Computational and Theoretical Chemistry最新文献_第10页

Structural studies, solubility, and aqueous solvation of Vitamin B6 using Car-Parrinello Molecular Dynamics 利用Car-Parrinello分子动力学研究维生素B6的结构、溶解度和水溶液溶剂化

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-08-09 DOI: 10.1016/j.comptc.2025.115411

Wilson R.L. Filho , Lóide O. Sallum , Yago F. Lopes , Lilian T.F. de M. Camargo , Allane C.C. Rodrigues , Ademir.J. Camargo

{"title":"Structural studies, solubility, and aqueous solvation of Vitamin B6 using Car-Parrinello Molecular Dynamics","authors":"Wilson R.L. Filho , Lóide O. Sallum , Yago F. Lopes , Lilian T.F. de M. Camargo , Allane C.C. Rodrigues , Ademir.J. Camargo","doi":"10.1016/j.comptc.2025.115411","DOIUrl":"10.1016/j.comptc.2025.115411","url":null,"abstract":"<div><div>This study aims to elucidate the influence of an aqueous environment on the geometric and electronic properties of pyridoxine through CPMD simulations. The supramolecular arrangement in the crystalline state was investigated using HS analysis, complemented by cohesive energy calculations comparing the solid and solution phases to understand the dissolution process. Helmholtz free energy calculations confirm that these interactions are thermodynamically favorable, with geometric analysis classifying them as moderately strong hydrogen bonds. Topological analysis of the electronic density revealed that two of these interactions range from weak to moderate in strength after stabilization, while the remaining two vary from weak to strong. HS analysis highlighted the presence of significant intermolecular hydrogen bonds, which are responsible for the formation of a zigzag-shaped, sheet-like crystalline network structure. Cohesive energy assessments support the experimental observation of pyridoxine's solubility in water. These findings provide valuable insights into the molecular behavior of vitamin B6 in solution, thereby enhancing our understanding of its chemical properties and biological activities.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1253 ","pages":"Article 115411"},"PeriodicalIF":3.0,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144826639","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}

引用次数: 0

Dynamic mediation 4f electron configurations in cerium monosulfide via temperature-dependent many-body effects 温度相关多体效应对单硫化铈中4f电子构型的动态中介作用

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-08-09 DOI: 10.1016/j.comptc.2025.115424

Ru-song Li , Rong Guo , Zheng Xie , Jin-tao Wang , Fei Wang

引用次数: 0

Mono-substituent effect of Al13, BO2, and BF4 superhalogens on the structure, electronic properties, and chemical reactivity of cisplatin: A DFT study Al13、BO2和BF4超卤素对顺铂结构、电子性质和化学反应性的单取代效应：DFT研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-08-09 DOI: 10.1016/j.comptc.2025.115417

Xin Cheng , Wei-Ming Sun , Qi-Jing Lin , Dan Yu , Jianping Zheng

{"title":"Mono-substituent effect of Al13, BO2, and BF4 superhalogens on the structure, electronic properties, and chemical reactivity of cisplatin: A DFT study","authors":"Xin Cheng , Wei-Ming Sun , Qi-Jing Lin , Dan Yu , Jianping Zheng","doi":"10.1016/j.comptc.2025.115417","DOIUrl":"10.1016/j.comptc.2025.115417","url":null,"abstract":"<div><div>Substituting the ligands of cisplatin is recognized as a significant strategy to create new platinum-based antitumor drugs. In this study, the mono-substituent effect of three typical superhalogens, namely Al<sub>13</sub>, BO<sub>2</sub>, and BF<sub>4</sub>, on the structure, electronic properties, and chemical reactivity of cisplatin has been investigated with the assistance of density functional theory (DFT). The mono-substitution of superhalogens for one chlorine ligand of cisplatin results in the formation of a weakly polar covalent bond in Pt-Al<sub>13</sub> and the strong polar covalent bonds in Pt-BO<sub>2</sub> and Pt-BF<sub>4</sub>. Interestingly, the energy barriers for the hydrolysis of superhalogen ligands of Pt-BO<sub>2</sub> and Pt-BF<sub>4</sub> are lower than that for the hydrolysis of Cl ligand of cisplatin, suggesting that these two derivatives may have enhanced biological activity. Thereby, this study provides a superhalogen-substituent strategy to develop analogues of cisplatin with improved anticancer activity from a theoretical point of view.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1253 ","pages":"Article 115417"},"PeriodicalIF":3.0,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144890829","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}

