Abstract
Phenylboronic acids (PBAs) have gained considerable interest in recent years due to their recognition for diol-containing molecules such as glucose. Their response to the elevated glucose concentrations can be reported by measuring the change in the size or optical properties of polymers-bearing PBAs. In this context, fast response and good mechanical properties are crucial factors for constructing glucose-responsive sensors. Toward this goal, we have synthesized glucose-responsive nanostructured gels (NSGs) using 3-acrylamidophenylboronic acid and N-isopropylacrylamide. Herein, activated nanogels with controllable size were prepared and used as nano-cross-linkers. The prepared NSGs showed glucose-responsiveness in a remarkable concentration-dependent manner, exhibited high elasticity upon compression and slicing and resisted high level of deformation such as bending, twisting and stretching.
Similar content being viewed by others
References
Yu J, Zhang Y, Bomba H, Gu Z (2016) Stimuli-responsive delivery of therapeutics for diabetes treatment. Bioeng Trans Med 1(3):323–337
Thérien-Aubin H, Wang Y, Nothdurft K, Prince E, Cho S, Kumacheva E (2016) Temperature-responsive nanofibrillar hydrogels for cell encapsulation. Biomacromolecules 17(10):3244–3251
Kim YJ, Tachibana M, Umezu M, Matsunaga YT (2016) Bio-inspired smart hydrogel with temperature-dependent properties and enhanced cell attachment. J Mater Chem B 4(9):1740–1746
Liu J, Yin Y (2015) Temperature responsive hydrogels: construction and applications. Polym Sci 1(13):1–6
Xiao Z, Wylie RAL, Brisson ERL, Connal LA (2016) pH-responsive fluorescent hydrogels using a new thioflavin T cross-linker. J Polym Sci Polym Chem 54(5):591–595
Puranik AS, Pao LP, White VM, Peppas NA (2016) Synthesis and characterization of pH-responsive nanoscale hydrogels for oral delivery of hydrophobic therapeutics. Eur J Pharm Biopharm 108:196–213
Carrick LM, Aggeli A, Boden N, Fisher J, Ingham E, Waigh TA (2007) Effect of ionic strength on the self-assembly, morphology and gelation of pH responsive β-sheet tape-forming peptides. Tetrahedron 63(31):7457–7467
Takashi N, Yoshinori T, Akihito H, Hiroyasu Y, Akira H (2014) A metal-ion-responsive adhesive material via switching of molecular recognition properties. Nat Commun 5:4622–4631
Huang YJ, Ouyang WJ, Wu X, Li Z, Fossey JS, James TD, Jiang YB (2013) Glucose sensing via aggregation and the use of “knock-out” binding to improve selectivity. J Am Chem Soc 135(5):1700–1703
Yang T, Ji R, Deng XX, Du FS, Li ZC (2014) Glucose-responsive hydrogels based on dynamic covalent chemistry and inclusion complexation. Soft Matter 10(15):2671–2678
Raja STK, Thiruselvi T, Mandal AB, Gnanamani A (2015) pH and redox sensitive albumin hydrogel: a self-derived biomaterial. Scientific Rep 5:15977
Fan Y, Zhou W, Yasin A, Li H, Yang H (2015) Dual-responsive shape memory hydrogels with novel thermoplasticity based on a hydrophobically modified polyampholyte. Soft Matter 11(21):4218–4225
Beebe DJ, Moore JS, Bauer JM, Yu Q, Liu RH, Devadoss CJ, Byung H (2000) Functional hydrogel structures for autonomous flow control inside microfluidic channels. Nature 404(6778):588–590
Dong L, Agarwal AK, Beebe DJ, Jiang H (2006) Adaptive liquid microlenses activated by stimuli-responsive hydrogels. Nature 442(7102):551–554
Qiu Y, Park K (2001) Environment-sensitive hydrogels for drug delivery. Adv Drug Deliv Rev 53(3):321–339
Caldorera-Moore M, Peppas NA (2009) Micro- and nanotechnologies for intelligent and responsive biomaterial-based medical systems. Adv Drug Deliv Rev 61(15):1391–1401
