Poly(2-isopropenyl-2-oxazoline) as a versatile platform towards thermoresponsive copolymers

Jerca, Florica Adriana; Jerca, Valentin Victor; Anghelache, Alina Maria; Vuluga, Dumitru Mircea; Hoogenboom, Richard

doi:10.1039/c8py00612a

Cited by 44 publications

(90 citation statements)

References 34 publications

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“…Due to this LCST-type phase transition, such PGEs are soluble in aqueous media below a critical temperature, whereas they undergo a coil-to-globule transition to form turbid solutions when the temperature is raised above their so-called cloud point temperature (CPT). Similar to various POx and POEGMA copolymers [ 42 , 43 ], the CPT of thermoresponsive PGEs can be adjusted via the GME:EGE comonomer ratio and the sharp phase transition is fully reversible and exhibits little to no thermal hysteresis [ 19 , 39 , 40 , 44 ]. In addition, PGEs exhibit a concentration-dependent as well as a strongly molecular weight-dependent CPTs in the range between 1 and 30 kDa [ 39 , 44 ].…”

Section: Resultsmentioning

confidence: 99%

Thermoresponsive Poly(glycidyl ether) Brush Coatings on Various Tissue Culture Substrates—How Block Copolymer Design and Substrate Material Govern Self-Assembly and Phase Transition

Stöbener

Weinhart

2020

Polymers

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Thermoresponsive poly(glycidyl ether) brushes can be grafted to applied tissue culture substrates and used for the fabrication of primary human cell sheets. The self-assembly of such brushes is achieved via the directed physical adsorption and subsequent UV immobilization of block copolymers equipped with a short, photo-reactive benzophenone-based anchor block. Depending on the chemistry and hydrophobicity of the benzophenone anchor, we demonstrate that such block copolymers exhibit distinct thermoresponsive properties and aggregation behaviors in water. Independent on the block copolymer composition, we developed a versatile grafting-to process which allows the fabrication of poly(glycidyl ether) brushes on various tissue culture substrates from dilute aqueous-ethanolic solution. The viability of this process crucially depends on the chemistry and hydrophobicity of, both, benzophenone-based anchor block and substrate material. Utilizing these insights, we were able to manufacture thermoresponsive poly(glycidyl ether) brushes on moderately hydrophobic polystyrene and polycarbonate as well as on rather hydrophilic polyethylene terephthalate and tissue culture-treated polystyrene substrates. We further show that the temperature-dependent switchability of the brush coatings is not only dependent on the cloud point temperature of the block copolymers, but also markedly governed by the hydrophobicity of the surface-bound benzophenone anchor and the subjacent substrate material. Our findings demonstrate that the design of amphiphilic thermoresponsive block copolymers is crucial for their phase transition characteristics in solution and on surfaces.

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Section: Resultsmentioning

confidence: 99%

Thermoresponsive Poly(glycidyl ether) Brush Coatings on Various Tissue Culture Substrates—How Block Copolymer Design and Substrate Material Govern Self-Assembly and Phase Transition

Stöbener

Weinhart

2020

Polymers

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“…The second notable difference between the partially modified PiPOx (PiPOx‐Ax) copolymers and the fully modified (AAc‐Ax) copolymers is that the T CP 's of the fully modified copolymers are lower, for example, 64.8 °C versus 45.3 °C for copolymers with 20 mol % APr, 58.5 °C versus 34.6 °C for copolymers with 15 mol % ABu and 77.6 °C versus 42.6 °C for copolymers with 12 mol % AiBu, respectively . This observation is in accordance with the more hydrophobic character of the acetyl ester amide functionality as compared to the 2‐oxazoline ring as indicated by the LCST behavior of the PiPOx fully modified with acetic acid, which increases the overall hydrophobicity of the polymer and decreases the transition temperatures.…”

Section: Resultsmentioning

confidence: 99%

Well‐Defined Thermoresponsive Polymethacrylamide Copolymers with Ester Pendent Groups through One‐Pot Statistical Postpolymerization Modification of Poly(2‐Isopropenyl‐2‐Oxazoline) with Multiple Carboxylic Acids

