Chemical and Biomolecular Engineering - Research Publications

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    3D nanoprinting via spatially controlled assembly and polymerization.
    Pattison, TG ; Wang, S ; Miller, RD ; Liu, G-Y ; Qiao, GG (Springer Science and Business Media LLC, 2022-04-11)
    Macroscale additive manufacturing has seen significant advances recently, but these advances are not yet realized for the bottom-up formation of nanoscale polymeric features. We describe a platform technology for creating crosslinked polymer features using rapid surface-initiated crosslinking and versatile macrocrosslinkers, delivered by a microfluidic-coupled atomic force microscope known as FluidFM. A crosslinkable polymer containing norbornene moieties is delivered to a catalyzed substrate where polymerization occurs, resulting in extremely rapid chemical curing of the delivered material. Due to the living crosslinking reaction, construction of lines and patterns with multiple layers is possible, showing quantitative material addition from each deposition in a method analogous to fused filament fabrication, but at the nanoscale. Print parameters influenced printed line dimensions, with the smallest lines being 450 nm across with a vertical layer resolution of 2 nm. This nanoscale 3D printing platform of reactive polymer materials has applications for device fabrication, optical systems and biotechnology.
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    Mechanochromophore-Linked Polymeric Materials with Visible Color Changes.
    Qiu, W ; Scofield, JMP ; Gurr, PA ; Qiao, GG (Wiley, 2022-05)
    Mechanical force as a type of stimuli for smart materials has obtained much attention in the past decade. Color-changing materials in response to mechanical stimuli have shown great potential in the applications such as sensors and displays. Mechanochromophore-linked polymeric materials, which are a growing sub-class of these materials, are discussed in detail in this review. Two main types of mechanochromophores which exhibit visible color change, summarized herein, involve either isomerization or radical generation mechanisms. This review focuses on their synthesis and incorporation into polymer matrices, the type of mechanical force used, factors affecting the mechanochromic properties, and their applications.
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    Vernetzte Polypeptide durch RAFT‐vermittelte Polymerisation zum kontinuierlichen Aufbau von Polymerfilmen
    Chan, NJ ; Lentz, S ; Gurr, PA ; Tan, S ; Scheibel, T ; Qiao, GG (Wiley, 2022-02-21)
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    Crosslinked Polypeptide Films via RAFT-Mediated Continuous Assembly of Polymers
    Chan, NJ ; Lentz, S ; Gurr, PA ; Tan, S ; Scheibel, T ; Qiao, GG (WILEY-V C H VERLAG GMBH, 2022-01-12)
    Polypeptide coatings are a cornerstone in the field of surface modification due to their widespread biological potential. As their properties are dictated by their structural features, subsequent control thereof using unique fabrication strategies is important. Herein, we report a facile method of precisely creating densely crosslinked polypeptide films with unusually high random coil content through continuous assembly polymerization via reversible addition-fragmentation chain transfer (CAP-RAFT). CAP-RAFT was fundamentally investigated using methacrylated poly-l-lysine (PLLMA) and methacrylated poly-l-glutamic acid (PLGMA). Careful technique refinement resulted in films up to 36.1±1.1 nm thick which could be increased to 94.9±8.2 nm after using this strategy multiple times. PLLMA and PLGMA films were found to have 30-50 % random coil conformations. Degradation by enzymes present during wound healing reveals potential for applications in drug delivery and tissue engineering.
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    Immobilization and Intracellular Delivery of Structurally Nanoengineered Antimicrobial Peptide Polymers Using Polyphenol-Based Capsules
    Song, J ; Cortez-Jugo, C ; Shirbin, SJ ; Lin, Z ; Pan, S ; Qiao, GG ; Caruso, F (WILEY-V C H VERLAG GMBH, 2022-02-02)
    Structurally nanoengineered antimicrobial peptide polymers (SNAPPs) are an emerging class of antimicrobials against multidrug-resistant bacteria. Their encapsulation in particle carriers can improve their therapeutic efficacy by preventing peptide degradation, reducing clearance, and enhancing intracellular delivery and dosage to bacteria-infected host cells. Herein, two template-mediated strategies are reported for immobilizing SNAPPs in microcapsules through 1) complexation of SNAPPs with tannic acid (TA) onto porous CaCO3 templates and subsequent removal of the templates (SNAPP–TA capsules) and 2) adsorption of SNAPPs onto CaCO3 templates and subsequent encapsulation within a metal–phenolic (FeIII–TA) coating and template removal (SNAPP–FeIII–TA capsules). The loading amounts of SNAPPs are 0.8 and 4.4 pg per SNAPP–TA and SNAPP–FeIII–TA capsule, respectively. At pH 7.4, there is sustained release of SNAPPs, which retain high antimicrobial activity with minimum inhibitory concentration values of ≈30 µg mL−1 in Escherichia coli. Both capsule systems are internalized by alveolar macrophages in vitro, with negligible cytotoxicity and are amenable to nebulization, remaining stable in nebulized droplets. This study demonstrates the potential of engineered polyphenol-based capsules for peptide drug immobilization and intracellular delivery, which have prospective application in the pulmonary delivery of antimicrobials against respiratory bacterial infections (e.g., pneumonia, tuberculosis).