Yoo EH, Lee SY (2010) Glucose biosensors: an overview of use in clinical practice. Sensors 10(5):4558–4576
Kissinger PT (2005) Biosensors-a perspective. Biosens Bioelectron 20(12):2512–2516
Yu B, Wang C, Ju YM, West L, Harmon J, Moussy Y, Moussy F (2008) Use of hydrogel coating to improve the performance of implanted glucose sensors. Biosens Bioelectron 23(8):1278–1284
Bahram M, Mohseni N, Moghtader M (2016) An introduction to hydrogels and some recent applications. In: Sutapa BM (ed) Emerging concepts in analysis and applications of hydrogels, pp 9–38. Intech, London
Wang Y, Huang F, Sun Y, Gao M, Chai Z (2017) Development of shell cross-linked nanoparticles based on boronic acid-related reactions for self-regulated insulin delivery. J Biomat Sci Polym Ed 28(1):93–106
Gallei M, Rüttiger C (2018) Recent trends in metallopolymer design: redox-controlled surfaces, porous membranes, and switchable optical materials using ferrocene-containing polymers. Chem A Eur J 24(40):10006–10021
Katz E (2017) Enzyme-based logic gates and networks with output signals analyzed by various methods. ChemPhysChem 18(13):1688–1713
Sung D, Yang S (2014) Facile method for constructing an effective electron transfer mediating layer using ferrocene-containing multifunctional redox copolymer. Electrochim Acta 133:40–48
Wang JY, Chen LC, Ho KC (2013) Synthesis of redox polymer nanobeads and nanocomposites for glucose biosensors. ACS Appl Mater Interfaces 5(16):7852–7861
Feng X, Zhang K, Hempenius MA, Vancso GJ (2015) Organometallic polymers for electrode decoration in sensing applications. RSC Adv 5(129):106355–106376
Li X, Zhou Y, Zheng Z, Yue X, Dai Z, Liu S, Tang Z (2009) Glucose biosensor based on nanocomposite films of CdTe quantum dots and glucose oxidase. Langmuir 25(11):6580–6586
Yin R, Tong Z, Yang D, Nie J (2011) Glucose and pH dual-responsive concanavalin a based microhydrogels for insulin delivery. Int J Biol Macromol 49(5):1137–1142
Wu Q, Wang L, Yu H, Wang J, Chen Z (2011) Organization of glucose-responsive systems and their properties. Chem Rev 111(12):7855–7875
Gu Z, Aimetti AA, Wang Q et al (2013) Injectable nano-network for glucose-mediated insulin delivery. ACS Nano 7(5):4194–4201
Guan Y, Zhang Y (2013) Boronic acid-containing hydrogels: synthesis and their applications. Chem Soc Rev 42(20):8106–8121
Brooks WLA, Sumerlin BS (2016) Synthesis and applications of boronic acid-containing polymers: from materials to medicine. Chem Rev 116(3):1375–1397
Fossey JS, D’Hooge F, van den Elsen JMH, Pereira M, Marta P, Pascu SI, Bull SD, Marken F, Jenkins A, Toby A, Jiang YB, James TD (2012) The development of boronic acids as sensors and separation tools. Chem Rec 12(5):464–478
Yingyu Li SZ (2013) A simple method to fabricate fluorescent glucose sensor based on dye-complexed microgels. Sens Actuators B Chem 177:792–799
Kim EY, Dryer SE (2011) Effects of insulin and high glucose on mobilization of slo1 BKCa channels in podocytes. J Cell Physiol 226(9):2307–2315
Yetisen AK (2015) Holographic sensors. Springer, Cham
Ruan JL, Chen C, Shen JH, Zhao XL, Qian SH, Zhu ZG (2017) A gelated colloidal crystal attached lens for noninvasive continuous monitoring of tear glucose. Polymers 9(4):125
Tierney S, Volden S, Stokke BT (2009) Glucose sensors based on a responsive gel incorporated as a fabry-perot cavity on a fiber-optic readout platform. Biosens Bioelectron 24(7):2034–2039
