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Glucose-responsive shape-memory cryogels

Published online by Cambridge University Press:  12 August 2020

Marc Behl ,
Qian Zhao  and
Andreas Lendlein
Marc Behl
Affiliation:
Institute of Biomaterial Science, Helmholtz-Zentrum Geesthacht, Teltow14513, Germany Tianjin University − Helmholtz-Zentrum Geesthacht Joint Laboratory for Biomaterials and Regenerative Medicine, Teltow14513, Germany
Qian Zhao
Affiliation:
Institute of Biomaterial Science, Helmholtz-Zentrum Geesthacht, Teltow14513, Germany Tianjin University − Helmholtz-Zentrum Geesthacht Joint Laboratory for Biomaterials and Regenerative Medicine, Teltow14513, Germany
Andreas Lendlein*
Affiliation:
Institute of Biomaterial Science, Helmholtz-Zentrum Geesthacht, Teltow14513, Germany Tianjin University − Helmholtz-Zentrum Geesthacht Joint Laboratory for Biomaterials and Regenerative Medicine, Teltow14513, Germany Institute of Chemistry, University of Potsdam, Potsdam14476, Germany
*
a)Address all correspondence to this author. e-mail: [email protected]
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Abstract

Boronic ester bonds can be reversibly formed between phenylboronic acid (PBA) and triol moieties. Here, we aim at a glucose-induced shape-memory effect by implementing such bonds as temporary netpoints, which are cleavable by glucose and by minimizing the volume change upon stimulation by a porous cryogel structure. The polymer system consisted of a semi-interpenetrating network (semi-IPN) architecture, in which the triol moieties were part of the permanent network and the PBA moieties were located in the linear polymer diffused into the semi-IPN. In an alkaline medium (pH = 10), the swelling ratio was approximately 35, independent of Cglu varied between 0 and 300 mg/dL. In bending experiments, shape fixity Rf ≈ 80% and shape recovery Rr ≈ 100% from five programming/recovery cycles could be determined. Rr was a function of Cglu in the range from 0 to 300 mg/dL, which accords with the fluctuation range of Cglu in human blood. In this way, the shape-memory hydrogels could play a role in future diabetes treatment options.

Keywords

shape memorypolymerporosity
Type
Invited Feature Paper
Information
Journal of Materials Research , Volume 35 , Issue 18 , 28 September 2020 , pp. 2396 - 2404
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Copyright
Copyright © Materials Research Society 2020

