Theoretical Chemistry Accounts最新文献_第4页

Quenching of reactive species by Avenanthramides: theoretical insight to the thermodynamics of electron transfer 文竹酰胺对活性物种的淬灭：电子转移热力学的理论启示

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-04-13 DOI: 10.1007/s00214-024-03111-2

P. C. Sumayya, K. Muraleedharan

{"title":"Quenching of reactive species by Avenanthramides: theoretical insight to the thermodynamics of electron transfer","authors":"P. C. Sumayya, K. Muraleedharan","doi":"10.1007/s00214-024-03111-2","DOIUrl":"https://doi.org/10.1007/s00214-024-03111-2","url":null,"abstract":"Avenanthramides (AVs) are the phytochemicals found in cereals exclusively in oats. These are widely known natural substances that have antioxidant properties. The free radical deactivation potential of the eight AVs against five reactive species has been studied in physiological pH. At physiological pH, the radical quenching processes were studied using the sequential proton loss followed by electron transfer (SPLET) from the phenolic hydroxyl groups. Using density functional theory (DFT) computations, theoretical studies have been carried out in the gas phase and aqueous solution at M06-2X/6-31 + G (d,p) level of theory. The free radical scavenging ability of the studied AVs was analyzed by using conceptual density functional theory-based parameters and electrostatic potential analysis. By examining the hydrogen atom and electron affinities of each reactive species, the relative destructive potential of each has been compared. The electron transfer capabilities between the studied compound and reactive species were identified by utilizing the ionization energy and electron affinity plots. Additionally, by calculating the redox potentials and equilibrium constants for the entire process in the aqueous solution, the viability of scavenging the free radical species by selected AVs (both in neutral and mono-deprotonated) has been investigated. From the analysis, the neutral as well as the mono-deprotonated form of AVs are found to scavenge •OH and •OOH, and •NO2 radicals effectively, while they are inefficacious toward the O2•‾ and •NO radicals.<h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140601450","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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First-principles calculations on the structures and electronic properties of the TMW2On (TM = Mn–Ni, n = 1–6) clusters 关于 TMW2On（TM = 锰-镍，n = 1-6）团簇结构和电子特性的第一性原理计算

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-04-12 DOI: 10.1007/s00214-024-03113-0

Zhi Li, Zi-hao Wu, Zhen Zhao

{"title":"First-principles calculations on the structures and electronic properties of the TMW2On (TM = Mn–Ni, n = 1–6) clusters","authors":"Zhi Li, Zi-hao Wu, Zhen Zhao","doi":"10.1007/s00214-024-03113-0","DOIUrl":"https://doi.org/10.1007/s00214-024-03113-0","url":null,"abstract":"Transition metals can enhance the electronic attributes of tungsten oxides. In this study, we focused on W2On (n = 1–6) clusters as a representative examples of tungsten oxide clusters with varying oxygen concentrations. The structures and electronic properties of the TMWOn (TM = Mn–Ni) clusters have been calculated using first-principles. The ground-state TMWOn clusters share some structural similarities with the ground-state W2On (n = 1–6) clusters. The W–O bonds of the TMWO2 (TM = Fe–Ni) clusters are significantly distorted into a triangular structure. The NiWOn (n = 1–2) and CoWOn (n = 3–5) clusters display greater thermodynamic stability than other TMWOn clusters. Among the TMWOn clusters, the W2O4, W2O6, MnWO, MnWO3, MnWO6, FeWO, FeWO4, FeWO6, CoWO, CoWO6, NiWO2, NiWO5 clusters are more kinetically stable. Furthermore, the amount of charge transfer between the TM atoms and W2On clusters increases from 0.050 |e| to 1.066 |e| as the number of oxygen atoms increases. The 4s orbital electrons of the TM atoms for the TMWOn clusters are partially transferred to the neighboring O atoms.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140601584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Reaction of [2-(3-hetaryl-1,2,4-triazol-5-yl)phenyl]amines with ketones: a density functional theory study 2-(3-乙酰基-1,2,4-三唑-5-基)苯基]胺与酮的反应：密度泛函理论研究

