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Thermoresponsive and Biodegradable Amphiphilic Block Copolymers with Pendant Functional Groups

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Tissue Engineering and Regenerative Medicine Aims and scope

Abstract

BACKGROUND:

To develop the biodegradability and thermoresponsive hydrogel, in this work we designed a pendant-functionalized, thermoresponsive, amphiphilic block copolymer.

METHODS:

Methoxy poly(ethylene glycol) (MPEG)-b-[poly(ε-caprolactone)-ran-poly(ε-caprolactone-3-one)-ran-polylactic acid] (MCL) and (MPEG-b-[PCL-ran-POD-ran-PLA]) [MCL-(CO)] block copolymers were prepared by ring-opening polymerization of ε-caprolactone, OD and lactide monomers. The subsequent derivatization of MCL-(CO) provided MPEG-b-[PCL-ran-poly(ε-caprolactone-3-COOH)-ran-PLA] [MCL-(COOH)] with COOH pendant groups and MPEG-b-[PCL-ran-poly(ε-caprolactone-3-NH2)-ran-PLA] [MCL-(NH2)] with NH2 pendant groups.

RESULTS:

The measured segment ratios of MCL-(CO), MCL-(COOH), and MCL-(NH2) agreed well with the target ratios. The abundances of the COOH and NH2 groups in the MCL-(COOH) and MCL-(NH2) copolymers were determined by 1H- and 13C-nuclear magnetic resonance spectroscopy, and agreed well with the target abundances. MCL-(CO), MCL-(COOH), and MCL-(NH2) formed homogeneous, white, opaque emulsions at room temperature. Rheological analysis of the block copolymer suspensions indicated a solution-to-hydrogel phase transition as a function of temperature. The solution-to-hydrogel phase transitions and the biodegradation of MCL-(CO), MCL-(COOH), and MCL-(NH2) were affected by varying the type (ketone, COOH, or NH2) and abundance of the pendant groups.

CONCLUSION:

MCL-(CO), MCL-(COOH), and MCL-(NH2) with ketone, COOH, and NH2 pendant groups showed solution-to-hydrogel phase transitions and biodegradation behaviors that depended on both the type and number of pendant groups.

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References

  1. Basu A, Kunduru KR, Doppalapudi S, Domb AJ, Khan W. Poly(lactic acid) based hydrogels. Adv Drug Deliv Rev. 2016;107:192–205.

    Article  PubMed  CAS  Google Scholar 

  2. Kim DY, Kwon DY, Kwon JS, Kim JH, Min BH, Kim MS. Stimuli-responsive injectable in situ-forming hydrogels for regenerative medicines. Polym Rev. 2015;55:407–52.

    Article  CAS  Google Scholar 

  3. Ramin MA, Latxague L, Sindhu KR, Chassande O, Barthélémy P. Low molecular weight hydrogels derived from urea based-bolaamphiphiles as new injectable biomaterials. Biomaterials. 2017;145:72–80.

    Article  PubMed  CAS  Google Scholar 

  4. Huang M, Li H, Ke W, Li J, Zhao C, Ge Z. Finely tuned thermo-responsive block copolymer micelles for photothermal effect-triggered efficient cellular internalization. Macromol Biosci. 2016;16:1265–72.

    Article  PubMed  CAS  Google Scholar 

  5. Zhou T, Li X, Li G, Tian T, Lin S, Shi S, et al. Injectable and thermosensitive TGF-β1-loaded PCEC hydrogel system for in vivo cartilage repair. Sci Rep. 2017;7:10553.

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  6. Song WY, Liu GM, Li J, Luo YG. Bone morphogenetic protein-2 sustained delivery by hydrogels with microspheres repairs rabbit mandibular defects. Tissue Eng Regen Med. 2016;13:750–61.

    Article  CAS  Google Scholar 

  7. Rijal G, Li W. 3D scaffolds in breast cancer research. Biomaterials. 2016;81:135–56.

    Article  PubMed  CAS  Google Scholar 

  8. Shimojo AAM, Galdames SEM, Perez AGM, Ito TH, Luzo ACM, Santana MHA. In vitro performance of injectable chitosan-tripolyphosphate scaffolds combined with platelet-rich plasma. Tissue Eng Regen Med. 2016;13:21–30.

    Article  CAS  Google Scholar 

  9. Hsieh FY, Tao L, Wei Y, Hsu SH. A novel biodegradable self-healing hydrogel to induce blood capillary formation. NPG Asia Mater. 2017;9:e363.