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References

Bunn, H.F. and Higgins, P.J.: Reaction of monosaccharides with proteins: Possible evolutionary significance. Science 213, 222 (1981).CrossRefGoogle ScholarPubMed
Danaei, G., Finucane, M.M., Lu, Y., Singh, G.M., Cowan, M.J., Paciorek, C.J., Lin, J.K., Farzadfar, F., Khang, Y.-H., Stevens, G.A., Rao, M., Ali, M.K., Riley, L.M., Robinson, C.A., and Ezzati, M.: National, regional, and global trends in fasting plasma glucose and diabetes prevalence since 1980: Systematic analysis of health examination surveys and epidemiological studies with 370 country-years and 2·7 million participants. Lancet 378, 31 (2011).CrossRefGoogle ScholarPubMed
Wu, Q., Wang, L., Yu, H., Wang, J., and Chen, Z.: Organization of glucose-responsive systems and their properties. Chem. Rev. 111, 7855 (2011).CrossRefGoogle ScholarPubMed
Li, C., Liu, X., Liu, Y., Huang, F., Wu, G., Liu, Y., Zhang, Z., Ding, Y., Lv, J., Ma, R., An, Y., and Shi, L.: Glucose and H2O2 dual-sensitive nanogels for enhanced glucose-responsive insulin delivery. Nanoscale 11, 9163 (2019).CrossRefGoogle ScholarPubMed
Zhao, L., Wang, L., Zhang, Y., Xiao, S., Bi, F., Zhao, J., Gai, G., and Ding, J.: Glucose oxidase-based glucose-sensitive drug delivery for diabetes treatment. Polymers 9, 255 (2017).CrossRefGoogle ScholarPubMed
Lin, K., Yi, J., Mao, X., Wu, H., Zhang, L.-M., and Yang, L.: Glucose-sensitive hydrogels from covalently modified carboxylated pullulan and concanavalin A for smart controlled release of insulin. React. Funct. Polym. 139, 112 (2019).CrossRefGoogle Scholar
Miller, P.R., Narayan, R.J., and Polsky, R.: Microneedle-based sensors for medical diagnosis. J. Mater. Chem. B 4, 1379 (2016).CrossRefGoogle ScholarPubMed
Miller, P.R., Gittard, S.D., Edwards, T.L., Lopez, D.M., Xiao, X., Wheeler, D.R., Monteiro-Riviere, N.A., Brozik, S.M., Polsky, R., and Narayan, R.J.: Integrated carbon fiber electrodes within hollow polymer microneedles for transdermal electrochemical sensing. Biomicrofluidics 5, 013415 (2011).CrossRefGoogle ScholarPubMed
Windmiller, J.R., Zhou, N., Chuang, M.-C., Valdés-Ramírez, G., Santhosh, P., Miller, P.R., Narayan, R., and Wang, J.: Microneedle array-based carbon paste amperometric sensors and biosensors. Analyst 136, 1846 (2011).CrossRefGoogle ScholarPubMed
Chua, B., Desai, S.P., Tierney, M.J., Tamada, J.A., and Jina, A.N.: Effect of microneedles shape on skin penetration and minimally invasive continuous glucose monitoring in vivo. Sens. Actuat. A 203, 373 (2013).CrossRefGoogle Scholar
Mukerjee, E.V., Collins, S.D., Isseroff, R.R., and Smith, R.L.: Microneedle array for transdermal biological fluid extraction and in situ analysis. Sens. Actuat. A 114, 267 (2004).CrossRefGoogle Scholar
Powell, A.E. and Leon, M.A.: Reversible interaction of human lymphocytes with the mitogen concanavalin A. Exp. Cell Res. 62, 315 (1970).CrossRefGoogle ScholarPubMed
Matsumoto, A., Yoshida, R., and Kataoka, K.: Glucose-responsive polymer gel bearing phenylborate derivative as a glucose-sensing moiety operating at the physiological pH. Biomacromolecules 5, 1038 (2004).CrossRefGoogle ScholarPubMed
Elshaarani, T., Yu, H., Wang, L., Zain ul, A., Ullah, R.S., Haroon, M., Khan, R.U., Fahad, S., Khan, A., Nazir, A., Usman, M., and Naveed, K.-U.-R.: Synthesis of hydrogel-bearing phenylboronic acid moieties and their applications in glucose sensing and insulin delivery. J. Mater. Chem. B 6, 3831 (2018).CrossRefGoogle ScholarPubMed
Kataoka, K., Miyazaki, H., Bunya, M., Okano, T., and Sakurai, Y.: 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, 12694 (1998).CrossRefGoogle Scholar
Roberts, M.C., Hanson, M.C., Massey, A.P., Karren, E.A., and Kiser, P.F.: Dynamically restructuring hydrogel networks formed with reversible covalent crosslinks. Adv. Mater. 19, 2503 (2007).CrossRefGoogle Scholar
