Abstract: Disclosed herein are compositions comprising globular proteins and diacrylate-containing compounds that can react in-situ to provide polymerized networks that can be formed into objects using additive manufacturing techniques, such as printing techniques that use vat photopolymerization. Objects printed using the disclosed compositions also are described, with embodiments of such objects exhibiting shape recovery behavior. Also disclosed are methods of making and using the disclosed compositions.

Abstract: Temperature-responsive pressure sensitive adhesives and articles of manufacture, such as bandages and medical tape, incorporating the adhesives are described. Methods for selection of a class of pressure sensitive adhesives for embedding a temperature sensitive polymer into the adhesive formulations are also provided.

Abstract: Hydrogels, bioplastics, and techniques for generating the same are described herein. An example method includes generating a resin including a globular protein, a co-monomer, water, and a photoinitiator. A hydrogel is generated by exposing the resin to light, thereby polymerizing the globular protein and the co-monomer. Further, the example method includes dehydrating the hydrogel by removing at least a portion of the water; and rehydrating the hydrogel in the presence of a hydrogen bonding agent.

Abstract: The present invention relates to a composition comprising a 3D printed hydrogel, wherein at least two different populations of cells are embedded in the 3D printed hydrogel. The different populations of cells can produce one or more products. The 3D printed hydrogel can be lyophilized and rehydrated, and the cells can continue to produce the product. Also disclosed are methods of producing a product, and methods of producing a 3D printed hydrogel comprising different populations of cells.

Abstract: Methods of fabricating 3D printed structures from biocompatible proteins include forming a photoreactive, proteinaceous resin, and 3D printing biocompatible structures from the resin by the patterned application of light in a select wavelength to cure the resin into the desired structures. Suitable photoreactive proteinaceous resins can be formed by reacting an aqueous solution of an acrylated or methacrylated globular protein with a photoreactive comonomer or photoinitiator. Structures printed from the photoreactive, proteinaceous resin can be photo-cured and dried to form bioplastic structures.

Abstract: Methods of fabricating a hydrogel tube, and related systems, employ extrusion of a cross-linkable hydrogel solution from an annular outer nozzle of a nozzle assembly to form a cross-linkable hydrogel tube. The cross-linkable hydrogel tube is cured to form a cross-linked hydrogel tube. A second hydrogel solution can be coextruded via the axial inner nozzle to form an inner hydrogel filament coaxially positioned within the cross-linkable hydrogel tube. The cross-linked hydrogel tube can be functionalized with collagen to enable cell adhesion, and cells can be cultured on the luminal surfaces of these tubes to yield tubular endothelial layers. A 3D printed coaxial nozzle can be used to fabricate biofunctional tubular conduits that can be utilized for engineering in vitro models of tubular biological structures.

Abstract: The present invention relates to a water-soluble polymer complex that includes a water-soluble block copolymer and a magnetic nanoparticle, wherein the water-soluble polymer complex has a nonzero net magnetic moment in the absence of an applied magnetic field at ambient temperatures. The water-soluble block copolymer is preferably a diblock or triblock copolymer and the magnetic nanoparticle is preferably a ferrimagnetic or ferromagnetic nanoparticle. The water-soluble complexes may be derivatized with reactive groups and conjugated to biomolecules. Exemplary water-soluble polymer complexes covered under the scope of the invention include PEG112-b-PAA40 modified CoFe2O4; NH2-PEG112-b-PAA40 modified CoFe2O4; PNIPAM68-b-PAA28 modified CoFe2O4; and mPEG-b-PCL-b-PAA modified CoFe2O4.

Abstract: Hydrogel compositions including a polymer uniformly embedded with a loading agent are provided. Also provided are methods for extrusion printing hydrogel compositions to provide extruded hydrogel compositions, which can be crosslinked to provide crosslinked hydrogel structures. Also provided are methods for using crosslinked hydrogel structures in chemical processes.

