College of Pharmacy, Weifang Medical University, Weifang, Shandong 261053, P. R. China.
College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, P. R. China.
ACS Appl Mater Interfaces. 2020 Apr 1;12(13):15615-15621. doi: 10.1021/acsami.0c02976. Epub 2020 Mar 17.
Construction of large-scale single-layer two-dimensional (2D) frameworks in water is significant due to their utilities in various fields. Utilizing macrocycle-mediated supramolecular self-assembly represents a promising approach; however, challenges still remain in their practical preparation. Here, we exploited a two-step supramolecular strategy to build 2D organic-inorganic hybrid frameworks at a micrometer scale in water. Taking advantage of the high binding affinity to cucurbit[7]uril (CB[7]), mono-quaternary ammonium tetraphenylethene (MQATPE) derivatives were first included with CB[7] to form a 1:1 complex (MQATPE@CB[7]). Then, just mixing the complex with anionic polyoxometalate Na[EuWO]·32HO (denoted as Eu-POM) in a 3:1 molar ratio leads to the formation of single-layer 2D films with tens of micrometers via electrostatic and π-π stacking interactions. The most unique feature of this strategy is that the steric effect imposed by CB[7] would not only lead the modules to adopt a periodic hexagonal assembly but also forbid stacking between layers through comparison with the merely multilayered 2D nanosheets self-assembled by MQATPE/Eu-POM. Interestingly, the charge interactions between MQATPE and Eu-POM would lead to the aggregation-induced emission (AIE) fluorescence of MQATPE, and white light emission could be obtained through the simple regulation of the contents of Eu-POM and MQATPE. Furthermore, due to the high surface areas and more accessible active sites, the single-layer films can act as an effective enzyme inhibitor to modulate the activity of α-chymotrypsin (ChT). These findings suggest a simple but universal approach for single-layer hybrid materials, which may hold promise for practical applications in photophysical and biomedical fields.
在水中构建大规模的单层二维(2D)框架具有重要意义,因为它们在各个领域都有应用。利用大环介导的超分子自组装是一种很有前途的方法;然而,在实际制备方面仍存在挑战。在这里,我们利用两步超分子策略在水中构建了微米级的二维有机-无机杂化框架。利用对葫芦[7]脲(CB[7])的高结合亲和力,首先将单季铵盐四苯乙烯(MQATPE)衍生物与 CB[7]包合形成 1:1 配合物(MQATPE@CB[7])。然后,只需将该配合物与阴离子多金属氧酸盐 Na[EuWO]·32H2O(表示为 Eu-POM)以 3:1 的摩尔比混合,通过静电和π-π堆积相互作用,就可以形成具有数十微米厚度的单层 2D 薄膜。这种策略的最独特之处在于,CB[7]施加的空间位阻不仅会导致模块采用周期性的六方组装,而且还会通过与仅仅由 MQATPE/Eu-POM 自组装形成的多层 2D 纳米片进行比较,阻止层间堆积。有趣的是,MQATPE 和 Eu-POM 之间的电荷相互作用会导致 MQATPE 的聚集诱导发射(AIE)荧光,并且通过简单调节 Eu-POM 和 MQATPE 的含量可以获得白光发射。此外,由于具有较高的比表面积和更多可及的活性位点,单层薄膜可以作为有效的酶抑制剂来调节α-糜蛋白酶(ChT)的活性。这些发现为单层杂化材料提供了一种简单但通用的方法,有望在光物理和生物医学领域得到实际应用。