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首页> 外文期刊>Chemistry: A European journal >A Nexus between Theory and Experiment: Non-Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[n]urilGuest Binding Interactions
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A Nexus between Theory and Experiment: Non-Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[n]urilGuest Binding Interactions

机译：理论与实验之间的纽带：应用于葫芦[n] urilGuest结合相互作用的非经验量子力学计算方法

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摘要

A training set of eleven X-ray structures determined for biomimetic complexes between cucurbit[n]uril (CB[7 or 8]) hosts and adamantane-/diamantane ammonium/aminium guests were studied with DFT-D3 quantum mechanical computational methods to afford G(calcd) binding energies. A novel feature of this work is that the fidelity of the BLYP-D3/def2-TZVPP choice of DFT functional was proven by comparison with more accurate methods. For the first time, the CB[n]guest complex binding energy subcomponents [for example, E-dispersion, E-electrostatic, G(solvation), binding entropy (-TS), and induced fit E-deformation(host), E-deformation(guest)] were calculated. Only a few weeks of computation time per complex were required by using this protocol. The deformation (stiffness) and solvation properties (with emphasis on cavity desolvation) of cucurbit[n]uril (n=5, 6, 7, 8) isolated host molecules were also explored by means of the DFT-D3 method. A high (2)=0.84 correlation coefficient between G(exptl) and G(calcd) was achieved without any scaling of the calculated terms (at 298K). This linear dependence was utilized for G(calcd) predictions of new complexes. The nature of binding, including the role of high energy water molecules, was also studied. The utility of introduction of tethered [-(CH2)(n)NH3](+) amino loops attached to N,N-dimethyl-adamantane-1-amine and N,N,N,N-tetramethyl diamantane-4,9-diamine skeletons (both from an experimental and a theoretical perspective) is presented here as a promising tool for the achievement of new ultra-high binding guests to CB[7] hosts. Predictions of not yet measured equilibrium constants are presented herein.
机译：使用DFT-D3量子力学计算方法研究了11个X射线结构训练集，用于确定葫芦[n]尿素（CB [7或8]）宿主与金刚烷/二金刚烷铵/铵客体之间的仿生复合物。 （计算）结合能。这项工作的新颖之处在于，通过与更准确的方法进行比较，证明了DFT功能的BLYP-D3 / def2-TZVPP选择的保真度。 CB [n]客体复合结合能子成分首次出现[例如，E分散，E静电，G（溶剂化），结合熵（-TS）和诱导拟合E形变（宿主），E -变形（宾客）]。使用此协议，每个复合体仅需要几周的计算时间。还通过DFT-D3方法研究了葫芦[n] uril（n = 5、6、7、8）分离的宿主分子的变形（刚度）和溶剂化性能（着重于腔的去溶剂化）。 G（exptl）和G（calcd）之间的相关系数高（2）= 0.84，而无需对计算项进行任何缩放（在298K）。该线性相关性用于新配合物的G（计算）预测。还研究了结合的性质，包括高能水分子的作用。引入连接到N，N-二甲基金刚烷-1-胺和N，N，N，N-四甲基二金刚烷-4,9-的束缚[-（CH2）（n）NH3]（+）氨基环的实用程序本文介绍了二胺骨架（从实验和理论的角度来看），它们是实现CB [7]宿主新的超高结合客体的有前途的工具。本文提供了尚未测量的平衡常数的预测。

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