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-04-04 DOI: 10.1007/s00214-024-03110-3

Olena O. Pylypenko, Liudmyla K. Sviatenko, Kostyantin P. Shabelnyk, Sergiy I. Kovalenko, Sergiy I. Okovytyy

{"title":"Reaction of [2-(3-hetaryl-1,2,4-triazol-5-yl)phenyl]amines with ketones: a density functional theory study","authors":"Olena O. Pylypenko, Liudmyla K. Sviatenko, Kostyantin P. Shabelnyk, Sergiy I. Kovalenko, Sergiy I. Okovytyy","doi":"10.1007/s00214-024-03110-3","DOIUrl":"https://doi.org/10.1007/s00214-024-03110-3","url":null,"abstract":"The derivatives of 1,2,4- triazole have attracted great attention among medicinal chemists due to their wide range of biological activity, good pharmacodynamic and pharmacokinetic profiles, and low toxicity, that necessitates the development of various synthesis methods and a comprehensive study of their reaction mechanisms. A detailed investigation of possible pathways for formation of new spiro-condensed [1,2,4]triazolo[1,5-c]quinazolines, that combine two structural domains with different biological properties, was performed by computational study at the SMD/B3lyp/6-31+G(d) theory level. The mechanism of interaction between [2-(3-hetaryl-1,2,4-triazol-5-yl)phenyl]amine and cyclohexanone in methanol involves three main processes: formation of carbinolamine by addition of an amine to double bond C=O, elimination of a water molecule, and intramolecular cyclization leading to formation of spiro compounds. Results show increase in reactivity of reactants during acid-catalyzed reaction compared to uncatalyzed one. The nature of the heterocyclic substituent on the triazole ring has little effect on the reaction energy, while the mechanism is unchanged.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140601457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Redox properties of PbO2, IrO2 and SnO2 (110) surfaces with an adsorbed OH molecule: a chemical reactivity study in the grand canonical ensemble 具有吸附 OH 分子的 PbO2、IrO2 和 SnO2 (110) 表面的氧化还原特性：大规范集合中的化学反应研究

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-30 DOI: 10.1007/s00214-024-03103-2

Claudia Islas-Vargas, A. Guevara-García, Marcelo Galván

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Theoretical investigation on phosphorescent platinum complexes based on two tetradentate bipyridine ligands 基于两个四价联吡啶配体的磷光铂配合物的理论研究

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-25 DOI: 10.1007/s00214-024-03107-y

Hadj Mezouar, Houari Brahim, Mostefa Boumediene, Fatima Yahia Cherif, Djebar Hadji, Abdelkrim Guendouzi

{"title":"Theoretical investigation on phosphorescent platinum complexes based on two tetradentate bipyridine ligands","authors":"Hadj Mezouar, Houari Brahim, Mostefa Boumediene, Fatima Yahia Cherif, Djebar Hadji, Abdelkrim Guendouzi","doi":"10.1007/s00214-024-03107-y","DOIUrl":"https://doi.org/10.1007/s00214-024-03107-y","url":null,"abstract":"In this work, the geometrical, optical, and phosphorescence properties of four complexes with general formula [dRpypy—C(OCH3)R′—dRpypy]Pt, with Pt-1 (R = F, R′ = methyl), Pt-2 (R = F, R′ = hexyl), Pt-3 (R = methoxy, R′ = methyl) and Pt-4 (R = methoxy, R′ = hexyl), were studied using the B3PW91 and TD-B3PW91 methods. The effect of the double substitution R and R′ on the electronic properties of the four complexes has been investigated. Replacing the two fluorine atoms with the two methoxy groups modifies the shape of the UV–vis spectra and red shift the phosphorescence spectra, while the substituents on the linker R′ do not induce changes in both absorption and phosphorescence spectra. Normal modes involved in the vibronic structure were identified and analyzed using adiabatic Hessian approaches according to the Franck–Condon approximation. The computed phosphorescence wavelengths agree with the observed ones and indicate that the fluorinated complexes exhibit a bright light blue color, while the methoxy complexes display a light spring green color. Further, temperature effects on simulated phosphorescence spectra were studied.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140303282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Adsorption and separation effects of typical metal nuclides on the WS2 surface: a DFT study 典型金属核素在 WS2 表面的吸附和分离效应：DFT 研究

