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Glycerol-modified poly(ε-caprolactone): an biocatalytic approach to improve the hydrophilicity of poly(ε-caprolactone)

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Abstract

Novel poly(ε-caprolactone) (PCL)–glycerol polyester was synthesized in one step in the presence of Novozym 435 under mild reaction conditions. The objective of the study was to investigate the feasibility of enhancing the hydrophilicity of PCL by condensing it with glycerol through biocatalytic approach. Effect of reaction time, glycerol-to-CL ratio and CL-to-toluene ratio was studied. The 1H NMR and GPC results established that self-condensation of CL units and condensation of CL with glycerol units take place simultaneously. When the glycerol content was 10 and 20 mol% with regard to CL, condensation continued for 6 h; further extension of reaction time resulted in the cleavage of ester linkages. When the glycerol content was increased to 40 mol%, the condensation of CL–glycerol units was accomplished in 4 h; however, the reaction had to get extended beyond 6 h for complete condensation of CL–CL units. The study revealed that the crystallinity and the melting temperature (Tm) of the products altered with an increase in the glycerol content. Furthermore, TGA and contact angle values of water on PCL and its glycerol derivative films revealed that the water uptake capacity of PCL too increased significantly with the increase in glycerol content, rendering PCL more hydrophilic.

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References

  1. Dash TK, Konkimalla VB (2012) Poly-є-caprolactone based formulations for drug delivery and tissue engineering: a review. J Control Release 158(1):15–33

    Article  CAS  PubMed  Google Scholar 

  2. Mondal D, Griffith M, Venkatraman SS (2016) Polycaprolactone-based biomaterials for tissue engineering and drug delivery: current scenario and challenges. Int J Polym Mater Polym Biomater 65(5):255–265

    Article  CAS  Google Scholar 

  3. Salerno A (2016) Overview of polycaprolactone-based drug delivery system. In: Ravi Kumar MNV (ed) Handbook of polyester drug delivery systems, pp 187–212

  4. Jiang Y-C, Jiang L, Huang A, Wang X-F, Li Q, Turng L-S (2017) Electrospun polycaprolactone/gelatin composites with enhanced cell–matrix interactions as blood vessel endothelial layer scaffolds. Mater Sci Eng, C 71:901–908

    Article  CAS  Google Scholar 

  5. Park JS, Lee SJ, Jo HH, Lee JH, Kim WD, Lee JY, Park SA (2017) Fabrication and characterization of 3D-printed bone-like β-tricalcium phosphate/polycaprolactone scaffolds for dental tissue engineering. J Ind Chem 46:175–181

    CAS  Google Scholar 

  6. Sun H, Mei L, Song C, Cui X, Wang P (2006) The in vivo degradation, absorption and excretion of PCL-based implant. Biomaterials 27(9):1735–1740

    Article  CAS  PubMed  Google Scholar 

  7. Woodruff MA, Hutmacher DW (2015) The return of a forgotten polymer: polycaprolactone in the 21st century. Polym Test 43:94–102

    Article  CAS  Google Scholar 

  8. Kang HU, Yu YC, Shin SJ, Kim J, Youk JH (2013) One-pot synthesis of poly (N-vinylpyrrolidone)-b-poly (ε-caprolactone) block copolymers using a dual initiator for RAFT polymerization and ROP. Macromolecules 46(4):1291–1295

    Article  CAS  Google Scholar 

  9. Wei X, Gong C, Gou M, Fu S, Guo Q, Shi S, Luo F, Guo G, Qiu L, Qian Z (2009) Biodegradable poly(ɛ-caprolactone)–poly(ethylene glycol) copolymers as drug delivery system. Int J Pharm 381(1):1–18

    Article  CAS  PubMed  Google Scholar 

  10. Sheikh FA, Barakat NA, Kanjwal MA, Aryal S, Khil MS, Kim HY (2009) Novel self-assembled amphiphilic poly(epsilon-caprolactone)-grafted-poly(vinyl alcohol) nanoparticles: hydrophobic and hydrophilic drugs carrier nanoparticles. J Mater Sci Mater Med 20(3):821–831

    Article  CAS  PubMed  Google Scholar 

  11. Li Z, Tan BH (2014) Towards the development of polycaprolactone based amphiphilic block copolymers: molecular design, self-assembly and biomedical applications. Mater Sci Eng, C 45:620–634

    Article  CAS  Google Scholar 

  12. Jahani H, Jalilian FA, Wu CY, Kaviani S, Soleimani M, Abassi N, Ou KL, Hosseinkhani H (2015) Controlled surface morphology and hydrophilicity of polycaprolactone toward selective differentiation of mesenchymal stem cells to neural like cells. J Biomed Mater Res A 103(5):1875–1881

    Article  CAS  PubMed  Google Scholar 

  13. Stefani S, Honzke S, Camacho JLC, Neumann F, Prasad AK, Hedtrich S, Haag R, Servin P (2016) Hyperbranched glycerol-based core-amphiphilic branched shell nanotransporters for dermal drug delivery. Polymer 96:156–166

