PDF(Pubmed)
Abstract：
Tailoring the hydrophobicity of supramolecular assembly building blocks enables the fabrication of well-defined functional materials. However, the selection of building blocks used in the assembly of metal-phenolic networks (MPNs), an emerging supramolecular assembly platform for particle engineering, has been essentially limited to hydrophilic molecules. Herein, we synthesized and applied biscatechol-functionalized hydrophobic polymers (poly(methyl acrylate) (PMA) and poly(butyl acrylate) (PBA)) as building blocks to engineer MPN particle systems (particles and capsules). Our method allowed control over the shell thickness (e.g., between 10 and 21 nm), stiffness (e.g., from 10 to 126 mN m-1 ), and permeability (e.g., 28-72 % capsules were permeable to 500 kDa fluorescein isothiocyanate-dextran) of the MPN capsules by selection of the hydrophobic polymer building blocks (PMA or PBA) and by controlling the polymer concentration in the MPN assembly solution (0.25-2.0 mM) without additional/engineered assembly processes. Molecular dynamics simulations provided insights into the structural states of the hydrophobic building blocks during assembly and mechanism of film formation. Furthermore, the hydrophobic MPNs facilitated the preparation of fluorescent-labeled and bioactive capsules through postfunctionalization and also particle-cell association engineering by controlling the hydrophobicity of the building blocks. Engineering MPN particle systems via building block hydrophobicity is expected to expand their use.
摘要：
定制超分子组装构件的疏水性使得能够制造明确定义的功能材料。然而,金属-酚醛网络(MPN)组装中使用的构建块的选择，一个新兴的粒子工程超分子组装平台，基本上仅限于亲水性分子。在这里，我们合成并应用双儿茶酚官能化的疏水聚合物（聚（丙烯酸甲酯）（PMA）和聚（丙烯酸丁酯）（PBA））作为构建块来设计MPN颗粒系统（颗粒和胶囊）。我们的方法允许控制外壳厚度(例如，介于10和21纳米之间)，刚度(例如，从10到126mNm-1)，和渗透率(例如，通过选择疏水性聚合物结构单元（PMA或PBA）并通过控制MPN组装溶液中的聚合物浓度（0.25-2.0mM）而无需额外的/工程化的组装过程，28-72％的胶囊对MPN胶囊的500kDa异硫氰酸荧光素-葡聚糖是可渗透的。分子动力学模拟提供了对组装过程中疏水结构单元的结构状态和成膜机理的见解。此外，疏水性MPN通过后官能化以及通过控制结构单元的疏水性来促进荧光标记和生物活性胶囊的制备。通过构建块疏水性工程MPN颗粒系统有望扩大其用途。
