葫芦脲在色谱固定相中的研究进展

葫芦脲是超分子化学中继冠醚、环糊精、杯芳烃之后发展起来的又一类新型高度对称的桶状大环主体分子,是一种由多个甘脲单元组成的大环穴状配体,被誉为"第四代超分子化合物"。由于其具有特殊的分离选择性和稳定性,在超分子化学和色谱的交叉领域备受关注。本文从葫芦脲的结构特征出发,侧重概述了葫芦脲同系物及其衍生物在色谱固定相中的研究现状和进展。     

瓜环{Q[n]}与染料碱性嫩黄O相互作用的研究

利用1H NMR和UV-vis研究了瓜环{Q[n](n=6,7)}与染料碱性嫩黄O(BO)的相互作用及其包结比【n{Q[n]}∶n(BO)】,结果表明,BO能穿过Q[7]空腔形成2∶1的包结配合物,能与Q[6]以端口的形式相互作用,配位比1∶1。     

In Vitro and In Vivo Sequestration of Phencyclidine by Me4Cucurbit[8]uril**

We report investigations of the use of cucurbit[8]uril (CB[8]) macrocycles as an antidote to counteract the in vivo biological effects of phencyclidine. We investigate the binding of CB[8] and its derivative Me₄CB[8] toward ten drugs of abuse ( 3 – 9 , 12 – 14 ) by a combination of ¹H NMR spectroscopy and isothermal titration calorimetry in phosphate buffered water. We find that the cavity of CB[8] and Me₄CB[8] are able to encapsulate the 1-amino-1-aryl-cyclohexane ring system of phencyclidine (PCP) and ketamine as well as the morphinan skeleton of morphine and hydromorphone with K_d values ≤50 nm . In vitro cytotoxicity (MTS metabolic and adenylate kinase cell death assays in HEK293 and HEPG2 cells) and in vivo maximum tolerated dose studies (Swiss Webster mice) which were performed for Me₄CB[8] indicated good tolerability. The tightest host⋅guest pair (Me₄CB[8]⋅PCP; K_d=2 nm ) was advanced to in vivo efficacy studies. The results of open field tests demonstrate that pretreatment of mice with Me₄CB[8] prevents subsequent hyperlocomotion induction by PCP and also that treatment of animals previously dosed with PCP with Me₄CB[8] significantly reduces the locomotion levels.     

Three‐Component Cucurbit[6]uril Framework with 1:2 Host‐Guest Motif and Dimeric Boric Acid

Three‐component framework of cucurbit[6]uril, 3‐(1‐methylimidazolium‐3‐yl)propane‐1‐sulfonate and boric acid has been constructed. The crystal structure reveals 1:2 host‐guest motif of cucurbit[6]uril and 3‐(1‐methyl‐imidazolium‐3‐yl)propane‐1‐sulfonate, demonstrating both cation binding of imidazolium moiety and anion binding of sulfonate moiety for the first time. Incorporation of dimeric boric acid facilitates the formation of metal‐free three‐dimensional framework.     

Hexanoate-Cucurbit[7]uril: Highly Soluble with Controlled Release Ability

Current drug delivery systems gain more functions with increased complexity. With the idea of less is more, we synthesized hexanoate-cucurbit[7]uril (CB[7]C₅COONa) with multiple promising features for drug delivery. The hexanoate group integrates multiple functions. It endows CB[7]C₅COONa extremely high solubility of over 600 mg mL⁻¹ and well-defined pH-controlled release ability without sacrificing on the high binding affinity of CB[7] cavity. Based on the pH-controlled release ability, CB[7]C₅COONa can be used for controlling the bioactivity of drug molecules. We anticipate that the strategy of function integration would be useful for the design of simple yet powerful drug delivery systems.