Abstract
Conventional polyurethanes (PUs) are among biomaterials not intended to degrade but are susceptible to hydrolytic, oxidative and enzymatic degradation in vivo. Biodegradable PUs are typically prepared from polyester polyols, aliphatic diisocyanates and chain extenders. In this work we have developed a degradable monomer based on α-amino acid to accelerate hard segment degradation. Thus a new class of degradable poly(ether–urethane–urea)s (PEUUs) was synthesized via direct reaction of 4,4′-methylene-bis(4-phenylisocyanate) (MDI), l-leucine anhydride (LA) and polyethylene glycol with molecular weight of 1,000 (PEG-1000) as polyether soft segment. The resulting polymers are environmentally biodegradable and thermally stable. Decomposition temperatures for 5 % weight loss occurred above 300 °C by TGA in nitrogen atmospheres. Some structural characterization and physical properties of these polymers before and after degradation in soil, river water and sludge are reported. The environmental degradation of the polymer films was investigated by SEM, FTIR, TGA, DSC, GPC and XRD techniques. A significant rate of degradation occurred in PEUU samples under river water and sludge condition. The polymeric films were not toxic to E. coli (Gram negative), Staphylococcus aureus and Micrococcus (Gram positive) bacteria and showed good biofilm formation on polymer surface. Our results show that hard segment degraded selectively as much as soft segment and these polymers are susceptible to degradation in soil and water. Thus our study shows that new environment-friendly polyurethane, which can degrade in soil, river water and sludge, is synthesized.
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Bruin P, Smegdinga J, Pennings AJ, Jonkman MF (1990) Biodegradable lysine diisocyanate-based poly(glycolide-co-ε-caprolactone)-urethane network in artificial skin. Biomaterials 11:291–295
Chandra R, Rustgi R (1998) Biodegradable polymers. Prog Polym Sci 23:1273–1335. doi:10.1016/S0079-6700(97)00039-7
Gorna K, Gogolewski S (2002a) Biodegradable polyurethanes for implants. II. In vitro degradation and calcification of materials from poly(ε-caprolactone)-poly(ethylene oxide) diols and various chain extenders. J Biomed Mater Res 60:592–606
Gorna K, Gogolewski S (2002b) In vitro degradation of novel medical biodegradable aliphatic polyurethanes based on ε-caprolactone and Pluronicss with various hydrophilicities. Polym Deg Stab 75:113–122
Guan J, Fujimoto KL, Sacks MS, Wagner WR (2005) Preparation and characterization of highly porous, biodegradable polyurethane scaffolds for soft tissue applications. Biomaterials 26:3961–3971
Gunatillake P, Mayadunne R, Adhikari R (2006) Recent developments in biodegradable polymers. Biotech Annu Rev 12:1387–2656
Hiltunen K, Tuominen J, Seppälä JV (1998) Hydrolysis of lactic acid-based poly(ester-urethane)s. Polym Int 47:186–192
Kumar N, Ezra A, Ehrenfroind T, Krasko MY, Domb AJ (2003) Biodegradable polymers, medical applications. Encyclopedia of polymer science and technology, vol 5, Wiley, New York, pp 264-265. doi:10.1002/0471440264.pst027
Mallakpour S, Zadehnazari A (2011) Advances in synthetic optically active condensation polymers—a review. Express Polym Lett 5:142–181
Matthews SE, Pouton CW, Threadgill MD (2000) A biodegradable multiblock co-polymer derived from an alpha, omega-bis(methylamino)peptide and an alpha, omega-bis(oxiranylmethyl)poly(ethylene glycol). J Controlled Release 67(2–3):129–139
Nayak P, Mishra DK, Sahoo KC, Pati NC, Jena PK, Lenka S et al (2001) Polymers from renewable resources. XIII. Interpenetrating polymer networks derived from castor oil–hexamethylene diisocyanate and polymethacrylamide. J Appl Polym Sci 80:1349–1353
NIIR Board (2006) The complete book on biodegradable plastics and polymers (Recent Developments, Properties, Analysis, Materials & Processes), Chap. 4, Asia Pacific Business Press Inc., Delhi
Okada M (2002) Chemical syntheses of biodegradable polymers. Prog Polym Sci 27(1):87–133
Rafiemanzelat F, Abdollahi E (2010) Synthesis and characterization of hydrolysable poly(ether-urethane-urea)s derived from l-leucine anhydride cyclopeptide; a green synthetic method for monomer. Polym Degrad Stab 95:901–911
Santerre JP, Woodhouse K, Laroche G, Labow RS (2005) Understanding the biodegradation of polyurethanes: from classical implants to tissue engineering materials. Biomaterials 26:7457–7470
Tang YW, Labow RS, Santerre JP (2001) Enzyme-induced biodegradation of polycarbonate polyurethanes: dependence on hard-segment concentration. J Biomed Mater Res 56:516–528
Torma V, Gyenes T, Szakacs Z, Noszal B, Nemethy A, Zrinyi M (2007) Novel amino acid-based polymers for pharmaceutical applications. Polym Bull 59:311–318
Warrer K, Karring T, Nyman S, Gogolewski S (1992) Guided tissue regeneration using biodegradable membranes of polylactic acid or polyurethane. J Clin Periodontol 19:633–640
Yeganeh H, Lakouraj MM, Jamshidi S (2005) Synthesis and characterization of novel biodegradable epoxy-modified polyurethane elastomers. J Polym Sci Part A: Polym Chem 43:2985–2996
Yeganeh H, Jamshidi H, Jamshidi S (2006) Synthesis and properties of novel biodegradable poly(ε-caprolactone)/poly(ethylene glycol)-based polyurethane elastomers. Polym Int 56(1):41–49
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Financial support of this work by Research Affairs Division University of Isfahan (UI), is gratefully acknowledged. We also extend our thanks to Miss Elahe Heidari, M.S. student of Department of Biology, Microbiology Division.
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Rafiemanzelat, F., Fathollahi Zonouz, A. & Emtiazi, G. Synthesis of new poly(ether–urethane–urea)s based on amino acid cyclopeptide and PEG: study of their environmental degradation. Amino Acids 44, 449–459 (2013). https://doi.org/10.1007/s00726-012-1353-4
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DOI: https://doi.org/10.1007/s00726-012-1353-4