Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Science, Wuhan University, Wuhan, Hubei, 430072, P. R. China.
Department of Chemical and Biological Engineering, Guangdong-Hong Kong-Macao Joint Laboratory for Intelligent Micro-Nano Optoelectronic Technology, William Mong Institute of Nano Science and Technology, and Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, the Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, 999077, P. R. China.
Macromol Rapid Commun. 2022 May;43(9):e2200020. doi: 10.1002/marc.202200020. Epub 2022 Feb 25.
Polymer syntheses in a high throughput format are still challenging due to the tedious procedures for prior deoxygenation and catalyst removal. 2D metal-organic framework (MOF) nanosheets are advantageous for elevating the catalytic efficiency and catalyst recyclability. Polymerization of a wide variety of monomers, including hydrophilic acrylamides and hydrophobic acrylates, is attempted directly in a multi-well plate by employing Zn-ZnPPF-2D nanosheets (PPF = porphyrin paddlewheel framework) as a heterogeneous photocatalyst. Various parameters such as monomer concentration, catalyst concentration, and light wavelength are investigated with respect to their effects on polymerization rate and the degree of control over the molecular weight and molecular weight distribution. Due to the larger surface area and more accessible catalytic sites, the top-performing Zn-ZnPPF-2D exhibits fast polymerization kinetics over the Zn-ZnPPF-3D bulk crystals. In addition, the synthesis of triblock copolymers with a single loading of catalysts confirms the outstanding catalytic performance of these 2D MOF catalysts. Finally, photopolymerization is demonstrated to be achievable entirely in a microliter-scale human cell culture medium. As such, this strategy provides high levels of control and precision over macromolecular synthesis outcomes that best align with the requirements of high throughput approaches toward biological applications.
由于先前脱氧和催化剂去除的繁琐程序，高通量格式的聚合物合成仍然具有挑战性。二维金属-有机骨架（MOF）纳米片有利于提高催化效率和催化剂的可回收性。通过在多孔板中直接使用 Zn-ZnPPF-二维纳米片（PPF=卟啉桨轮骨架）作为多相光催化剂，尝试聚合各种单体，包括亲水性丙烯酰胺和疏水性丙烯酸酯。研究了各种参数，如单体浓度、催化剂浓度和光波长度，以研究它们对聚合速率以及对分子量和分子量分布的控制程度的影响。由于更大的表面积和更多可及的催化位点，表现最佳的 Zn-ZnPPF-二维纳米片在 Zn-ZnPPF-3D 块状晶体上表现出更快的聚合动力学。此外，使用单一催化剂负载量合成三嵌段共聚物证实了这些二维 MOF 催化剂的出色催化性能。最后，证明了在微升级别的人细胞培养基中可以实现光聚合。因此，该策略为大分子合成结果提供了高水平的控制和精度，这与高通量方法在生物应用中的要求最吻合。
