Tunable temperature‐ and shear‐responsive hydrogels based on poly(alkyl glycidyl ether)s

Fellin, Christopher R.; Adelmund, Steven M; Karis, Dylan; Shafranek, Ryan T.; Ono, Robert J.; Martin, Cecilia G; Johnston, Trevor G.; DeForest, Cole A.; Nelson, Alshakim

doi:10.1002/pi.5716

Cited by 19 publications

(38 citation statements)

References 67 publications

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“…This type of shear disordering has been reported for the body-centered cubic (BCC) phase of polystyrenepolyisoprene di-and triblock copolymer melts, albeit at high temperatures T > 100°C with slow reversibility, inconvenient attributes for DIW. We are unaware of any previous reports describing the use of these or other block copolymers in 3D printing at room temperature without the use of solvent [e.g., water (28,36) or oil (27)], which complicates the printing process and creates potential longterm stability issues. (iii) Fast and reversible yielding at room temperature.…”

Section: Molecular Design and Synthesismentioning

confidence: 99%

Room temperature 3D printing of super-soft and solvent-free elastomers

et al. 2020

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Super-soft elastomers derived from bottlebrush polymers show promise as advanced materials for biomimetic tissue and device applications, but current processing strategies are restricted to simple molding. Here, we introduce a design concept that enables the three-dimensional (3D) printing of super-soft and solvent-free bottlebrush elastomers at room temperature. The key advance is a class of inks comprising statistical bottlebrush polymers that self-assemble into well-ordered body-centered cubic sphere phases. These soft solids undergo sharp and reversible yielding at 20°C in response to shear with a yield stress that can be tuned by manipulating the length scale of microphase separation. The addition of a soluble photocrosslinker allows complete ultraviolet curing after extrusion to form super-soft elastomers with near-perfect recoverable elasticity well beyond the yield strain. These structure–property design rules create exciting opportunities to tailor the performance of 3D-printed elastomers in ways that are not possible with current materials and processes.

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Section: Molecular Design and Synthesismentioning

confidence: 99%

Room temperature 3D printing of super-soft and solvent-free elastomers

et al. 2020

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“…Unfunctionalized PGE: The unfunctionalized PGE precursor polymer was synthesized by anionic ring opening polymerization as described in the literature. 11 Briefly, PEO was added to the reaction vessel and dried under vacuum overnight. Dry THF was added and a potassium naphthalenide solution was titrated into the flask under an argon atmosphere.…”

Section: F127-bummentioning

confidence: 99%

“…The Nelson group recently developed BAB triblock copolymer hydrogels for direct-write extrusion printing with hydrophobic poly(alkyl glycidyl ether) 'B' blocks that flank a central poly(ethylene oxide) 'A' block that exhibits similar stimuli-responsive behaviors as F127. 11 In contrast to F127, the BAB triblock copolymers form reverse flower micelles in solution. [11][12][13] Furthermore, the chain-end modification of BAB and ABA triblock copolymers allows for cross-linking by means of photo-initiated polymerization while or after completion of the 3D printing process to afford robust hydrogel structures.…”

Section: Introductionmentioning

confidence: 99%

“…11 In contrast to F127, the BAB triblock copolymers form reverse flower micelles in solution. [11][12][13] Furthermore, the chain-end modification of BAB and ABA triblock copolymers allows for cross-linking by means of photo-initiated polymerization while or after completion of the 3D printing process to afford robust hydrogel structures. [14][15][16] Polymer hydrogels based on F127dimethacrylate (F127-DMA), F127-bisurethane methacrylate (F127-BUM), and poly(isopropyl glycidyl ether-stat-ethyl glycidyl ether)-block-poly(ethylene oxide)block-poly(isopropyl glycidyl ether-stat-ethyl glycidyl ether) dimethacrylate (PGE-DMA) have previously been reported for encapsulation and direct-write extrusion printing of microbes.…”

Section: Introductionmentioning

confidence: 99%

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Physical confinement impacts cellular phenotype within living materials

