Skip to main content
SpringerLink
Log in

Chemical synthesis of a biodegradable PEGylated copolymer from ε-caprolactone and γ-valerolactone: evaluation of reaction and functional properties

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

This paper reports the chemical synthesis of methoxy poly(ethyleneglycol)-block-poly(ε-caprolactone-co-4-hydroxyvalerate) from ε-caprolactone and γ-valerolactone, a five-membered ring rarely used in chemical synthesis due to its low reactivity. This procedure enabled production of copolymers with controlled ratios of repeating units and molecular weights, as demonstrated by GPC, FT-IR and NMR characterization. Copolymer degradation rate was found to depend on macromolecular composition, and finely tuneable in a wide range of values. Similarly, hydrophilicity was dependent on γ-valerolactone content, and could be accurately controlled by varying the composition of the reaction feed. Importantly, this copolymer showed lower levels of acidic degradation products than other biodegradable polymers, thus resulting in improved biocompatibility. These encouraging results demonstrate the feasibility of the chemical synthesis of a novel and versatile material with interesting properties that fill a gap in the range of commercially available biodegradable polymers.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Luten J, van Nostrum C, De Smedt S, Hennink W (2008) J Control Release 126:97–110

    Article  CAS  Google Scholar 

  2. Jain A, Jain A, Gulbake ASS, Hurkat P, Jain S (2013) Crit Rev Ther Drug Carrier Syst 30:293–329

    Article  CAS  Google Scholar 

  3. Gong C, Qi T, Wei X, Qu Y, Wu Q, Luo F, Qian Z (2013) Curr Med Chem 20:79–94

    Article  CAS  Google Scholar 

  4. Weldon C, Tsui J, Shankarappa S, Nguyen V, Ma M, Anderson D, Kohane D (2012) J Control Release 161:903–909

    Article  CAS  Google Scholar 

  5. Alan Barber F, Boothby M, Richards D (2006) Sports Med Arthrosc 14:177–184

    Article  CAS  Google Scholar 

  6. Liu X, Holzwarth J, Ma P (2012) Macromol Biosci 12:911–919

    Article  CAS  Google Scholar 

  7. Li Y, Rodrigues J, Tomás H (2012) Chem Soc Rev 41:2193–2221

    Article  CAS  Google Scholar 

  8. Siracusa V, Rocculi P, Romani S, Dalla Rosa M (2008) Trends Food Sci Tech 19:634–643

    Article  CAS  Google Scholar 

  9. Peelman N, Ragaert P, De Meulenaer B, Adons D, Peeters R, Cardon L, Van Impe F, Devlieghere F (2013) Trends Food Sci Tech 32:128–141

