The direct synthesis of sulfobetaine-containing amphiphilic block copolymers and their self-assembly behavior

Doncom, Kay E. B.; Willcock, Helen; O’Reilly, Rachel K.

doi:10.1016/j.eurpolymj.2016.09.002

Cited by 32 publications

(27 citation statements)

References 55 publications

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“…On the contrary, the Q 6 PDMAEA 20 -b-PNIPAM 11 -b-POEGA 18 triblock terpolymer displays a rather different aggregation behavior at both temperatures (comparatively higher M w, app and N agg values at both 25 • C and 45 • C, Table 2) compared to the Q 1 PDMAEA 20 -b-PNIPAM 11 -b-POEGA 18 , which is most probably due to the existence of hydrophobic alkyl (C 6 H 13 ) side chains attached to the DMAEA units, leading to secondary aggregation phenomena via hydrophobic interactions between the coronas of the formed aggregates even at room temperature, as also reported in the literature [62]. In the case of SPDMAEA 20 -b-PNIPAM 11 -b-POEGA 18 , the aggregation tendency also may be enhanced by the formation of intramolecular and intermolecular electrostatic interactions between the zwitterionic sulfobetaine groups attached to the DMAEA segments [68].…”

Section: Aqueous Solution Properties Of Triblock Terpolymerssupporting

confidence: 53%

Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer

Giaouzi

Pispas

2020

Polymers

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In this work, the synthesis, selective chemical modifications, and self-assembly behavior in aqueous media of a novel poly(2-(dimethylamino)ethyl acrylate)20-b-poly(N-isopropylacrylamide)11-b-poly(oligo ethylene glycol methyl ether acrylate)18 (PDMAEA20-b-PNIPAM11-b-POEGA18) dual-responsive (pH and temperature) and triply hydrophilic amino-based triblock terpolymer are reported. The amine functional triblock terpolymer was synthesized by sequential reversible addition fragmentation chain transfer polymerization (RAFT) polymerization and molecularly characterized by size exclusion chromatography (SEC) and 1H-NMR spectroscopy that evidenced the success of the three-step polymerization scheme. The tertiary amine pendant groups of the PDMAEA block were chemically modified in order to produce the Q1PDMAEA20-b-PNIPAM11-b-POEGA18 as well as the Q6PDMAEA20-b-PNIPAM11-b-POEGA18 quaternized triblock terpolymers (Q1 and Q6 prefixes show the number of carbon atoms (C1 and C6) attached on the PDMAEA groups) using methyl iodide (CH3I) and 1-iodohexane (C6H13I) as the quaternizing agents and the SPDMAEA20-b-PNIPAM11-b-POEGA18 sulfobetainized triblock terpolymer using 1,3 propanesultone (C3H6O3S) as the sulfobetainization agent. The self-assembly properties of the triblock terpolymers in aqueous solutions upon varying temperature and solution pH were studied by light scattering and fluorescence spectroscopy experiments. The novel triblock terpolymers self-assemble into nanosized aggregates upon solution temperature rise above the nominal lower critical solution temperature (LCST) of the temperature-responsive PNIPAM block. The remarkable stimuli-responsive self-assembly behavior of the novel triblock terpolymers in aqueous media make them interesting candidates for biomedical applications in the fields of drug and gene delivery.

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Section: Aqueous Solution Properties Of Triblock Terpolymerssupporting

confidence: 53%

Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer

Giaouzi

Pispas

2020

Polymers

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“…Fully charged polymers are not expected to exhibit UCST behavior in water between 0 and 100 °C. Yet, zwitterionic polymers possess this phase transition due to attractive Coulomb interactions between groups of opposite charges [9,20,21].…”

Section: Introductionmentioning

confidence: 99%

Unexpected aqueous UCST behavior of a cationic comb polymer with pentaarginine side chains

Zydziak

Iqbal

Chaumont

et al. 2020

European Polymer Journal

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Thermoresponsive polymers, undergoing a reversible chemical or physical change using temperature as stimulus, attract increasing interest in particular as adaptable biomaterials. Except for zwitterionic polymers, fully charged polymers require the presence of specific ions to exhibit an upper critical solution temperature (UCST) in water. Herein, we report the discovery of an UCST in pure water for fully cationic comb polymers based on oligoarginine pendent grafts. These polymers were prepared using an original strategy based on solid-phase peptide synthesis of pentaarginine methacrylate-based macromonomer and its polymerization through reversible addition-fragmentation chain transfer. Despite their cationic nature, guanidinium groups from the arginine have the ability to self-associate at low temperature through hydrophobic interactions into stacked pair configuration defying the expected Coulomb interactions. These results pave the way to biomedical applications such as antimicrobial materials and drug delivery systems through the tuning of the polymer structure.

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“…Hence, PGLBT-b-PSPE formed micelles with PSPE core and PGLBT shell below UCST but this assembly disrupt upon heating above UCST [23]. Similarly, micelle formation and temperature induced disassembly of block copolymers containing derivative of poly(sulfobetaine) as one of the block were reported [28][29][30]. There are several other reports presenting the synthesis of thermoresponsive derivatives of poly(sulfobetaine) with tunable UCST, however, the application part of such polymers were sparsely explored due to the high fluctuations of UCST in the presence of electrolytes.…”

Section: Polymers Exhibiting Upper Critical Solution Temperature 21mentioning

confidence: 91%

Advances in thermo-responsive polymers exhibiting upper critical solution temperature (UCST)

Bansal¹,

Upadhyay²,

Saraogi³

et al. 2019

Express Polym. Lett.

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Immense work has been conducted in the field of thermoresponsive polymers specifically of lower critical solution temperature (LCST) type, but upper critical solution temperature (UCST) type polymers remain a significantly unexplored domain. However, in recent years, UCST polymers have attracted increased attention as evidenced by the rise in publications in the same domain, and therefore, this review is an attempt to compile the reported UCST-type polymers. Unlike LCST, UCST polymers are insoluble at low temperature but solubilize in a given solvent as the temperature increases. The synthesis approaches and applications of reported UCST polymers are discussed in this article. Emphasis has been given to the polymers exhibiting UCST behavior in aqueous medium, due to the obvious advantage of their wide applicability. It is quite apparent from this study that the attempts to synthesize novel polymers and copolymers exhibiting UCST has faced an upsurge, but their application part still requires considerable attention. Figure 4. (a) Representative structure of poly(acrylamide-co-acrylonitrile) and (b) turbidity cooling curves of poly(AAmco-AN) with different acrylonitrile content in mole% (numbers in graph). Reproduced with permission from [33],

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The direct synthesis of sulfobetaine-containing amphiphilic block copolymers and their self-assembly behavior

Cited by 32 publications

References 55 publications

Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer

Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer

Unexpected aqueous UCST behavior of a cationic comb polymer with pentaarginine side chains

Advances in thermo-responsive polymers exhibiting upper critical solution temperature (UCST)

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