Shibata H, Heo YJ, Okitsu T, Matsunaga Y, Kawanishi T, Takeuchi S (2010) Injectable hydrogel microbeads for fluorescence-based in vivo continuous glucose monitoring. PNAS 107(42):17894–17898
Wu W, Zhou T, Shen J, Zhou S (2009) Optical detection of glucose by CdS quantum dots immobilized in smart microgels. Chem Commun 29:4390–4392
Kajisa T, Sakata T (2017) Glucose-responsive hydrogel electrode for biocompatible glucose transistor. Sci Technol Adv Mater 18(1):26–33
Yetisen AK, Jiang N, Fallahi A, Montelongo Y, Ruiz-Esparza GU, Tamayol A, Zhang YS, Mahmood I, Yang SA, Kim KS, Butt H, Khademhosseini A, Yun SH (2017) Glucose-sensitive hydrogel optical fibers functionalized with phenylboronic acid. Adv Mater 29(15):1606380
Heo YJ, Shibata H, Okitsu T, Kawanishi T, Takeuchi S (2011) Long-term in vivo glucose monitoring using fluorescent hydrogel fibers. PNAS 108(33):13399–13403
Badugu R, Lakowicz JR, Geddes CD (2005) A glucose-sensing contact lens: from bench top to patient. Curr Opin Biotechnol 16(1):100–107
Yan Z, Xue M, He Q, Lu W, Meng Z, Yan D, Qiu L, Zhou L, Yu Y (2016) A non-enzymatic urine glucose sensor with 2-D photonic crystal hydrogel. Anal Bioanall Chem 408(29):8317–8323
Kataoka K, Miyazaki H, Bunya M, Okano T, Sakurai Y (1998) Totally synthetic polymer gels responding to external glucose concentration: their preparation and application to on − off regulation of insulin release. J Am Chem Soc 120(48):12694–12695
Matsumoto A, Yoshida R, Kataoka K (2004) Glucose-responsive polymer gel bearing phenylborate derivative as a glucose-sensing moiety operating at the physiological pH. Biomacromol 5(3):1038–1045
Ancla C, Lapeyre V, Gosse I, Catargi B, Ravaine V (2011) Designed glucose-responsive microgels with selective shrinking behavior. Langmuir 27(20):12693–12701
Cheng R, Meng F, Deng C, Klok HA, Zhong Z (2013) Dual and multi-stimuli responsive polymeric nanoparticles for programmed site-specific drug delivery. Biomaterials 34(14):3647–3657
Kharkar PM, Kiick KL, Kloxin AM (2013) Designing degradable hydrogels for orthogonal control of cell microenvironments. Chem Soc Rev 42(17):7335–7372
Zhang SB, Chu LY, Xu D, Zhang J, Ju XJ, Rui X (2008) Poly(N-isopropylacrylamide)-based comb-type grafted hydrogel with rapid response to blood glucose concentration change at physiological temperature. Polym Adv Technol 19:937–943
Yoshida R, Uchida K, Kaneko Y, Sakai K, Kikuchi A, Sakurai Y, Okano T (1995) Comb-type grafted hydrogels with rapid deswelling response to temperature changes. Nature 374(6519):240–242
Xu XD, Zhang XZ, Yang J, Cheng SX, Zhuo RX, Huang YQ (2007) Strategy to introduce a pendent micellar structure into poly(N-isopropylacrylamide) hydrogels. Langmuir 23(8):4231–4236
Sun JY, Zhao X, Illeperuma WRK, Chaudhuri O, Oh KH, Mooney DJ, Vlassak JJ, Suo Z (2012) Highly stretchable and tough hydrogels. Nature 489(7414):133–136
Haraguchi K, Li HJ (2005) Control of the coil-to-globule transition and ultrahigh mechanical properties of pnipa in nanocomposite hydrogels. Angew Chem Int Ed 44(40):6500–6504
Xia LW, Xie R, Ju XJ, Wang W, Chen Q, Chu LY (2013) Nano-structured smart hydrogels with rapid response and high elasticity. Nat Commun 4:2226
Gao H, Wang N, Hu X, Nan W, Han Y, Liu W (2013) Double hydrogen-bonding ph-sensitive hydrogels retaining high-strengths over a wide pH range. Macromol Rapid Commun 34(1):63–68
Zhang MJ, Wang W, Xie R, Ju XJ, Liu L, Gu YY (2013) Microfluidic fabrication of monodisperse microcapsules for glucose-response at physiological temperature. Soft Matter 9(16):4150–4159