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-25 DOI: 10.1007/s00214-024-03108-x

Haifei Chen, Yawei Chen, Yongsheng Cui, Shaoyang Ren, Xuan Chen

{"title":"Adsorption and separation effects of typical metal nuclides on the WS2 surface: a DFT study","authors":"Haifei Chen, Yawei Chen, Yongsheng Cui, Shaoyang Ren, Xuan Chen","doi":"10.1007/s00214-024-03108-x","DOIUrl":"https://doi.org/10.1007/s00214-024-03108-x","url":null,"abstract":"The fission products brought about by the growth of nuclear energy is increasing, and their radioactivity will seriously jeopardize human health and pollute the environment. The recycling of radioactive materials has become a problem that needs to be solved nowadays. In this paper, we simulate the adsorption behaviors of typical fission products Cs, Sr, and Co on the surface of WS2 based on first-principle study. 3 × 3 supercell is selected by convergence test and calculate and compare the parameters of adsorption sites, adsorption energy, and charge transfer. At the microelectronic level, we analyze the interactions of WS2 with the three nuclides in detail. In addition, the effect of temperature on the adsorption rate of each nuclide on the WS2 surface is further evaluated by empirical equations. The results show that fissionable metal nuclides tend to be located at the top of the metal atoms of two-dimensional transition metal sulfides (top site of the W atom of WS2), and Co, moreover, has a much larger adsorption energy than that of Cs and Sr due to its binding to W in a form similar to covalent bonds. Moreover, under high temperature conditions, WS2 is more favorable for selecting Co and separating it from Cs and Sr. WS2 is expected to be an excellent material for the separation and recovery of radionuclide Co.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140299916","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Foreword to the special issue on the “Electronic structure: principles and applications (ESPA 2022)” conference 电子结构：原理与应用（ESPA 2022）"会议特刊前言

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-22 DOI: 10.1007/s00214-024-03105-0

Manuel F. Ruiz-López, Angeles Peña-Gallego

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Size-dependent optical properties of [6]-, [8]- and [10]Cycloparaphenylene dications: the role of degenerate states 6]-、[8]- 和 [10]Cycloparaphenylene dications 大小相关的光学特性：退化态的作用

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-22 DOI: 10.1007/s00214-024-03106-z

Akhil Chakravarthy Kakarlamudi, Probal Nag, Sivaranjana Reddy Vennapusa

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Formation of alkoxymethyl hydroperoxides and alkyl formates from simplest Criegee intermediate (CH2OO) + ROH (R=CH3, CH3CH2, and (CH3)2CH) reaction systems 从最简单的克里基中间体 (CH2OO) + ROH（R=CH3、CH3CH2 和 (CH3)2CH）反应体系中生成烷氧基甲基氢过氧化物和甲酸烷基酯

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-22 DOI: 10.1007/s00214-024-03104-1

