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Licensed Unlicensed Requires Authentication Published by De Gruyter February 1, 2021

Preparation and swelling behavior of end-linked hydrogels prepared from linear poly(ethylene glycol) and dendrimer-star polymers

  • Jun Wang EMAIL logo , Guangna Qu , Xiangbin Liu , Qin Yu and Na Zhang

Abstract

Linear diepoxide-terminated poly(ethylene glycol) (PEG) of molar mass 600, 1000 and 2000 g mol−1 was end-linked with dendrimer-star polymer (PAMAM) of generations 1.0 in water to prepare architecturally well-defined copolymer hydrogels. The structures and properties of the products were characterized using infrared, 1H NMR, DSC measurements, scanning electron microscopy (SEM) and swelling behavior tests. The swelling behavior of these hydrogels was tested in distilled water at constant temperature and the equilibrium swelling ratio (ESR) was determined for structurally different hydrogels and various environmental conditions, which showed that ESR was influenced by the molecular weight of PEG, the molar ratio of H amine groups/epoxy groups, temperature and pH. Higher ESR was obtained for either longer-chain PEG, non-stoichiometric H amine/epoxy groups ratio, acidic pH or lower temperatures. When the hydrogel was switched from 10 °C to 65 °C and pH 3.5 to 11.5, the swelling behavior of the hydrogels showed good reversibility for swelling–deswelling. When the molecular weight of PEG was changed in the range of 600–2000, the lower critical solution temperature (LCST) of hydrogel increased from 30 to 40 °C. When the molar ratio of H amine/epoxy groups was changed, the LCST was not significantly changed.


Corresponding author: Jun Wang, Provincial Key Laboratory of Oil & Gas Chemical Technology, College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing, 163318, China, E-mail:

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

References

1. dos Santos, T. C., Hernández, R., Rescignano, N., Boff, L., Reginatto, F. H., Simões, C. M. O., de Campos, A. M., Mijangos, C. Nanocomposite chitosan hydrogels based on PLGA nanoparticles as potential biomedical materials. Eur. Polym. J. 2017, 99, 456–463.10.1016/j.eurpolymj.2017.12.039Search in Google Scholar

2. Shen, Y. F., Huang, J. H., Wu, Z. E., Wang, K. Y., Zheng, J., Cai, L., Li, X. L., Gao, H., Jin, X. Y., Li, J. F. Cationic superabsorbent hydrogel composed of mesoporous silica as a potential haemostatic material. Mat. Sci. Eng. C Mater. 2020, 111, 110841. https://doi.org/10.1016/j.msec.2020.110841.Search in Google Scholar PubMed

3. Mohammadinezhad, A., Marandi, G. B., Farsadrooh, M., Javadian, H. Synthesis of poly (acrylamide-co-itaconic acid)/MWCNTs superabsorbent hydrogel nanocomposite by ultrasound-assisted technique: swelling behavior and Pb (II) adsorption capacity. Ultrason. Sonochem. 2018, 49, 1–12. https://doi.org/10.1016/j.ultsonch.2017.12.028.Search in Google Scholar PubMed

4. Alam, M. N., Christopher, L. P. Natural cellulose-chitosan cross-linked superabsorbent hydrogels with superior swelling properties. ACS Sustain. Chem. Eng. 2018, 6, 8736–8742. https://doi.org/10.1021/acssuschemeng.8b01062.Search in Google Scholar

5. Zhai, D. Y., Liu, B. R., Shi, Y., Pan, L. J., Wang, Y. Q., Li, W. B., Zhang, R., Yu, G. H. Highly sensitive glucose sensor based on Pt nanoparticle/polyaniline hydrogel heterostructures. ACS Nano 2013, 7, 3540–3546. https://doi.org/10.1021/nn400482d.Search in Google Scholar PubMed

