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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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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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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ItemNanostructured particles assembled from natural building blocks for advanced therapies(ROYAL SOC CHEMISTRY, 2022-06-06)Advanced treatments based on immune system manipulation, gene transcription and regulation, specific organ and cell targeting, and/or photon energy conversion have emerged as promising therapeutic strategies against a range of challenging diseases. Naturally derived macromolecules (e.g., proteins, lipids, polysaccharides, and polyphenols) have increasingly found use as fundamental building blocks for nanostructured particles as their advantageous properties, including biocompatibility, biodegradability, inherent bioactivity, and diverse chemical properties make them suitable for advanced therapeutic applications. This review provides a timely and comprehensive summary of the use of a broad range of natural building blocks in the rapidly developing field of advanced therapeutics with insights specific to nanostructured particles. We focus on an up-to-date overview of the assembly of nanostructured particles using natural building blocks and summarize their key scientific and preclinical milestones for advanced therapies, including adoptive cell therapy, immunotherapy, gene therapy, active targeted drug delivery, photoacoustic therapy and imaging, photothermal therapy, and combinational therapy. A cross-comparison of the advantages and disadvantages of different natural building blocks are highlighted to elucidate the key design principles for such bio-derived nanoparticles toward improving their performance and adoption. Current challenges and future research directions are also discussed, which will accelerate our understanding of designing, engineering, and applying nanostructured particles for advanced therapies.
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ItemAssembly of Bioactive Nanoparticles via Metal-Phenolic Complexation(Wiley, 2022)The integration of bioactive materials (e.g., proteins and genes) into nanoparticles holds promise in fields ranging from catalysis to biomedicine. However, it is challenging to develop a simple and broadly applicable nanoparticle platform that can readily incorporate distinct biomacromolecules without affecting their intrinsic activity. Herein, a metal-phenolic assembly approach is presented whereby diverse functional nanoparticles can be readily assembled in water by combining various synthetic and natural building blocks, including poly(ethylene glycol), phenolic ligands, metal ions, and bioactive macromolecules. The assembly process is primarily mediated by metal-phenolic complexes through coordination and hydrophobic interactions, which yields uniform and spherical nanoparticles (mostly <200 nm), while preserving the function of the incorporated biomacromolecules (siRNA and five different proteins used). The functionality of the assembled nanoparticles is demonstrated through cancer cell apoptosis, RNA degradation, catalysis, and gene downregulation studies. Furthermore, the resulting nanoparticles can be used as building blocks for the secondary engineering of superstructures via templating and cross-linking with metal ions. The bioactivity and versatility of the platform can potentially be used for the streamlined and rational design of future bioactive materials.
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ItemLuminescent Metal-Phenolic Networks for Multicolor Particle Labeling(WILEY-V C H VERLAG GMBH, 2021-11-15)The development of fluorescence labeling techniques has attracted widespread interest in various fields, including biomedical science as it can facilitate high-resolution imaging and the spatiotemporal understanding of various biological processes. We report a supramolecular fluorescence labeling strategy using luminescent metal-phenolic networks (MPNs) constructed from metal ions, phenolic ligands, and common and commercially available dyes. The rapid labeling process (<5 min) produces ultrathin coatings (≈10 nm) on diverse particles (e.g., organic, inorganic, and biological entities) with customized luminescence (e.g., red, blue, multichromatic, and white light) simply through the selection of fluorophores. The fluorescent coatings are stable at pH values from 1 to 8 and in complex biological media owing to the dominant π interactions between the dyes and MPNs. These coatings exhibit negligible cytotoxicity and their strong fluorescence is retained even when internalized into intracellular compartments. This strategy is expected to provide a versatile approach for fluorescence labeling with potential in diverse fields across the physical and life sciences.