Chemical and Biomolecular Engineering - Research Publications
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ItemCytoprotective Metal-Phenolic Network Sporulation to Modulate Microalgal Mobility and Division(WILEY, 2024-01)Synthetic cell exoskeletons created from abiotic materials have attracted interest in materials science and biotechnology, as they can regulate cell behavior and create new functionalities. Here, a facile strategy is reported to mimic microalgal sporulation with on-demand germination and locomotion via responsive metal-phenolic networks (MPNs). Specifically, MPNs with tunable thickness and composition are deposited on the surface of microalgae cells via one-step coordination, without any loss of cell viability or intrinsic cell photosynthetic properties. The MPN coating keeps the cells in a dormant state, but can be disassembled on-demand in response to environmental pH or chemical stimulus, thereby reviving the microalgae within 1 min. Moreover, the artificial sporulation of microalgae resulted in resistance to environmental stresses (e.g., metal ions and antibiotics) akin to the function of natural sporulation. This strategy can regulate the life cycle of complex cells, providing a synthetic strategy for designing hybrid microorganisms.
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ItemNo Preview AvailableModular Metal‐Quinone Networks with Tunable Architecture and Functionality(Wiley, 2023-03-27)Abstract Nanostructured materials with tunable structures and functionality are of interest in diverse areas. Herein, metal ions are coordinated with quinones through metal‐acetylacetone coordination bonds to generate a class of structurally tunable, universally adhesive, hydrophilic, and pH‐degradable materials. A library of metal‐quinone networks (MQNs) is produced from five model quinone ligands paired with nine metal ions, leading to the assembly of particles, tubes, capsules, and films. Importantly, MQNs show bidirectional pH‐responsive disassembly in acidic and alkaline solutions, where the quinone ligands mediate the disassembly kinetics, enabling temporal and spatial control over the release of multiple components using multilayered MQNs. Leveraging this tunable release and the inherent medicinal properties of quinones, MQN prodrugs with a high drug loading (>89 wt %) are engineered using doxorubicin for anti‐cancer therapy and shikonin for the inhibition of the main protease in the SARS‐CoV‐2 virus.
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ItemPeptide-Based Coacervate Protocells with Cytoprotective Metal-Phenolic Network Membranes(AMER CHEMICAL SOC, 2023-10-03)Protocells have garnered considerable attention from cell biologists, materials scientists, and synthetic biologists. Phase-separating coacervate microdroplets have emerged as a promising cytomimetic model because they can internalize and concentrate components from dilute surrounding environments. However, the membrane-free nature of such coacervates leads to coalescence into a bulk phase, a phenomenon that is not representative of the cells they are designed to mimic. Herein, we develop a membranized peptide coacervate (PC) with oppositely charged oligopeptides as the molecularly crowded cytosol and a metal-phenolic network (MPN) coating as the membrane. The hybrid protocell efficiently internalizes various bioactive macromolecules (e.g., bovine serum albumin and immunoglobulin G) (>90%) while also resisting radicals due to the semipermeable cytoprotective membrane. Notably, the resultant PC@MPNs are capable of anabolic cascade reactions and remain in discrete protocellular populations without coalescence. Finally, we demonstrate that the MPN protocell membrane can be postfunctionalized with various functional molecules (e.g., folic acid and fluorescence dye) to more closely resemble actual cells with complex membranes, such as recognition molecules, which allows for drug delivery. This membrane-bound cytosolic protocell structure paves the way for innovative synthetic cells with structural and functional complexity.
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ItemNo Preview AvailableSite‐Selective Coordination Assembly of Dynamic Metal‐Phenolic Networks(Wiley, 2022-08-22)Abstract Coordination states of metal‐organic materials are known to dictate their physicochemical properties and applications in various fields. However, understanding and controlling coordination sites in metal‐organic systems is challenging. Herein, we report the synthesis of site‐selective coordinated metal‐phenolic networks (MPNs) using flavonoids as coordination modulators. The site‐selective coordination was systematically investigated experimentally and computationally using ligands with one, two, and multiple different coordination sites. Tuning the multimodal Fe coordination with catechol, carbonyl, and hydroxyl groups within the MPNs enabled the facile engineering of diverse physicochemical properties including size, selective permeability (20–2000 kDa), and pH‐dependent degradability. This study expands our understanding of metal‐phenolic chemistry and provides new routes for the rational design of structurally tailorable coordination‐based materials.
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ItemDirect synthesis of amorphous coordination polymers and metal-organic frameworks(NATURE PORTFOLIO, 2023-04)Coordination polymers (CPs) and their subset, metal-organic frameworks (MOFs), can have porous structures and hybrid physicochemical properties that are useful for diverse applications. Although crystalline CPs and MOFs have received the most attention to date, their amorphous states are of growing interest as they can be directly synthesized under mild conditions. Directly synthesized amorphous CPs (aCPs) can be constructed from a wider range of metals and ligands than their crystalline and crystal-derived counterparts and demonstrate numerous unique material properties, such as higher mechanical robustness, increased stability and greater processability. This Review examines methods for the direct synthesis of aCPs and amorphous MOFs, as well as their properties and characterization routes, and offers a perspective on the opportunities for the widespread adoption of directly synthesized aCPs.
