Facile synthesis of thermo-, pH-, CO<sub>2</sub>- and oxidation-responsive poly(amido thioether)s with tunable LCST and UCST behaviors

Zhang, Hongcan; Zhang, Jian; Dai, Wenxue; Zhao, Youliang

doi:10.1039/c7py01351e

Cited by 33 publications

(29 citation statements)

References 78 publications

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“…The thermoresponsive behavior can be tuned to UCST‐type with different cloud points, LCST‐type, and temperature‐independent solubility just by changing the copolymer composition. This effect is different from the commonly observed phenomenon of changed cloud points on use of hydrophobic comonomer in thermoresponsive polymers and is rarely observed …”

Section: Methodscontrasting

confidence: 95%

Tuning the Phase Transition from UCST‐Type to LCST‐Type by Composition Variation of Polymethacrylamide Polymers

Käfer

Pretscher

Agarwal

2018

Macromol. Rapid Commun.

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Polymethacrylamide copolymers with hydrophobic N‐substituted acrylamides, such as N‐cyclohexylacrylamide and N‐tert‐butylacrylamide, are rare examples of polymers showing composition‐dependent thermoresponsive behavior in water. They show unexpected behavior different from the conventional copolymers of a thermoresponsive polymer with hydrophobic comonomers. On increasing the amount of the hydrophobic comonomer in the polymer, there is a change from UCST‐type phase behavior to complete solubility, followed by compositions showing LCST‐type transition and insolubility in water (U‐S‐L‐I‐type change). At 50 mol% of less hydrophobic N‐tert‐butyl acrylamide (logP 0.87) in contrast to ≈25 mol% of N‐cyclohexylacrylamide (logP 1.51), the broad UCST‐type transition of polymethacrylamide is turned to LCST‐type transitions with very narrow hysteresis in water and PBS buffer. The use of H‐bond and water‐structure breaker showed the role of H‐bonding and hydrophobic interactions in phase transitions of UCST‐type and LCST‐type, respectively. This work is an important add‐on to the infant field of nonionic polymers of UCST‐type.

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Section: Methodscontrasting

confidence: 95%

Tuning the Phase Transition from UCST‐Type to LCST‐Type by Composition Variation of Polymethacrylamide Polymers

Käfer

Pretscher

Agarwal

2018

Macromol. Rapid Commun.

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“…All the aqueous solutions of PAA‐ co ‐CB[6]MA copolymers displayed visible UCST‐responsive behaviors. The UCST is defined as the temperature at which the transmittance reached 50% in the heating curve 25–27 . The UCST values are presented in Table 1.…”

Section: Resultsmentioning

confidence: 99%

“…Each sample was equilibrated for 5 min at constant temperature before collecting the data. The UCST is defined as the temperature at which the transmittance reached 50% in the heating curve 25–27 . The effects of pH on the thermoresponsive behaviors of the CB[6]‐based copolymers were studied following procedures similar to those described above, except for the corresponding solution conditions.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of cucurbit[6]uril pendent upper critical solution temperature type copolymers: self‐assembly and multi‐stimuli‐responsive behavior

Yang

Pei

et al. 2021

Polymer International

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Cucurbit[6]uril‐derivatized vinyl monomer (cucurbit[6]uril methacrylate) was synthesized. Acrylic acid (AA) was used as the comonomer for copolymerization with the cucurbit[6]uril‐derivatized monomer. A series of copolymers of poly(acrylic acid‐co‐cucurbit[6]uril methacrylate) (PAA‐co‐CB[6]MA) were synthesized by free radical polymerization. The cucurbit[6]uril‐derivatized monomer and PAA‐co‐CB[6]MA copolymers were characterized by 1H NMR spectra, high‐resolution mass spectroscopy and gel permeation chromatography. The solution behavior was examined using UV–visible spectroscopy and dynamic light scattering. The PAA‐co‐CB[6]MA showed an upper critical solution temperature (UCST) in water. The UCST‐type thermoresponsive behavior of these CB[6]‐derivatized copolymers was highly dependent on the composition of the copolymer. For the same type of copolymer, changes in its composition gave rise to different UCSTs. Additionally, the PAA‐co‐CB[6]MA copolymers were successful in trapping azocarmine B. The stimuli‐responsive release of encapsulated azocarmine B was achieved by a combination of temperature and pH value stimuli. According to the results, the novel PAA‐co‐CB[6]MA copolymers can be used as carriers. © 2021 Society of Industrial Chemistry.

