2 phosphatase family encoded by PTPN6, plays an inhibitory role in tumorigenesis. Recently, a monobody, Mb (SHP2PTP_13) (Mb13), has been designed to bind to the SHP2-PTP structure specifically. However, the detailed mechanism involved in selective inhibition remains to be clarified. To achieve this objective, we conducted extensive molecular dynamics simulations of the Mb13−SHP2-PTP and Mb13−SHP1-PTP systems, together with multiple analyses, including cluster analysis, principal component analysis, a cross-correlation matrix, analysis of free energy landscapes and calculation of binding free energies. Our results demonstrated that Mb13 bound more stably to SHP2-PTP compared to SHP1-PTP. The SHP2 complex exhibited conformational stability and reduced flexibility, indicating a more substantial interaction. Detailed analysis revealed that key residues within SHP2-PTP formed more robust interactions with Mb13, enhancing the complex’s overall stability. These findings suggested that the selective binding mechanism was primarily driven by specific stabilizing interactions at the molecular level. Overall, the enhanced understanding of SHP2’s binding dynamics and stability offers valuable guidance for designing more effective anticancer drugs targeting SHP2.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"183 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766376","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":"Mesoscopic theory for a double layer capacitance in concentrated ionic systems","authors":"Alina Ciach, Oksana Patsahan","doi":"10.1039/d4cp04669b","DOIUrl":"https://doi.org/10.1039/d4cp04669b","url":null,"abstract":"Effect of an oscillatory decay of the charge density in concentrated ionic solutions and ionic liquids on the double-layer capacitance is studied in a framework of a mesoscopic theory. Only Coulomb and steric forces between the ions that are present in all ionic systems are taken into account. We show that the charge oscillations lead to a rescaled distance between the electrode and the virtual monolayer of counterions in the Helmholtz capacitance, and the scaling factor depends on the period of the charge oscillations. Our very simple formula for large density of ions and small voltage can serve as a reference point for the double layer capacitance in concentrated ionic solutions and ionic liquids, and can help to disentangle the universal and specific contributions to the capacitance in particular systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"16 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766377","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":"Density functional benchmark for quadruple hydrogen bonds","authors":"Usman Ahmed, Mikael P. Johansson, Susi Lehtola, Dage Sundholm","doi":"10.1039/d5cp00836k","DOIUrl":"https://doi.org/10.1039/d5cp00836k","url":null,"abstract":"Hydrogen bonding is an important non-covalent interaction that plays a major role in molecular self-organization and supramolecular structures. It can be described accurately with ab initio quantum chemical wave function methods, which become computationally expensive for large molecular assemblies. Density functional theory (DFT) offers a better balance between accuracy and computational cost, and can be routinely applied to large systems. A large number of density functional approximations (DFAs) has been developed, but their accuracy depend on the application, necessitating benchmark studies to guide their selection for use in applications. Some of us have recently determined highly accurate hydrogen bonding energies of 14 quadruply hydrogen-bonded dimers by extrapolating coupled-cluster energies to the complete basis set limit as well as extrapolating electron correlation contributions with a continued-fraction approach [U. Ahmed et al., Phys. Chem. Chem. Phys., 2024, 26, 24470]. In this work, we study the reproduction of these bonding energies at the DFT level using 152 DFAs. The top ten density functional approximations are composed of eight variants of the Berkeley functionals both with and without dispersion corrections, and two Minnesota 2011 functionals augmented with a further dispersion correction. We find the B97M-V functional with the non-local correlation functional replaced by an empirical D3BJ dispersion correction to be the best DFA, while changes to the dispersion part in other Berkeley functionals lead to poorer performance in our study.