Chemical and Biomedical Engineering - Research Publications
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ItemExpanding the Toolbox of Metal-Phenolic Networks via Enzyme-Mediated Assembly(Wiley, 2020-01-01)Functional coatings are of considerable interest because of their fundamental implications for interfacial assembly and promise for numerous applications. Universally adherent materials have recently emerged as versatile functional coatings; however, such coatings are generally limited to catechol, (ortho‐diphenol)‐containing molecules, as building blocks. Here, we report a facile, biofriendly enzyme‐mediated strategy for assembling a wide range of molecules (e.g., 14 representative molecules in this study) that do not natively have catechol moieties, including small molecules, peptides, and proteins, on various surfaces, while preserving the molecule's inherent function, such as catalysis (≈80 % retention of enzymatic activity for trypsin). Assembly is achieved by in situ conversion of monophenols into catechols via tyrosinase, where films form on surfaces via covalent and coordination cross‐linking. The resulting coatings are robust, functional (e.g., in protective coatings, biological imaging, and enzymatic catalysis), and versatile for diverse secondary surface‐confined reactions (e.g., biomineralization, metal ion chelation, and N‐hydroxysuccinimide conjugation).
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ItemModular Assembly of Host-Guest Metal-Phenolic Networks Using Macrocyclic Building Blocks(Wiley, 2020-01-02)The manipulation of interfacial properties has broad implications for the development of high‐performance coatings. Metal–phenolic networks (MPNs) are an emerging class of responsive, adherent materials. Herein, host–guest chemistry is integrated with MPNs to modulate their surface chemistry and interfacial properties. Macrocyclic cyclodextrins (host) are conjugated to catechol or galloyl groups and subsequently used as components for the assembly of functional MPNs. The assembled cyclodextrin‐based MPNs are highly permeable (even to high molecular weight polymers: 250–500 kDa), yet they specifically and noncovalently interact with various functional guests (including small molecules, polymers, and carbon nanomaterials), allowing for modular and reversible control over interfacial properties. Specifically, by using either hydrophobic or hydrophilic guest molecules, the wettability of the MPNs can be readily tuned between superrepellency (>150°) and superwetting (ca. 0°).
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ItemMetal-Phenolic Coatings as a Platform to Trigger Endosomal Escape of Nanoparticles.(American Chemical Society, 2019-10-22)The intracellular delivery of functional nanoparticles (NPs) and the release of therapeutic payloads at a target site are central issues for biomedical applications. However, the endosomal entrapment of NPs typically results in the degradation of active cargo, leading to poor therapeutic outcomes. Current advances to promote the endosomal escape of NPs largely involve the use of polycationic polymers and cell-penetrating peptides (CPPs), which both can suffer from potential toxicity and convoluted synthesis/conjugation processes. Herein, we report the use of metal-phenolic networks (MPNs) as versatile and nontoxic coatings to facilitate the escape of NPs from endo/lysosomal compartments. The MPNs, which were engineered from the polyphenol tannic acid and FeIII or AlIII, enabled the endosomal escape of both inorganic (mesoporous silica) and organic (polystyrene and melamine resin) NPs owing to the "proton-sponge effect" arising from the buffering capacity of MPNs. Postfunctionalization of the MPN-coated NPs with low-fouling polymers did not impair the endosomal escape, indicating the modular and generalizable nature of this approach. We envisage that the ease of fabrication, versatility, low cytotoxicity, and promising endosomal escape performance displayed by the MPN coatings offer opportunities for such coatings to be used for the efficient delivery of cytoplasm-targeted therapeutics using NPs.
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ItemLigand-Functionalized Poly(ethylene glycol) Particles for Tumor Targeting and Intracellular Uptake.(American Chemical Society, 2019)Drug carriers typically require both stealth and targeting properties to minimize nonspecific interactions with healthy cells and increase specific interaction with diseased cells. Herein, the assembly of targeted poly(ethylene glycol) (PEG) particles functionalized with cyclic peptides containing Arg-Gly-Asp (RGD) (ligand) using a mesoporous silica templating method is reported. The influence of PEG molecular weight, ligand-to-PEG molecule ratio, and particle size on cancer cell targeting to balance stealth and targeting of the engineered PEG particles is investigated. RGD-functionalized PEG particles (PEG-RGD particles) efficiently target U-87 MG cancer cells under static and flow conditions in vitro, whereas PEG and cyclic peptides containing Arg-Asp-Gly (RDG)-functionalized PEG (PEG-RDG) particles display negligible interaction with the same cells. Increasing the ligand-to-PEG molecule ratio improves cell targeting. In addition, the targeted PEG-RGD particles improve cell uptake via receptor-mediated endocytosis, which is desirable for intracellular drug delivery. The PEG-RGD particles show improved tumor targeting (14% ID g-1) when compared with the PEG (3% ID g-1) and PEG-RDG (7% ID g-1) particles in vivo, although the PEG-RGD particles show comparatively higher spleen and liver accumulation. The targeted PEG particles represent a platform for developing particles aimed at balancing nonspecific and specific interactions in biological systems.
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ItemMetal-dependent inhibition of amyloid fibril formation: synergistic effects of cobalt-tannic acid networks(ROYAL SOC CHEMISTRY, 2019-01-28)Metal-phenolic networks (MPNs) have received widespread interest owing to their modular incorporation of functional metal ions and phenolic ligands. However, the interaction between MPNs and biomolecules is still relatively unexplored. Herein, we studied the effects of MPN-coated gold nanoparticles on amyloid fibril formation (which is associated with Alzheimer's disease) as a function of the metal ion in the MPN systems. All coated particles examined inhibited amyloid formation, with cobalt(ii) MPN-coated particles exhibiting the highest inhibition activity (90%). Molecular dynamics simulations and quantum mechanics calculations suggested that the geometry of the exposed cobalt coordination site in the cobalt-tannic acid networks facilitates its interactions with histidine and methionine residues in the amyloid beta peptides. Furthermore, the unique structure of cobalt MPNs may enable a wider variety of biomedical applications.
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ItemSpray Assembly of Metal-Phenolic Networks: Formation, Growth, and Applications(AMER CHEMICAL SOC, 2018-10-03)Hybrid conformal coatings, such as metal-phenolic networks (MPNs) that are constructed from the coordination-driven assembly of natural phenolic ligands, are of interest in areas including biomedicine, separations, and energy. To date, most MPN coatings have been prepared by immersing substrates in solutions containing the phenolic ligands and metal ions, which is a suitable method for coating small or flexible objects. In contrast, more industrially relevant methods for coating and patterning large substrates, such as spray assembly, have been explored to a lesser extent toward the fabrication of MPNs, particularly regarding the effect of process variables on MPN growth. Herein, a spray assembly method was used to fabricate MPN coatings with various phenolic building blocks and metal ions and their formation and patterning were explored for different applications. Different process parameters including solvent, pH, and metal-ligand pair allowed for control over the film properties such as thickness and roughness. On the basis of these investigations, a potential route for the formation of spray-assembled MPN films was proposed. Conditions favoring the formation of bis complexes could produce thicker coatings than those favoring the formation of mono or tris complexes. Finally, the spray-assembled MPNs were used to generate superhydrophilic membranes for oil-water separation and colorless films for UV shielding. The present study provides insights into the chemistry of MPN assembly and holds promise for advancing the fabrication of multifunctional hybrid materials.