Metal–Phenolic Networks: From Simple Composites to Tailored Architectures
AffiliationChemical and Biomolecular Engineering
Document TypePhD thesis
Access StatusThis item is embargoed and will be available on 2023-06-10.
© 2021 Zhixing Lin
Metal–phenolic networks (MPNs), which are made using metal ions and phenolic ligands, have attracted widespread interest owing to their hybrid physicochemical properties and high affinity to diverse substrates. The combination of MPNs with functional materials can lead to MPN composites capable of outperforming the individual components in a wide range of emerging applications. However, the small pore size of MPNs limits the possibilities of loading MPN-based materials with other functional components. In addition, the controlled assembly of MPN composites for functional thin films with tailored structures has been largely unexplored. This thesis focuses on the engineering of the composition and structure of MPN composites for various applications. Firstly, a supramolecular fluorescent labeling strategy was developed using luminescent MPN composites that consist of a MPN and commercially available dyes. To demonstrate the versatility of this strategy, 16 types of particle substrates that are formed from different materials, and have different sizes and surface chemistries, were successfully labeled. This strategy obviated the need to covalently conjugate the dyes or to modify the surface chemistry of the substrates. In addition, customized luminescence regimes (e.g., red, blue, multichromatic, and white light) were readily achieved using common fluorophores. The fluorescent coating is stable in many biological environments, such as in serum and the cytosol, which demonstrates its potential to study the cell association and internalization of particles in real-time. Secondly, a cubosome templating strategy was developed to prepare ordered mesoporous MPN particles with uniformly large pores (around 40 nm). The large mesopores allow various cargos (e.g., biomacromolecules) to diffuse into the particles while the phenolic groups stabilize the cargos. This led to considerably higher loading amounts than those typically achieved when using commercially available SiO2 with 50 nm pores. In addition, meso-MPN particles that are loaded with enzymes acted as highly efficient bioreactors, displaying catalytic activities that exceed those prepared from porous silica particles. Thirdly, cubosome templates were also engineered in the form of monoliths using diffusion-induced self-assembly, and the formation mechanism and precise molecular organization of the monoliths were investigated by both experiments and all-atom molecular dynamics simulations. The large pores of the polymer monoliths were then used to synthesize ordered MPN-based monoliths. These results show the significant potential of using MPN composites in various fields, including chemistry, biology, and materials science.
KeywordsSupramolecular Chemistry; Metal−Phenolic Networks; Fluorescent Materials; Nanobiotechnology; Block Copolymers; Self-Assembly; Triply Periodic Minimal Surface; Mesoporous Materials; Colloid and Surface Chemistry; Functional Composites; Metal−Organic Frameworks; Nanomaterials
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