6. Zhang, X. J., Lin, G., Kumar, S. R., Mark, J. E. Hydrogels prepared from polysiloxane chains by end linking them with trifunctional silanes containing hydrophilic groups. Polymer 2009, 50, 5414–5421. https://doi.org/10.1016/j.polymer.2009.01.047.Search in Google Scholar

7. Sukumar, V. S., Lopina, S. T. Network model for the swelling properties of end-linked linear and star poly(ethylene oxide) hydrogels. Macromolecules 2002, 35, 10189–10192. https://doi.org/10.1021/ma0213753.Search in Google Scholar

8. Lutolf, M. P., Hubbell, J. A. Synthesis and physicochemical characterization of end-linked poly(ethylene glycol)-co-peptide hydrogels formed by michael-type addition. Biomacromolecules 2003, 4, 713–722. https://doi.org/10.1021/bm025744e.Search in Google Scholar PubMed

9. Unal, B., Hedden, R. C. Gelation and swelling behavior of end-linked hydrogels prepared from linear poly(ethylene glycol) and poly(amidoamine) dendrimers. Polymer 2006, 47, 8173–8182. https://doi.org/10.1016/j.polymer.2006.09.048.Search in Google Scholar

10. Cao, W. Q., Zhu, L. Synthesis and unimolecular micelles of amphiphilic dendrimer-like star polymer with various functional surface groups. Macromolecules 2011, 44, 1500–1512. https://doi.org/10.1021/ma1021242.Search in Google Scholar

11. Cloninger, M. J. Biological applications of dendrimers. Curr. Opin. Chem. Biol. 2002, 6, 742–748. https://doi.org/10.1016/s1367-5931(02)00400-3.Search in Google Scholar PubMed

12. Bekhradnia, S., Zhu, K. Z., Knudsen, K. D., Sande, S. A., Nyström, B. Structure, swelling, and drug release of thermoresponsive poly(amidoamine) dendrimer–poly(N-isopropylacrylamide) hydrogels. J. Mater. Sci. 2014, 49, 6102–6110. https://doi.org/10.1007/s10853-014-8340-y.Search in Google Scholar

13. Kesharwani, P., Jain, K., Jain, N. K. Dendrimer as nanocarrier for drug delivery. Prog. Polym. Sci. 2014, 39, 268–307. https://doi.org/10.1016/j.progpolymsci.2013.07.005.Search in Google Scholar

14. Esfand, R., Tomalia, D. A. Poly(amidoamine) (PAMAM) dendrimers: from biomimicry to drug delivery and biomedical applications. Drug Discov. Today 2001, 6, 427–436. https://doi.org/10.1016/s1359-6446(01)01757-3.Search in Google Scholar PubMed

15. Zinselmeyer, B. H., Mackay, S. P., Schatzlein, A. G., Uchegbu, I. F. The lower-generation polypropylenimine dendrimers are effective gene-transfer agents. Pharm. Res. (N. Y.) 2002, 19, 960–967. https://doi.org/10.1023/a:1016458104359.10.1023/A:1016458104359Search in Google Scholar

16. Kihara, F., Arima, H., Tsutsumi, T., Hirayama, F., Uekama, K. Effects of structure of polyamidoamine dendrimer on gene transfer efficiency of the dendrimer conjugate with α-cyclodextrin. Bioconjugate Chem. 2002, 13, 1211–1219. https://doi.org/10.1021/bc025557d.Search in Google Scholar PubMed

17. Lee, J. J., Ford, W. T., Moore, J. A., Li, Y. Reactivity of organic anions promoted by a quaternary ammonium ion dendrimer. Macromolecules 1994, 27, 4632–4634. https://doi.org/10.1021/ma00094a033.Search in Google Scholar

18. Oosterom, G. E., Reek, J. N. H., Kamer, P. C. J., van Leeuwen, P. W. N. M. Transition metal catalysis using functionalized dendrimers. Angew. Chem. Int. Ed. 2001, 40, 1828–1849. https://doi.org/10.1002/1521-3773(20010518)40:10<1828::aid-anie1828>3.0.co;2-y.10.1002/1521-3773(20010518)40:10<1828::AID-ANIE1828>3.0.CO;2-YSearch in Google Scholar

