Dual hydrophilic and salt responsive schizophrenic block copolymers – synthesis and study of self-assembly behavior

Vasantha, Vivek Arjunan; Jana, Satyasankar; Lee, Serina Siew Chen; Lim, Chin-Sing; Teo, Serena Lay‐Ming; Parthiban, Anbanandam; Vancso, G. Julius

doi:10.1039/c4py01113a

Cited by 37 publications

(32 citation statements)

References 43 publications

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“…13 . Calcd: C = 50.96%, H = 8.55%, N = 9.14%, S = 10.46%; found: C = 50.73%, H = 8.52%, N = 9.02%, S = 10.51%.…”

Section: Methodsmentioning

confidence: 99%

“…Moreover, by virtue of the delicate balance of attractive or repulsive interactions between the numerous charged groups themselves and with water, zwitterionic polymers often display cloud points in aqueous media with an upper critical solution temperature (UCST), or occasionally, a lower critical solution temperature (LCST) behaviour, and thus have been employed in the design of responsive polymer systems. [8][9][10][11][12][13] Amidst the three main families of polyzwitterions, namely polymeric phosphobetaines, carboxybetaines, and sulfobetaines, 1,3 the latter are chemically the most inert and exhibit a zwitterionic character over the broadest pH window (typically 2-14 minimum). Such poly(sulfobetaine)s are most conveniently prepared via free radical polymerisation.…”

Section: Introductionmentioning

confidence: 99%

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Modulating the solubility of zwitterionic poly((3-methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties

2016

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Modulating the solubility of zwitterionic poly((3-methacrylamidopropyl) ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties Postprint Complementary to the well-established zwitterionic monomer 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (SPP), the closely related monomers 2-hydroxy-3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (SHPP) and 4-((3-methacrylamidopropyl)dimethylammonio)-butane-1-sulfonate (SBP) were synthesised and polymerised by reversible addition-fragmentation chain transfer (RAFT) polymerisation, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar masses were characterised with respect to their solubility in water and aqueous salt solutions. Both poly(sulfobetaine)s show thermoresponsive behaviour in water, exhibiting phase separation at low temperatures and upper critical solution temperatures (UCST). For both polySHPP and polySBP, cloud points depend notably on the molar mass, and are much higher in D 2 O than in H 2 O. Also, the cloud points are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed nature of the spacer group separating the anionic and the cationic charges of the betaine moiety, on the other hand. As anticipated, the cloud points of polySBP are much higher than the ones of the analogous polySPP of identical molar mass.Surprisingly, the cloud points of polySHPP are also somewhat higher than the ones of their polySPP analogues, despite the additional hydrophilic hydroxyl group present in the spacer separating the ammonium and the sulfonate moieties. These findings point to a complicated interplay of the various hydrophilic components in polyzwitterions with respect to their overall hydrophilicity. Thus, the spacer group in the betaine moiety proves to be an effective additional molecular design parameter, apparently small variations of which strongly influence the phase behaviour of the polyzwitterions in specific aqueous environments.

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“…13 . Calcd: C = 50.96%, H = 8.55%, N = 9.14%, S = 10.46%; found: C = 50.73%, H = 8.52%, N = 9.02%, S = 10.51%.…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Modulating the solubility of zwitterionic poly((3-methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties

2016

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“…Only recently has interest in the UCST behaviour of polysulfobetaines gained more impetus, mostly in order to † Electronic supplementary information (ESI) available: Synthesis of tertiary amine bearing methacrylates; a enlarge the scope of the "traditional" thermo-responsive polymers with LCST behaviour 15,[24][25][26][27][28][29][30] or to obtain stimuli-responsive materials of increasing complexity. [31][32][33][34][35][36][37][38][39][40] Chemically well-defined polysulfobetaines are most conveniently prepared via free radical polymerisation of the underlying monomers. 16,18 Yet, only a few such monomers are commercially available at present.…”

Section: Introductionmentioning

confidence: 99%

Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)

Hildebrand

Laschewsky

Päch³

et al. 2017

Polym. Chem.

135

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A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents of the zwitterionic group. Radical polymerisation via the RAFT (reversible addition-fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and was well controlled, yielding polymers with predictable molar masses. Molar mass analysis and control of the end-group fidelity were facilitated by end-group labeling with a fluorescent dye. The polymers showed distinct thermo-responsive behaviour of the UCST (upper critical solution temperature) type in an aqueous solution, which could not be simply correlated to their molecular structure via an incremental analysis of the hydrophilic and hydrophobic elements incorporated within them. Increasing the spacer length separating the ammonium and the sulfonate groups of the zwitterion moiety from three to four carbons increased the phase transition temperatures markedly, whereas increasing the length of the spacer separating the ammonium group and the carboxylate ester group on the backbone from two to three carbons provoked the opposite effect. Moreover, the phase transition temperatures of the analogous polyzwitterions decreased in the order dimethylammonio > morpholinio > piperidinio alkanesulfonates. In addition to the basic effect of the polymers' precise molecular structure, the concentration and the molar mass dependence of the phase transition temperatures were studied. Furthermore, we investigated the influence of added low molar mass salts on the aqueous-phase behaviour for sodium chloride and sodium bromide as well as sodium and ammonium sulfate. The strong effects evolved in a complex way with the salt concentration. The strength of these effects depended on the nature of the anion added, increasing in the order sulfate < chloride < bromide, thus following the empirical Hofmeister series. In contrast, no significant differences were observed when changing the cation, i.e. when adding sodium or ammonium sulfate.

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“…Zwitterionic polymers have been explored as a novel class of functional materials for many decades . The interest in zwitterionic polymers surged ever since the report on its usefulness for antifouling applications though recent trends point to its limited application scope in this regard . Even before that zwitterionic polymers like carboxybetaines have been widely used as functional polymers for personal care applications in particular hair care applications for its effectiveness to control the texture of hair after washing thereby signifying the importance of this class of polymeric materials .…”

Section: Introductionmentioning

confidence: 99%

Polysulfobetaine bearing tertiary amide between counterions and its applications

Vasantha

Biying

Parthiban

2017

J of Applied Polymer Sci

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Modified sulfobetaine bearing tertiary amide spacer between the counterions is synthesized and polymerized by reversible addition-fragmentation chain transfer polymerization technique. The tertiary amide spacer influences various characteristics of the zwitterionic polymer. The modified polyzwitterion, PZI, forms coacervates in deionized water. The coacervates are thoroughly characterized by scanning electron microscopy, transmission electron microscopy, and transmittance studies. The ability to form coacervate complexes with functional ingredients has been demonstrated by encapsulating renewable resource actives like ferulic acid. The coacervate complexes have been studied by optical microscopy, transmission electron microscopy, and automated sunscreen sun protection factor analyzer. Synergism is noticed in the coacervate complex. Because of its ability to form self-coacervates, this novel addition to the zwitterionic family is potentially useful for encapsulating many functional ingredients through coacervate complex formation.

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Dual hydrophilic and salt responsive schizophrenic block copolymers – synthesis and study of self-assembly behavior

Abstract: Block copolymers undergoing conversion from “conventional” to “inverse” micelles upon changing the medium are described.

Cited by 37 publications

References 43 publications

Modulating the solubility of zwitterionic poly((3-methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties

Modulating the solubility of zwitterionic poly((3-methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties

Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)

Polysulfobetaine bearing tertiary amide between counterions and its applications

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