Jerca

Hoogenboom

2018

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

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This manuscript is dedicated to Professor Mitsuo Sawamoto's outstanding achievements in polymer chemistry and recognizes his recent retirement from 40 years of exceptional service to Kyoto University.ABSTRACT: Thermoresponsive polymers that undergo a solubility phase transition in water are important as basis for the development for a wide variety of responsive and smart materials. In this study, the synthesis of thermoresponsive copolymers is demonstrated by the straightforward one-pot statistical postpolymerization modification of well-defined poly(2-isopropenyl-2-oxazoline) (PiPOx) by ring-opening reaction with multiple carboxylic acids. The reactions are carried out using dual, triple, and quadruple mixtures of up to four different aliphatic carboxylic acids. The cloud point temperatures of the resulting polymethacrylamide copolymers with ester pendent groups can be finely tuned by adjusting the feed ratio and the hydrophilic-hydrophobic balance of the acids that are used for the ring-opening modification of PiPOx.

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“…The reaction temperature was chosen according to our previous studies regarding the ring opening addition reaction of PiPOx with different monocarboxylic acid to ensure a quantitative conversion of the 2-oxazoline rings and an optimum reaction time. 53,58 FT-IR analysis was used to investigate the chemical structure of the dry polymer networks. The FT-IR spectrum of PiPOx displayed the characteristic signals of the 2-oxazoline ring at 1648 cm -1 (C=N stretching) and 1121 cm -1 (C-O stretching) (see Fig S1).…”

Section: Synthesis and Characterization Of The Pipox Hydrogelsmentioning

confidence: 99%

“…In a recent study, we demonstrated that PiPOx can be chemically modified with mono carboxylic acids yielding soluble thermoresponsive polymers. 53,63 Modulation of the cloud point temperature was achieved by controlling the modification degree and/or by changing the hydrophobic character of the acid.…”

Section: Thermoresponsive Properties Of the H4-h12 Hydrogelsmentioning

confidence: 99%

Poly(2-isopropenyl-2-oxazoline) Hydrogels for Biomedical Applications

et al. 2018

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Synthetic polymers have had a major impact on the biomedical field. However, all polymers have their advantages and disadvantages, so that the selection of a certain polymeric material always is a compromise with regard to many properties, such as synthetic accessibility, solubility, thermal properties, biocompatibility and degradability. The development of novel polymers with superior properties for medical applications is the focus of many research groups. The present study highlights the use of poly(2-isopropenyl-2-oxazoline) (PiPOx), as biocompatible functional polymer to develop synthetic hydrogel materials using a simple straightforward synthesis protocol. A library of hydrogels was obtained by chemical cross-linking of PiPOx, using eight different non-toxic and bio-based dicarboxylic acids. The equilibrium swelling degree (ESD) of the final material can be modulated by simple modification of the composition of the reaction mixture, including the polymer concentration in the feed ratio between the 2-oxazoline pendent groups and the carboxylic acid groups as well as the cross-linker 2 length. The hydrogels with the highest water uptake were selected for further investigations regarding their potential use as biomaterials. We evaluated the thermoresponsiveness, the pH-degradability under physiological conditions and demonstrated proof-of-concept drug delivery experiments. The in vitro cellular studies demonstrated the noncytotoxic character of the PiPOx hydrogels, and its protein repellent properties, while mineralization studies revealed that such scaffolds do not promote mineralization/calcification phenomena. In view, of these results, these hydrogels show potential use as ophthalmologic materials or in drug delivery applications.

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Poly(2-isopropenyl-2-oxazoline) as a versatile platform towards thermoresponsive copolymers

Abstract: Thermoresponsive (co)polymers with LCST behavior based on a well-defined PiPOx scaffold showing high versatility in tuning up the TCP as well as the interval of response.

Cited by 44 publications

References 34 publications

Thermoresponsive Poly(glycidyl ether) Brush Coatings on Various Tissue Culture Substrates—How Block Copolymer Design and Substrate Material Govern Self-Assembly and Phase Transition

Thermoresponsive Poly(glycidyl ether) Brush Coatings on Various Tissue Culture Substrates—How Block Copolymer Design and Substrate Material Govern Self-Assembly and Phase Transition

Well‐Defined Thermoresponsive Polymethacrylamide Copolymers with Ester Pendent Groups through One‐Pot Statistical Postpolymerization Modification of Poly(2‐Isopropenyl‐2‐Oxazoline) with Multiple Carboxylic Acids

Poly(2-isopropenyl-2-oxazoline) Hydrogels for Biomedical Applications

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