Abstract: Star polymer occlusion complexes were prepared comprising i) an amphiphilic unimolecular star polymer having a crosslinked core covalently linked to 6 or more independent amphiphilic polymer arms, ii) a nutraceutical (such as coenzyme Q10), and iii) a cholesterol-lowering drug (such as simvastatin). An initial occlusion complex formed with the nutraceutical and the star polymer exhibited improved binding properties for the cholesterol-lowering drug, resulting in improved loading efficiencies for the cholesterol-lowering drug. The star polymer occlusion complexes have utility in the medical treatment of high blood cholesterol.

Abstract: Star polymer occlusion complexes were prepared comprising i) an amphiphilic unimolecular star polymer having a crosslinked core covalently linked to 6 or more independent amphiphilic polymer arms, ii) a nutraceutical (such as coenzyme Q10), and iii) a cholesterol-lowering drug (such as simvastatin). An initial occlusion complex formed with the nutraceutical and the star polymer exhibited improved binding properties for the cholesterol-lowering drug, resulting in improved loading efficiencies for the cholesterol-lowering drug. The star polymer occlusion complexes have utility in the medical treatment of high blood cholesterol.

Abstract: A number of cationic antimicrobial polymers have been synthesized by a condensation polymerization in bulk. The initial polymer formed has backbone tertiary nitrogens, which are subsequently quaternized using a suitable quaternizing agent (e.g., alkyl halide). The cationic polymers include polyamides, polycarbonates, polypolyureas and polyguanidiniums having a cationic repeat unit comprising the quaternary ammonium nitrogen as a backbone nitrogen. The cationic polymers can be active against Gram-negative, Gram-positive microbes, and/or fungi.

Abstract: This application describes methods of forming an object. The methods described include forming a mixture with i) one or more primary diamines, ii) one or more polymerizable monomers, iii) a formaldehyde-type reagent, and iv) a polymerization initiator; forming a gel by heating the mixture to a temperature of at least 50° C.; and curing the one or more polymerizable monomers by activating the polymerization initiator. The one or more primary diamines may include one or more amine functional oligomers and/or primary aromatic diamine small molecules. The one or more polymerizable monomers may include styrenics, acrylates, methacrylates, vinyl esters, unsaturated polyesters, and derivatives thereof. The gel is a polyhemiaminal (PHA), a polyhexahydrotriazine (PHT), and/or a polyoctatriazacane (POTA) polymer, and curing of the gel forms an interpenetrating network of the PHA/PHT/POTA and the polymer formed from the polymerizable monomers.

Abstract: This application describes methods of forming an object. The methods described include flowing a polyhemiaminal (PHA), polyhexhydrotriazine (PHT), or polyoctatriazacane (POTA) precursor mixture to a nozzle of a 3D printer, heating the PHA, PHT, or POTA precursor to a temperature of at least 50° C., dispensing the PHA, PHT, or POTA precursor in a pattern; and, hardening the PHA, PHT, or POTA precursor into a polymer. The PHA and PHT polymers are formed by reacting a primary diamine with a formaldehyde-type reagent. The POTA polymer is formed by reacting a primary diamine with a formaldehyde-type reagent and formic acid. The objects formed using the methods described herein may be made of a single polymer, a single polymer type using multiple diamine monomers, or a mixture of PHA, PHT, and/or POTA polymers with different desired physical properties.

Abstract: A thermo-responsive shear-thinning photo-curable composition comprises water, a linear amphiphilic polyether ABA triblock copolymer comprising at least one pendent ene group (*—CH?CH2) capable of undergoing a thiol-ene reaction, a water-soluble crosslinking agent comprising two or more methylenethiol groups (*—CH2SH), and a photoinitiator. Under non-shear conditions and a triblock copolymer concentration suitable for direct-write printing, the composition is a viscoelastic solid (hydrogel) at a temperature of about 15° C. to about 45° C., and is a free-flowing liquid (sol) between 0° C. and about 10° C. The hydrogel form can be shear-thinned at about 15° C. to about 45° C. to form a sol suitable for a direct-write printer using an extruding print-head. The compositions covalently crosslink when flood-exposed to ultraviolet radiation. The compositions have utility in forming three-dimensional scaffolds for growing living cells.

