Designed, Synthesis, And Property Of Biodegradable Poly (ε-caprolactone)/glycopolymer Biohybrids

Considering from both the biological and structure-size functions, to design and synthesize cell-targeted polymeric nanobiomaterials is an advanced and challenging topic in the interdisciplines of polymer chemistry, biomedicine and material sciences.In this work, biodegradable and biomimetic poly(ε-caprolactone)-b-poly (lactobionamidoethyl methacrylate) biohybrids with star-shaped architecture (SPCL-PLAMA) were synthesized from the atom transfer radical polymerization (ATRP) of unprotected lactobionamidoethyl methacrylate (LAMA) glycomonomer using atetra(2-bromo-2-methylpropionyl)-terminated poly(ε-caprolactone) (SPCL-Br) as a macroinitiator in NMP solution at room temperature. The as-synthesized SPCL-PLAMA biohybrids were characterized by means of FT-IR, 1H NMR, GPC, and DSC. It was demonstrated that the SPCL-PLAMA biohybrids with narrow polydispersity index were successfully obtained, and the block length of PLAMA glycopolymer could be adjusted linearly by the molar ratio of LAMA glycomonomer to SPCL-Br macroinitiator. The outer PLAMA glycopolymer greatly restrained the crystallization of inner PCL segments, and the degree of crystallization of PCL decreased with the increasing weight fraction of PLAMA. The self-assembly properties of amphiphilic SPCL-PLAMA biohybrids were further investigated by the techniques of 1H NMR, UV-vis, DLS, and TEM. The lactose-installed aggregates were fabricated in aqueous solution, which changed from spherical micelles to vesicles with the increasing weight fraction of hydrophobic PCL. Furthermore, both UV-vis and DLS analyses showed that the SPCL-PLAMA biohybrids had specific recognition with RCA120 lectin compared with BSA protein, and the self-assembled aggregates were surfaced by lactose shell.PGAMA glycopolymer was synthesized in a similar method. The product was characterized by 1H NMR,GPC,etc. Both DLS and TEM results evidenced that PGAMA generated polydisperse nanoparticles in aqueous solution. In addition, PGAMA had specific recognition with ConA compared with BSA protein.