    Article  CAS  Google Scholar 

  10. Riggi E, Santagata G, Malinconico M (2011) Recent Pat Food Nutr Agric 3:49–63

    Article  CAS  Google Scholar 

  11. Kadokawa J, Kobayashi S (2010) Curr Opin Chem Biol 14:145–153

    Article  CAS  Google Scholar 

  12. Gross R, Kumar A, Kalra B (2001) Chem Rev 101:2097–2124

    Article  CAS  Google Scholar 

  13. Verlinden R, Hill D, Kenward M, Williams C, Radecka I (2007) J Appl Microbiol 102:1437–1449

    Article  CAS  Google Scholar 

  14. Jin W, Ding L, Chu Z, Chen L, Lü X, Zheng X, Song J, Fan D (2011) J Mol Catal A Chem 337:25–32

    Article  CAS  Google Scholar 

  15. Yoo J, Kim Y, Ko Y (2013) J Ind Eng Chem 19:1137–1143

    Article  CAS  Google Scholar 

  16. Yao L, Wang L, Zhang J, Tang N, Wu J (2012) J Mol Catal A Chem 352:57–62

    Article  CAS  Google Scholar 

  17. Cheshmedzhieva D, Angelova I, Ilieva S, Georgiev G, Galabov B (2012) Comput Theor Chem 995:8–16

    Article  CAS  Google Scholar 

  18. Kwong DY, Tai GZ, Park JH, Lee BK, Lee JH, Kim JH, Lee KW, Lee B, Jang JW, Kim MS (2014) J Polym Res 21:474

    Article  Google Scholar 

  19. Amine H, Karima O, Amine B, Belbachir M, Meghabar R (2005) J Polym Res 12:361–365

    Article  CAS  Google Scholar 

  20. Meelua W, Molloy R, Meepowpan P, Punyodom W (2012) J Polym Res 19:1–11

    Article  CAS  Google Scholar 

  21. Vivas M, Contreras J (2003) Eur Polym J 39:43–47

    Article  CAS  Google Scholar 

  22. Contreras JM, Medina D, López-Carrasquero F, Contreras RR (2013) J Polym Res 20:244

    Article  Google Scholar 

  23. Cheng G, Fan X, Pan W (2010) J Polym Res 17:847–851

    Article  CAS  Google Scholar 

  24. Nakayama Y, Sasaki K, Watanabe N, Cai Z, Shiono T (2009) Polymer 50:4788–4793

    Article  CAS  Google Scholar 

  25. Wei Z, Liu L, Qi M (2007) Eur Polym J 4:1210–1218

    Article  Google Scholar 

  26. Hori Y, Hagiwara T (1999) Int J Biol Macromol 25:237–245

    Article  CAS  Google Scholar 

  27. Guillaume C, Carpentier JF, Guillaume SM (2009) Polymer 50:5909–5917

    Article  CAS  Google Scholar 

  28. Kurcok P, Dubois P, Jèrôme R (1996) Polym Int 41:479–485

    Article  CAS  Google Scholar 

  29. Chen T, Qin Z, Qi Y, Deng T, Ge X, Wang J, Hou X (2011) Polym Chem 2:1190–1194

    Article  CAS  Google Scholar 

  30. Houk K, Jabbari A, Hall H, Aleman C (2008) J Org Chem 73:2674–2678

    Article  CAS  Google Scholar 

  31. Korte F, Glet W (1966) J Polym Sci Pol Lett 4:685–689

    Article  CAS  Google Scholar 

  32. Kricheldorf H, Mang T, Jonté J (1985) Makromol Chem 186:955–976

    Article  CAS  Google Scholar 

  33. Jedliński Z, Kowalczuk M, Glówkowski W, Grobelny J, Szwarc M (1991) Macromol 24:349–352

    Article  Google Scholar 

  34. Agarwal S, Xie X (2003) Macromol 36:3545–3549

    Article  CAS  Google Scholar 

  35. Moore T, Adhikari R, Gunatillake P (2005) Biomaterials 26:3771–3782

    Article  CAS  Google Scholar 

  36. Saiyasombat W, Molloy R, Nicholson T, Johnson A, Ward I, Poshyachinda S (1998) Polymer 39:5581–5585

    Article  CAS  Google Scholar 

  37. Middleton J, Tipton A (2000) Biomaterials 21:2335–2346

    Article  CAS  Google Scholar 

  38. Hakkarainen M, Höglund A, Odelius K, Albertsson A (2007) J Am Chem Soc 129:6308–6312

    Article  CAS  Google Scholar 

  39. Liu H, Slamovich E, Webster T (2006) Nanomedicine 1:541–545

    Article  CAS  Google Scholar 

  40. Cheng D, Cao X, Gao H, Wang Y (2013) RSC Adva 3:6871–6878

    Article  CAS  Google Scholar 

  41. Zhang P, Wu L, Li B (2006) Acta Polym Sin 1:510–515, article in Chinese

    Article  Google Scholar 

  42. Lin W (1999) J Biomed Mater Res 47:420–423

    Article  CAS  Google Scholar 

  43. Suzuki S, Ikada Y (2012) Biomaterials for surgical operation. Springer-Verlag, New York

    Book  Google Scholar 

  44. Wu Y, Liu S, He L (2010) Biosens Bioelectr 26:970–975

    Article  CAS  Google Scholar 

  45. Dubuois P, Coulembier O, Raquez J (2009) Handbook of ring-opening polymerization. Wiley, Weinheim

    Book  Google Scholar 

  46. Duda ABT, Libiszowski J, Penczek S, Dubuois P, Mecerreyes D, Jerome R (1998) Polym Degrad Stabil 59:215–222

    Article  CAS  Google Scholar 

  47. Barbanti S, Santos AJ, Zavaglia C, Duek E (2004) J Mater Sci Mater Med 15:1315–1321

    Article  CAS  Google Scholar 

  48. Faÿ F, Renard E, Langlois V, Linossier I, Vallée-Rehel K (2007) Eur Polym J 43:4800–4813

    Article  Google Scholar 

  49. Callister WJ, Rethwisch D (2012) Fundamentals of materials science and engineering, an integrated approach, 4th edn. Wiley, United States of America

    Google Scholar 

  50. Cheeseman M, Machuga E, Baile A (1999) Food Chem Toxicol 37:387–412

    Article  CAS  Google Scholar 

  51. Muzaiyanah A, Amirul A (2013) Appl Biochem Biotech 170:1194–1215

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Center for Micro-BioRobotics @SSSA, Istituto Italiano di Tecnologia, Viale Rinaldo Piaggio 34, 56025, Pontedera, Italy

    Mariacristina Gagliardi, Federica Di Michele & Barbara Mazzolai

  2. Center for Neuroscience and Cognitive Systems @UniTn, Istituto Italiano di Tecnologia, Corso Bettini 31, 38068, Rovereto, Italy

    Angelo Bifone

Authors
  1. Mariacristina Gagliardi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Federica Di Michele
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Barbara Mazzolai
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Angelo Bifone
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mariacristina Gagliardi.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gagliardi, M., Di Michele, F., Mazzolai, B. et al. Chemical synthesis of a biodegradable PEGylated copolymer from ε-caprolactone and γ-valerolactone: evaluation of reaction and functional properties. J Polym Res 22, 17 (2015). https://doi.org/10.1007/s10965-015-0661-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-015-0661-2

Keywords

Search

Navigation