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ItemModular Metal-Quinone Networks with Tunable Architecture and Functionality(WILEY-V C H VERLAG GMBH, 2023-03-27)Nanostructured materials with tunable structures and functionality are of interest in diverse areas. Herein, metal ions are coordinated with quinones through metal-acetylacetone coordination bonds to generate a class of structurally tunable, universally adhesive, hydrophilic, and pH-degradable materials. A library of metal-quinone networks (MQNs) is produced from five model quinone ligands paired with nine metal ions, leading to the assembly of particles, tubes, capsules, and films. Importantly, MQNs show bidirectional pH-responsive disassembly in acidic and alkaline solutions, where the quinone ligands mediate the disassembly kinetics, enabling temporal and spatial control over the release of multiple components using multilayered MQNs. Leveraging this tunable release and the inherent medicinal properties of quinones, MQN prodrugs with a high drug loading (>89 wt %) are engineered using doxorubicin for anti-cancer therapy and shikonin for the inhibition of the main protease in the SARS-CoV-2 virus.
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ItemHighly Stable and Active Flexible Electrocatalysts Derived from Lotus Fibers(WILEY-V C H VERLAG GMBH, 2023-03)Abstract The stability and activity of electrocatalysts are fundamental in energy‐related applications (e.g., hydrogen generation and energy storage). Electrocatalysts degrade over time when the active centers are not strongly anchored to the support. However, if the active centers are too strongly anchored, the activity of the electrocatalysts decreases due to reduced accessibility to reactants. Herein, a strategy is presented to balance the stability and activity of different active materials using a natural and flexible support material that can be woven and carbonized. Lotus fibers, which have surface hydroxyl and phenolic groups, high mechanical strength, and a mesoscale porosity post‐pyrolysis, are used to load diverse functional metal‐containing materials such as metal–organic frameworks, 2D materials, metal sulfide nanoparticles, metal ions, and high‐entropy alloys. After pyrolysis, the electrocatalysts display flexibility, high catalytic performance, and long‐term stability, outperforming commercial benchmarks (e.g., Pt/C) in specific scenarios for water splitting, liquid batteries, and flexible electronics.
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ItemSite-Selective Coordination Assembly of Dynamic Metal-Phenolic Networks(WILEY-V C H VERLAG GMBH, 2022-08-22)Coordination states of metal-organic materials are known to dictate their physicochemical properties and applications in various fields. However, understanding and controlling coordination sites in metal-organic systems is challenging. Herein, we report the synthesis of site-selective coordinated metal-phenolic networks (MPNs) using flavonoids as coordination modulators. The site-selective coordination was systematically investigated experimentally and computationally using ligands with one, two, and multiple different coordination sites. Tuning the multimodal Fe coordination with catechol, carbonyl, and hydroxyl groups within the MPNs enabled the facile engineering of diverse physicochemical properties including size, selective permeability (20-2000 kDa), and pH-dependent degradability. This study expands our understanding of metal-phenolic chemistry and provides new routes for the rational design of structurally tailorable coordination-based materials.
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ItemRole of Molecular Interactions in Supramolecular Polypeptide-Polyphenol Networks for Engineering Functional Materials(AMER CHEMICAL SOC, 2022-07-13)Supramolecular assembly affords the development of a wide range of polypeptide-based biomaterials for drug delivery and nanomedicine. However, there remains a need to develop a platform for the rapid synthesis and study of diverse polypeptide-based materials without the need for employing complex chemistries. Herein, we develop a versatile strategy for creating polypeptide-based materials using polyphenols that display multiple synergistic cross-linking interactions with different polypeptide side groups. We evaluated the diverse interactions operating within these polypeptide-polyphenol networks via binding affinity, thermodynamics, and molecular docking studies and found that positively charged polypeptides (Ka of ∼2 × 104 M-1) and polyproline (Ka of ∼2 × 106 M-1) exhibited stronger interactions with polyphenols than other amino acids (Ka of ∼2 × 103 M-1). Free-standing particles (capsules) were obtained from different homopolypeptides using a template-mediated strategy. The properties of the capsules varied with the homopolypeptide used, for example, positively charged polypeptides produced thicker shell walls (120 nm) with reduced permeability and involved multiple interactions (i.e., electrostatic and hydrogen), whereas uncharged polypeptides generated thinner (10 nm) and more permeable shell walls due to the dominant hydrophobic interactions. Polyarginine imparted cell penetration and endosomal escape properties to the polyarginine-tannic acid capsules, enabling enhanced delivery of the drug doxorubicin (2.5 times higher intracellular fluorescence after 24 h) and a corresponding higher cell death in vitro when compared with polyproline-tannic acid capsules. The ability to readily complex polyphenols with different types of polypeptides highlights that a wide range of functional materials can be generated for various applications.
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ItemUltrastrong underwater adhesion on diverse substrates using non-canonical phenolic groups(NATURE PORTFOLIO, 2022-04-13)Robust underwater adhesion is challenging because a hydration layer impedes the interaction between substrates and adhesives. Phenolic adhesives inspired by marine creatures such as mussels were extensively studied, but these adhesives have not reached the adhesion strength and substrate diversity of Man-made dry adhesives. Here, we report a class of ultrastrong underwater adhesives with molecular phenolic designs extending beyond what nature has produced. These non-canonical phenolic polymers show versatile adhesion on various materials, with adhesion strengths exceeding 10 MPa on metal. Incorporating even just a small amount (<10%) of non-canonical phenolic groups into a polymer is sufficient for dramatically enhancing underwater adhesion, suggesting that this new class of phenolic materials will be incorporated into various industrial polymer systems in the future.