Priks

Butelmann

Illarionov

et al. 2020

Preprint

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Additive manufacturing allows three-dimensional printing of polymeric materials together with cells, creating living materials for applications in biomedical research and biotechnology. However, understanding the cellular phenotype within living materials is lacking and a key limitation for their wider application. Herein, we present an approach to characterize the cellular phenotype within living materials. We immobilized the budding yeast Saccharomyces cerevisiae in three different photocross-linkable triblock polymeric hydrogels containing F127-bis-urethane methacrylate, F127-dimethacrylate, or poly(alkyl glycidyl ether)-dimethacrylate. Using optical and scanning electron microscopy, we showed that hydrogels based on these polymers were stable under physiological conditions, but yeast colonies showed differences in the interaction within the living materials. We found that the physical confinement, imparted by compositional and structural properties of the hydrogels, impacted the cellular phenotype by reducing the size of cells in living materials compared with suspension cells. These properties also contributed to the differences in immobilization patterns, growth of colonies, and colony coatings. We observed that a composition-dependent degradation of polymers was likely possible by cells residing in the living materials. In conclusion, our investigation highlights the need for a holistic understanding of the cellular response within hydrogels to facilitate the synthesis of application-specific polymers and the design of advanced living materials in the future.

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“…Finally, the fifth paper, from Nelson and workers, investigates the direct‐write 3D printing of polymer hydrogels. The authors designed and prepared a series of poly(alkyl glycidyl ether)‐ block ‐poly(ethylene oxide)‐ block ‐poly(alkyl glycidyl ether) ABA triblock copolymers, several of which gelled in water below their lower critical solution temperature.…”

mentioning

confidence: 99%

Polymers for biology, medicine and sustainability

Matson

Baker

2019

Polymer International

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The symposium included a variety of talks from researchers around the world on applications of polymers in biomedical fields. As organizers of this symposium, we expanded the topic in this In Focus section to include polymers derived from biological sources for promoting sustainable materials. Submitted papers to be included in this section went through the peer review process with Polymer International reviewers, yielding five outstanding contributions to our field.The first paper, 1 from Schulz and coworkers, reviews polymers that are used to sequester toxins in the body and contaminants in the environment. Polymers are discussed that can remove toxins in the body, including bacteria and bacterial-derived toxins, heavy and/or radioactive metals, and biomolecules such as cholesterol. They also review recent progress in developing polymers for removing contaminants from the environment, such as in wastewater. These include heavy and/or radioactive metals and organic pollutants such as pesticides, organophosphates, and polycyclic aromatic hydrocarbons. Sequestration of toxins, whether in the body or the environment, is a growing field with goals of addressing some very difficult problems. Polymers will undoubtedly play a major role in this field in the years to come.The second paper, 2 from Matson and coworkers, examines blends of two bio-derived polymers: polylactic acid (PLA) and cellulose triacetate (CTA). A compatibilizing graft copolymer was designed to promote adhesion between the two polymers. Made by ring-opening polymerization from a small number of free hydroxyl groups on CTA, these graft polymers led to increased tensile stress at yield when added to PLA-CTA blends. Compatibilization also afforded films with more consistent mechanical properties than uncompatibilized films, highlighting the potential for biopolymer blends as sustainable and degradable materials.The third paper 3 is from Joy and coworkers and focuses on antimicrobial peptidomimetic polyurethanes. The authors appended fatty acid side chains onto a cationic polymer backbone in varying amounts with the goal of determining structure-property relationships. They found that these modifications increased the antimicrobial activity of the polymers but at the expense of increased toxicity, as indicated by hemolysis assays. This work emphasizes the complex interplay between cationic/hydrophobic balance in antimicrobial polymers and its relationship to antimicrobial efficacy and toxicity toward mammalian cells.The fourth paper, 4 from O'Reilly and coworkers, discusses labeling of enzymes with fluorophores and poly(ethylene glycol) using functionalized bromomaleimides. Two enzymes, -chromotrypsin and human lysozyme, were tagged in the reaction of protein thiols or amines with dibromo-or monobromomaleimides, forming fluorescent/PEGylated conjugates of the enzymes. Stability of the enzymes at room temperature remained the same before and after tagging, as did their catalytic activity, demonstrating the potential of this conjugation reaction in enzyme-...

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Tunable temperature‐ and shear‐responsive hydrogels based on poly(alkyl glycidyl ether)s

Cited by 19 publications

References 67 publications

Room temperature 3D printing of super-soft and solvent-free elastomers

Room temperature 3D printing of super-soft and solvent-free elastomers

Physical confinement impacts cellular phenotype within living materials

Polymers for biology, medicine and sustainability

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