Manas Ranjan Dash, Balaganesh Muthiah, Subhashree Subhadarsini Mishra

{"title":"Formation of alkoxymethyl hydroperoxides and alkyl formates from simplest Criegee intermediate (CH2OO) + ROH (R=CH3, CH3CH2, and (CH3)2CH) reaction systems","authors":"Manas Ranjan Dash, Balaganesh Muthiah, Subhashree Subhadarsini Mishra","doi":"10.1007/s00214-024-03104-1","DOIUrl":"https://doi.org/10.1007/s00214-024-03104-1","url":null,"abstract":"Gas-phase reactions involving simplest Criegee intermediate (CH2OO) have been the current hot topic due to its vital role in atmospheric chemistry. In this study, high-level ab initio calculations are used to investigate the energetics and kinetics for the reaction of CH2OO + ROH → ROCHO + H2O (R=CH3, CH3CH2 and (CH3)2CH). Energies of the stationary points are computed at the CCSD(T)/M06-2X/6-311++G(3d,3pd)//M06-2X/6-311++G(3d,3pd) level of theory. Reaction is going through a 1,2-addition and water elimination step leading to the formation of alkoxymethyl hydroperoxides and alkyl formates, respectively. The barrier heights for the 1,2-addition step with methanol, ethanol, and isopropanol were found to be − 3.1, − 3.7, and − 4.8 kcal mol−1, and water elimination steps were found to be 2.2, 1.5, and 1.6 kcal mol−1, respectively, relative to the energies of the starting reactants. The rate constants for addition and elimination channels were calculated using canonical variational transition state theory in conjugation with small-curvature tunneling and the interpolated single point energy method between the temperature range of 200 and 500 K. In addition, the thermochemistry analysis indicates that addition and elimination channels are thermodynamically feasible and the formation of alkyl formates is entropically more favored when compared to the formation of alkoxymethyl hydroperoxide along the reaction path in the potential energy surface. The pressure-dependent microcanonical rate constants for both addition and elimination channels were also estimated using the Rice–Ramsperger–Kassel–Marcus theory and discussed in this study.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140197124","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Insights into the HO· and HOO· radical scavenging activity of aryl carbamate derivative: a computational mechanistic and kinetic investigation 深入了解氨基甲酸芳基衍生物的 HO 和 HOO 自由基清除活性：计算机理和动力学研究

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-19 DOI: 10.1007/s00214-024-03102-3

Chhinderpal Kaur, Debasish Mandal

{"title":"Insights into the HO· and HOO· radical scavenging activity of aryl carbamate derivative: a computational mechanistic and kinetic investigation","authors":"Chhinderpal Kaur, Debasish Mandal","doi":"10.1007/s00214-024-03102-3","DOIUrl":"https://doi.org/10.1007/s00214-024-03102-3","url":null,"abstract":"Aryl carbamates exhibit significant utility due to their diverse range of biological activities, including anticancer, antituberculosis, and antioxidant properties. This study will focus on a comparative evaluation of the antioxidant capabilities of two aryl carbamate derivatives, namely Methyl(Z)-(1-(hydroxyamino) ethyl)-5-(methoxycarbonyl) amino)-2-methyl-1H-indole 1 carboxylate (Compound 1) and Dimethyl (1,3-dioxo-2,3-dihydro-1H-indene-2,2-diyl) bis (4,1 phenylene) dicarbamate (Compound 2). To assess the anti-oxidant capacity, two distinct reactive oxygen species, such as highly reactive hydroxyl (HO·) and moderately reactive hydroperoxyl (HOO·), have been taken into consideration. Four distinct scavenging processes, including RAF, HAT, SETPT, and SPLET, have been investigated here. The RAF mechanism was determined to be the most effective anti-oxidant pathway, regardless of the compounds or free radicals investigated here. For both HO· and HOO·, compound 1 demonstrated more potent scavenging capabilities than compound 2. Compounds 1 and 2 react with the HO· radical very quickly due to its extraordinarily high reactivity; in contrast, the less reactive HOO· provides a rather moderate rate. The calculated values of overall rate constant of Comp. 1 reaction with HOO· are 3.7 × 103 M−1 s−1 (gas phase), 5.3 × 101 M−1 s−1 (water), and 3.6 × 100 M−1 s−1 (pentyl ethanoate). With this context it is clear both of the compounds can work as strong and mild antioxidant against HO· and HOO· radical, respectively.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140168836","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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