Double thermoresponsive graft copolymers with different chain ends: feasible precursors for covalently crosslinked hydrogels

Xu, Jingcong; Abetz, Volker

doi:10.1039/d1sm01692j

Cited by 8 publications

(15 citation statements)

References 54 publications

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“…First, a thermoresponsive graft copolymer of di(ethylene glycol) methyl ether methacrylate (MEO 2 MA) and N,N-dimethylacrylamide (DMA) was synthesized as a precursor for the hydrogel. In contrast to our recent work, [29] the LCST of PDMA side chains is supposed to be much higher than that of the PMEO 2 MA backbone in water. [30,31] Inspired by the report of Shanmugam et al, [32] the graft copolymer was synthesized via photoiniferter reversible addition−fragmentation chain transfer (RAFT) polymerization in this work (Scheme 1).…”

Section: Introductioncontrasting

confidence: 99%

“…As the presented PMEO 2 MA‐ g ‐PDMA shows two separate LCST transitions in water, it can nicely be compared with another double thermoresponsive system, POEGMA‐ g ‐PNIPAM, investigated in our recent research. [ 29 ] Figure shows their different self‐assembling behaviors in dilute aqueous solutions. In the case of PMEO 2 MA‐ g ‐PDMA, PMEO 2 MA backbone starts aggregating first at a lower temperature, leading to the formation of star‐like micelles, while the side chains collapse at a higher temperature.…”

Section: Resultsmentioning

confidence: 99%

“…Hence, flower-like micelles are formed between two T CP s. Another important difference is that the amphiphilic micelles formed by PMEO 2 MA-g-PDMA above the first T CP are relatively loose, whereas the PNI-PAM side chains from POEGMA-g-PNIPAM tend to form denser cores due to additional intra-and interchain hydrogen bonding, which were evidenced by the disappearance of the PNIPAM Comparison between the self-assembling behaviors of PMEO 2 MA-g-PDMA presented in this work (top) and POEGMA-g-PNIPAM (bottom, effect of the end group is not considered) in the dilute aqueous solutions. [29] signal in the 1 H-NMR spectrum at high temperatures. [29] Apart from the micellar morphologies, the positions of chain ends are different in the micelles of these two systems, which may lead to different application possibilities.…”

Section: Polymerization and Characterization Of The Graft Copolymermentioning

confidence: 96%

“…[29] signal in the 1 H-NMR spectrum at high temperatures. [29] Apart from the micellar morphologies, the positions of chain ends are different in the micelles of these two systems, which may lead to different application possibilities. TTC-groups of PMEO 2 MAg-PDMA are around the surfaces of the micelles above the first T CP .…”

Section: Polymerization and Characterization Of The Graft Copolymermentioning

confidence: 96%

“…[25][26][27][28] Recently, our group has shown an efficient route to prepare a thermoresponsive hydrogel from a well-defined graft copolymer with poly[oligo(ethylene glycol) methacrylate] (POEGMA) backbone and PNIPAM side chains. [29] The graft copolymer itself is double thermoresponsive in aqueous solutions. The LCST-type cloud point (T CP ) of the backbone is higher than that of the side chains.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of a Degradable Hydrogel Based on a Graft Copolymer with Unexpected Thermoresponsiveness

Abetz

2022

Macro Chemistry & Physics

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Incorporating multiple pyridyl disulfide (PDS) moieties into polymer chains allows the fabrication of a chemically cross‐linked hydrogel through the rapid thiol–disulfide exchange reaction. By aminolysis in the presence of 2,2′‐dithiodipyridine (DTP), the end groups of polymers synthesized via reversible addition−fragmentation chain transfer (RAFT) polymerization can readily be converted into PDS‐groups. In this contribution, a RAFT‐synthesized graft copolymer with thermoresponsive poly[di(ethylene glycol) methyl ether methacrylate] forming the backbone and hydrophilic poly(N,N‐dimethylacrylamide) as the side chains is presented. The copolymer chains exhibit surprisingly a two‐step lower critical solution temperature transition in aqueous solutions. After modification of the end groups of the backbone and side chains, the PDS‐terminated chains can react with a dithiol cross‐linker to form a thermoresponsive hydrogel. In a reducing environment, the cleavable disulfide linkages lead to on‐demand dissolution of the hydrogel. The resulting thiol‐terminated chains undergo a reversible sol–gel transition in response to redox variations, expanding the potential application areas of such a polymer system.

