Chemical and Biomolecular Engineering - Research Publications
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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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ItemEngineering Metal-Phenolic Networks for Solar Desalination with Directional Salt Crystallization(WILEY-V C H VERLAG GMBH, 2023-01)Solar desalination is one of the most promising strategies to address the global freshwater shortage crisis. However, the residual salt accumulated on the top surface of solar evaporators severely reduces light absorption and steam evaporation efficiency, thus impeding the further industrialization of this technology. Herein, a metal-phenolic network (MPN)-engineered 3D evaporator composed of photothermal superhydrophilic/superhydrophobic sponges and side-twining hydrophilic threads for efficient desalination with directional salt crystallization and zero liquid discharge is reported. The MPN coatings afford the engineering of alternating photothermal superhydrophilic/superhydrophobic sponges with high heating efficiency and defined vapor escape channels, while the side-twining threads induce site-selective salt crystallization. The 3D evaporator exhibits a high and stable indoor desalination rate (≈2.3 kg m-2 h-1 ) of concentrated seawater (20 wt%) under simulated sun irradiation for over 21 days without the need for salt crystallization inhibitors. This direct desalination is also achieved in outdoor field operations with a production rate of clean water up to ≈1.82 kg m-2 h-1 from concentrated seawater (10 wt%). Together with the high affinity and multiple functions of MPNs, this work is expected to facilitate the rational design of solar desalination devices and boost the research translation of MPN materials in broader applications.
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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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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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ItemBioresponsive Polyphenol-Based Nanoparticles as Thrombolytic Drug Carriers(AMER CHEMICAL SOC, 2022-01-12)Thrombolytic (clot-busting) therapies with plasminogen activators (PAs) are first-line treatments against acute thrombosis and ischemic stroke. However, limitations such as narrow therapeutic windows, low success rates, and bleeding complications hinder their clinical use. Drug-loaded polyphenol-based nanoparticles (NPs) could address these shortfalls by delivering a more targeted and safer thrombolysis, coupled with advantages such as improved biocompatibility and higher stability in vivo. Herein, a template-mediated polyphenol-based supramolecular assembly strategy is used to prepare nanocarriers of thrombolytic drugs. A thrombin-dependent drug release mechanism is integrated using tannic acid (TA) to cross-link urokinase-type PA (uPA) and a thrombin-cleavable peptide on a sacrificial mesoporous silica template via noncovalent interactions. Following drug loading and template removal, the resulting NPs retain active uPA and demonstrate enhanced plasminogen activation in the presence of thrombin (1.14-fold; p < 0.05). Additionally, they display lower association with macrophage (RAW 264.7) and monocytic (THP-1) cell lines (43 and 7% reduction, respectively), reduced hepatic accumulation, and delayed blood clearance in vivo (90% clearance at 60 min vs 5 min) compared with the template-containing NPs. Our thrombin-responsive, polyphenol-based NPs represent a promising platform for advanced drug delivery applications, with potential to improve thrombolytic therapies.
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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.
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ItemRobust and Versatile Coatings Engineered via Simultaneous Covalent and Noncovalent Interactions(WILEY-V C H VERLAG GMBH, 2021-09-06)Interfacial modular assembly has emerged as an adaptable strategy for engineering the surface properties of substrates in biomedicine, photonics, and catalysis. Herein, we report a versatile and robust coating (pBDT-TA), self-assembled from tannic acid (TA) and a self-polymerizing aromatic dithiol (i.e., benzene-1,4-dithiol, BDT), that can be engineered on diverse substrates with a precisely tuned thickness (5-40 nm) by varying the concentration of BDT used. The pBDT-TA coating is stabilized by covalent (disulfide) bonds and supramolecular (π-π) interactions, endowing the coating with high stability in various harsh aqueous environments across ionic strength, pH, temperature (e.g., 100 mM NaCl, HCl (pH 1) or NaOH (pH 13), and water at 100 °C), as well as surfactant solution (e.g., 100 mM Triton X-100) and biological buffer (e.g., Dulbecco's phosphate-buffered saline), as validated by experiments and simulations. Moreover, the reported pBDT-TA coating enables secondary reactions on the coating for engineering hybrid adlayers (e.g., ZIF-8 shells) via phenolic-mediated adhesion, and the facile integration of aromatic fluorescent dyes (e.g., rhodamine B) via π interactions without requiring elaborate synthetic processes.
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ItemStereoselective Growth of Small Molecule Patches on Nanoparticles(AMER CHEMICAL SOC, 2021-08-11)Patchy nanoparticles featuring tunable surface domains with spatial and chemical specificity are of fundamental interest, especially for creating three-dimensional (3D) colloidal structures. Guided assembly and regioselective conjugation of polymers have been widely used to manipulate such topography on nanoparticles; however, the processes require presynthesized specialized polymer chains and elaborate assembly conditions. Here, we show how small molecules can form 3D patches in aqueous environments in a single step. The patch features (e.g., size, number, conformation, and stereoselectivity) are modulated by a self-polymerizable aromatic dithiol and comixed ligands, which indicates an autonomous assembly mechanism involving covalent polymerization and supramolecular assembly. Moreover, this method is independent of the underlying nanoparticle material and dimension, offering a streamlined and powerful toolset to design heterogeneous patches on the nanoscale.
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ItemInfluence of Poly(ethylene glycol) Molecular Architecture on Particle Assembly and Ex Vivo Particle-Immune Cell Interactions in Human Blood(AMER CHEMICAL SOC, 2021-06-22)Poly(ethylene glycol) (PEG) is widely used in particle assembly to impart biocompatibility and stealth-like properties in vivo for diverse biomedical applications. Previous studies have examined the effect of PEG molecular weight and PEG coating density on the biological fate of various particles; however, there are few studies that detail the fundamental role of PEG molecular architecture in particle engineering and bio-nano interactions. Herein, we engineered PEG particles using a mesoporous silica (MS) templating method and investigated how the PEG building block architecture impacted the physicochemical properties (e.g., surface chemistry and mechanical characteristics) of the PEG particles and subsequently modulated particle-immune cell interactions in human blood. Varying the PEG architecture from 3-arm to 4-arm, 6-arm, and 8-arm generated PEG particles with a denser, stiffer structure, with increasing elastic modulus from 1.5 to 14.9 kPa, inducing an increasing level of immune cell association (from 15% for 3-arm to 45% for 8-arm) with monocytes. In contrast, the precursor PEG particles with the template intact (MS@PEG) were stiffer and generally displayed higher levels of immune cell association but showed the opposite trend-immune cell association decreased with increasing PEG arm numbers. Proteomics analysis demonstrated that the biomolecular corona that formed on the PEG particles minimally influenced particle-immune cell interactions, whereas the MS@PEG particle-cell interactions correlated with the composition of the corona that was abundant in histidine-rich glycoproteins. Our work highlights the role of PEG architecture in the design of stealth PEG-based particles, thus providing a link between the synthetic nature of particles and their biological behavior in blood.