Thermoresponsive properties of 3-, 4-, 6-, and 12-armed star-shaped poly[2-(dimethylamino)ethyl methacrylate]s prepared by core-first group transfer polymerization

Kikuchi, Seiya; Chen, Yougen; Fuchise, Keita; Takada, Kenji; Kitakado, Junsuke; Sato, Shin‐ichiro; Satoh, Toshifumi; Kakuchi, Toyoji

doi:10.1039/c4py00290c

Cited by 31 publications

(13 citation statements)

References 38 publications

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“…37 Chen and Li et al prepared covalent dynamic poly(triazole) gels containing both acylhydrazone and disufide bonds by crosslinking of benzohydrazide-containing poly(triazole) with disulfide-containing dialdehyde in DMF at ambient temperature. [40][41][42][43][44][45][46][47][48][49][50] The majority of these smart materials are based on the lower critical solution temperature (LCST) of the polymer, i.e. 39 Moreover, temperature-responsive amphiphilic polymers have been one of the greatest research focuses in recent years as temperature signal can be operated easily in vivo and a large amount of promising biomaterials can be used for hyperthermia-induced drug delivery, smart bioactive surface, protein chromatography and tissue engineering.…”

Section: Introductionmentioning

confidence: 99%

A star-shaped amphiphilic block copolymer with dual responses: synthesis, crystallization, self-assembly, redox and LCST–UCST thermoresponsive transition

2016

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synthesized by the combination of ring-opening polymerization (ROP), dicyclohexylcarbodiimide (DCC) reaction and atom transfer radical polymerization (ATRP). After the quaternization reaction of the PDMAEMA segment with excess 1,3propane sultone, poly(ε-caprolactone)-SS-poly(3-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate (SPCL-SS-PDMAPS) was obtained. The star-shaped structure of the copolymers and the presence of the amorphous PDMAEMA and PDMAPS in copolymers decreased or even completely suppressed the crystallizability of PCL in copolymers. These copolymers could self-assemble into spherical micelles in water. The thermoresponsive micelle solutions showed transition from a lower critical solution temperature (LCST) of SPCL-SS-PDMAEMA to an upper critical solution temperature (UCST) of SPCL-SS-PDMAPS, indicating that the LCST-UCST transition of the micellar solutions can be accomplished by the transition of PDMAEMA to PDMAPS. Moreover, the redox-responsive investigation showed that the distributions of hydrodynamic radius (Rh) broadened with the emergence of aggregates when DL-dithiothreitol (DTT) was added into the micellar systems, since the DTT would cause the breakage of disulfide bonds linking PCL and the PDMAEMA/PDMAPS blocks in copolymers.The micelles/aggregates that were self-assembled from star-shaped copolymer presented redox-responsive behaviour and LCST-UCST thermoresponsive transition.

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Section: Introductionmentioning

confidence: 99%

A star-shaped amphiphilic block copolymer with dual responses: synthesis, crystallization, self-assembly, redox and LCST–UCST thermoresponsive transition

2016

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“…[7] tert-Bu-P 4 has also been employed as an efficient catalyst for the wellcontrolled group-transfer polymerization of MMA and other functionalized methacrylates initiated by as ilyl ketene acetal. [8] We recently found that tert-Bu-P 4 can directly generate highly active species through its reaction with an appropriate monomer in the absence of any co-initiating component. [9,10] Fore xample, tert-Bu-P 4 brought about rapid polymerization of g-methyl-a-methylene-g-butyrolactone ( g MMBL), proceeding through chain initiation that involves abstraction of an b-H of g MMBL by tert-Bu-P 4 to generate the highly reactive anionic monomer species [ g MMBL -H ] À and chain propagation that involves rapid conjugate addition of the resulting enolate anion stabilized by the nanosized cation [tert-Bu-P 4 H] + to monomer.…”

mentioning

confidence: 99%

Towards Truly Sustainable Polymers: A Metal‐Free Recyclable Polyester from Biorenewable Non‐Strained γ‐Butyrolactone

Miao

Chen

2016

Angewandte Chemie

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The first effective organopolymerization of the biorenewable “non‐polymerizable” γ‐butyrolactone (γ‐BL) to a high‐molecular‐weight metal‐free recyclable polyester is reported. The superbase tert‐Bu‐P4 is found to directly initiate this polymerization through deprotonation of γ‐BL to generate reactive enolate species. When combined with a suitable alcohol, the tert‐Bu‐P4‐based system rapidly converts γ‐BL into polyesters with high monomer conversions (up to 90 %), high molecular weights (Mn up to 26.7 kg mol−1), and complete recyclability (quantitative γ‐BL recovery).

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“…Phase transitions in thermoresponsive systems relate to the solubility properties that incorporates the common concepts of LCSTs and upper critical solution temperatures (UCSTs), also known as the cloud point [ 43 , 44 ]. Below the LCST temperature, the structural network of thermoresponsive systems is loosely arranged.…”

Section: Overview Of the Properties And Functionality Of Diverse Tmentioning

confidence: 99%

A Review of Thermo- and Ultrasound-Responsive Polymeric Systems for Delivery of Chemotherapeutic Agents

et al. 2016

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Abstract:There has been an exponential increase in research into the development of thermal-and ultrasound-activated delivery systems for cancer therapy. The majority of researchers employ polymer technology that responds to environmental stimuli some of which are physiologically induced such as temperature, pH, as well as electrical impulses, which are considered as internal stimuli. External stimuli include ultrasound, light, laser, and magnetic induction. Biodegradable polymers may possess thermoresponsive and/or ultrasound-responsive properties that can complement cancer therapy through sonoporation and hyperthermia by means of High Intensity Focused Ultrasound (HIFU). Thermoresponsive and other stimuli-responsive polymers employed in drug delivery systems can be activated via ultrasound stimulation. Polyethylene oxide/polypropylene oxide co-block or triblock polymers and polymethacrylates are thermal-and pH-responsive polymer groups, respectively but both have proven to have successful activity and contribution in chemotherapy when exposed to ultrasound stimulation. This review focused on collating thermal-and ultrasound-responsive delivery systems, and combined thermo-ultrasonic responsive systems; and elaborating on the advantages, as well as shortcomings, of these systems in cancer chemotherapy. The mechanisms of these systems are explicated through their physical alteration when exposed to the corresponding stimuli. The properties they possess and the modifications that enhance the mechanism of chemotherapeutic drug delivery from systems are discussed, and the concept of pseudo-ultrasound responsive systems is introduced.

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Thermoresponsive properties of 3-, 4-, 6-, and 12-armed star-shaped poly[2-(dimethylamino)ethyl methacrylate]s prepared by core-first group transfer polymerization

Abstract: The thermoresponsive behavior of a variety of star-shaped poly[2-(dimethylamino)ethyl methacrylate]s was intensively investigated by evaluating the effect of mass concentration in aqueous solution, molecular weight, or arm number of the polymers on their cloud points.

Cited by 31 publications

References 38 publications

A star-shaped amphiphilic block copolymer with dual responses: synthesis, crystallization, self-assembly, redox and LCST–UCST thermoresponsive transition

A star-shaped amphiphilic block copolymer with dual responses: synthesis, crystallization, self-assembly, redox and LCST–UCST thermoresponsive transition

Towards Truly Sustainable Polymers: A Metal‐Free Recyclable Polyester from Biorenewable Non‐Strained γ‐Butyrolactone

A Review of Thermo- and Ultrasound-Responsive Polymeric Systems for Delivery of Chemotherapeutic Agents

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