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首页> 外文期刊>Chemistry: A European journal >How Important Is Molecular Rigidity for the Complex Stability of Artificial Host-Guest Systems?A Theoretical Study on Self-Assembly of Gas-Phase Arginine
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How Important Is Molecular Rigidity for the Complex Stability of Artificial Host-Guest Systems?A Theoretical Study on Self-Assembly of Gas-Phase Arginine

机译：分子刚性对于人工宿主系统的复杂稳定性有多重要？气相精氨酸自组装的理论研究

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摘要

Arginine forms much less stable dimers than 2-(guanidiniocar-bonyl)-1H-pyrrole-5-carboxylate although the principal binding interactions are very similar.The reasons for this difference are addressed in this work by state-of-the-art ab initio computations.The investigation shows that the extraordinary high stability of the 2-(guanidiniocarbonyl)-1H-pyrrole-5-carboxylate dimer results to about 50 % from the rigidity of its monomer.Within this study monomer and dimer conformers of arginine were calculated leading to new low lying structures which have not been reported before as well as new global minima are pre-dicted.In these structures stacking interactions with the guanidinium moiety are especially important.For the monomer we predict the energy minimum to be the canonical form with the lowest lying zwitterionic structure being only 9 kJ mol~(-1) less stable.During the course of these calculations we found that DFT did not predict the structures and their relative energy correctly in comparison to perturbation theory (MP2) and some potential reasons for the failure of DFT in these cases are discussed.Vibrational frequencies of the various structures are presented and a suitable wavenumber region for an experimental determination of the global minimum of the arginine monomer is identified.The effect of molecular rigidity on the self-assembly is probed using a local minimum of the arginine monomer which does not possess any intramolecular stabilizing effects.Our results suggest that the deliberate control of the conformational flexibility is a powerful instrument to steer the complex affinity of artificial hosts.
机译：尽管主要的结合相互作用非常相似，但精氨酸形成的稳定二聚体比2-（胍基碘基-芳基）-1H-吡咯-5-羧酸酯的稳定性差得多。这项工作中最先进的抗体解决了这种差异的原因。从头计算计算结果表明，2-（胍基碘羰基）-1H-吡咯-5-羧酸酯二聚体具有极高的稳定性，其单体的刚性约为50％。在此研究中，精氨酸的单体和二聚体构象得以计算导致新的低洼结构的出现以及新的全局最小值被预测。在这些结构中，与胍基部分的堆积相互作用尤为重要。对于单体，我们预测能量的最小值为正则形式在这些计算过程中，我们发现DFT不能正确地预测结构及其相对能量。讨论了与微扰理论（MP2）的比较以及这些情况下DFT失效的一些潜在原因。给出了各种结构的振动频率，并确定了用于实验确定精氨酸单体整体最小值的合适波数区域。使用不具有任何分子内稳定作用的精氨酸单体的局部最小值来探究分子刚性对自组装的影响。我们的结果表明，有意控制构象柔韧性是一种有效的工具，可以控制Aβ的复杂亲和力人工宿主。

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