Chemical and Biomolecular Engineering - Research Publications

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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, 2022-07-01)
    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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    Ultrastrong underwater adhesion on diverse substrates using non-canonical phenolic groups.
    Cheng, B ; Yu, J ; Arisawa, T ; Hayashi, K ; Richardson, JJ ; Shibuta, Y ; Ejima, H (Springer Science and Business Media LLC, 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.
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    Alloyed nanostructures integrated metal-phenolic nanoplatform for synergistic wound disinfection and revascularization.
    Xie, Y ; Chen, S ; Peng, X ; Wang, X ; Wei, Z ; Richardson, JJ ; Liang, K ; Ejima, H ; Guo, J ; Zhao, C (Elsevier BV, 2022-10)
    New materials for combating bacteria-caused infection and promoting the formation of microvascular networks during wound healing are of vital importance. Although antibiotics can be used to prevent infection, treatments that can disinfect and accelerate wound healing are scarce. Herein, we engineer a coating that is both highly compatible with current wound dressing substrates and capable of simultaneously disinfecting and revascularizing wounds using a metal-phenolic nanoplatform containing an alloyed nanostructured architecture (Ag@Cu-MPNNC). The alloyed nanostructure is formed by the spontaneous co-reduction and catalytic disproportionation reaction of multiple metal ions on a foundation metal-phenolic supramolecular layer. This synergistic presence of metals greatly improves the antibacterial activity against both Gram-negative and Gram-positive pathogenic bacteria, while demonstrating negligible cytotoxicity to normal tissue. In infected rat models, the Ag@Cu-MPNNC could kill bacteria efficiently, promoting revascularization and accelerate wound closure with no adverse side effects in infected in vivo models. In other words, this material acts as a combination therapy by inhibiting bacterial invasion and modulating bio-nano interactions in the wound.
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    Rapid assembly of colorless antimicrobial and anti-odor coatings from polyphenols and silver.
    Richardson, JJ ; Liao, W ; Li, J ; Cheng, B ; Wang, C ; Maruyama, T ; Tardy, BL ; Guo, J ; Zhao, L ; Aw, W ; Ejima, H (Springer Science and Business Media LLC, 2022-02-08)
    The development of antimicrobial fabrics and textiles that can sustainably inhibit a broad spectrum of microbes is crucial for protecting against pathogens in various environments. However, engineering antimicrobial textiles is challenging due to issues with discoloration and inhibited breathability, the use of harmful or harsh reagents and synthesis conditions, and complex and/or time-consuming processing. Herein, we develop a facile and rapid approach to deposit antimicrobial coatings using universally adherent plant polyphenols and antimicrobial silver ions. Importantly, the coatings are colorless, thin (< 10 nm), rapidly assembled (< 20 min), and can be deposited via immersion or spraying. We demonstrate that these metal-phenolic coatings on textiles can inhibit lipid-enveloped viruses over one thousand times more efficiently than coatings composed of other metal ions, while maintaining their efficacy even after 5 washes. Moreover, the coatings also inhibit Gram positive and negative bacteria, and fungi, and can prevent odors on clothes for at least 10 washes. Collectively, the ease of synthesis, use of simple and safe precursors, and amenability to at-home and industrial application suggests that the coatings will find practical application in various settings.
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    Exploiting Molecular Dynamics in Composite Coatings to Design Robust Super-Repellent Surfaces
    Guo, R ; Goudeli, E ; Xu, W ; Richardson, JJ ; Xu, W ; Pan, S (WILEY, 2022-01-07)
    Fluorinated motifs are promising for the engineering of repellent coatings, however, a fundamental understanding of how to effectively bind these motifs to various substrates is required to improve their stability in different use scenarios. Herein, the binding of fluorinated polyhedral oligomeric silsesquioxanes (POSS) using a cyanoacrylate glue (binder) is computationally and experimentally evaluated. The composite POSS-binder coatings display ultralow surface energy (≈10 mJ m-2 ), while still having large surface adhesions to substrates (300-400 nN), highlighting that super-repellent coatings (contact angles >150°) can be readily generated with this composite approach. Importantly, the coatings show super-repellency to both corrosive liquids (e.g., 98 wt% H2 SO4 ) and ultralow surface tension liquids (e.g., alcohols), with ultralow roll-off angles (<5°), and tunable resistance to liquid penetration. Additionally, these coatings demonstrate the potential in effective cargo loading and robust self-cleaning properties, where experimental datasets are correlated with both relevant theoretical predictions and systematic all-atom molecular dynamics simulations of the repellent coatings. This work not only holds promise for chemical shielding, heat transfer, and liquid manipulations but offers a facile yet robust pathway for engineering advanced coatings by effectively combining components for their mutually desired properties.
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    Superstructured mesocrystals through multiple inherent molecular interactions for highly reversible sodium ion batteries.
    Qiu, X ; Wang, X ; He, Y ; Liang, J ; Liang, K ; Tardy, BL ; Richardson, JJ ; Hu, M ; Wu, H ; Zhang, Y ; Rojas, OJ ; Manners, I ; Guo, J (American Association for the Advancement of Science (AAAS), 2021-09-10)
    Soft structures in nature, such as supercoiled DNA and proteins, can organize into complex hierarchical architectures through multiple noncovalent molecular interactions. Identifying new classes of natural building blocks capable of facilitating long-range hierarchical structuring has remained an elusive goal. We report the bottom-up synthesis of a hierarchical metal-phenolic mesocrystal where self-assembly proceeds on different length scales in a spatiotemporally controlled manner. Phenolic-based coordination complexes organize into supramolecular threads that assemble into tertiary nanoscale filaments, lastly packing into quaternary mesocrystals. The hierarchically ordered structures are preserved after thermal conversion into a metal-carbon hybrid framework and can impart outstanding performance to sodium ion batteries, which affords a capability of 72.5 milliampere hours per gram at an ultrahigh rate of 200 amperes per gram and a 90% capacity retention over 15,000 cycles at a current density of 5.0 amperes per gram. This hierarchical structuring of natural polyphenols is expected to find widespread 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, 2022-04-26)
    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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    Oxidation‐Mediated Kinetic Strategies for Engineering Metal–Phenolic Networks
    Zhong, Q ; Li, S ; Chen, J ; Xie, K ; Pan, S ; Richardson, JJ ; Caruso, F (Wiley, 2019-09-02)