Computations of Noncovalent π Interactions
Computations of Noncovalent π Interactions
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DOI：
10.1002/9780470399545.ch1
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发表时间：
2009-01
期刊：
影响因子：
--
通讯作者：
C. Sherrill
中科院分区：
文献类型：
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作者：
C. Sherrill
非共价相互作用控制蛋白质折叠、超分子组装、有机物晶体堆积和药物结合等过程。在氢键和强静电相互作用（例如，电荷-电荷、电荷-偶极和偶极-偶极）之后，生物应用中最重要的非共价相互作用可能是涉及芳香族π系统的相互作用。 1 例如，芳香环之间的 π-π 相互作用有助于稳定 DNA 和 RNA 的双螺旋。 2 蛋白质结构受到多种非共价相互作用的影响，包括侧链之间的 π-π、3、4 C-H/π、5 和 S/π 相互作用6-8。插入 DNA 和 RNA 碱基对之间的药物主要由于 π-π 和阳离子-π 相互作用而结合。 9 结合 DNA 或 RNA 的蛋白质利用阳离子-π、10、11 π-π、11 和 C-H/π 等非共价相互作用。 12 这些 π 相互作用在材料化学应用中同样重要，包括自组装超分子结构。 13, 14 例如，分子线可以由芳香大环的堆叠形成。 15 小分子与碳纳米管 16 的结合以及石墨烯片 17 之间的吸引力均由非共价 π 相互作用决定。 π共轭有机材料的晶体结构和电荷传输特性也很大程度上取决于π-π相互作用。 18
Noncovalent interactions govern such processes as protein folding, supramolecular assembly, crystal packing of organics, and drug binding. After hydrogen bonding and strong electrostatic interactions (eg, charge–charge, charge–dipole, and dipole–dipole), the most significant noncovalent interactions in biological applications are probably those involving aromatic π systems. 1 For example, π–π interactions between aromatic rings help stabilize the double helix of DNA and RNA. 2 Protein structures are influenced by a variety of noncovalent interactions including π–π, 3, 4 C–H/π, 5 and S/π interactions6–8 between side chains. Drugs that intercalate between base pairs in DNA and RNA are bound largely due to π–π and cation–π interactions. 9 Proteins that bind DNA or RNA utilize such noncovalent interactions as cation–π, 10, 11 π–π, 11 and C–H/π. 12 These π interactions can be equally critical in materials chemistry applications, including self-assembled supramolecular architectures. 13, 14 For example, molecular wires can be formed from stacks of aromatic macrocycles. 15 The binding of small molecules to carbon nanotubes16 and attraction between graphene sheets17 are both determined by noncovalent π interactions. The crystal structure and charge-transport properties of π-conjugated organic materials are also largely determined by π–π interactions. 18