19. Deraedt, C., Ye, R., Ralston, W. T., Toste, F. D., Somorjai, G. A. Dendrimer-stabilized metal nanoparticles as efficient catalysts for reversible dehydrogenation/hydrogenation of N-heterocycles. J. Am. Chem. Soc. 2017, 139, 18084–18092. https://doi.org/10.1021/jacs.7b10768.Search in Google Scholar

20. Parrott, M. C., Marchington, E. B., Valliant, J. F., Adronov, A. Synthesis and properties of carborane-functionalized aliphatic polyester dendrimers. J. Am. Chem. Soc. 2005, 127, 12081–12089. https://doi.org/10.1021/ja053730l.Search in Google Scholar

21. Degoricija, L., Carnahan, M. A., Johnson, C. S., Kim, T., Grinstaff, M. W. Synthesis and characterization of bola-type amphiphilic dendritic macromolecules. Macromolecules 2006, 39, 8952–8958. https://doi.org/10.1021/ma062189q.Search in Google Scholar

22. Takahashi, H., Shibayama, M., Fujisawa, H., Nomura, S. Equilibrium swelling and small-angle neutron-scattering study on end-linked poly(tetrahydrofuran) networks. Macromolecules 1995, 28, 8824–8828. https://doi.org/10.1021/ma00130a015.Search in Google Scholar

23. Sharaf, M. A., Mark, J. E., Ahmed, E. Elastomeric properties of end-linked networks of high cross-link functionality. Accounting for possible changes in effective functionality with extent of reaction and chain-length distribution. Colloid Polym. Sci. 1994, 272, 504–515. https://doi.org/10.1007/bf00653214.Search in Google Scholar

24. Teodorescu, M., Cursaru, B., Stanescu, P., Draghici, C., Stanciu, N. D., Vuluga, D. M. Novel hydrogels from diepoxy-terminated poly(ethylene glycol)s and aliphatic primary diamines: synthesis and equilibrium swelling studies. Polym. Adv. Technol. 2009, 20, 907–915. https://doi.org/10.1002/pat.1330.Search in Google Scholar

25. Liu, X. B., Qu, G. N., Yu, Q., Zhang, N., Wang, L., Wang, J. Synthesis of poly(ethylene glycol) grafted polyamidoamine dendrimer hydrogels and their temperature and pH sensitive properties. Polym. Sci. Ser. B 2020, 62, 400–410. https://doi.org/10.1134/s1560090420040089.Search in Google Scholar

26. Krsko, P., Libera, M. Biointeractive hydrogels. Mater. Today 2005, 8, 36–44. https://doi.org/10.1016/s1369-7021(05)71223-2.Search in Google Scholar

27. Yoon, J. A., Kowalewski, T., Matyjaszewski, K. Comparison of thermoresponsive deswelling kinetics of poly(oligo(ethylene oxide) methacrylate)-based thermoresponsive hydrogels prepared by “graft-from” ATRP. Macromolecules 2011, 44, 2261–2268. https://doi.org/10.1021/ma1029696.Search in Google Scholar

28. Zhang, Y. L., Xu, L., Yi, M., Zhai, M. L., Wang, J. R., Ha, H. F. Radiation synthesis of poly[(dimethylaminoethyl methacrylate)-co-(diallyl dimethyl ammonium chloride)] hydrogels and its application as a carrier for notoginsenoside delivery. Eur. Polym. J. 2006, 42, 2959–2967; https://doi.org/10.1016/j.eurpolymj.2006.08.008.Search in Google Scholar

Received: 2020-08-26
Accepted: 2020-11-24
Published Online: 2021-02-01
Published in Print: 2021-03-26

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