Synthesis of Thermo‐Responsive Polymers With Both Tunable UCST and LCST

Tian, Haiying; Yan, Junjie; Wang, Di; Gu, Chen; You, Ye‐Zi; Chen, Xuesi

doi:10.1002/marc.201000713

Cited by 61 publications

(47 citation statements)

References 20 publications

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“…There are mainly two types of temperature‐responsive behaviors for hydrophilic polymers in water . One is characterized by a lower critical solution temperature (LCST), above which phase separation occurs .…”

Section: Resultsmentioning

confidence: 99%

Thermoresponsive polymeric nanoparticles based on poly(2‐oxazoline)s and tannic acid

Wang

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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Hydrogen bonding is widely present and plays a significant role in material science and supramolecular chemistry. This work reports a straightforward strategy for the preparation of polymeric nanoparticles from neutral poly(2‐oxazoline)s (POx) and tannic acid (TA) driven by their intermolecular hydrogen bonding. Dynamic light scattering (DLS) and scanning electron microscope (SEM) measurements showed that POx bearing different substituents, that is, methyl, ethyl and n‐propyl in the 2‐position all could assemble with TA into stable nanoparticles in water or ethanol. The diameter of the assembled nanoparticles could be manipulated by varying parameters such as molecular weight of POx, concentration and ratio of POx, and TA. Interestingly, POx/TA nanoparticles exhibited upper critical solution temperature (UCST)‐type thermoresponsive properties in ethanol or water depending on the molecular weight and substituent in the 2‐position of POx. Increasing or decreasing the temperature at the transition point resulted in the reversible transformation between assembled nanoparticles and disassembled poly(2‐n‐propyl‐2‐oxazoline) (PnPrOx) and TA. In view of the tailored size of the stable nanoparticles and the biocompatibilities of POx and TA, the prepared thermoresponsive nanoparticles are promising candidates as carriers for medicine toward related biomedical applications. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1520–1527

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Section: Resultsmentioning

confidence: 99%

Thermoresponsive polymeric nanoparticles based on poly(2‐oxazoline)s and tannic acid

Wang

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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“…Such a behavior was shown for a diblock copolymer consisting of poly(3-dimethyl-(methacryloyloxyethyl) ammonium propanesulfonate) (PdMMAEAPS), as a UCST block, and poly(N,N-diethylacrylamide) (PdEA), as a LCST block, 13 and quaternized block copolymers of 2-(2 methoxyethoxy)ethyl meth acrylate (MEO 2 MA), oligo(ethylene glycol) methacrylate (OEGMA), and N-(3-(dimethylamino)propyl)methacrylamide (DMAP-MA) (poly(OEGMA-co-MEO 2 MA)-b-poly(DMAPMA)). 14 Poly(acrylamide-co-acrylonitrile) poly(AAm-co-AN) is one of the rare examples of uncharged polymers showing a UCSTtype single phase transition in water and physiological medium as shown in our previous work. 15 In the present work, we show a simple method of making block copolymers of poly(ethylene glycol) (PEG) and poly(AAm-co-AN) using a PEG based macro-azoinitiator for a radical polymerization.…”

Section: ■ Introductionmentioning

confidence: 97%

LCST and UCST in One: Double Thermoresponsive Behavior of Block Copolymers of Poly(ethylene glycol) and Poly(acrylamide-co-acrylonitrile)

et al. 2015

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The change in thermoresponsive behavior from a single phase transition of upper critical solution temperature (UCST)-type of an acrylamide-acrylonitrile copolymer (AAm-co-AN) to a double responsive behavior (LCST-UCST-type (LCST, lower critical solution temperature)) in water by the introduction of a poly(ethylene glycol) (PEG) block is highlighted in the present work. The polymer is synthesized in a simple way by free-radical polymerization of acrylamide and acrylonitrile using a poly(ethylene glycol) (PEG) macro-azoinitiator. The dual thermoresponsive behavior was observed in a wide range of concentrations repeatable for many cycles with very small hysteresis depending upon the ratio of AAm, AN and PEG. Static light scattering (SLS) and dynamic light scattering (DLS) together with turbidity photometry and transmission electron microscopy confirmed a unique phase transition behavior due to the temperature dependent change in the morphology from micelles to agglomerates. The low cytotoxicity and two-in-one thermoresponsive behavior makes the polymer promising for biomedical applications in the future.

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“…A block copolymer displaying an UCST and a LCST was also prepared through selective quaternization of poly(2‐(dimethylamino)ethyl methacrylate)‐ block ‐poly(2‐( N ‐morpholino)ethyl methacrylate) using 1,3‐propane sultone . Other examples involve copolymers consisting of zwitterionic segments with UCST and LCST blocks . The dual thermoresponsivities of the aforementioned copolymers arise from electrostatic interactions (UCST) and hydrophobic interactions (LCST) in aqueous solutions.…”

Section: Introductionmentioning

confidence: 99%

Tunable Dual‐Thermoresponsive Phase Behavior of Zwitterionic Polysulfobetaine Copolymers Containing Poly(N,N‐dimethylaminoethyl methacrylate)‐Grafted Silica Nanoparticles in Aqueous Solution

Zhou

Mao

Wang

et al. 2013

Macro Chemistry & Physics

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Novel thermoresponsive copolymers of zwitterionic sulfobetaine methacrylate (SBMA)‐ and N,N‐dimethylaminoethyl methacrylate (DMAEMA)‐grafted silica nanoparticles are prepared via surface‐initiated atom transfer radical polymerization. The phase behavior of these nanoparticles is investigated. The hybrid nanoparticles exhibit tunable phase transition temperature between the upper critical solution temperature (UCST) and the lower critical solution temperature (LCST) in aqueous solution. A high PSBMA content in P(SBMA‐co‐DMAEMA) copolymer in the hybrid nanoparticles leads to aggregation at low temperatures because of dominant electrostatic interactions of ionic pairs, whereas a relatively low PSBMA content in the hybrid nanoparticles results in a phase transition at high temperatures as a result of predominant hydrophobic interactions of the PDMAEMA. Interestingly, hybrid nanoparticles with a suitable molar ratio of SBMA/DMAEMA exhibit both UCST and LCST in aqueous solution, where the water‐insoluble microdomains of hybrid nanoparticles are generated by the PSBMA or PDMAEMA region depending on the temperature. The above dual‐thermoresponsive phase transition is also controllable in salt solution. A facile change in the molar content of copolymer grafted on silica nanoparticles will tune the UCST and LCST readily.

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Synthesis of Thermo‐Responsive Polymers With Both Tunable UCST and LCST

Cited by 61 publications

References 20 publications

Thermoresponsive polymeric nanoparticles based on poly(2‐oxazoline)s and tannic acid

Thermoresponsive polymeric nanoparticles based on poly(2‐oxazoline)s and tannic acid

LCST and UCST in One: Double Thermoresponsive Behavior of Block Copolymers of Poly(ethylene glycol) and Poly(acrylamide-co-acrylonitrile)

Tunable Dual‐Thermoresponsive Phase Behavior of Zwitterionic Polysulfobetaine Copolymers Containing Poly(N,N‐dimethylaminoethyl methacrylate)‐Grafted Silica Nanoparticles in Aqueous Solution

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