    Article  CAS  Google Scholar 

  14. Frey H, Haag R (2002) Dendritic polyglycerol: a new versatile biocompatible material. J Biotechnol 90(3–4):257–267

    CAS  PubMed  Google Scholar 

  15. Kulshrestha A, Gao W, Gross RA (2005) Glycerol copolyesters: control of branching and molecular weight using a lipase catalyst. Macromolecules 38(8):3193–3204

    Article  CAS  Google Scholar 

  16. Li Z, Zhang Z, Liu KL, Ni X, Li J (2012) Biodegradable hyperbranched amphiphilic polyurethane multiblock copolymers consisting of poly(propylene glycol), poly(ethylene glycol), and polycaprolactone as in situ thermogels. Biomacromol 13(12):3977–3989

    Article  CAS  Google Scholar 

  17. Cai T, Li M, Zhang B, Neohab K-G, Kang E-T (2014) Hyperbranched polycaprolactone-click-poly(N-vinylcaprolactam) amphiphilic copolymers and their applications as temperature-responsive membranes. J Mater Chem B 2:814–825

    Article  CAS  Google Scholar 

  18. Zheng Y, Turner W, Zong M, Irvine DJ, Howdle SM, Thurecht KJ (2011) Biodegradable core-shell materials via RAFT and ROP: characterization and comparison of hyperbranched and microgel particles. Macromolecules 44(6):1347–1354

    Article  CAS  Google Scholar 

  19. Huskic M, Pulko I (2015) The synthesis and characterization of multiarm star-shaped graft copolymers of polycaprolactone and hyperbranched polyester. Eur Polym J 70:384–391

    Article  CAS  Google Scholar 

  20. Li Z, Li J (2013) Control of hyperbranched structure of polycaprolactone/poly(ethylene glycol) polyurethane block copolymers by glycerol and their hydrogels for potential cell delivery. J Phys Chem B 117:14763–14774

    Article  CAS  PubMed  Google Scholar 

  21. Kumar A, Gross RA (2000) Candida antarctica lipase B-catalyzed transesterification: new synthetic routes to copolyesters. J Am Chem Soc 122(48):11767–11770

    Article  CAS  Google Scholar 

  22. Deng F, Gross RA (1999) Ring-opening bulk polymerization of ε-caprolactone and trimethylene carbonate catalyzed by lipase Novozym 435. Int J Biol Macromol 25(1–3):153–159

    Article  CAS  PubMed  Google Scholar 

  23. Meyer U, Palmans ARA, Loontjens T, Heise A (2002) Enzymatic ring-opening polymerization and atom transfer radical polymerization from a bifunctional initiator. Macromolecules 35(8):2873–2875

    Article  CAS  Google Scholar 

  24. Kobayashi S, Uyama H, Takamoto T (2000) Lipase-catalyzed degradation of polyesters in organic solvents: a new methodology of polymer recycling using enzyme as catalyst. Biomacromol 1(1):3–5

    Article  CAS  Google Scholar 

  25. Crescenzi V, Manzini G, Calzolari G, Borri C (1972) Thermodynamics of fusion of poly-β-propiolactone and poly-ϵ-caprolactone. Comparative analysis of the melting of aliphatic polylactone and polyester chains. Eur Polym J 8:449–463

    Article  CAS  Google Scholar 

  26. Iida S (1981) Effect of entanglement on crystallinity of semicrystalline polymer. Kobunshi Ronbunshu 38(5):291–299

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors would like to acknowledge the Loyola Schools faculty grant for scholarly work committee for financial support and Mr. Adam Ferry for performing some of the experiments. This work was partly supported by JST PRESTO “Molecular Technology” under the direction of Prof. Takashi Kato.

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Authors and Affiliations

  1. Department of Chemistry, Ateneo de Manila University, Manila, Philippines

    Soma Chakraborty, James Nicolas M. Pagaduan & Zara Kryzel A. Melgar

  2. Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5, Takayama-cho, Ikoma, Nara, 630-0192, Japan

    Steffen Seitz, Kai Kan & Hiroharu Ajiro

  3. Institute for Research Initiatives, Nara Institute of Science and Technology, 8916-5, Takayama-cho, Ikoma, Nara, 630-0192, Japan

    Kai Kan & Hiroharu Ajiro

  4. JST PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan

    Hiroharu Ajiro

Authors
  1. Soma Chakraborty
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  2. James Nicolas M. Pagaduan
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  3. Zara Kryzel A. Melgar
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  4. Steffen Seitz
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  5. Kai Kan
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Correspondence to Soma Chakraborty.

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Chakraborty, S., Pagaduan, J.N.M., Melgar, Z.K.A. et al. Glycerol-modified poly(ε-caprolactone): an biocatalytic approach to improve the hydrophilicity of poly(ε-caprolactone). Polym. Bull. 76, 1915–1928 (2019). https://doi.org/10.1007/s00289-018-2443-6

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  • DOI: https://doi.org/10.1007/s00289-018-2443-6

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