引用次数: 0

Structural stability and thermodynamic properties of (La2O3)n (n = 1–7) clusters system based on density functional theory 基于密度泛函理论的（La2O3）n （n = 1-7）团簇体系的结构稳定性和热力学性质

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-08-07 DOI: 10.1016/j.comptc.2025.115407

Ziyi Lai , Tangping Dan , ZiXin Huang , Xin Jiang , Xuanwei Lei , Min Liu , Chaobin Lai

{"title":"Structural stability and thermodynamic properties of (La2O3)n (n = 1–7) clusters system based on density functional theory","authors":"Ziyi Lai , Tangping Dan , ZiXin Huang , Xin Jiang , Xuanwei Lei , Min Liu , Chaobin Lai","doi":"10.1016/j.comptc.2025.115407","DOIUrl":"10.1016/j.comptc.2025.115407","url":null,"abstract":"<div><div>The initial configurations of nano‑lanthanum oxide clusters (La<sub>2</sub>O<sub>3</sub>)<sub>n</sub> (<em>n</em> = 1–7) were constructed using a combination of the artificial bee colony algorithm and density functional theory. For the first time, the medium-sized cluster structure with seven lanthanum oxide molecules was established. By optimizing different structures and calculating the vibration frequency, many new configurations different from previous studies were obtained. The average binding energy, second-order difference energy, HOMO-LUMO energy gap, density of states, and molecular orbital properties of the cluster system were analyzed. On this basis, the thermodynamic properties and behavior of nano‑lanthanum oxide clusters under different temperature and molecular number conditions were discussed. The results show that with an increase in the number of molecules, the cluster structure gradually changes from cage-like to spatial ladder-like, and finally to ellipsoid-like. The nanoclusters are stable overall, with relatively higher stability when <em>n</em> = 2,4, and the effect of the lanthanum oxygen atomic orbital on the molecular orbital of the cluster is analyzed. The Cv, Cp, S, and H of (La<sub>2</sub>O<sub>3</sub>)<sub>n</sub> (<em>n</em> = 1–7) clusters increase with temperature, and increase with the number of molecules, while G and Gv decrease with temperature, with changes in the number of molecules greatly affected by E (0 K) and T. The thermodynamic properties of lanthanum oxide clusters with larger molecular numbers are more sensitive to temperature changes. The results provide a theoretical basis for the evolution mechanism of lanthanum oxide clusters-crystals and valuable information for further study of the growth law of rare earth oxide molecular clusters.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1253 ","pages":"Article 115407"},"PeriodicalIF":3.0,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144865047","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}

引用次数: 0

Optimization of Cs-O and Cs-NF3 adsorption on As-rich and Ga-rich GaAs(100) photocathode surfaces: An ab-initio study 富as和富ga GaAs（100）光电阴极表面对Cs-O和Cs-NF3吸附的优化研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-08-07 DOI: 10.1016/j.comptc.2025.115420

Kaimin Zhang , Yijun Zhang , Jingzhi Zhang , Xindi Ma , Song Tang , Shiman Li , Feng Shi , Xin Guo , Yunsheng Qian , Cheng Feng

