Structural Chemistry最新文献_第6页

Comments on the review process 关于审查程序的意见

IF 2.1 4区化学

Structural Chemistry Pub Date : 2024-05-18 DOI: 10.1007/s11224-024-02335-z

Roald Hoffmann

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Reactions of chlorophyll with hydroxyl radicals via RAF, HAT and SET mechanisms: A theoretical study 叶绿素通过 RAF、HAT 和 SET 机制与羟自由基发生反应：理论研究

IF 2.1 4区化学

Structural Chemistry Pub Date : 2024-05-16 DOI: 10.1007/s11224-024-02331-3

Swarnadeep Biswas, Pradeep Kumar Shukla

{"title":"Reactions of chlorophyll with hydroxyl radicals via RAF, HAT and SET mechanisms: A theoretical study","authors":"Swarnadeep Biswas, Pradeep Kumar Shukla","doi":"10.1007/s11224-024-02331-3","DOIUrl":"10.1007/s11224-024-02331-3","url":null,"abstract":"<div>To understand the scavenging action of chlorophyll (Chla) found in most of the vegetables towards hydroxyl (({{text{OH}}}^{bullet })) radicals, its reactions with ({{text{OH}}}^{bullet }) radicals via RAF, HAT, and SET mechanisms have been investigated theoretically using two layer ONIOM [M06-2X/6-31G(d) (High):M06-2X/3-21G (Low)] method and M06-2X/6–311 + G(d,p) level of density functional theory. The molecular electrostatic potential (MEP), highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) plots, HOMO–LUMO energy gap, global hardness (η), global softness (S), electronegativity (χ), and electrophilicity index (ω) of Chla molecule were computed and analyzed to determine its stability and reactive sites. It is found that RAF and HAT reactions are exergonic in both gaseous and aqueous media whereas SET reactions are endergonic in both media. However, all the RAF, HAT and SET reactions studied here are found to be more favourable in aqueous media vs. gas phase. The rate constants of RAF reactions at different sites are found to be of the order of ~ 6.2 × 107–1.8 × 1010 s−1 indicating that RAF reactions would be appreciably fast. This study concludes that chlorophyll can efficiently scavenge ({{text{OH}}}^{bullet }) radicals preferably via RAF and HAT mechanisms and intake of water with chlorophyll can enhance its scavenging actions.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"1905 - 1916"},"PeriodicalIF":2.1,"publicationDate":"2024-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140971164","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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Radical scavenging mechanism of aryl carbamate: a computational case study using 3-morpholinopropyl phenyl carbamate 氨基甲酸芳基酯的自由基清除机制：使用 3-吗啉丙基苯基氨基甲酸酯的计算案例研究

IF 2.1 4区化学

Structural Chemistry Pub Date : 2024-05-10 DOI: 10.1007/s11224-024-02333-1

Chhinderpal Kaur, Debasish Mandal

{"title":"Radical scavenging mechanism of aryl carbamate: a computational case study using 3-morpholinopropyl phenyl carbamate","authors":"Chhinderpal Kaur, Debasish Mandal","doi":"10.1007/s11224-024-02333-1","DOIUrl":"10.1007/s11224-024-02333-1","url":null,"abstract":"<div>A systematic computational mechanistic and kinetics investigation has been performed on the antioxidant activity of phenyl carbamate, namely 3-morpholinopropyl phenyl carbamate (3-MPPC), against HO• and HOO• radicals. The standard density functional theory (DFT) method (M062X) is used for electronic structure calculation, and conventional transition state theory and Marcus theory are used for H-transfer and electron transfer kinetics, respectively. Four types of possible reaction mechanisms, such as hydrogen atom transfer (HAT), radical adduct formation (RAF), single electron transfer followed by proton transfer (SETPT), and sequential proton loss electron transfer (SPLET) have been considered here for investigation. 3-MPPC showed excellent HO• radical scavenging activity in the gas phase (koverall = 1.58 × 1011 M−1 s−1), water (koverall = 3.0 × 109 M−1 s−1) and pentyl ethanoate solvents (koverall = 3.8 × 109 M−1 s−1). In the case of HOO• radical scavenging activity, endothermic reactions with quite high activation energy are observed irrespective of the type of mechanisms. It was found that HAT is the most possible mechanism as it contributes approximately 97% and 93% to the overall rate (koverall) in the gas phase and the lipid medium, respectively. The RAF mechanism has a minor contribution to the scavenging of HO• radical in all the studied environments. In contrast, the SET mechanism is favorable in aqueous solution. The detailed theoretical studies will be helpful for better understanding the antioxidant activities of carbamate compounds and for further designing new potential antioxidants.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"1893 - 1903"},"PeriodicalIF":2.1,"publicationDate":"2024-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140937446","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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Combined computational and experimental studies of tripropylammonium 2-sulfobenzoate protic ionic liquid 2-磺基苯甲酸三丙基铵原生离子液体的计算与实验联合研究