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“…Poly( N , N -dimethyl acrylamide) (PDMA) is a hydrophilic polymer, poly( N -(2-(diethylamino)ethyl) acrylamide) (PDEAEAM) , and poly( N -methacryloyl- l -alanine 2-(diethylamino)ethylamide) (PMAEE) are LCST polymers, while poly( N -acryloylglycinamide) (PNAGA) and its derivatives − are representative non-ionic UCST polymers (Scheme ), revealing the important influence of chemical composition on phase transition. In addition, the combination of HBs and EIs allows access to dual LCST and UCST phase transitions. ,− …”

Section: Introductionmentioning

confidence: 99%

Multitunable Thermoresponsive and Aggregation Behaviors of Linear and Cyclic Polyacrylamide Copolymers Comprising Heterofunctional Y Junctions

Zhang

Wang

et al. 2021

Macromolecules

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The incorporation of asymmetric Y junctions into thermoresponsive polymers allows access to hierarchical selfassembly, and self-assembly of cyclic polymers can further amplify the topology effect. At present, systematic insights into the influence of Y junctions on physicochemical properties remain at the early stage. A diversity of linear and cyclic polyacrylamide copolymers with substituent-variable Y junctions are designed to reveal the effects of topology, chain length, composition, concentration, and temperature. With the increasing size of substituents, copolymer aqueous solutions gradually shift from dual upper and lower critical solution temperatures (UCST/ LCST) to a single LCST until the lack of phase transition. The LCST can be elevated by introduction of a cyclic architecture, longer polymer chain, and smaller substituent. Owing to the changes in degree of hydration of subunits, heat can induce sphere− vesicle−nanosheet−nanoribbon−sphere (linear copolymer) and sphere−nanosheet−nanoribbon (cyclic copolymer) transitions. In addition, the cyclization effect is also reflected in cooperative hydration of distinct subunits upon heating, higher ceiling temperatures to form stable lamellae, and more pronounced hysteresis of the turbidity curve upon cooling. This research using Y junction bearing thermoresponsive copolymers may provide a promising platform to achieve on-demand phase transitions and nanostructures.

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Facile synthesis of thermo-, pH-, CO₂- and oxidation-responsive poly(amido thioether)s with tunable LCST and UCST behaviors

Abstract: Multi-responsive N-substituted poly(amido thioether) copolymers synthesized by one-pot amine–thiol–acrylate polyaddition could exhibit composition-dependent and stimuli-triggered single or double thermoresponsivity.

Cited by 33 publications

References 78 publications

Tuning the Phase Transition from UCST‐Type to LCST‐Type by Composition Variation of Polymethacrylamide Polymers

Tuning the Phase Transition from UCST‐Type to LCST‐Type by Composition Variation of Polymethacrylamide Polymers

Synthesis of cucurbit[6]uril pendent upper critical solution temperature type copolymers: self‐assembly and multi‐stimuli‐responsive behavior

Multitunable Thermoresponsive and Aggregation Behaviors of Linear and Cyclic Polyacrylamide Copolymers Comprising Heterofunctional Y Junctions

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Facile synthesis of thermo-, pH-, CO2- and oxidation-responsive poly(amido thioether)s with tunable LCST and UCST behaviors

Abstract: Multi-responsive N-substituted poly(amido thioether) copolymers synthesized by one-pot amine–thiol–acrylate polyaddition could exhibit composition-dependent and stimuli-triggered single or double thermoresponsivity.

Cited by 33 publications

References 78 publications

Tuning the Phase Transition from UCST‐Type to LCST‐Type by Composition Variation of Polymethacrylamide Polymers

Tuning the Phase Transition from UCST‐Type to LCST‐Type by Composition Variation of Polymethacrylamide Polymers

Synthesis of cucurbit[6]uril pendent upper critical solution temperature type copolymers: self‐assembly and multi‐stimuli‐responsive behavior

Multitunable Thermoresponsive and Aggregation Behaviors of Linear and Cyclic Polyacrylamide Copolymers Comprising Heterofunctional Y Junctions

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Facile synthesis of thermo-, pH-, CO₂- and oxidation-responsive poly(amido thioether)s with tunable LCST and UCST behaviors