Synthesis of Amphiphilic and Double‐Hydrophilic Block Copolymers Containing Poly(vinyl amine) Segments by RAFT Polymerization of <i>N</i>‐Vinylphthalimide

Maki, Yuya; Mori, Hideharu; Endō, Takeshi

doi:10.1002/macp.200900332

Cited by 25 publications

(15 citation statements)

References 44 publications

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“…The increase of the cloud points of copolymers P1-P3 with increasing relative length of the PNEAM is explained by the thus increasing hydrophilicity of the end of the collapsing PNPAM block, which is known to raise often the thermal transition temperature. 19,[49][50][51] The first transition with the collapse of the PNPAM block converts a double hydrophilic block copolymer into an amphiphilic one, while the second transition turns the amphiphilic into a double hydrophobic structure (cf. Scheme 1).…”

Section: Temperature Induced Self-assemblymentioning

confidence: 99%

Self-assembly of double thermoresponsive block copolymers end-capped with complementary trimethylsilyl groups

2011

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A set of double thermoresponsive diblock copolymers poly(N-n-propylacrylamide)-block-poly(N-ethylacrylamide) (PNPAM-b-PNEAM) was synthesised by sequential reversible addition–fragmentation chain transfer (RAFT) polymerisations. Using a twofold trimethylsilyl (TMS)-labeled RAFT-agent, the relative size of the two blocks was varied. While soluble as unimers below 15 °C, all copolymers exhibited thermally induced two-step self-assembly in water, due to distinct lower critical solution temperature (LCST) phase transitions of PNPAM (around 20 °C) and PNEAM (around 70 °C). Their temperature-dependent self-organisation in dilute aqueous solution was studied by turbidimetry, dynamic light scattering, transmission electron microscopy, and 1H NMR spectroscopy. The copolymers show distinct, two-step self-organisation behaviour with respect to transition temperatures, aggregate type and size, which can be correlated to the relative lengths of the low and high LCST blocks. For polymers having short blocks with low LCST, the first thermal transition induces the formation of individual micelles. Further heating above the second thermal transition results reversibly either in a shrink of the micelle size or in aggregation of the micelles, with hydrodynamic diameters below 250 nm. In contrast in the case of polymers having a long block with low LCST, the first thermal transition already leads to clusters of micelles, while the second thermal transition makes the clusters shrink. Noteworthy, the twofold TMS-labeled end groups report not only on the molar masses of the polymers, but can simultaneously serve as NMR-probes for the self-assembly process. The signal of the TMS-aryl end group displays a reversible temperature dependent, two-step splitting that is indicative of the self-organisation of the block copolymers

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Section: Temperature Induced Self-assemblymentioning

confidence: 99%

Self-assembly of double thermoresponsive block copolymers end-capped with complementary trimethylsilyl groups

2011

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“…Following a procedure adapted from references 34,43,44 , NVPi (5.00 g, 28.9 mmol) was dissolved in a solution of DMF (14 mL), containing AIBN (23.5 mg, 0.143 mmol) and CTA-X1 (132 mg, 0.594 mmol) ( Table 3, Table S2).…”

Section: Synthesis Of Pnvpi By Raft Polymerizationmentioning

confidence: 99%

Use of Primary and Secondary Polyvinylamines for Efficient Gene Transfection

et al. 2017

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Gene transfection with polymeric carrier remains a challenge; particularly, high transfection levels combined with low toxicity are hard to achieve. We herein revisit polyvinylamines, an old and neglected family of cationic polymers. They can be readily obtained by controlled hydrolysis of polyvinylamides prepared through (controlled) radical polymerization. A series of tailor-made and well-defined polyvinylamines bearing primary amino groups, and poly(N-methylvinylamine) bearing secondary amines, were evaluated for the transfection of cells with pDNA as a function of their molar mass, molar mass distribution, and degree of deacetylation. Unexpected high transfection levels, in combination with low cytotoxicity were recorded for both series. Surprisingly, a great impact of the molar mass was observed for the primary amine polyvinylamine series, whereas the results were mostly independent of molar mass or dispersity for the polymer bearing secondary amine. It was further established that a certain percentage of acetamide groups increased the transfection level, while maintaining low cytotoxicity. These results highlight for the first time the real potential of polyvinylamines as gene carriers, and make these polymers very attractive for further development in gene therapy.

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“…In general, the controlled radical polymerization of the N-vinyl and O-vinyl monomers was considered difficult, since the generated radical species are highly reactive due to their nonconjugated nature and strong electron-donating pendant groups. However, dithiocarbonates (xanthates) were recently reported to be useful for controlling the radical polymerization of highly reactive O-vinyl and N-vinyl monomers, such as vinyl acetate [57][58][59][60], N-vinylpyrrolidone [61][62][63], Nvinylcarbazole (NVC) [53], N-vinylindole derivatives [64], N-vinylphthalimide [65][66][67], N-vinylnaphthalimide [66], and N-vinylimidazolium salts [68].…”

Section: Controlled Radical Polymerization Of N-vinylcarbazolementioning

confidence: 99%

Novel Complex Polymers with Carbazole Functionality by Controlled Radical Polymerization

Nakabayashi

Mori

2012

International Journal of Polymer Science

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This review summarizes recent advances in the design and synthesis of novel complex polymers with carbazole moieties using controlled radical polymerization techniques. We focus on the polymeric architectures of block copolymers, star polymers, including star block copolymers and miktoarm star copolymers, comb-shaped copolymers, and hybrids. Controlled radical polymerization ofN-vinylcarbazole (NVC) and styrene and (meth)acrylate derivatives having carbazole moieties is well advanced, leading to the well-controlled synthesis of complex macromolecules. Characteristic optoelectronic properties, assembled structures, and three-dimensional architectures are briefly introduced.

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Synthesis of Amphiphilic and Double‐Hydrophilic Block Copolymers Containing Poly(vinyl amine) Segments by RAFT Polymerization of N‐Vinylphthalimide

Cited by 25 publications

References 44 publications

Self-assembly of double thermoresponsive block copolymers end-capped with complementary trimethylsilyl groups

Self-assembly of double thermoresponsive block copolymers end-capped with complementary trimethylsilyl groups

Use of Primary and Secondary Polyvinylamines for Efficient Gene Transfection

Novel Complex Polymers with Carbazole Functionality by Controlled Radical Polymerization

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