Kim Chan-Jin, Goudeli Eirini, Ercole Francesca, Ju Yi, Gu Yuang, Xu Wanjun, Quinn John F, Caruso Frank
Department of Chemical Engineering, The University of Melbourne, Parkville, Victoria, 3010, Australia.
Drug Delivery, Disposition and Dynamics Theme, Monash Institute of Pharmaceutical Sciences, Monash University, Parkville, Victoria, 3052, Australia.
Angew Chem Int Ed Engl. 2024 Jan 22;63(4):e202315297. doi: 10.1002/anie.202315297. Epub 2023 Dec 20.
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 ), 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.
调整超分子组装结构单元的疏水性能够制备出结构明确的功能材料。然而，用于金属酚醛网络（MPN）组装的结构单元选择，作为一种新兴的用于粒子工程的超分子组装平台，基本上仅限于亲水分子。在此，我们合成并应用了双儿茶酚功能化的疏水聚合物（聚丙烯酸甲酯（PMA）和聚丙烯酸丁酯（PBA））作为结构单元来构建MPN粒子系统（粒子和胶囊）。我们的方法能够通过选择疏水聚合物结构单元（PMA或PBA）以及控制MPN组装溶液中的聚合物浓度（0.25 - 2.0 mM），在无需额外/工程化组装过程的情况下，控制MPN胶囊的壳厚度（例如，在10至21 nm之间）、硬度（例如，从10至126 mN m）和渗透性（例如，28 - 72%的胶囊对500 kDa异硫氰酸荧光素 - 葡聚糖具有渗透性）。分子动力学模拟为组装过程中疏水结构单元的结构状态和成膜机制提供了见解。此外，疏水性MPN通过后功能化促进了荧光标记和生物活性胶囊的制备，并且通过控制结构单元的疏水性实现了粒子 - 细胞缔合工程。通过结构单元疏水性来构建MPN粒子系统有望扩大其应用范围。
