苯基分子笼的合成及性能研究

SYNTHESIS AND PROPERTIES OF PHENYL GROUP-BASED MOLECULAR CAGES

黄启诚

11849270

硕士

化学工程领域工程

蒋伟

2020-05-30

2020-07-20

哈尔滨工业大学

深圳

超分子化学是化学学科的重要分支及重要组成部分。部分有机阳离子，如乙酰胆碱、肌酐阳离子等具有生物重要性，因此对这些有机阳离子的高强度识 别以及高灵敏度检测具有十分重要的意义。相较于大环主体分子，具有永久三 维空腔的笼状主体分子对客体的封装性更好，加上多键合位点协同作用，往往 使其具有更加独特且优异的分子识别性能。 在分子识别的过程中，刚性分子笼虽具有很好的预组织能力，但对主客体结构的匹配性要求较高。柔性分子笼则具有很好的诱导适合能力，但主客体键 合过程中构象的变化带来的熵的不利也会降低键合强度。因此本课题将“预组 织”与“诱导适合”的理念引入分子笼设计之中，在课题组已报道的萘基醚氧 分子笼的基础之上，设计并合成出了苯基醚氧分子笼。本文对苯基分子笼的合 成以及性能进行了详细的探究，例如，对合成分子笼的前体进行了优化，合成 出苯基分子笼 C2，随后对其进行了详细的结构表征，揭示了其立体结构信息。 在分子笼 C2 的主客体化学研究部分，实验结果表明分子笼 C2 和有机阳离子有比较强的键合。通过与课题组已报道的萘基分子笼 2,3-NC 和 2,6-NC 进行 对比研究，我们讨论了这三类结构相似的分子笼的空腔特征与识别特性。最后 讨论探索了分子笼 C2 作为阳离子受体对生物重要性的有机阳离子的识别与检 测可能。 为研究分子笼的柔性以及醚氧链对有机阳离子高强度识别的影响，在成功制备醚氧分子笼 C2 的基础上，本论文还探索合成出了较为刚性的酯链分子笼 C3、C4，并对其进行了结构表征和主客体化学研究。发现这类笼状主体化合物 对有机阳离子的识别性能较差，这也揭示了柔性醚氧分子笼在对有机阳离子识 别上的独特性。

Supramolecular chemistry is an important branch as well as an important partof chemistry. Some organic cations, such as acetylcholine and creatinine cations, are of biological significance, so the high-intensity identification and high-sensitivity detection of these organic cations are very meaningful. Compared with macrocyclic host molecules, cage-shaped host molecules with permanent three-dimensional cavities have better encapsulation of guests and the synergy of multiple binding sites often makes the molecular cages more unique and excellent in the performance of molecular recognition. Although rigid molecular cages have good pre-organization capabilities in theprocess of molecular recognition, they require higher matching of structures between hosts and guests. The flexible molecular cages have good abilities of induced-fit, but the conformational changes during the host-guest binding process may lead to entropy penalty that reduce the binding strengh. Therefore, the concepts of “pre-organization” and “induced-fit” are introduced into the molecualr cage design in this research. Baesd on the naphthol-based ether-oxygen molecular cages reported by our group, a phenyl-based ether-oxygen molecular cage was designed and synthesized. In this article, the synthesis and performance of the phenyl molecular cage was investigated in detail, for exemple, the design optimization of the precursor of the molecular cage. The phenyl-based molecular cage C2 was synthesized, then its detailed structural characterization was performed to reveal its three-dimensional structural information. In the section of host-guest chemistry study of molecular cage C2, theexperimental results show that molecular cage C2 and organic cations have a relatively strong binding. By comparing with the naphthol-based molecular cages 2,3-NC and 2,6-NC reported by our group, the cavity charateristic and recognition characteristic of these three types of structurally similar molecular cages were discussed. Finally, the possibility of molecular cage C2 as a cation recerptor for the recognition and detection of biologically important organic cations is discussed.In order to study the flexibility of molecular cagess and the effect ofether-oxygen chains on the high-intensity recognition of organic cations. Derived from the successful preparation of ether-oxygen molecular cages C2, this article explored and synthesized the relatively rigid ester-based molecular cages C3 and C4, carring out structural characterizaiton and host-guest chemistry research. It was found that these molecular cages have poor recognition capabilities towards organic cations, this also reveals the uniqueness of the flexible ether-oxygen molecular cage in the recognition of organic cations.

超分子化学 主客体性能 有机阳离子 分子笼 分子识别

supramolecular chemistry host-guest property organic cations molecular cages molecular recognition

中文

联合培养

南方科技大学

黄启诚. 苯基分子笼的合成及性能研究[D]. 深圳. 哈尔滨工业大学,2020.