{"title":"Optimization of Cs-O and Cs-NF3 adsorption on As-rich and Ga-rich GaAs(100) photocathode surfaces: An ab-initio study","authors":"Kaimin Zhang , Yijun Zhang , Jingzhi Zhang , Xindi Ma , Song Tang , Shiman Li , Feng Shi , Xin Guo , Yunsheng Qian , Cheng Feng","doi":"10.1016/j.comptc.2025.115420","DOIUrl":"10.1016/j.comptc.2025.115420","url":null,"abstract":"<div><div>Based on density functional theory, the preferred adsorption sites and ratios of Cs-O and Cs-NF<sub>3</sub> adsorption on GaAs(100) β<sub>2</sub>(2 × 4) As-rich surface and β<sub>2</sub>(4 × 2) Ga-rich surface were explored. For Cs-O adsorption, 6Cs-3O-adsorbed As-rich surface with lowest O adsorption energy and 8Cs-6O-adsorbed Ga-rich surface yield the lowest work function values. For Cs-NF<sub>3</sub> adsorption, 6Cs-1NF<sub>3</sub> configurations minimize the work function on both surfaces, excess NF<sub>3</sub> increase work function, whereas 8Cs-1NF<sub>3</sub> configuration on Ga-rich surface show the most negative NF<sub>3</sub> adsorption energy. Residual gases increase work function, with CO<sub>2</sub> adsorbing stably and H<sub>2</sub> having minimal effect. Notably, 6Cs-3O-adsorbed As-rich surface and 8Cs-1NF<sub>3</sub>-adsorbed Ga-rich surface exhibit superior resistance to residual gases. Charge transfer analysis reveals that surface Ga/As charges depend on reconstruction and adsorbate ratios, Cs atoms mediate charge redistribution between adsorbates and the surface, influencing dipole moments and work function. These findings improve understanding of optimal Cs-O and Cs-NF<sub>3</sub> activation configurations on GaAs photocathodes.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1253 ","pages":"Article 115420"},"PeriodicalIF":3.0,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144809819","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}

引用次数: 0

Insights into mechanism and selectivity in palladium-catalyzed oxidative carbocyclization-borylation of enallenes via olefin assistance 钯催化烯烯烯氧化碳环化-烯烃辅助硼化的机理和选择性研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-08-06 DOI: 10.1016/j.comptc.2025.115418

Huimin Xu, Zhiqing Zhao, Ying Ren , Jianfeng Jia , Hai-Shun Wu

{"title":"Insights into mechanism and selectivity in palladium-catalyzed oxidative carbocyclization-borylation of enallenes via olefin assistance","authors":"Huimin Xu, Zhiqing Zhao, Ying Ren , Jianfeng Jia , Hai-Shun Wu","doi":"10.1016/j.comptc.2025.115418","DOIUrl":"10.1016/j.comptc.2025.115418","url":null,"abstract":"<div><div>A systematic theoretical study has been carried out with the aid of density functional theory calculations on the mechanism for the Pd-catalyzed oxidative carbocyclization-borylation of enallenes. Our computational analysis reveals that the catalytic cycle comprises four principal stages, including C<img>H bond activation, olefin insertion, transmetalation, and reductive elimination. The reaction initiates via C(sp<sup>3</sup>)<img>H activation through a concerted metalation-deprotonation pathway, generating a vinylpalladium intermediate. Stereochemical control is governed by the regioselectivity of alkene insertion: proximal insertion leads to spirocyclic products, whereas distal insertion preferentially forms cyclohexene products, with the latter pathway exhibiting more favorable in both kinetics and thermodynamics. The transmetalation step follows two paths through four- or six-membered ring transition states, depending on which oxygen atom of the nucleophile attacks. Reductive elimination occurs and the catalyst is regenerated using benzoquinone as the oxidant to complete the catalytic cycle. Comparative analysis of alternative C<img>C coupling pathways further validates the proposed mechanism.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1253 ","pages":"Article 115418"},"PeriodicalIF":3.0,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144809818","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}

引用次数: 0

Humidity-dependent CO2 capture in ultraporous MOF-177: Insights from hybrid GCMC/MD simulations 超多孔MOF-177中依赖湿度的二氧化碳捕获：来自混合GCMC/MD模拟的见解

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-08-06 DOI: 10.1016/j.comptc.2025.115419