Abstract: Hydrogel compositions including a polymer uniformly embedded with a loading agent are provided. Also provided are methods for extrusion printing hydrogel compositions to provide extruded hydrogel compositions, which can be crosslinked to provide crosslinked hydrogel structures. Also provided are methods for using crosslinked hydrogel structures in chemical processes.

Abstract: A thermo-responsive shear-thinning photo-curable composition comprises water, a linear amphiphilic polyether ABA triblock copolymer comprising at least one pendent ene group (*—CH?CH2) capable of undergoing a thiol-ene reaction, a water-soluble crosslinking agent comprising two or more methylenethiol groups (*—CH2SH), and a photoinitiator. Under non-shear conditions and a triblock copolymer concentration suitable for direct-write printing, the composition is a viscoelastic solid (hydrogel) at a temperature of about 15° C. to about 45° C., and is a free-flowing liquid (sol) between 0° C. and about 10° C. The hydrogel form can be shear-thinned at about 15° C. to about 45° C. to form a sol suitable for a direct-write printer using an extruding print-head. The compositions covalently crosslink when flood-exposed to ultraviolet radiation. The compositions have utility in forming three-dimensional scaffolds for growing living cells.

Abstract: A number of cationic antimicrobial polymers have been synthesized by a condensation polymerization in bulk. The initial polymer formed has backbone tertiary nitrogens, which are subsequently quaternized using a suitable quaternizing agent (e.g., alkyl halide). The cationic polymers include polyamides, polycarbonates, polypolyureas and polyguanidiniums having a cationic repeat unit comprising the quaternary ammonium nitrogen as a backbone nitrogen. The cationic polymers can be active against Gram-negative, Gram-positive microbes, and/or fungi.

Abstract: This application describes methods of forming an object. The methods described include forming a mixture with i) one or more primary diamines, ii) one or more polymerizable monomers, iii) a formaldehyde-type reagent, and iv) a polymerization initiator; forming a gel by heating the mixture to a temperature of at least 50° C.; and curing the one or more polymerizable monomers by activating the polymerization initiator. The one or more primary diamines may include one or more amine functional oligomers and/or primary aromatic diamine small molecules. The one or more polymerizable monomers may include styrenics, acrylates, methacrylates, vinyl esters, unsaturated polyesters, and derivatives thereof. The gel is a polyhemiaminal (PHA), a polyhexahydrotriazine (PHT), and/or a polyoctatriazacane (POTA) polymer, and curing of the gel forms an interpenetrating network of the PHA/PHT/POTA and the polymer formed from the polymerizable monomers.

Abstract: A number of cationic antimicrobial polymers have been synthesized by a condensation polymerization in bulk. The initial polymer formed has backbone tertiary nitrogens, which are subsequently quaternized using a suitable quaternizing agent (e.g., alkyl halide). The cationic polymers include polyamides, polycarbonates, polypolyureas and polyguanidiniums having a cationic repeat unit comprising the quaternary ammonium nitrogen as a backbone nitrogen. The cationic polymers can be active against Gram-negative, Gram-positive microbes, and/or fungi.

Abstract: A number of cationic antimicrobial polymers have been synthesized by a condensation polymerization in bulk. The initial polymer formed has backbone tertiary nitrogens, which are subsequently quaternized using a suitable quaternizing agent (e.g., alkyl halide). The cationic polymers include polyamides, polycarbonates, polypolyureas and polyguanidiniums having a cationic repeat unit comprising the quaternary ammonium nitrogen as a backbone nitrogen. The cationic polymers can be active against Gram-negative, Gram-positive microbes, and/or fungi.