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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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