Abstract
A glucose-sensitive polymer, poly(N-isopropylacrylamide-co-2-acrylamidophenylboronic acid) (P(NIPAM-co-2-AAPBA)), was synthesized by reversible addition fragmentation chain transfer (RAFT) copolymerization. Addition of glucose results in reduced solubility and hence increased turbidity, rather than the normal increase in solubility (decreased turbidity) observed for other PBA-based glucose-sensitive polymers. The novel glucose-sensitive behavior is explained by a new mechanism, in which glucose acts as an additive and depresses the lower critical solution temperature (LCST) of the polymer, instead of increasing solubility by increasing the degree of ionization of the PBA groups. Experimental and theoretic analysis for the influence of glucose on the thermal behavior of P(NIPAM-co-2-AAPBA) reveals that glucose depresses the LCST of P(NIPAM-co-2- AAPBA) copolymers in a two-stage manner, a fast decrease at low glucose concentrations followed by a slow decrease at high glucose concentrations. For low glucose concentrations, the binding of glucose with PBA groups on the polymer chain increases the number of glucose molecules proximal to the polymer which influences the thermal behavior of the polymer, causing a rapid decrease in LCST. Importantly, the transition occurs at a glucose concentration equal to the reciprocal of the binding constant between PBA and glucose, thus providing a novel method to determine the binding constant. Other saccharides, including mannose, galactose and fructose, also depress the LCST of P(NIPAM-co-2-AAPBA) copolymer in the same way.
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Wu X, Li Z, Chen XX, Fossey JS, James TD, Jiang YB. Chem Soc Rev, 2013, 42: 8032–8048
Guan Y, Zhang Y. Chem Soc Rev, 2013, 42: 8106–8121
Brooks WLA, Sumerlin BS. Chem Rev, 2016, 116: 1375–1397
Sun X, James TD. Chem Rev, 2015, 115: 8001–8037
Zhang X, Guan Y, Zhang Y. Biomacromolecules, 2012, 13: 92–97
Jia S, Tang Z, Guan Y, Zhang Y. ACS Appl Mater Interfaces, 2018, 10: 14254–14258
Liu Y, Zhang Y, Guan Y. Chem Commun, 2009, 620: 1867–1869
Asher SA, Alexeev VL, Goponenko AV, Sharma AC, Lednev IK, Wilcox CS, Finegold DN. J Am Chem Soc, 2003, 125: 3322–3329
Alexeev VL, Sharma AC, Goponenko AV, Das S, Lednev IK, Wilcox CS, Finegold DN, Asher SA. Anal Chem, 2003, 75: 2316–2323
Xu S, Sedgwick AC, Elfeky SA, Chen W, Jones AS, Williams GT, Jenkins ATA, Bull SD, Fossey JS, James TD. Front Chem Sci Eng, 2019, 6
Zhang X, Guan Y, Zhang Y. J Mater Chem, 2012, 22: 16299–16305
Liu P, Luo Q, Guan Y, Zhang Y. Polymer, 2010, 51: 2668–2675
Kataoka K, Miyazaki H, Bunya M, Okano T, Sakurai Y. J Am Chem Soc, 1998, 120: 12694–12695
Kang SI, Bae YH. J Control Release, 2003, 86: 115–121
Wang X, Li Q, Guan Y, Zhang Y. Mater Today Chem, 2016, 1–2: 7–14
Kim JJ, Park K. J Control Release, 2001, 77: 39–47
Li Q, Guan Y, Zhang Y. Sens Actuat B-Chem, 2018, 272: 243–251
Kataoka K, Miyazaki H, Okano T, Sakurai Y. Macromolecules, 1994, 27: 1061–1062
Matsumoto A, Ikeda S, Harada A, Kataoka K. Biomacromolecules, 2003, 4: 1410–1416
Kim KT, Cornelissen JJLM, Nolte RJM, van Hest JCM. J Am Chem Soc, 2009, 131: 13908–13909
Roy D, Cambre JN, Sumerlin BS. Chem Commun, 2009, 55: 2106–2108
Roy D, Cambre JN, Sumerlin BS. Chem Commun, 2008, 34: 2477–2479
Lv J, Wu G, Liu Y, Li C, Huang F, Zhang Y, Liu J, An Y, Ma R, Shi L. Sci China Chem, 2019, 62: 637–648
Zhao YN, Yuan Q, Li C, Guan Y, Zhang Y. Biomacromolecules, 2015, 16: 2032–2039
Tang Z, Jia S, Yao L, Guan Y, Zhang Y. Langmuir, 2018, 34: 8288–8293
Zhang Y, Liu K, Guan Y, Zhang Y. RSC Adv, 2012, 2: 4768–4776
Xing S, Guan Y, Zhang Y. Macromolecules, 2011, 44: 4479–4486
Zhang Y, Guan Y, Zhou S. Biomacromolecules, 2006, 7: 3196–3201
Zhang Y, Guan Y, Zhou S. Biomacromolecules, 2007, 8: 3842–3847
Yang X, Lee MC, Sartain F, Pan X, Lowe CR. Chem Eur J, 2006, 12: 8491–8497
Lai JT, Filla D, Shea R. Macromolecules, 2002, 35: 6754–6756
Van Durme K, Rahier H, Van Mele B. Macromolecules, 2005, 38: 10155–10163
Inomata H, Goto S, Otake K, Saito S. Langmuir, 1992, 8: 687–690
Kim YH, Kwon IC, Bae YH, Kim SW. Macromolecules, 1995, 28: 939–944
Lee SB, Sohn YS, Song SC. Bull Korean Chem Soc, 2003, 24: 901–905
Shpigelman A, Paz Y, Ramon O, Livney YD. Colloid Polym Sci, 2011, 289: 281–290
Kawasaki H, Sasaki S, Maeda H, Mihara S, Tokita M, Komai T. J Phys Chem, 1996, 100: 16282–16284
Xu R, Tian J, Guan Y, Zhang Y. Macromolecules, 2019, 52: 365–375
Tang Z, Guan Y, Zhang Y. Polym Chem, 2018, 9: 1012–1021
Tang Z, Weng J, Guan Y, Zhang Y. Macromol Chem Phys, 2017, 218: 1700364
Hofmann C, Schönhoff M. Colloid Polym Sci, 2009, 287: 1369–1376
Cho EC, Lee J, Cho K. Macromolecules, 2003, 36: 9929–9934
Otake K, Inomata H, Konno M, Saito S. Macromolecules, 1990, 23: 283–289
Springsteen G, Wang B. Tetrahedron, 2002, 58: 5291–5300
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This work was supported by the National Natural Science Foundation of China (51625302, 51873091) and the National Key Research and Development Program of China (2017YFC1103501).
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Wang, Q., Fu, M., Guan, Y. et al. Mechanistic insights into the novel glucose-sensitive behavior of P(NIPAM-co-2-AAPBA). Sci. China Chem. 63, 377–385 (2020). https://doi.org/10.1007/s11426-019-9680-6
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DOI: https://doi.org/10.1007/s11426-019-9680-6