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Polymers 2012, 4(2), 1195-1210; doi:10.3390/polym4021195

Random Poly(Amino Acid)s Synthesized by Ring Opening Polymerization as Additives in the Biomimetic Mineralization of CaCO3

Received: 12 March 2012 / Revised: 8 May 2012 / Accepted: 9 May 2012 / Published: 23 May 2012
(This article belongs to the Special Issue Enzymes in Monomer and Polymer Synthesis)
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Biominerals such as bones, teeth and seashells, very often have advanced material properties and are a source of inspiration for material chemists. As in biological systems acidic proteins play an important role in regulating the formation of CaCO3 biominerals, we employ poly(amino acid)s to mimic the processes involved in the laboratory. Here we report on the synthesis of random aminoacid copolymers of glutamic acid (Glu), lysine (Lys) and alanine (Ala) using the ring opening polymerization (ROP) of their respective N-carboxy anhydrides (NCA). The synthetic approach yields a series of polymers with different monomer composition but with similar degrees of polymerization (DP 45–56) and comparable polydispersities (PDI 1.2–1.6). Using random copolymers we can investigate the influence of composition on the activity of the polymers without having to take into account the effects of secondary structure or specific sequences. We show that variation of the Glu content of the polymer chains affects the nucleation and thereby also the particle size. Moreover, it is shown that the polymers with the highest Glu content affect the kinetics of mineral formation such that the first precipitate is more soluble than in the case of the control.
Keywords: biomineralization; polypeptide; NCA; vaterite; hybrid materials biomineralization; polypeptide; NCA; vaterite; hybrid materials
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Dmitrovic, V.; Habraken, G.J.; Hendrix, M.M.; Habraken, W.J.; Heise, A.; de With, G.; Sommerdijk, N.A. Random Poly(Amino Acid)s Synthesized by Ring Opening Polymerization as Additives in the Biomimetic Mineralization of CaCO3. Polymers 2012, 4, 1195-1210.

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