IF 2.1 4区化学

Structural Chemistry Pub Date : 2024-05-08 DOI: 10.1007/s11224-024-02338-w

Irina V. Fedorova, Liudmila E. Shmukler, Yuliya A. Fadeeva, Matvey S. Gruzdev, Michail A. Krestyaninov, Lyubov P. Safonova

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José Elguero – an introduction and tribute 何塞-埃尔圭罗--介绍和致敬

IF 2.1 4区化学

Structural Chemistry Pub Date : 2024-05-02 DOI: 10.1007/s11224-024-02334-0

Istvan Hargittai

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Seventy-three years riding heterocycles 驰骋杂环七十三载

IF 2.1 4区化学

Structural Chemistry Pub Date : 2024-05-01 DOI: 10.1007/s11224-024-02329-x

José Elguero

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Synthesis, structure characterization, Hirshfeld surface analysis, and computational studies of 3-nitro-1,2,4-triazol-5-one (NTO):acridine 3-nitro-1,2,4-triazol-5-one (NTO):acridine 的合成、结构表征、Hirshfeld 表面分析和计算研究

IF 2.1 4区化学

Structural Chemistry Pub Date : 2024-04-30 DOI: 10.1007/s11224-024-02326-0

Nilgün Şen, Jean-François Pons, Yunus Zorlu, Eleftheria Dossi, Federica Persico, Tracey Temple, Nazife Aslan, Akachai Khumsri

{"title":"Synthesis, structure characterization, Hirshfeld surface analysis, and computational studies of 3-nitro-1,2,4-triazol-5-one (NTO):acridine","authors":"Nilgün Şen, Jean-François Pons, Yunus Zorlu, Eleftheria Dossi,  Federica Persico, Tracey Temple, Nazife Aslan, Akachai Khumsri","doi":"10.1007/s11224-024-02326-0","DOIUrl":"10.1007/s11224-024-02326-0","url":null,"abstract":"<div>To modify the physical features and extend applications of the 3-nitro-1,2,4-triazol-5-one (NTO), we synthesized NTO with acridine (ACR) at a molar ratio of 1:1, a neutralization reaction. Through altering the chemical composition, it was possible to alter physical properties such as thermal stability, free space (voids), packing coefficient, crystal density, difference in pKa of co-formers, morphology, solubility, and impact sensitivity, and detonation parameters . It appears that physical attributes could be entirely altered. Single-crystal and powder X-ray diffraction methods, infrared spectroscopy, mass spectrometry, nuclear magnetic resonance spectroscopy (1H-NMR and 13C-NMR), and thermal analysis were utilized to comprehensively characterize and confirm the formation of the structure of NTO:ACR. The substantial hydrogen bond interactions and planar layered structures observed between the cations and anions generated a complex 3D network, providing insight into the structure–property interrelationship. One intriguing feature discovered is the layered structure present in NTO:ACR, which may be responsible for the low impact sensitivity. According to the experimental results, NTO:ACR showed good thermal stability (Td = 229 °C) and outstanding impact sensitivity (IS = 100 J). Detonation velocity and pressure were calculated using the EXPLO5 software program and found to be 7006 m·s−1 and 20.02 GPa, respectively. </div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"1865 - 1879"},"PeriodicalIF":2.1,"publicationDate":"2024-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140839757","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}

引用次数: 0

Effects of graphene and thermoplastic elastomer on tailoring the bulk properties of asphaltenes: an exploration from classical and quantum simulations 石墨烯和热塑性弹性体对定制沥青块体特性的影响：经典和量子模拟探索

