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Rationalizing the Activity of an “Artificial Diels-Alderase”: Establishing Efficient and Accurate Protocols for Calculating Supramolecular Catalysis
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-12-19 , DOI: 10.1021/jacs.9b10302 Tom A Young 1 , Vicente Martí-Centelles 2 , Jianzhu Wang 2 , Paul J Lusby 2 , Fernanda Duarte 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-12-19 , DOI: 10.1021/jacs.9b10302 Tom A Young 1 , Vicente Martí-Centelles 2 , Jianzhu Wang 2 , Paul J Lusby 2 , Fernanda Duarte 1
Affiliation
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Self-assembled cages have emerged as novel platforms to explore bio-inspired catalysis. While many different size and shape supramolecular structures are now readily accessible, only a few are known to accelerate chemical reactions under sub-stoichiometric conditions. These limited examples point to a poor understanding of cage catalysis in general, limiting the ability to design new systems. Here we show that a simple and efficient density functional theory-based methodology, in-formed by explicitly solvated molecular dynamics and coupled-cluster calculations is sufficient to accurately reproduce experimental guest binding affinities (MAD = 1.9 kcal mol-1) and identify the catalytic Diels-Alder proficiencies (>80 % accuracy) of two homologous Pd2L4 metallocages with a variety of substrates. This analysis reveals how subtle structural differences in the cage framework affect binding and catalysis. These effects manifest in a smaller distortion and more favorable interaction energy for the catalytic cage compared to the inactive structure. This study gives a detailed insight that would otherwise be difficult to obtain from experiments, providing new opportunities in the design catalytically active supramolecular cages.
中文翻译：
合理化“人工 Diels-Alderase”的活性：建立计算超分子催化的有效和准确的方案
自组装笼已成为探索仿生催化的新平台。虽然现在很容易获得许多不同大小和形状的超分子结构，但已知只有少数能在亚化学计量条件下加速化学反应。这些有限的例子表明对笼式催化的一般理解不足，限制了设计新系统的能力。在这里，我们展示了一种简单有效的基于密度泛函理论的方法，通过明确的溶剂化分子动力学和耦合簇计算，足以准确再现实验客体结合亲和力（MAD = 1.9 kcal mol-1）并识别催化具有多种底物的两种同源 Pd2L4 金属定位的 Diels-Alder 熟练度（>80% 准确度）。该分析揭示了笼框架中细微的结构差异如何影响结合和催化。与非活性结构相比，这些效应表现为催化笼的变形更小，相互作用能更有利。这项研究提供了否则难以从实验中获得的详细见解，为设计催化活性超分子笼提供了新的机会。
更新日期：2019-12-19
中文翻译：
合理化“人工 Diels-Alderase”的活性：建立计算超分子催化的有效和准确的方案
自组装笼已成为探索仿生催化的新平台。虽然现在很容易获得许多不同大小和形状的超分子结构，但已知只有少数能在亚化学计量条件下加速化学反应。这些有限的例子表明对笼式催化的一般理解不足，限制了设计新系统的能力。在这里，我们展示了一种简单有效的基于密度泛函理论的方法，通过明确的溶剂化分子动力学和耦合簇计算，足以准确再现实验客体结合亲和力（MAD = 1.9 kcal mol-1）并识别催化具有多种底物的两种同源 Pd2L4 金属定位的 Diels-Alder 熟练度（>80% 准确度）。该分析揭示了笼框架中细微的结构差异如何影响结合和催化。与非活性结构相比，这些效应表现为催化笼的变形更小，相互作用能更有利。这项研究提供了否则难以从实验中获得的详细见解，为设计催化活性超分子笼提供了新的机会。
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