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Section: Introductioncontrasting

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Polymerization and Characterization Of The Graft Copolymermentioning

confidence: 96%

Section: Polymerization and Characterization Of The Graft Copolymermentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

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Synthesis of a Degradable Hydrogel Based on a Graft Copolymer with Unexpected Thermoresponsiveness

Abetz

2022

Macro Chemistry & Physics

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Defining New Benchmarks of Low CTAB‐Concentration‐Based Gold Nanorod Synthesis: The Underestimated Potential of Polymer‐Directed Anisotropic Growth

Lemich,

Soltau,

Weißpflog

et al. 2024

Adv Funct Materials

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This work presents new anisotropic growth‐directing copolymers suitable for the seed‐mediated growth of gold nanorods (GNRs). Copolymers with different architectures are studied. They all contain dimethylaminomethyl methacrylate (DMAEMA) functionalized with 1‐bromohexadecane (BHD) as the vital component. For the synthesis of the different copolymers, the photo‐iniferter reversible addition–fragmentation chain transfer (photoRAFT) polymerization is used, where DMAEMA is combined with a lower critical solution temperature (LCST) polymer block for better solubility after the functionalization. The results show that the presented copolymers can induce anisotropic growth of gold nanoparticles. Additionally, the influence of the LCST of the water‐soluble block and the temperature of the growth solution on the GNR synthesis are investigated. Furthermore, the plasmonic behavior of the resulting GNRs solution is investigated at temperatures around the LCST of the copolymer.

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Synthesis of Multiresponsive Gold@Polymer‐Nanohybrid Materials Using Polymer Precursors Obtained by Photoiniferter RAFT Polymerization

Lemich¹,

Sobania²,

Meyer³

et al. 2022

Macro Chemistry & Physics

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Combining gold nanoparticles (GNP) with stimuli-responsive polymers is a fascinating field for applications as sensor materials or in biomedical applications. The synthesis of multiresponsive Au@Polymer hybrid systems in an in situ approach using tailor-made poly(2-(dimethylamino)ethyl methacrylate) (P(DMAEMA)) precursor synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization is introduced. In particular, because of its multiresponsive behavior, P(DMAEMA) is of great interest and is used as the precursor for the synthesis. For the polymerization of the precursor, an approach is introduced that applies the photoiniferter RAFT (photoRAFT) mechanism applicable for tertiary amine-bearing methacrylic monomers like DMAEMA. By varying the chain transfer agents (CTA), the influence of different RAFT Z-groups on the solubility of the Au-hybrids is studied. Aging effects are observed by transmission electron microscopy (TEM) analyses. A comprehensive dynamic light scattering (DLS) study reveals the thermoresponsive behavior of the Au-hybrids in an aqueous solution. The influence of free polymer in solution on the suspension stability is observed. The capability of crosslinking using 1,5-dibromopentane (DBP) and the CO 2 sensitivity of the synthesized hybrids expands the area of their potential application.

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Double thermoresponsive graft copolymers with different chain ends: feasible precursors for covalently crosslinked hydrogels

Abstract: The tailored synthesis of graft copolymers from acrylic and methacrylic monomers can be accomplished solely through photoiniferter reversible addition−fragmentation chain transfer (RAFT) polymerization. Samples with poly[oligo(ethylene glycol) methacrylate] (POEGMA) backbones...

Cited by 8 publications

References 54 publications

Synthesis of a Degradable Hydrogel Based on a Graft Copolymer with Unexpected Thermoresponsiveness

Synthesis of a Degradable Hydrogel Based on a Graft Copolymer with Unexpected Thermoresponsiveness

Defining New Benchmarks of Low CTAB‐Concentration‐Based Gold Nanorod Synthesis: The Underestimated Potential of Polymer‐Directed Anisotropic Growth

Synthesis of Multiresponsive Gold@Polymer‐Nanohybrid Materials Using Polymer Precursors Obtained by Photoiniferter RAFT Polymerization

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