IF 2.1 4区化学

Structural Chemistry Pub Date : 2024-04-30 DOI: 10.1007/s11224-024-02330-4

Pabitra Narayan Samanta, Devashis Majumdar, Jerzy Leszczynski

{"title":"Effects of graphene and thermoplastic elastomer on tailoring the bulk properties of asphaltenes: an exploration from classical and quantum simulations","authors":"Pabitra Narayan Samanta, Devashis Majumdar, Jerzy Leszczynski","doi":"10.1007/s11224-024-02330-4","DOIUrl":"10.1007/s11224-024-02330-4","url":null,"abstract":"<div>The modulation of bulk properties including the cohesive strength and the solubility of the asphaltenes, due to the inclusion of graphene nanosheets and the thermoplastic polymer, is probed by performing all-atom classical molecular dynamics (MD) simulations. The impact of morphological heterogeneity, including the size of the aromatic core of the asphaltene molecule, the nature of the heteroatom attached to the aromatic core, the orientation of the graphene nanosheets, and the surface area of the nanomaterial, on the bulk properties of the model systems of nanocomposites and interfaces is explored. The cohesive strength of the asphaltene composites is significantly enhanced by the introduction of graphene nanosheets. The addition of styrene–butadiene–styrene (SBS) block copolymer into the graphene-reinforced asphaltene systems improves the cohesive strength, structural plasticity, and compatibility between the nanomaterial and the asphaltenes. The π–π stacking interaction between the graphitic surface and the aromatic core of the asphaltene is identified to be the major driving force for modulating the cohesive strength. The dispersion interaction maximizes in the hierarchical layered structure compared to the randomly oriented structure of the graphene nanosheets and the asphaltene molecules. The energetics of non-covalent interaction are further assessed within the framework of dispersion-corrected density functional theory (DFT)-based methods. The DFT-derived adsorption energies and thermochemical properties substantiate the stronger interaction and the thermodynamic favorability of the adsorption processes in both the gas phase and solvent medium (toluene). The simulated IR and Raman spectra are also analyzed to reveal the nature of the interaction.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 4","pages":"1059 - 1073"},"PeriodicalIF":2.1,"publicationDate":"2024-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140839759","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}

引用次数: 0

Structural, electrical, optical, and DFT studies of phenothiazine-based D–π–A frameworks for dye-sensitized solar cell applications 用于染料敏化太阳能电池的吩噻嗪基 D-π-A 框架的结构、电学、光学和 DFT 研究

IF 2.1 4区化学

Structural Chemistry Pub Date : 2024-04-30 DOI: 10.1007/s11224-024-02327-z

K. S. Dhivya, C. Senthilkumar, K. Karthika, P. Srinivasan

{"title":"Structural, electrical, optical, and DFT studies of phenothiazine-based D–π–A frameworks for dye-sensitized solar cell applications","authors":"K. S. Dhivya, C. Senthilkumar, K. Karthika, P. Srinivasan","doi":"10.1007/s11224-024-02327-z","DOIUrl":"10.1007/s11224-024-02327-z","url":null,"abstract":"<div>The phenothiazine-derivative dyes have been designed using phenothiazine group (donor part), thienothiophene (spacer part), and different acid groups (electron-acceptor part). Time-dependent density functional theory (TD-DFT) and density functional theory (DFT) have been used to study the electronic and optical properties of the designed dyes (B1–B10). The dye B8 has planar conformations with a dihedral angle of 0.15° which indicates electron delocalization over the molecules. The dye B6 has a low chemical hardness value. The energy gap, ionization potential, electron affinity, and chemical hardness of the dyes have been computed, and efficiency has been analyzed. The B8 dye sensitizer has a higher dipole moment (5.324 Debye) compared to the other sensitizers, due to the presence of two cyano groups in the acceptor parts. The NLO characteristics have been determined based on the polarizability and first-order hyperpolarizability values of the designed dyes. The LHE values of dye molecules ranged from 0.75 to 0.89 eV. The dye sensitizers B6 and B8 have high efficient values compared with other designed dyes.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"1843 - 1863"},"PeriodicalIF":2.1,"publicationDate":"2024-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140839998","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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Aromaticity – a theoretical notion 芳香性--一个理论概念

IF 2.1 4区化学

Structural Chemistry Pub Date : 2024-04-23 DOI: 10.1007/s11224-024-02328-y

Israel Agranat

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