Non-isocyanate urethane linkage formation using l-lysine residues as amine sources
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Bio-based polyurethane materials are broadly applied in medicine as drug delivery systems. Nevertheless, their synthesis comprises the use of petroleum-based toxic amines, isocyanates and polyols, and their biocompatibility or functionalization is limited. Therefore, the use of lysine residues as amine sources to create non-isocyanate urethane (NIU) linkages was investigated. Therefore, a five-membered biscyclic carbonate (BCC) was firstly synthetized and reacted with a protected lysine, a tripeptide and a heptapeptide to confirm the urethane linkage formation with lysine moiety and to optimize reaction conditions. Afterwards, the reactions between BCC and a model protein, elastin-like protein (ELP), and β-Lactoglobulin (BLG) obtained from whey protein, respectively, were performed. The synthesized protein materials were structural, thermally and morphologically characterized to confirm the urethane linkage formation. The results demonstrate that using both simple and more complex source of amines (lysine), urethane linkages were effectively achieved. This pioneering approach opens the possibility of using proteins to develop non-isocyanate polyurethanes (NIPUs) with tailored properties.
Keywordsl-Lysine Peptides Proteins ELP β-Lactoglobulin Cyclic carbonate
TSSIPRO—Technologies For Sustainable And Smart Innovative Products, NORTE-01-0145-FEDER-000015 and COMPETE 2020 Programme and National Funds through FCT—Portuguese Foundation for Science and Technology under the project UID/CTM/50025/2013. The authors would like to thank Professor Sílvia Lima and Professor Susana Costa from the Chemistry Department at the University of Minho for kindly allow the use of Microwave CEM Discover SPS equipment and for all knowledge shared during this work.
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
Research involving human participants and/or animals
This research did not involve human participants or animals.
- Booysen J, Marx S, Muller LC. Vermeulen U, Grobler A (2015) Synthesis of novel non-isocyanate polyhydroxyurethane from l-lysine and its application. In: 7th International Conference on Latest Trends in Engineering & Technology, pp 184–190Google Scholar
- Butnaru M, Bredetean O, Macocinschi D, Dimitriu CD, Knieling L, Harabagiu V (2012) Biocompatibility and biological performance of the improved polyurethane membranes for medical applications. Polyurethane 10:201–228Google Scholar
- Elena D, Vincent F, Guillaume M, Frédéric S, Rémi A, Stéphane F, Sylvain C (2016) Thermoresponsive crosslinked isocyanate-free polyurethanes by Diels-Alder polymerization. J Appl Polym Sci 134:44408–44419Google Scholar
- Fabian H, Mäntele W (2006) Infrared spectroscopy of proteins. Handbook of Vibrational Spectroscopy. Biochem Appl 2006:3399–3425Google Scholar
- Gerard L (2014) Renewable polyols for polyurethane synthesis via thiol-ene/yne couplings of plant oils. Macromol Chem Phys 214:415–422Google Scholar
- Hu X, Cebe P, Weiss AS, Omenetto F, Kaplan DL (2012) Protein-based composite materials. Mater Today 15:208–215Google Scholar
- Mallakpour S, Rafiee Z (2008) Use of ionic liquid and microwave irradiation as a convenient, rapid and eco-friendly method for synthesis of novel optically active and thermally stable aromatic polyamides containing N-phthaloyl-l-alanine pendent group. Polym Degrad Stab 93:753–759CrossRefGoogle Scholar
- Poussard L, Mariage J, Grignard B, Detrembleur C, Jéroîme C, Calberg C, Heinrichs B, De Winter J, Gerbaux P, Raquez JM (2016) Non-isocyanate polyurethanes from carbonated soybean oil using monomeric or oligomeric diamines to achieve thermosets or thermoplastics. Macromolecules 49:2162–2171CrossRefGoogle Scholar
- Spicer CD, Davis BG (2014) Selective chemical protein modification. Nat Commun 5:4740Google Scholar
- Thomas S, Datta J, Haponiuk J, Reghunadhan A (2017) Polyurethane polymers: composites and nanocomposites, 1st edn. Elsevier, AmsterdamGoogle Scholar
- Wang C, Zheng Y, Sun Y, Fan J, Qin Q, Zhao Z (2016) A novel biodegradable Polyurethane based on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(ethylene glycol) as promising biomaterials with the improvement of mechanical properties and hemocompatibility. Polym Chem 7:6120–6132CrossRefGoogle Scholar