Chemical and Biomolecular Engineering - Research Publications

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    Site-Selective Coordination Assembly of Dynamic Metal-Phenolic Networks
    Xu, W ; Pan, S ; Noble, BB ; Chen, J ; Lin, Z ; Han, Y ; Zhou, J ; Richardson, JJ ; Yarovsky, I ; Caruso, F (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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    Role of Molecular Interactions in Supramolecular Polypeptide-Polyphenol Networks for Engineering Functional Materials
    Han, Y ; Lafleur, RPM ; Zhou, J ; Xu, W ; Lin, Z ; Richardson, JJ ; Caruso, F (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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    Nanostructured particles assembled from natural building blocks for advanced therapies
    Ju, Y ; Liao, H ; Richardson, JJ ; Guo, J ; Caruso, F (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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    Assembly of Bioactive Nanoparticles via Metal-Phenolic Complexation
    Chen, J ; Pan, S ; Zhou, J ; Lin, Z ; Qu, Y ; Glab, A ; Han, Y ; Richardson, JJ ; Caruso, F (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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    Luminescent Metal-Phenolic Networks for Multicolor Particle Labeling
    Lin, Z ; Zhou, J ; Qu, Y ; Pan, S ; Han, Y ; Lafleur, RPM ; Chen, J ; Cortez-Jugo, C ; Richardson, JJ ; Caruso, F (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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    Robust and Versatile Coatings Engineered via Simultaneous Covalent and Noncovalent Interactions
    Zhou, J ; Penna, M ; Lin, Z ; Han, Y ; Lafleur, RPM ; Qu, Y ; Richardson, JJ ; Yarovsky, I ; Jokerst, JV ; Caruso, F (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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    Engineered Coatings via the Assembly of Amino‐Quinone Networks
    Zhong, Q ; Richardson, JJ ; He, A ; Zheng, T ; Lafleur, RPM ; Li, J ; Qiu, W ; Furtado, D ; Pan, S ; Xu, Z ; Wan, L ; Caruso, F (Wiley, 2021-02)
    Abstract Engineering coatings with precise physicochemical properties allows for control over the interface of a material and its interactions with the surrounding environment. However, assembling coatings with well‐defined properties on different material classes remains a challenge. Herein, we report a co‐assembly strategy to precisely control the structure and properties (e.g., thickness, adhesion, wettability, and zeta potential) of coatings on various materials (27 substrates examined) using quinone and polyamine building blocks. By increasing the length of the amine building blocks from small molecule diamines to branched amine polymers, we tune the properties of the films, including the thickness (from ca. 5 to ca. 50 nm), interfacial adhesion (0.05 to 5.54 nN), water contact angle (130 to 40°), and zeta potential (−42 to 28 mV). The films can be post‐functionalized through the in situ formation of diverse nanostructures, including nanoparticles, nanorods, and nanocrystals. Our approach provides a platform for the rational design of engineered, substrate‐independent coatings for various applications.
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    Fluorinated Metal-Organic Coatings with Selective Wettability
    Pan, S ; Richardson, JJ ; Christofferson, AJ ; Besford, QA ; Zheng, T ; Wood, BJ ; Duan, X ; Fornerod, MJJ ; McConville, CF ; Yarovsky, I ; Guldin, S ; Jiang, L ; Caruso, F (AMER CHEMICAL SOC, 2021-07-07)
    Surface chemistry is a major factor that determines the wettability of materials, and devising broadly applicable coating strategies that afford tunable and selective surface properties required for next-generation materials remains a challenge. Herein, we report fluorinated metal-organic coatings that display water-wetting and oil-repelling characteristics, a wetting phenomenon different from responsive wetting induced by external stimuli. We demonstrate this selective wettability with a library of metal-organic coatings using catechol-based coordination and silanization (both fluorinated and fluorine-free), enabling sensing through interfacial reconfigurations in both gaseous and liquid environments, and establish a correlation between the coating wettability and polarity of the liquids. This selective wetting performance is substrate-independent, spontaneous, durable, and reversible and occurs over a range of polar and nonpolar liquids (60 studied). These results provide insight into advanced liquid-solid interactions and a pathway toward tuning interfacial affinities and realizing robust, selective superwettability according to the surrounding conditions.
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    Exploiting Supramolecular Dynamics in Metal-Phenolic Networks to Generate Metal-Oxide and Metal-Carbon Networks
    Pan, S ; Goudeli, E ; Chen, J ; Lin, Z ; Zhong, Q-Z ; Zhang, W ; Yu, H ; Guo, R ; Richardson, JJ ; Caruso, F (WILEY-V C H VERLAG GMBH, 2021-06-21)
    Supramolecular complexation is a powerful strategy for engineering materials in bulk and at interfaces. Metal-phenolic networks (MPNs), which are assembled through supramolecular complexes, have emerged as suitable candidates for surface and particle engineering owing to their diverse properties. Herein, we examine the supramolecular dynamics of MPNs during thermal transformation processes. Changes in the local supramolecular network including enlarged pores, ordered aromatic packing, and metal relocation arise from thermal treatment in air or an inert atmosphere, enabling the engineering of metal-oxide networks (MONs) and metal-carbon networks, respectively. Furthermore, by integrating photo-responsive motifs (i.e., TiO2 ) and silanization, the MONs are endowed with reversible superhydrophobic (>150°) and superhydrophilic (≈0°) properties. By highlighting the thermodynamics of MPNs and their transformation into diverse materials, this work offers a versatile pathway for advanced materials engineering.
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    Metal–Phenolic Networks as Tunable Buffering Systems
    Chen, J ; Pan, S ; Zhou, J ; Seidel, R ; Beyer, S ; Lin, Z ; Richardson, JJ ; Caruso, F (American Chemical Society (ACS), 2021)
    The buffering effects displayed by pH‐responsive polymers have recently gained attention in diverse fields such as nanomedicine and water treatment. However, creating libraries of modular and versatile polymers that can be readily integrated within existing materials remains challenging, hence restricting applications inspired by their buffering capacity. Herein, we propose the use of metal–phenolic networks (MPNs) as tunable buffering systems and through mechanistic studies show that their buffering effects are driven by pH‐responsive, multivalent metal–phenolic coordination. Owing to such supramolecular interactions, MPNs exhibit ~2‐fold and 3‐fold higher buffering capacity than polyelectrolyte complexes and commercial buffer solutions, respectively. We demonstrate that the MPN buffering effects are retained after deposition onto solid supports, thereby allowing stabilization of aqueous environmental pH for 1 week. Moreover, by using different metals and ligands for the films, the endosomal escape capabilities of coated nanoparticles can be tuned, where higher buffering capacity leads to greater endosomal escape. This study forms a fundamental basis for developing future metal–organic buffering materials.