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"216 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766420","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":"A study on the construction of spherical MnCO3–Cu2O composites with enhanced electrochemical lithium storage performance","authors":"Lei Wang, Guifen Du, Piyu Gong, Chuansheng Cui, Shuo Tao, Haibo Li, Suyuan Zeng","doi":"10.1039/d4cp04509b","DOIUrl":"https://doi.org/10.1039/d4cp04509b","url":null,"abstract":"In this work, thermodynamic multifunctional MnCO<small>₃</small>–Cu<small>₂</small>O composites with coral sphere shaped and pompon-like microstructures were constructed using a one chemical co-precipitation solvothermal process. The synergistic effect, the pseudocapacitive contribution and the p–n heterojunction enhance the electrochemical lithium storage performance and cycling stability of the formed MnCO<small>₃</small>–Cu<small>₂</small>O composites. At a current density of 2.0 A g<small>⁻¹</small>, the coral sphere shaped MnCO<small>₃</small>–Cu<small>₂</small>O and pompon-like MnCO<small>₃</small>–Cu<small>₂</small>O electrodes exhibit discharge capacities of 804.6 mA h g<small>⁻¹</small> and 650.2 mA h g<small>⁻¹</small> after 400 cycles. The coral sphere shaped MnCO<small>₃</small>–Cu<small>₂</small>O microstructure exhibits excellent electrochemical performance. This study presents a design strategy for the construction of MnCO<small>₃</small>-based composites that can be used in novel lithium-ion batteries.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758497","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":"Size-Selected Anion Photoelectron Spectroscopy and Density Functional Theory Calculations of Ferromagnetic Fe2Cn−/0 (n = 2–6) Clusters","authors":"Xi-Long Li, Zhen-Chao Long, Kai-Wen Liu, Baibai Wan, Xi-Ling Xu, Hong-Guang Xu, Weijun Zheng","doi":"10.1039/d5cp00662g","DOIUrl":"https://doi.org/10.1039/d5cp00662g","url":null,"abstract":"The structural and electronic properties of iron carbide clusters Fe2Cn−/0 (n = 2–6) were investigated using size-selected anion photoelectron spectroscopy and theoretical calculations. The adiabatic and vertical detachment energies of Fe2Cn− (n = 2–6) were obtained from their photoelectron spectra. The ground state structures of Fe2Cn− (n = 2–6) were determined by comparing the theoretical results with the experimental data. The most stable isomers of Fe2Cn− adopt planar structures, except for Fe2C5−, in which the carbon atoms deviate slightly from the plane. The ground state structures of neutral Fe2Cn clusters are generally similar to their corresponding anions, except for Fe2C3, which adopts a planar cyclic structure containing a C3 unit. The magnetic moments of the Fe2Cn− clusters are 7 µB for even sizes and 5 µB for odd sizes, whereas those of neutral Fe2Cn are 8 µB (6 µB for n = 2) for even sizes and 6 µB for odd sizes. The magnetic moments primarily originate from Fe atoms. The Fe–Fe bond lengths increase gradually with the growth of the cluster size, resulting in the transition from double-bond to single-bond character. The spin multiplicities and relative stabilities of Fe2Cn− exhibit odd-even alternations.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"57 5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758503","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":"The Reaction of Sulfenic Acids with OH and HO2 Radicals in different Environments.","authors":"Josep M. Anglada, Ramon Crehuet, Marilia T.C. Martins-Costa, Joseph S Francisco, Manuel F. Ruiz-López","doi":"10.1039/d4cp04106b","DOIUrl":"https://doi.org/10.1039/d4cp04106b","url":null,"abstract":"Sulfenic acids are involved in major chemical processes occurring in the atmosphere, in food chemistry and in biological systems. In these diverse environments, oxidation reactions caused by reactive oxygen species, especially hydroxyl (OH) and hydroperoxyl (HO2) radicals, are very important, but their mechanisms remain poorly understood. To address this question, in this paper we present high-level theoretical results on selected reactions in gas phase and in aqueous solution. The study shows that the abstraction of the acidic hydrogen by OH or HO2 is the most important process in all cases. It leads to the formation of sulfinyl radicals and H2O or H2O2, respectively, following a proton-coupled electron transfer (pcet) mechanism. The associated rate constants depend on sulfenic acid derivative when the oxidizing species is HO2, but all processes are diffusion controlled in the case of reaction with OH. From structurally simple systems to a cysteine-derived model peptide, this work provides a systematic study that contributes to a comprehensive understanding of the reactivity of sulfenic acids with radicals.