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    Ultrapermeable Composite Membranes Enhanced Via Doping with Amorphous MOF Nanosheets
    Liu, M ; Xie, K ; Nothling, MD ; Zu, L ; Zhao, S ; Harvie, DJE ; Fu, Q ; Webley, PA ; Qiao, GG (AMER CHEMICAL SOC, 2021-03-25)
    Thin-film composite (TFC) polymeric membranes have attracted increasing interest to meet the demands of industrial gas separation. However, the development of high-performance TFC membranes within their current configuration faces two key challenges: (i) the thickness-dependent gas permeability of polymeric materials (mainly poly(dimethylsiloxane) (PDMS)) and (ii) the geometric restriction effect due to the limited pore accessibility of the underlying porous substrate. Here we demonstrate that the incorporation of trace amounts (∼1.8 wt %) of amorphous metal-organic framework (MOF) nanosheets into the gutter layer of TFC assemblies can simultaneously address these two limitations by the creation of rapid, transmembrane gas diffusion pathways. The resultant PDMS&MOF membrane displayed excellent CO2 permeance of 10450 GPU and CO2/N2 selectivity of 9.1. Leveraging this strategy, we successfully fabricate a novel TFC membrane, consisting of a PDMS&MOF gutter and an ultrathin (∼54 nm) poly(ethylene glycol) top selective layer via surface-initiated atom transfer radical polymerization. The complete TFC membrane exhibits excellent processability and remarkable CO2/N2 separation performance (1990 GPU with a CO2/N2 ideal selectivity of 39). This study reveals a strategy for the design and fabrication of a new TFC membrane system with unprecedented gas-separation performance.
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    From UV to NIR: A Full-Spectrum Metal-Free Photocatalyst for Efficient Polymer Synthesis in Aqueous Conditions
    Allison-Logan, S ; Fu, Q ; Sun, Y ; Liu, M ; Xie, J ; Tang, J ; Qiao, GG (WILEY-V C H VERLAG GMBH, 2020-09-15)
    Photo-mediation offers unparalleled spatiotemporal control over controlled radical polymerizations (CRP). Photo-induced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization is particularly versatile owing to its oxygen tolerance and wide range of compatible photocatalysts. In recent years, broadband- and near-infrared (NIR)-mediated polymerizations have been of particular interest owing to their potential for solar-driven chemistry and biomedical applications. In this work, we present the first example of a novel photocatalyst for both full broadband- and NIR-mediated CRP in aqueous conditions. Well-defined polymers were synthesized in water under blue, green, red, and NIR light irradiation. Exploiting the oxygen tolerant and aqueous nature of our system, we also report PET-RAFT polymerization at the microliter scale in a mammalian cell culture medium.
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    Accelerated Polypeptide Synthesis viaN-Carboxyanhydride Ring Opening Polymerization in Continuous Flow
    Vrijsen, JH ; Rasines Mazo, A ; Junkers, T ; Qiao, GG (WILEY-V C H VERLAG GMBH, 2020-07-20)
    In nature, polypeptide-based materials are ubiquitous, yet their synthetic production is hampered by high cost, limited scalability, and often stringent reaction conditions. Herein an elegant approach is presented for N-carboxyanhydride ring opening polymerization (NCA ROP) of Nε-benzyloxycarbonyl-l-lysine (ZLL) and γ-benzyl-l-glutamate (BLG) NCA in continuous flow. The polymerization is initiated by primary amine initiators using N,N-dimethylformamide (DMF) as solvent. Carrying out the reaction in a silicon microflow reactor speeds up the rate of ROP (92% conversion in 40 min in flow as opposed to 6 h in batch) due to highly efficient permeation of CO2 through the reactor tubing. The polymerization strategy provides a facile, scale-up friendly alternative to traditional batch mode polymerization and has the capability of streamlining NCA ROP.
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    Biomaterials functionalized with nanoclusters of integrin- and syndecan-binding ligands improve cell adhesion and mechanosensing under shear flow conditions
    Karimi, F ; Thombare, VJ ; Hutton, CA ; O'Connor, AJ ; Qiao, GG ; Heath, DE (WILEY, 2020-06-29)
    We have engineered biomaterials that display nanoclusters of ligands that bind both integrin and syndecan-4 cell receptors. These surfaces regulate cell behaviors under static conditions including adhesion, spreading, actin stress fiber formation, and migration. The syndecan-4 receptors are also critical mediators of cellular mechanotransduction. In this contribution we assess whether this novel class of materials can regulate the response of cells to applied mechanical stimulation, using the shear stress imparted by laminar fluid flow as a model stimulus. Specifically, we assess endothelial cell detachment due to flow, cell alignment due to flow, and cell adhesion from the flowing fluid. A high degree of cell retention was observed on surfaces containing integrin-binding ligands or a mixed population of integrin- and syndecan-binding ligands. However, the presence of both ligand types was necessary for the cells to align in the direction of flow. These results imply that integrin engagement is necessary for adhesion strength, but engagement of both receptor types aids in appropriate mechanotransduction. Additionally, it was found that surfaces functionalized with both ligand types were able to scavenge a larger number of cells from flow, and to do so at a faster rate, compared to surfaces functionalized with only integrin- or syndecan-binding ligands. These results show that interfaces functionalized with both integrin- and syndecan-binding ligands regulate a significant range of biophysical cell behaviors in response to shear stress.
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    From UV to NIR: A Full-Spectrum Metal-Free Photocatalyst for Efficient Polymer Synthesis in Aqueous Conditions
    Allison-Logan, S ; Fu, Q ; Sun, Y ; Liu, M ; Xie, J ; Tang, J ; Qiao, GG (Wiley, 2020-01-01)