Xu, J., Yang, D.G., Li, W.J., Gao, Y., Chen, H.B., and Li, H.M.: Phenylboronate-diol crosslinked polymer gels with reversible sol-gel transition. Polymer 52, 4268 (2011).CrossRefGoogle Scholar
Springsteen, G. and Wang, B.: A detailed examination of boronic acid–diol complexation. Tetrahedron 58, 5291 (2002).CrossRefGoogle Scholar
Shiino, D., Murata, Y., Kataoka, K., Koyama, Y., Yokoyama, M., Okano, T., and Sakurai, Y.: Preparation and characterization of a glucose-responsive insulin-releasing polymer device. Biomaterials 15, 121 (1994).CrossRefGoogle ScholarPubMed
Qiu, Y. and Park, K.: Environment-sensitive hydrogels for drug delivery. Adv. Drug Delivery Rev. 53, 321 (2001).CrossRefGoogle ScholarPubMed
Kim, A., Lee, H., Jones, C.F., Mujumdar, S.K., Gu, Y., and Siegel, R.A.: Swelling, mechanics, and thermal/chemical stability of hydrogels containing phenylboronic acid side chains. Gels 4, 4 (2018).CrossRefGoogle Scholar
Kitano, S., Kataoka, K., Koyama, Y., Okano, T., and Sakurai, Y.: Glucose-responsive complex formation between poly(vinyl alcohol) and poly(N-vinyl-2-pyrrolidone) with pendent phenylboronic acid moieties. Macromol. Chem. Rapid Commun. 12, 227 (1991).CrossRefGoogle Scholar
Shiomori, K., Ivanov, A.E., Galaev, I.Y., Kawano, Y., and Mattiasson, B.: Thermoresponsive properties of sugar sensitive copolymer of N-isopropylacrylamide and 3-(acrylamido)phenylboronic acid. Macromol. Chem. Phys. 205, 27 (2004).CrossRefGoogle Scholar
Hisamitsu, I., Kataoka, K., Okano, T., and Sakurai, Y.: Glucose-responsive gel from phenylborate polymer and poly (vinyl alcohol): Prompt response at physiological pH through the interaction of borate with amino group in the gel. Pharm. Res. 14, 289 (1997).CrossRefGoogle ScholarPubMed
Ivanov, A.E., Larsson, H., Galaev, I.Y., and Mattiasson, B.: Synthesis of boronate-containing copolymers of N,N-dimethylacrylamide, their interaction with poly(vinyl alcohol) and rheological behaviour of the gels. Polymer 45, 2495 (2004).CrossRefGoogle Scholar
Chen, S., Matsumoto, H., Moro-oka, Y., Tanaka, M., Miyahara, Y., Suganami, T., and Matsumoto, A.: Smart microneedle fabricated with silk fibroin combined semi-interpenetrating network hydrogel for glucose-responsive insulin delivery. ACS Biomater. Sci. Eng. 5, 5781 (2019).CrossRefGoogle Scholar
Plieva, F.M., Karlsson, M., Aguilar, M.-R., Gomez, D., Mikhalovsky, S., and Galaev’, I.Y.: Pore structure in supermacroporous polyacrylamide based cryogels. Soft Matter 1, 303 (2005).CrossRefGoogle ScholarPubMed
Lozinsky, V.I., Galaev, I.Y., Plieva, F.M., Savina, I.N., Jungvid, H., and Mattiasson, B.: Polymeric cryogels as promising materials of biotechnological interest. Trends Biotechnol. 21, 445 (2003).CrossRefGoogle ScholarPubMed
Steiner, M.-S., Duerkop, A., and Wolfbeis, O.S.: Optical methods for sensing glucose. Chem. Soc. Rev. 40, 4805 (2011).CrossRefGoogle ScholarPubMed
Wang, J.: Electrochemical glucose biosensors. Chem. Rev. 108, 814 (2008).CrossRefGoogle ScholarPubMed
Zhao, Q., Behl, M., and Lendlein, A.: Shape-memory polymers with multiple transitions: Complex actively moving polymers. Soft Matter 9, 1744 (2013).CrossRefGoogle Scholar
Löwenberg, C., Balk, M., Wischke, C., Behl, M., and Lendlein, A.: Shape-memory hydrogels: Evolution of structural principles to enable shape switching of hydrophilic polymer networks. Acc. Chem. Res. 50, 723 (2017).CrossRefGoogle ScholarPubMed
Fang, Y., Han, E., Zhang, X.-X., Jiang, Y., Lin, Y., Shi, J., Wu, J., Meng, L., Gao, X., Griffin, P.J., Xiao, X., Tsai, H.-M., Zhou, H., Zuo, X., Zhang, Q., Chu, M., Zhang, Q., Gao, Y., Roth, L.K., Bleher, R., Ma, Z., Jiang, Z., Yue, J., Kao, C.-M., Chen, C.-T., Tokmakoff, A., Wang, J., Jaeger, H.M., and Tian, B.: Dynamic and programmable cellular-scale granules enable tissue-like materials. Matter 2, 948 (2020).CrossRefGoogle Scholar

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