四内酰胺大环的分子识别与应用研究进展

doi:10.6023/cjoc202401021

摘要/Abstract

分子识别在自然界中广泛存在, 是许多生物过程以及超分子化学的核心. 水的极性环境会显著削弱特定的非共价相互作用(如氢键), 因此利用人工大环主体在水相中进行分子识别具有挑战性. 四内酰胺大环是一类疏水空腔内部具有极性结合位点的人工大环主体, 通过模仿生物受体的识别特性实现了水中亲水分子的识别, 在疏水效应以及氢键的协同作用下可以实现药物分子、糖类、染料、有机污染物及疾病标志物等物质的选择性识别. 总结了近三十年来四内酰胺大环在分子识别与应用方面的研究进展, 尤其是在水相中的分子识别与应用研究, 希望为今后四内酰胺大环的发展提供参考.

关键词: 超分子化学, 四内酰胺大环, 分子识别, 氢键

Molecular recognition is ubiquitous in nature and plays a crucial role in numerous biological processes and supramolecular chemistry. Due to the significant weakening of specific non-covalent interactions (e.g., hydrogen bonding) by the polar environment of water, the use of artificial macrocyclic hosts for molecular identification in the water is challenging. Tetralactam macrocycles are artificial macrocyclic hosts with polar binding sites inside the hydrophobic cavity, which can realize the recognition of hydrophilic molecules in the water by mimicking the molecular recognition of bioreceptors. Through the synergistic effect of hydrophobic effect and hydrogen bonds, it can selectively recognize drug molecules, saccharides, dyes, organic pollutants, disease markers and other substances in the aqueous environment. The research advances of tetralactam macrocycles in molecular recognition and application over the last 30 years are summarized, with a particular emphasis on its molecular recognition and application in the water, hoping to provide a reference for the development of tetralactam macrocycles in the future.

Key words: supramolecular chemistry, tetralactam macrocycle, molecular recognition, hydrogen bond

引用此文

郭静, 李诗瑶, 姚欢, 杨留攀, 王力立. 四内酰胺大环的分子识别与应用研究进展[J]. 有机化学, 2024, 44(6): 1777-1785.

Jing Guo, Shiyao Li, Huan Yao, Liupan Yang, Lili Wang. Research Progress of Tetralactam Macrocycle-Based Molecular Recognition and Applications[J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1777-1785.

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图/表 6

图1. (a)芳基杯[4]吡咯, (b)笼状人工凝集素和(c)酰胺萘管的化学结构式[22?-24]

Figure 1. Chemical structures of (a) aryl-extended calix[4]pyrroles, (b) cage-like artificial lectin and (c) amide naphthotubes[22?-24]

图2. 本文中涉及到的四内酰胺大环的化学结构

Figure 2. Chemical structures of the tetralactam macrocycles covered by this review

图3. (a)大环主体H1和H2的化学结构式、(b)二羰基底物1~8的化学结构式和(c)对苯醌的潜在识别位点[37,47,51]

Figure 3. (a) Chemical structures of macrocyclic host H1 and H2, (b) chemical structures of dicarbonyl substrates 1~8 and (c) potential sites for recognition of p-benzoquinone[37,47,51]

图4. (a)大环主体H3和H4的化学结构式、(b) [2]轮烷中酶促释放甲硫氨酸脑啡肽、(c)方酸染料通过客体后折叠及芳香堆积与四内酰胺大环形成稳定复合物和(d)大环主体H6的化学结构式、分子庙示意图及其结合葡萄糖底物的原理[39,41,52-53]

Figure 4. (a) Chemical structures of macrocyclic host H3 and H4, (b) enzyme-triggered release of Met-enkephalin from [2]rotaxane, (c) formation of a stable complex by squaraine dye with tetralactam macrocycle through guest back-folding and aromatic stacking and (d) chemical structure of macrocyclic host H6, graphical illustration of the molecular temple and its principle of binding a glucose substrate[39,41,52-53]

图5. (a)大环主体H7~H12的化学结构式、(b)用Spartan’14得到的吩嗪@H7主客体复合物能量最小化结构和(c)基于四内酰胺大的荧光、比色双模式IDA传感器检测尿酸示意图[44,56]

Figure 5. (a) Chemical structures of macrocyclic host H7~H12, (b) energy-minimized structure of phenazine@H7 by using Spartan’14 and (c) schematic illustration of the tetralactam macrocycle based dual-mode colorimetric and fluorescence indicator displacement assay for UA[44,56]

图6. (a)大环主体H13~H16的化学结构式、(b) β-吡喃葡萄糖@H14主客体复合物的单晶结构、(c)次黄嘌呤@H14的结合模型、(d)大环主体H17的化学结构式及方酸染料@H17结合模型、(e)多价探针在阴离子膜表面展开并发出强烈荧光用于微生物和哺乳动物细胞以及大鼠肿瘤模型成像[58???-62]

Figure 6. (a) Chemical structure of macrocyclic host H13~H16, (b) crystal structure of β-glucopyranose@H14, (c) binding model of hypoxanthin@H14, (d) chemical structure of macrocyclic host H17 and binding model of squaraine dye@H17, and (e) multivalent probes unfold on the anionic membrane surface and emite strong fluoresce for imaging of microbial and mammalian cells, as well as in rats tumor model[58???-62]

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