Bishwas Adhikari , Aabiskar Bhusal , Qian Sun , Kapil Adhikari

{"title":"Humidity-dependent CO2 capture in ultraporous MOF-177: Insights from hybrid GCMC/MD simulations","authors":"Bishwas Adhikari , Aabiskar Bhusal , Qian Sun , Kapil Adhikari","doi":"10.1016/j.comptc.2025.115419","DOIUrl":"10.1016/j.comptc.2025.115419","url":null,"abstract":"<div><div>With rising atmospheric CO<sub>2</sub> levels, the need for efficient adsorbent materials has become increasingly important. Among all the porous materials, metal-organic frameworks (MOFs) are gaining considerable attention because of their large surface area, tunable pore sizes, and diverse chemical and physical properties. In this study, we used hybrid Grand Canonical Monte Carlo and Molecular Dynamics (GCMC/MD) simulations in LAMMPS to explore CO<sub>2</sub> adsorption and diffusion in MOF-177 under varying pressures, temperatures, and humidity levels. CO<sub>2</sub> uptake increased from 17.19 to 26.92 mmol/g (56.6 %) as pressure rose from 10 to 100 bar. Adsorption decreased by 30.1 % when temperature increased from 298 K to 318 K due to enhanced molecular motion. The diffusion coefficient dropped exponentially with pressure but increased with temperature. At 15 wt% humidity, CO<sub>2</sub> adsorption decreased by 12.5 % due to competition with water, which also reduced diffusion. These findings help to understand CO<sub>2</sub> sequestration under realistic conditions.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1253 ","pages":"Article 115419"},"PeriodicalIF":3.0,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144829775","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}

引用次数: 0

Corrigendum to “Investigation of methyl radical with methane and methanol reactions in the framework of a non-equilibrium approach; dynamic aspect” [Comput. Theor. Chem. 1239 (2024) 114725] “在非平衡方法框架下甲基与甲烷和甲醇反应的研究”的勘误；动态方面”[计算。定理。化学。1239 (2024)114725]

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-08-06 DOI: 10.1016/j.comptc.2025.115408

Igor Romanskii

引用次数: 0

DFT study of the origin of enantioselectivity of Ni-catalyzed asymmetric hydrogenation of cyclic sulfamidate imine to chiral cyclic sulfamidates 镍催化环氨基磺酸亚胺不对称加氢制手性环氨基磺酸对映选择性的DFT研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-08-05 DOI: 10.1016/j.comptc.2025.115401

Pavee Apilardmongkol , Manussada Ratanasak , Vudhichai Parasuk , Yasuteru Shigeta

{"title":"DFT study of the origin of enantioselectivity of Ni-catalyzed asymmetric hydrogenation of cyclic sulfamidate imine to chiral cyclic sulfamidates","authors":"Pavee Apilardmongkol , Manussada Ratanasak , Vudhichai Parasuk , Yasuteru Shigeta","doi":"10.1016/j.comptc.2025.115401","DOIUrl":"10.1016/j.comptc.2025.115401","url":null,"abstract":"<div><div>In this study, we elucidate the origin of enantioselectivity in Ni-catalyzed asymmetric hydrogenation of cyclic sulfamidate imines to chiral cyclic sulfamidates using the chiral (<em>S</em>,<em>S</em>)-Ph-BPE ligand, based on DFT calculations (ωB97XD/6–311 + G(d,p), SMD(TFE) // ωB97XD/6-31G(d,p), SMD(TFE), SDD for Ni). The DFT results reveal that the addition of [Ni]-H to the C<img>N bond of the cyclic sulfamidate imine is the enantioselectivity-determining step. The high enantioselectivity of the desired <em>S</em>-product is attributed to favorable CH-π attractive interactions in the <em>S</em>-pathway, whereas the <em>R</em>-pathway, characterized by lone-pair-π repulsion, is energetically less favorable, leading to lower enantioselectivity. Furthermore, the enantiomeric excess (ee), calculated using the Energetic Span Model and Transition State Theory, exceeds 99 % in favor of the <em>S</em>-enantiomer. Despite this, the DFT-predicted %ee values qualitatively align with the experimentally observed enantioselectivity of ee >94 %. Additionally, modifying the R substituent of the substrate from phenyl to methyl resulted in a significant decrease in ΔΔ<em>G</em><sup>‡</sup>, from 3.9 kcal/mol for the phenyl group to 2.2 kcal/mol for the methyl group. This trend aligns with experimental results. These findings lay the groundwork for the development of advanced chiral catalysts for the enantioselective hydrogenation of cyclic sulfamidate imine substrates.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1252 ","pages":"Article 115401"},"PeriodicalIF":3.0,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144771507","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}

引用次数: 0

MOF-303 as a multifunctional host: DFT analysis of metal binding and gas storage potential MOF-303作为多功能宿主：DFT分析金属结合和气体储存潜力

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-08-05 DOI: 10.1016/j.comptc.2025.115409

Madhu Samolia

引用次数: 0