Aqueous solution behavior of thermoresponsive polyzwitterionic microgels based on poly(N-vinylcaprolactam) synthesized via RAFT precipitation polymerization

Saha, Pabitra; Kather, Michael; Banerjee, Shib Shankar; Singha, Nikhil K.; Pich, Andrij

doi:10.1016/j.eurpolymj.2019.05.063

Cited by 19 publications

(22 citation statements)

References 31 publications

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“…Often in literature, it has been reported that the polymerization carried out via precipitation method incorporates lower amount of high molecular weight polyzwitterionic chains in thermoresponsive PVCL or PNIPAM microgels 34 . However in this study, an improvement in loading of higher molecular chain length polyzwitterions (PMPC) has been achieved using a “grafting to” technique.…”

Section: Resultsmentioning

confidence: 93%

“…Previously, Schröder et al synthesized microgels based on sulfobetaine with differently sized vinyllactam rings in w/o inverse mini‐emulsion polymerization 33 . Recently, we have reported PVCL‐based zwitterionic sulfobetaine microgels via macro‐RAFT approach in both precipitation polymerization and inverse mini‐emulsion technique 34,35 . Recently, Tian et al have reported the synthesis of redox‐responsive bio‐degradable zwitterionic PMPC nanogels with a diselenide type cross‐linker via reflux precipitation polymerization and studied the drug release in the presence of different oxidant and reductants, which led to the degradation of the cross‐linked network in the nanogels 29 …”

Section: Introductionmentioning

confidence: 99%

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Thermoresponsive zwitterionic poly(phosphobetaine) microgels: Effect of macro‐RAFT chain length and cross‐linker molecular weight on their antifouling properties

Saha

Palanisamy

Santi

et al. 2021

Polymers for Advanced Techs

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Adsorption of proteins on biological surfaces is a detrimental phenomenon that reduces the work‐life of the implants in various biomedical applications. Here, we synthesized a new class of thermoresponsive zwitterionic poly(phosphobetaine) (PMPC) microgel with excellent surface antifouling property by macro‐RAFT mediated thiol‐epoxy click reaction. End‐group modified zwitterionic PMPC homopolymers with well‐defined molecular weight and narrow dispersity were grafted onto poly(N‐vinylcaprolactam‐co‐glycidyl methacrylate) (PVG) copolymer backbone followed by addition of a cross‐linker, leading to microgel formation. While no upper critical solution temperature (UCST) was found in poly(N‐vinylcaprolactam‐co‐glycidyl methacrylate‐g‐2‐methacryloyloxyethyl phosphorylcholine) (PVGP) graft copolymers, the corresponding microgels exhibited both UCST and lower critical solution temperature (LCST) transitions, related to the swelling and collapse of PMPC and poly (N‐vinylcaprolactam) (PVCL) components respectively. An increase in the molecular chain length of the PMPC increased the shifting of UCST and LCST of the microgels to higher temperatures, due to the ability of zwitterionic groups to coordinate a large number of water molecules. The effect of the variation in the molecular weights of amphiphilic poly(ethylene glycol) diamine (PEG‐NH2) cross‐linker was also reflected in both temperature and salt responsiveness of the microgels. The efficacy of the microgels as potential antifouling materials was further studied by fluorescence microscopy and XPS analysis on microgel coatings treated with FITC‐BSA solution and pure BSA solution respectively. Lower protein adsorption was observed for microgels grafted with higher molecular chain length of PMPC, whereas, the microgels synthesized using higher molecular weight PEG‐NH2 diamine cross‐linker displayed greater protein adsorption on their surfaces.

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Section: Resultsmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Thermoresponsive zwitterionic poly(phosphobetaine) microgels: Effect of macro‐RAFT chain length and cross‐linker molecular weight on their antifouling properties

Saha

Palanisamy

Santi

et al. 2021

Polymers for Advanced Techs

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“…The addition of hydrophobic groups into a thermoresponsive polymer shifts the LCST toward lower temperatures . This phenomenon could be observed when the higher hydrophobic PBA part helped the BCP micelles to self‐aggregate at 24 °C (83–165 nm), which is lower than the VPTT of pure PNIPAM under basic condition (at pH 8).…”

