Synthesis and characterization of poly [N-acryloyl-(D/L), (+/−)-phenylalanine-co-(D/L), (−/+)N-methacryloyloxyethyl-N′-2-hydroxybutyl(urea)] copolymers

Abstract

Two monomers of (D/L), (+/−)-N-methacryloyloxyethyl-N′-2-hydroxybutyl(urea) methacrylate (D/L-MABU) type were prepared and further polymerized through free radical polymerization with optically active monomers containing phenylalanine sequences such as N-acryloyl-(D/L), (−/+)-phenylalanine (A-D/L-Phe). The resulting copolymers, i.e., poly[N-acryloyl-(D/L), (−/+)-phenylalanine-co-(D/L), (+/−)-N-methacryloyloxyethyl-N′-2-hydroxybutyl(urea)], A-D/L-Phe-co-D/L-MABU, were characterized by FT-IR, 1D/2D NMR (¹H and ¹³C), UV-vis, and circular dichroism (CD) spectroscopies, differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). The copolymers obtained with a molar fraction of 0.76: 0.24 / 0.64: 0.36 monomer units had optical rotation values of −25° and +15°, respectively. Upon chemical modification of the phenylalanine-based copolymers with fluorescein-isothiocyanate, new fluorescent copolyacrylates (A-D/L-Phe-co-D/L-MABU-F) were synthesized and further studied for pH measurements in DMF solutions using HCl and NaOH 10⁻¹M. It was found that sterioselectivity of the A-L-Phe-co-L-MABU-F copolymer is higher than of its dextro-form, especially at basic pH.