We compared the influence of the polymerization mechanism onto the physical characteristics of thermoresponsive hydrogels. The Poly(-isopropylacrylamide) (PNIPAAm) hydrogels were successfully synthesized using reversible addition-fragmentation chain-transfer (RAFT) and free radical polymerization (FRP). The gels were prepared while using different crosslinker feed and monomer concentration. The swelling, dye release, and hydrolytic stability of the gels were investigated in water, or in representative komostrope and chaotrope salt solutions at room temperature and at 37 °C. It was found that the swelling ratio (SR) of the RAFT gels was significantly higher than that of the FRP gels; however, an increased crosslinking density resulted in a decrease of the SR of the RAFT gels as compared to the corresponding gels that are made by FRP, which indicates the limitation of the cross-linking efficiency that is attained in RAFT polymerization. Additionally, an increased monomer concentration decreased the SR of the RAFT gels, whereas a similar SR was observed for the FRP gels. However, the SR of both RAFT and FRP gels in NaSCN and NaSO solutions were similar. Finally, the rate of dye release was significantly slower from the RAFT gels than the FRP gels and the hydrolytic stability of the RAFT gels was lower than that of FRP gels in water, but maintained similar stability in NaSO and NaSCN solutions.
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http://dx.doi.org/10.3390/ma12172697 | DOI Listing |
Macromol Rapid Commun
September 2024
Department of Applied Chemistry, Rajiv Gandhi Technological University, Bhopal, Madhya Pradesh, 462033, India.
Stimuli-responsive low molecular weight hydrogel interventions for Biomedical challenges are a rapidly evolving paradigm in the bottom-up approach recently. Peptide-based self-assembled nano biomaterials present safer alternatives to their non-degradable counterparts as demanded for today's most urged clinical needs.Although a plethora of work has already been accomplished, programming hydrogelators with appropriate functionalities requires a better understanding as the impact of the macromolecular structure of the peptides and subsequently, their self-assembled nanostructures remain unidentified.
View Article and Find Full Text PDFSoft Matter
February 2024
Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan.
The structures of gels synthesized by controlled radical copolymerization (CRP) and conventional free radical copolymerization (FRP) were studied by a coarse-grained molecular dynamics simulation. It was confirmed that the CRP gel has a larger number of elastically effective chains and fewer cyclic structures and entanglements than the FRP gel, , the network structure of the CRP gel is more uniform than that of the FRP gel. However, the difference in the shear modulus between the two gels was small due to the opposing changes in the number of elastically effective chains and that of entanglements.
View Article and Find Full Text PDFJ Am Chem Soc
November 2023
Department of Materials, School of Natural Sciences, University of Manchester, Manchester M13 9PL, U.K.
Polymeric frustrated Lewis pairs, or poly(FLP)s, have served to bridge the gap between functional polymer science and main group catalysis, pairing the uniqueness of sterically frustrated Lewis acids and bases with a polymer scaffold to create self-healing gels and recyclable catalysts. However, their utilization in radical chemistry is unprecedented. In this paper, we disclose the synthesis of polymeric frustrated radical pairs, or poly(FRP)s, by in situ photoinduction of FLP moieties, where their Lewis acidic and basic centers are tuned to promote single electron transfer (SET).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2023
Cluster for Advanced Macromolecular Design, Australian Centre for Nanomedicine, School of Chemical Engineering, The University of New South Wales, 2052, Sydney, NSW, Australia.
We report an aqueous and near-infrared (NIR) light mediated photoinduced reversible addition-fragmentation chain transfer (photo-RAFT) polymerization system catalyzed by tetrasulfonated zinc phthalocyanine (ZnPcS ) in the presence of peroxides. Taking advantage of its fast polymerization rates and high oxygen tolerance, this system is successfully applied for the preparation of hydrogels. Exploiting the enhanced penetration of NIR light, photoinduced gelation is effectively performed through non-transparent biological barriers.
View Article and Find Full Text PDFSoft Matter
April 2023
Department of Chemistry and Materials Engineering, Kansai University, 3-3-35, Yamate-cho, Suita, Osaka 564-8680, Japan.
The network structures of poly(-isopropylacrylamide) (PNIPAAm) gels prepared by atom transfer radical polymerization (ATRP) were compared with those prepared by free radical polymerization (FRP), as a conventional radical polymerization. Temperature-responsive shrinkage was observed in the PNIPAAm gels prepared by ATRP and FRP (ATRP and FRP gels), which depended on the cross-linker content. From the light-scattered intensities, 〈〉, measured at the different sample positions, we used the partial heterodyne method to determine the dynamic fluctuation, 〈〉, spatial component, 〈〉, and correlation length, , of the ATRP and FRP gels, as a function of the cross-linker content and temperature.
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