Thermoresponsive poly(oligo ethylene glycol acrylates) |
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Authors: | Gertjan Vancoillie Daniel FrankRichard Hoogenboom |
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Affiliation: | Supramolecular Chemistry Group, Department of Organic Chemistry, Ghent University, Krijgslaan 281 S4, Ghent, Belgium |
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Abstract: | Thermoresponsive polymers have been the subject of numerous publications and research topics in the last few decades mostly driven by their easily controllable temperature stimulus and high potential for in vitro and in vivo applications. P(NIPAAm) is the most studied amongst these polymers, but recently other types of polymers are increasingly being investigated for their thermoresponsive behavior. In particular, polymers bearing a short oligo ethylene glycol (OEG) side chain have been shown to combine the biocompatibility of polyethylene glycol (PEG) with a versatile and controllable LCST behavior. These polymers can be synthesized via controlled radical polymerization techniques from various monomers consisting of an OEG chain and a polymerizable group like a (meth)acrylate, styrene or acrylamide. OEG acrylates offer significant advantages over, e.g., OEG methacrylates as the lower hydrophilicity of the backbone facilitates thermoresponsive behavior with smaller, more defined side chains. Furthermore, PEG acrylates can be polymerized using all major controlled radical polymerization techniques, unlike OEG methacrylates. This review will focus on OEG acrylate based (co)polymers and will provide a comprehensive overview of their reported thermoresponsive properties. The combination and comparison of this data will not only highlight the potential of these monomers, but will also serve as a starting point for future studies. |
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Keywords: | AA, acrylic acid AIBN, azobisisobutyronitrile AMHS, aminoethyl methacrylate hydrochloride Amor, N-acryloyl-morpholine ATRP, atom-transfer radical polymerization BB, blocbuilder® BSPA, 3-(benzylsulfanylthiocarbonylsulfanyl)propionic acid CBDB, 2-cyano-2-butyl dithiobenzoate CBI, cholesteryl-2-bromoisobutyrate CTA1, 1,2-bis-(4-(t-butoxy-carbonyl)benzyl sulfanylthiocarbonyl sylfanyl) ethane CTA2, 4-butylsulfanyl-thiocarbonyl-sulfanylmethyl-benzoic acid CTA3, 1,1,1-tris(3-(4-(tert-butoxycarbonyl)-benzylsulfanyl-thiocarbonyl-sulfanyl-propanoyl-oxy))-ethane CTA4, 2-[[(dodecylthio)thioxomethyl]thio]-2-methyl propanoic acid CTA5, S,S&prime -bis(α,α&prime -dimethylacetic acid) trithiocarbonate ?, dispersity DBTTC, dibenzyltrithiocarbonate DCPA, 2-[(dodecylsulfanylcarbonylthiolsulfanyl) propionic acid] DEA, 2-(1,3-dioxan-2-yloxy)ethyl acrylate DLS, dynamic light scattering DMA, N,N-dimethylacrylamide DMDEA, 2-(5,5-dimethyl-1,3-dioxan-2-yloxy)ethyl acrylate 4-DMNMA, 2-(6-(dimethylamino)-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethyl methacrylate DMP, 2-dodecylsulfanylthiocarbonylsulfanyl-2-methyl-propionic acid DP, degree of polymerization EBiB, ethyl 2-bromoisobutyrate EBP, ethyl 2-bromopropionate eDEGA, di(ethylene glycol) ethyl ether acrylate EGFP, enhanced green fluorescent protein eTEGA, tri(ethylene glycol) ethyl ether acrylate FM, fraction of monomer M incorporated in the polymer fM, fraction of monomer M in the polymerization mixture FRP, free radical polymerization GC, gas chromatography GOx, glucose oxidase HEA, hydroxyethyl acrylate HPA, hydroxypropyl acrylate LCST, lower critical solution temperature MALDI, matrix assisted laser desorption/ionization MBP, methyl 2-bromopropionate MBSP, 4-methoxybenzylsulfanylthiocarbonylsulfanylpropane mDEGA, di(ethylene glycol) methyl ether acrylate mDEGMA, di(ethylene glycol) methyl ether methacrylate Mn, number average molecular weight mEGA, ethylene glycol methyl ether acrylate mOEGA, oligo(ethylene glycol) methyl ether acrylate mOEGMA, oligo(ethylene glycol) methyl ether methacrylate mTEGA, tri(ethylene glycol) methyl ether acrylate NBA, nitrobenzyl acrylate NMP, nitroxide mediated polymerization OEG, oligo(ethylene glycol) OEGA, oligo(ethylene glycol) acrylate PBS, phosphate buffer solution PEG, poly(ethylene glycol) PNIPAAm, poly(N,N-dimethylacrylamide) SPNP, superparamgnetic nanoparticle RAFT, reversible addition-fragmentation chain-transfer polymerization SEC, size exclusion chromatography SG1, N-tert-butyl-N-(1&prime -diethylphosphono-2.2&prime -dimethylpropyl)-nitroxide Tcp, cloud point temperature TEGSt, 4-vinylbenzyl methoxytris(oxyethylene) ether TFA, trifluoroacetic acid TGA, thermogravimetric analysis TPANO, 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide TPPA, 2,2,5-trimethyl-3-(2-phenylethoxy)-4-phenyl-3-azahexane UCST, upper critical solution temperature |
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