在密度泛函理论下，溶剂对 C20 纳米富勒烯与 indoline-2-one 环加成的影响,Journal of Physical Organic Chemistry

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在密度泛函理论下，溶剂对 C20 纳米富勒烯与 indoline-2-one 环加成的影响
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2022-04-04 , DOI: 10.1002/poc.4354
Manzarbanou Asnaashariisfahani ₁ , Evan Abdulkareem Mahmood ₂ , Mohammad Reza Poor Heravi ₃ , Sepideh Habibzadeh ₃ , Abdol Ghaffar Ebadi ₄ , Sarvin Mohammadi‐Aghdam ₃

Affiliation

在气相中研究了具有生物活性的 ( E )-3-(furan-2-yl)methylene-indoline-2-one ( I )，C ₆ H ₆、C ₂ H ₄ Cl ₂、EtOH、MeNO ₂、DMSO 和 H ₂ O 使用自洽反应场 (SCRF) - 密度泛函理论 (DFT)。该物种已用于肿瘤生长、转移和血管生成。一个主要有趣的问题是溶剂对I与C ₂₀的分子间异质 Diels-Alder 环加成产生药物递送 ( I _a ) 的稳定性、几何形状和能量的影响。通过优化加合物 (I _a ) 从气相到非极性再到极性溶剂，得到以下结果： (1) 热力学和动力学稳定性的趋势以及极性似乎与所用溶剂的介电常数和氢键的形成成正比。(2) 与一般认为内异构体比外异构体更稳定的观点相反，在这里，外异构体似乎比内异构体更稳定。(3)外环加成可以在室温下热进行，目前负责区域选择性。(4) endo的可能性在苯中探测到的最低能垒为 4.2 kcal/mol，而在水中估计的最高能垒为 7.3 kcal/mol，环加成是有利的。(5) 硫杂原子和纳米笼之间的非键静电相互作用，以及 π-π 芳族堆积，似乎对内异构体具有显着的不稳定效应。(6) 在从外过渡态 (TS) 和内TS 转变_为环加合物时，分子静电势随形状、大小、对称性和区域选择性的变化而变化。

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Solvent effect on cycloaddition of C20 nanofullerene with indoline-2-one, at density functional theory

The biologically active (E)-3-(furan-2-yl)methylene-indoline-2-one (I) is studied, in the gas phase, C₆H₆, C₂H₄Cl₂, EtOH, MeNO₂, DMSO, and H₂O using the self-consistent reaction field (SCRF)—density functional theory (DFT). This species has been used in tumor growth, metastasis, and angiogenesis. A mainly interesting issue is the solvent effect on the stability, geometry, and energy of intermolecular hetero-Diels–Alder cycloaddition of I with C₂₀ to yield drug delivery (I_a). By optimization of adduct (I_a) from gas phase to nonpolar and then polar solvent, the following results is obtained: (1) The trend of thermodynamic and kinetic stability and also polarity seem proportional to the dielectric constant of the used solvent and formation of the hydrogen bonding. (2) In contrast to general belief that the endo isomer appears more stable than exo isomer, here, the exo isomer appears more stable than endo isomer. (3) The exo cycloaddition can be carried out thermally at room temperature and currently hold responsible for regioselectivity. (4) The possibility of endo cycloaddition is favorable by the lowest energy barrier of 4.2 kcal/mol probed in benzene, while the highest energy barrier of 7.3 kcal/mol is estimated in water. (5) Nonbonding electrostatic interaction between the sulfur heteroatom and nanocage, as well as the π–π aromatic stacking, appears to have significant destabilizing effect on the endo isomer. (6) In going from exo transition state (TS) and endo TS to and I_a cycloadduct, the molecular electrostatic potential is changed as a function of shape, size, symmetry, and regioselectivity.

更新日期：2022-04-04

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