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Thermoresponsive poly(oligo ethylene glycol acrylates)
Authors:Gertjan Vancoillie  Daniel FrankRichard Hoogenboom
Affiliation:Supramolecular Chemistry Group, Department of Organic Chemistry, Ghent University, Krijgslaan 281 S4, Ghent, Belgium
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.
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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