Synthesis of SET–LRP‐induced galactoglucomannan‐diblock copolymers

Abstract

Polysaccharides are biorenewable and biodegradable starting materials for the development of functional materials. The synthesis of a monofunctional macroinitiator for single electron transfer-living radical polymerization was successfully developed from a wood polysaccharide-O-acetyl galactoglucomannan (GGM) using a beforehand synthesized amino-functional a-bromoisobutyryl derivative applying reductive amination. The GGM macroinitiator was employed to initiate a controlled radical polymerization of [2-(methacryloyloxy) ethyl]trimethylammonium chloride (MeDMA), methyl methacrylate (MMA), and N-isopropylacrylamide (NIPAM) using Cu 0 / Me 6 -Tren as a catalyst. The either charged or amphiphilic GGM-b-copolymers with different chain lengths of the synthetic block were successfully synthesized without prior hydro-V C 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 5100-5110

Synthesis of naringin‐based polymer brushes via seATRP

“…Flavonoid‐based copolymer brushes with a naringin core and block copolymer side chains composed of amphiphilic PMMA‐ b ‐PNIPAM have been synthesized for the first time using only 40 ppm of Cu catalyst complex, following the se ATRP procedure (Table ). Until now, PMMA‐ b ‐PNIPAM block copolymers were synthesized by ATRP approaches but always with huge amounts of catalyst: 6 300 to 147 400 ppm.…”

“…Until now, PMMA-b-PNIPAM block copolymers were synthesized by ATRP approaches [79][80][81][82] but always with huge amounts of catalyst:…”

“…69,73,75 Until now, synthesis of temperature-responsive naringin-based macromolecular brushes composed of poly(methyl methacrylate) (PMMA) and poly(N-isopropylacrylamide) (PNIPAM) has not yet been reported. Meanwhile, PMMA-b-PNIPAM block copolymers were synthesized by free radical copolymerization, [41][42][43] reverse iodine transfer polymerization (RITP), 77 RAFT, 78 and by the combination of RAFT polymerization and click chemistry, 13 or by ATRP [79][80][81] and electrochemically mediated ATRP (eATRP), 82 but with significant amounts of catalyst (in the last two cases: 6 300−20 000 ppm and 147 400 ppm, respectively). It is expected that these synthesized thermos-responsive amphiphilic copolymer brushes can become key elements of microfluidics devices and drug delivery systems.…”

Recent Developments in the Synthesis of Biomacromolecules and their Conjugates by Single Electron Transfer–Living Radical Polymerization

“…In this line, a monofunctional initiator was successfully synthesized from galactoglucomannan on its reducing end using an amino functional α-bromoisobutyric derivative. 201 The macroinitiator was used to initiate SET-LRP of MMA, MAETC, and NIPAM using Cu(0)/Me 6 -TREN as a catalyst producing diblock copolymers with molar masses ranging from 5,200 to 50,000 g mol −1 . The formed diblock copolymers could be used in food formulations as stabilization agents due to their easily tunable properties such as amphiphilicity or charge.…”

Methylcelluloses end-functionalized with peptides as thermoresponsive supramolecular hydrogelators

“…However, polysaccharide-derivative-blockoligosaccharides (Breitenbach et al 2017;de Medeiros Modolon et al 2012) or polysaccharide-derivative-block-oligopeptides have not received much attention from researchers. Carbohydrate-based block copolymers with polyester (Fajardo et al 2014;Liu and Zhang 2007), poly(methyl methacrylate) (Dax et al 2013;Togashi et al 2014), poly(styrene) (Loos and Müller 2002;Otsuka et al 2013;Yagi et al 2010), poly(N-isopropylacrylamide) (Dax et al 2013;Otsuka et al 2012), poly(γ-benzyl-L-glutamate) (Kamitakahara et al 2014), and poly(3hexylthiophene) (Sakai-Otsuka et al 2017) polyisoprene (Hung et al 2017), and poly(ethyleneoxide) (Akiyoshi et al 1999) have been reported. Shoichet and her colleagues focused on a physical blend of hyaluronan and methylcellulose covalently linked to peptides for tissue-engineering purposes (Parker et al 2016).…”