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"15 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758504","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":"Theoretical Understanding of CO2 Reduction Products on Nitrogen-Doped Graphene Supported Dual-Atom Catalysts","authors":"Chunyuan Feng, Lixiang Zhong","doi":"10.1039/d5cp00875a","DOIUrl":"https://doi.org/10.1039/d5cp00875a","url":null,"abstract":"In recent years, nitrogen-doped graphene supported dual-atom catalysts (DAC@NC) for CO<small>₂</small> reduction reaction (CO<small>₂</small>RR) have attracted widespread research interest. Although some DAC structures for deep reduction C<small>₁</small> products and C<small>₂</small> products have been proposed in previous theoretical calculations, the desired products are still difficult to be realized in experiments. This work systematically investigates the reaction pathways and products of CO<small>₂</small> reduction on bimetallic DAC@NC (M<small>₁</small>-M<small>₂</small>@NC, M<small>₁</small>, M<small>₂</small> = Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, and Pt) by first-principles calculations. After excluding improper M<small>₁</small>-M<small>₂</small>@NC in terms of catalyst poisoning and hydrogen evolution competition, C−C coupling processes always have much higher free-energy increments than the corresponding hydrogenation, making it difficult to form multi-carbon structures. For most of the C<small>₁</small> intermediates on M<small>₁</small>-M<small>₂</small>@NC, the free-energy increments of C−C coupling are higher than 0.8 eV. Some C<small>₁</small> intermediates could couple with a second carbon, but it is much more difficult than hydrogenation toward C<small>₁</small> products. This work reveals why C<small>₂</small> products are still difficult to be achieved for CO<small>₂</small>RR on M<small>₁</small>-M<small>₂</small>@NC, and identifies the M<small>₁</small>-M<small>₂</small> combinations for deep reduction C<small>₁</small> products (methane and methanol), which is inspiring for the future design of CO<small>₂</small>RR catalysts.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"183 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758592","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":"Near Zero Singlet-Triplet Gap Through Nonfullerene Core Modification with Phenalene Derivatives Building Blocks","authors":"Leandro Benatto, Marlus Koehler, Rodrigo Capaz, Graziâni Candiotto","doi":"10.1039/d5cp00767d","DOIUrl":"https://doi.org/10.1039/d5cp00767d","url":null,"abstract":"Recent advances in data-driven machine learning have highlighted the critical importance of the singlet-triplet gap (ΔE<small>_ST</small>=E<small>_S1</small>-E<small>_T1</small>) in non-fullerene acceptors (NFAs) molecules as an useful figure of merit to predict the efficiency of organic photovoltaic devices. By reducing ΔE<small>_ST</small>, the photovoltaic performance can be improved through the suppression of triplet state channels for non-geminate charge recombination. Encouraged by this strategy, we propose and theoretically explore the properties (specially relative to ΔE<small>_ST</small>) of a new class of NFAs derived from modifications of the central core of the Y6 molecule (C<small>₈₂</small>H<small>₈₆</small>F<small>₄</small>N<small>₈</small>O<small>₂</small>S<small>₅</small>). The idea is to replace the benzothiadiazole chemical group by building blocks of phenalene derivatives, recognized for their unique inverted ΔE<small>_ST</small>. Using a computational analysis that incorporates double-hybrid exchange-correlation functional as a benchmark method, we anticipate a remarkable reduction of ΔE<small>_ST</small> upon phenalene derivatives substitution, with some molecules achieving near zero singlet-triplet gap. This is the first report that call attention to new chemical strategies to synthesize NFA molecules with very low (eventually zero) ΔE<small>_ST</small>. Moreover, some modified molecules exhibited higher E<small>_T1</small> compared to Y6, which is interesting to mitigate non-geminate recombination. The molecular modifications also improve the electron transfer properties, such as the intramolecular reorganization energy and the quadrupole moment, leading to more rigid and polarized molecules. The molecular modifications also lead to a decrease in intramolecular reorganization energy, thereby lowering the energy barrier for electron transfer. Additionally, a significant increase in the quadrupole moment component along the π-π stacking direction was observed—an essential property for strengthening quadrupole-quadrupole intermolecular interactions, which play a crucial role in molecular packing and charge transport. Overall, our research yields valuable insights into optimizing NFAs, opening the possibility of alternative molecular architectures to further development of high-efficiency organic photovoltaic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"35 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758501","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}