Section: Resultsmentioning

confidence: 99%

Dual Stimuli‐Responsive Self‐Assembly Behavior of a Tailor‐Made ABC‐Type Amphiphilic Tri‐Block Copolymer

Pal

Kather

Banerjee

et al. 2020

Journal of Polymer Science

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This investigation describes the synthesis of a dual stimuli‐responsive, amphiphilic ABC tri‐block copolymer (BCP) based on the functional monomers via RAFT polymerization. In this case, ABC‐type BCP was prepared based on N‐isopropylacrylamide, n‐butyl acrylate, and 4‐vinylpyridine in DMF solvent using cyanomethyl dodecyl trithiocarbonate as the RAFT agent and azobisisobutyronitrile as a thermal initiator in a subsequent macro‐RAFT approach, respectively. The BCPs were characterized by SEC, 1H‐NMR, FTIR spectroscopy, and DSC analyses. Temperature and pH‐dependent properties of the smart BCP micelles in aqueous medium were investigated using dynamic light scattering. Transmission electron microscopic images were taken at cryogenic and dry conditions to study the morphology of molecular assemblies of block copolymers in an aqueous medium. The phase and topographical images were captured by atomic force microscopy to understand the assembly of block copolymers in solvents of different polarities. The morphology of BCP micelles was transformed from flower‐like to spherical in the presence of solvents with different polarities (H2O or CHCl3).

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“…With the continuous development of nanotechnology, RAFT polymerization is also more used in the preparation of nanomaterials. It is worth mentioning that many nano‐objects are usually prepared by macro‐RAFT agent 18–20 . This is an effective method for preparing nano‐objects, but this process is cumbersome due to the need for two‐step RAFT polymerization.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a hydrosoluble reversible addition‐fragmentation chain transfer agent and application in the preparation of micro/nano‐polyacrylamide gel dispersions

Yang

Dai

Zhang

et al. 2021

J of Applied Polymer Sci

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A hydrosoluble reversible addition‐fragmentation chain transfer (RAFT) agent named S‐(2‐propionic acid)‐S′‐(2‐methylpropionic acid) trithiocarbonate (PAMPATTC) is successfully synthesized. Then the micro/nano‐polyacrylamide gel dispersions are prepared via one‐pot RAFT polymerization in water to solve the problems of complicated preparation process and particle size control of common profile‐controlling and flooding agents. The structure of the RAFT agent is characterized and confirmed by fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (1H‐NMR). The effects of different reaction conditions on the properties of polyacrylamide gel dispersions are studied. The polymer dispersity index (PDI) of the polyacrylamide gel dispersions is tested by aqueous gel permeation chromatography, confirming the activity characteristics of RAFT polymerization. The rheological characteristics of the polyacrylamide gel dispersions and liner polyacrylamide are characterized. Compared with the liner polyacrylamide at similar viscosities, it is confirmed that the polyacrylamide gel dispersions were closer to Newtonian fluid, especially at high shear rates and the increasing amount of RAFT agent. The viscoelasticity tests under frequency scanning further confirm that the polyacrylamide gel dispersions are successfully synthesized via aqueous RAFT polymerization. The particle sizes are measured to show that the particle size of the polyacrylamide gel dispersions is micro/nano‐scale. The micromorphology of polyacrylamide gel dispersions is determined to indicate the irregular spherical structure, confirming that the micro‐particles are indeed formed by the aggregation of nano‐particles.

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Aqueous solution behavior of thermoresponsive polyzwitterionic microgels based on poly(N-vinylcaprolactam) synthesized via RAFT precipitation polymerization

Cited by 19 publications

References 31 publications

Thermoresponsive zwitterionic poly(phosphobetaine) microgels: Effect of macro‐RAFT chain length and cross‐linker molecular weight on their antifouling properties

Thermoresponsive zwitterionic poly(phosphobetaine) microgels: Effect of macro‐RAFT chain length and cross‐linker molecular weight on their antifouling properties

Dual Stimuli‐Responsive Self‐Assembly Behavior of a Tailor‐Made ABC‐Type Amphiphilic Tri‐Block Copolymer

Synthesis of a hydrosoluble reversible addition‐fragmentation chain transfer agent and application in the preparation of micro/nano‐polyacrylamide gel dispersions

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