PMID- 30970709 OWN - NLM STAT- PubMed-not-MEDLINE LR - 20200930 IS - 2073-4360 (Electronic) IS - 2073-4360 (Linking) VI - 9 IP - 1 DP - 2017 Jan 20 TI - A Comprehensive Systematic Study on Thermoresponsive Gels: Beyond the Common Architectures of Linear Terpolymers. LID - 10.3390/polym9010031 [doi] LID - 31 AB - In this study, seven thermoresponsive methacrylate terpolymers with the same molar mass (MM) and composition but various architectures were successfully synthesized using group transfer polymerization (GTP). These terpolymers were based on tri(ethylene glycol) methyl ether methacrylate (TEGMA, A unit), n-butyl methacrylate (BuMA, B unit), and 2-(dimethylamino)ethyl methacrylate (DMAEMA, C unit). Along with the more common ABC, ACB, BAC, and statistical architectures, three diblock terpolymers were also synthesized and investigated for the first time, namely (AB)C, A(BC), and B(AC); where the units in the brackets are randomly copolymerized. Two BC diblock copolymers were also synthesized for comparison. Their hydrodynamic diameters and their effective pK(a)s were determined by dynamic light scattering (DLS) and hydrogen ion titrations, respectively. The self-assembly behavior of the copolymers was also visualized by transmission electron microscopy (TEM). Both dilute and concentrated aqueous copolymer solutions were extensively studied by visual tests and their cloud points (CP) and gel points were determined. It is proven that the aqueous solution properties of the copolymers, with specific interest in their thermoresponsive properties, are influenced by the architecture, with the ABC and A(BC) ones to show clear sol-gel transition. FAU - Constantinou, Anna P AU - Constantinou AP AD - Department of Materials, Imperial College London, Royal School of Mines, Exhibition Road, London SW7 2AZ, UK. anna.constantinou14@imperial.ac.uk. FAU - Zhao, Hanyi AU - Zhao H AD - Department of Materials, Imperial College London, Royal School of Mines, Exhibition Road, London SW7 2AZ, UK. hanyi.zhao15@imperial.ac.uk. FAU - McGilvery, Catriona M AU - McGilvery CM AUID- ORCID: 0000-0002-4849-0251 AD - Department of Materials, Imperial College London, Royal School of Mines, Exhibition Road, London SW7 2AZ, UK. catriona.mcgilvery@imperial.ac.uk. FAU - Porter, Alexandra E AU - Porter AE AD - Department of Materials, Imperial College London, Royal School of Mines, Exhibition Road, London SW7 2AZ, UK. a.porter@imperial.ac.uk. FAU - Georgiou, Theoni K AU - Georgiou TK AUID- ORCID: 0000-0003-4474-6931 AD - Department of Materials, Imperial College London, Royal School of Mines, Exhibition Road, London SW7 2AZ, UK. t.georgiou@imperial.ac.uk. LA - eng PT - Journal Article DEP - 20170120 PL - Switzerland TA - Polymers (Basel) JT - Polymers JID - 101545357 PMC - PMC6432086 OTO - NOTNLM OT - 2-(dimethylamino)ethyl methacrylate OT - 3-D printing OT - complex architectures OT - group transfer polymerization (GTP) OT - injectable gels OT - terpolymers OT - thermoresponsive polymers OT - well-defined polymers COIS- The authors declare no conflict of interest. EDAT- 2017/01/20 00:00 MHDA- 2017/01/20 00:01 PMCR- 2017/01/20 CRDT- 2019/04/12 06:00 PHST- 2016/12/04 00:00 [received] PHST- 2017/01/12 00:00 [revised] PHST- 2017/01/16 00:00 [accepted] PHST- 2019/04/12 06:00 [entrez] PHST- 2017/01/20 00:00 [pubmed] PHST- 2017/01/20 00:01 [medline] PHST- 2017/01/20 00:00 [pmc-release] AID - polym9010031 [pii] AID - polymers-09-00031 [pii] AID - 10.3390/polym9010031 [doi] PST - epublish SO - Polymers (Basel). 2017 Jan 20;9(1):31. doi: 10.3390/polym9010031.