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Abstract A series of glucose‐based degradable superabsorbent hydrogels with potential to tackle issues associated with sustainability, flooding, and drought has been designed and fabricated. These hydrophilic networks were constructed through integrating glucose as a primary building block –into cyclic oligomers and block polymers, which were combined into mechanically‐interlocked slide‐ring crosslinked materials. Crosslinking of slide ring α‐cyclodextrin/poly(ethylene glycol)‐type polyrotaxanes with acid‐functionalized ABA triblock copolymers comprised of mercaptopropionic acid‐functionalized poly(glucose carbonate (ethyl propargyl carbonate))‐b‐poly(ethylene glycol)‐b‐mercaptopropionic acid‐functionalized poly(glucose carbonate (ethyl propargyl carbonate)), afforded degradable superabsorbent hydrogels through establishment of chemically‐labile ester linkages, in addition to glycosidic and carbonate groups of the polymer precursors. With an emphasis on development of fundamental synthetic design strategies to achieve high‐performance superabsorbent hydrogels that could behave as robust materials, which are derived from natural components and exhibit hydrolytic degradability, effort went into optimization of the composition, structure, and topology leading to water uptake capacities >30× by mass. Investigations of composition‐structure‐topology‐morphology effects on properties as a function of variations of PEG main chain length, degree of α‐cyclodextrin coverage, and concentration of pre‐gel solution, indicated that the slide‐ring polymer and triblock copolymer networks feature high water uptake, tunable mechanical properties, and sustainability with construction from renewable natural products and in‐built degradability.
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Understanding the Mechanism of Star-Block Copolymers as Nanoreactors for Synthesis of Well-Defined Silver Nanoparticles
Facile and large-scale synthesis of well-defined, thermally stable silver nanoparticles protected by polymer brushes for use in practical applications is still a challenge. Recent work has reported a nanoreactor approach that can be used to synthesize these silver nanoparticles. This approach uses amphiphilic star-block copolymers, which have a hydrophilic core surrounded by a hydrophobic exterior. These polymers thus can serve as the nanoreactors. In this study, we hypothesize that the local high concentration of silver ions in the inner hydrophilic cores of these star-block copolymers facilitates the nucleation and subsequent growth of silver nanoparticles. When all silver nanoparticles nucleate from the cores of the star-block copolymers in solution, the particle size can be controlled by the core size of the polymer. To test this hypothesis, a polyisoprene-b-poly(p-tert-butylstyrene) (PI-b-PtBS) star-block copolymer was functionalized with carboxylic acid groups using a high-efficiency, photo-initiated thiol-ene click reaction. We characterized this modified polymer using proton nuclear magnetic resonance spectroscopy, and the results indicated that ~60% of the double bonds in the polyisoprene block were successfully functionalized with carboxylic acid groups. When silver ions were added to a solution of these functionalized star-block copolymers, the negatively charged carboxylic acid groups would attract the positively charged silver ions. Subsequent reduction of these Ag+ by a tert-butylamine-borane complex at room temperature produced nanosized silver particles. However, transmission electron microscopy images showed that a significant amount of relatively large silver nanoparticles grew outside the star-block copolymer nanoreactors.
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- Award ID(s):
- 1709420
- PAR ID:
- 10095065
- Date Published:
- Journal Name:
- Journal of emerging investigators
- ISSN:
- 2638-0870
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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