Pelton RH, Chibante P (1986) Preparation of aqueous latices with N-isopropylacrylamide. Colloid Surf 20(3):247–256
McPhee W, Tam KC, Pelton R (1993) Poly(N-isopropylacrylamide) latices prepared with sodium dodecyl sulfate. J Colloid Interface Sci 156(1):24–30
Wolff HJM, Kather M, Breisig H, Richtering W, Pich A, Wessling M (2018) From batch to continuous precipitation polymerization of thermoresponsive microgels. ACS Appl Mater Interfaces 10(29):24799–24806
Guillermo A, Cohen Addad JP, Bazile JP, Duracher D, Elaissari A, Pichot C (2000) NMR investigations into heterogeneous structures of thermosensitive microgel particles. J Polym Sci Part B Polym Phys 38(6):889–898
Zhang S, Shi Z, Xu H, Ma X, Yin J, Tian M (2016) Revisiting the mechanism of redox-polymerization to build the hydrogel with excellent properties using a novel initiator. Soft Matter 12(9):2575–2582
Feng XD, Guo XQ, Qiu KY (1988) Study of the initiation mechanism of the vinyl polymerization with the system persulfate/N, N, N′, N′-tetramethylethylenediamine. Die Makromol Chem 189(1):77–83
Cheng CJ, Chu LY, Zhang J, Wang HD, Wei G (2008) Effect of freeze-drying and rehydrating treatment on the thermo-responsive characteristics of poly(N-isopropylacrylamide) microspheres. Colloid Polym Sci 286(5):571–577
Kang HW, Tabata Y, Ikada Y (1999) Fabrication of porous gelatin scaffolds for tissue engineering. Biomaterials 20(14):1339–1344
Tenório-Neto ET, Lima DdS, Guilherme MR, Lima-Tenório MK, Scariot DB, Nakamura CV, Kunita MH, Rubira AF (2017) Synthesis and drug release profile of a dual-responsive poly(ethylene glycol) hydrogel nanocomposite. RSC Adv 7(44):27637–27644
Fujishige S, Kubota K, Ando I (1989) Phase transition of aqueous solutions of poly(N-isopropylacrylamide) and poly(N-isopropylmethacrylamide). J Phys Chem 93(8):3311–3313
Tanaka T (1986) Kinetics of phase transition in polymer gels. Phys A 140(1):261–268
Chiessi E, Lonardi A, Paradossi G (2010) Toward modeling thermoresponsive polymer networks: a molecular dynamics simulation study of N-isopropyl acrylamide co-oligomers. J Phys Chem B 114(25):8301–8312
Oliveira TEd, Mukherji D, Kremer K, Netz PA (2017) Effects of stereochemistry and copolymerization on the lcst of pnipam. J Chem Phys 146(3):034904
Xu H, Meng F, Zhong Z (2009) Reversibly crosslinked temperature-responsive nano-sized polymersomes: synthesis and triggered drug release. J Mater Chem 19(24):4183–4190
Brooks WLA, Vancoillie G, Kabb CP, Hoogenboom R, Sumerlin BS (2017) Triple responsive block copolymers combining pH-responsive, thermoresponsive, and glucose-responsive behaviors. J Polym Sci Pol Chem 55(14):2309–2317
Morawetz H (1974) Pure Appl Chem 38:267–277
Sawant S, Morawetz H (1984) Microstructure, neighboring group inhibition, and electrostatic effects in the base-catalyzed degradation of polyacrylamide. Macromolecules 17(11):2427–2431
Xing S, Guan Y, Zhang Y (2011) Kinetics of glucose-induced swelling of p(nipam-aapba) microgels. Macromolecules 44(11):4479–4486
Acknowledgements
Financial support from the National Natural Science Foundation of China (21472168 and 21611530689) and the fundamental research funds for the central universities (2017FZA4023) are gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding authors
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Elshaarani, T., Yu, H., Wang, L. et al. Glucose-responsive nanostructured hydrogels with enhanced elastic and swelling properties. J Mater Sci 54, 10009–10023 (2019). https://doi.org/10.1007/s10853-019-03505-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-019-03505-9