Development of High Throughput Photopolymerizations Using Micron-Sized Ultrathin Metal-Organic Framework Nanosheets

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.