水相酰胺萘管与葫芦脲的分子识别及半缩醛胺的捕获

  分子识别广泛存在于自然界中，是很多复杂生物功能的基础。基于大环主体的人工分子识别不仅可以作为模型体系帮助理解复杂的生物分子识别现象，而且能够被用于环境科学、分析化学、生物医药、精细化工、材料科学等领域。有机相分子识别体系比较容易构建，相关研究也较为广泛，但能够对亲水分子进行选择性键合的水相分子识别体系却很难构建。通过模拟生物受体的结构，将极性识别位点置于深穴疏水空腔内部而构筑的仿生大环主体酰胺萘管，能够在水中高选择性识别亲水分子。

      虽然亲水分子的水相识别研究取得了一定进展，但发展新的人工亲水分子识别体系仍然较为困难，因为亲水分子的水相识别机理仍不清晰。此外，在水中进行化学反应在生物分子修饰、节约成本、环境保护等方面具有重要意义。然而一些反应的中间体或最终产物对水敏感，反应很难在水中进行；而且水相化学反应的机理研究也较为困难，因为水环境通常会增加反应中间体的捕获难度。

      本文利用仿生大环酰胺萘管与经典大环葫芦脲详细研究了水相亲水分子的识别机理；并基于酰胺萘管的水相识别性质，设计合成了单修饰酰胺萘管衍生物，使其能够在水中生成对水敏感的脂肪族亚胺，并捕获活泼中间体半缩醛胺。

      研究了葫芦脲在水中对中性亲水分子的识别，揭示了由疏水空腔引起的疏水效应在水相亲水分子识别中的重要作用。研究发现葫芦脲可以在水中有效的键合中性亲水分子，例如1,4-二氧六环、冠醚、单糖等。其中葫芦[8]脲与12-冠-4醚的键合常数高达10⁷ L/mol；葫芦[7]脲与2-脱氧-D-核糖的键合常数也有10³ L/mol。葫芦脲与这些亲水分子之间不存在明显的非共价相互作用；它们的键合主要是由疏水效应驱动的；所形成的主客体复合物的空腔占有率在52%至65%之间，客体被适宜的容纳在主体的空腔中，既没有造成空间位阻，也没有过分松散。

      进一步测定了葫芦[7]脲对35个中性亲水分子的键合参数，并将其与酰胺萘管的水相识别性质进行对比。主成分分析表明葫芦[7]脲的本征键合强度与客体的体积呈正相关，与客体的非球面系数呈负相关，即葫芦[7]脲选择性键合分子体积与其空腔匹配的球形客体；而酰胺萘管的本征键合强度主要与客体中的杂原子个数、有效氢键碱性呈正相关，与客体的油水分配系数呈负相关，即酰胺萘管选择性键合能与其形成匹配氢键的亲水分子。酰胺萘管不键合绝大多数氨基酸、脱氧核糖核苷酸、D-葡萄糖以及D-果糖，其对中性分子的水相识别也不受盐、PBS和Tris-HCl的缓冲体系的干扰；但HEPES缓冲溶液会通过竞争键合抑制酰胺萘管对客体的识别强度。

      在酰胺萘管选择性识别亲水分子的基础上，模拟生物受体醛缩酶的结构，设计合成了连有氨基尾链的单修饰酰胺萘管。单修饰酰胺萘管的氨基尾链在水中是弯入空腔内部的，能够捕获溶液中的脂肪族醛或者苯甲醛，并与其反应生成亚胺；且所生成的亚胺具有较好的稳定性，不受热、强碱、亲核试剂或亲电试剂的干扰。在该主体与乙醛或丙醛的反应过程中，利用核磁氢谱以及质谱能够检测到反应的活泼中间体半缩醛胺；对于具有更大疏水基团的正丁醛、正戊醛、正己醛以及苯甲醛，则不能观察到中间体半缩醛胺。无论是亚胺，还是半缩醛，它们的官能团均能与主体空腔内部的酰胺形成氢键，同时被主体的疏水空腔严密包裹。

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