    Article  CAS  Google Scholar 

  10. Kim SK, Cho TH, Han JJ, Kim IS, Park Y, Hwang SJ. Comparative study of BMP-2 alone and combined with VEGF carried by hydrogel for maxillary alveolar bone regeneration. Tissue Eng Regen Med. 2016;13:171–81.

    Article  CAS  Google Scholar 

  11. Kang YM, Lee SH, Lee JY, Son JS, Kim BS, Lee B, et al. A biodegradable, injectable, gel system based on MPEG-b-(PCL-ran-PLLA) diblock copolymers with an adjustable therapeutic window. Biomaterials. 2010;31:2453–60.

    Article  PubMed  CAS  Google Scholar 

  12. Jang JY, Park SH, Park JH, Lee BK, Yun JH, Lee B, et al. In vivo osteogenic differentiation of human dental pulp stem cells embedded in an injectable in vivo-forming hydrogel. Macromol Biosci. 2016;16:1158–69.

    Article  PubMed  CAS  Google Scholar 

  13. Kwon JS, Kim SW, Kwon DY, Park SH, Son AR, Kim JH, et al. In vivo osteogenic differentiation of human turbinate mesenchymal stem cells in an injectable in situ-forming hydrogel. Biomaterials. 2014;35:5337–46.

    Article  PubMed  CAS  Google Scholar 

  14. Kim JI, Kim DY, Kwon DY, Kang HJ, Kim JH, Min BH, et al. An injectable biodegradable temperature-responsive gel with an adjustable persistence window. Biomaterials. 2012;33:2823–34.

    Article  PubMed  CAS  Google Scholar 

  15. Shim SW, Kwon DY, Park JH, Kim JH, Chun HJ, Koh YJ, et al. Preparation of zwitterionic sulfobetaine end-functionalized poly(ethylene glycol)-b-poly(caprolactone) diblock copolymers and examination of their thermogelling properties. J Polym Sci A Polym Chem. 2014;52:2185–91.

    Article  CAS  Google Scholar 

  16. Lee BK, Park JH, Park SH, Kim JH, Oh SH, Lee SJ, et al. Preparation of pendant group-functionalized diblock copolymers with adjustable thermogelling behavior. Polymers. 2017;9:239.

    Article  CAS  Google Scholar 

  17. Park SH, Kwon JS, Lee BS, Park JH, Lee BK, Yun JH, et al. BMP2-immobilized injectable hydrogel for osteogenic differentiation of human periodontal ligament stem cells. Sci Rep. 2017;7:6603.

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  18. Lee HY, Park SH, Kim JH, Kim MS. Temperature-responsive hydrogels via electrostatic interaction of amphiphilic diblock copolymers with pendant-ion groups. Polym Chem. 2017;8:6606–16.

    Article  CAS  Google Scholar 

  19. Park JH, Park SH, Lee HY, Lee JW, Lee BK, Lee BY, et al. An injectable, electrostatically interacting drug depot for the treatment of rheumatoid arthritis. Biomaterials. 2018;154:86–98.

    Article  PubMed  CAS  Google Scholar 

  20. Timbart L, Amsden BG. Functionalizable biodegradable photocrosslinked elastomers based on 2-oxepane-1,5-dione. J Polym Sci A Polym Chem. 2008;46:8191–9.

    Article  CAS  Google Scholar 

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Acknowledgements

This study was supported by a grant from a Basic Science Research Program (2016R1A2B3007448) through the National Research Foundation of Korea (NRF) funded by the Ministry of Education.

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Authors and Affiliations

  1. Department of Molecular Science and Technology, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon, 16499, Republic of Korea

    Bo Keun Lee, Jung Hyun Noh, Ji Hoon Park, Seung Hun Park, Jae Ho Kim & Moon Suk Kim

  2. Department of Nanobiomedical Science, Dankook University, 119, Dandae-ro, Dongnam-gu, Cheonan-si, Chungnam, 31116, Republic of Korea

    Se Heang Oh

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  1. Bo Keun Lee
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  2. Jung Hyun Noh
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  3. Ji Hoon Park
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  4. Seung Hun Park
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Correspondence to Moon Suk Kim.

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The authors declare no competing financial interests.

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There are no animal experiments carried out for this article.

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Lee, B.K., Noh, J.H., Park, J.H. et al. Thermoresponsive and Biodegradable Amphiphilic Block Copolymers with Pendant Functional Groups. Tissue Eng Regen Med 15, 393–402 (2018). https://doi.org/10.1007/s13770-018-0121-2

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  • DOI: https://doi.org/10.1007/s13770-018-0121-2

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