Synthesis and characterization of poly(ethylene oxide)‐based glycopolymers and their biocompatibility with osteoblast cells

Poly(ethylene oxide)‐block‐poly(methacryl‐d ‐glucopyranoside) (PEO‐GP) and poly(methacryl‐d ‐glucopyranoside) (H‐GP) glycopolymers were synthesized by deacetylation of acetylated polymers which were synthesized via atom transfer radical polymerization. The synthesized glycopolymers were characterized using ¹H NMR, ¹³C NMR and Fourier transform infrared (FTIR) spectroscopies, gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The deacetylated polymers exhibited onset decomposition temperatures about 60 °C lower compared to the polymers having acetyl pendants. The glass transition temperature (T_g) of the acetylated homopolymer was 133 °C and that of the PEO‐based block copolymer was 124 °C. The deacetylated polymers H‐GP and PEO‐GP exhibited T_g values of about ?30 °C. Biocompatibility of the H‐GP and PEO‐GP glycopolymers was obtained by studying osteoblast cell adhesion, viability and proliferation in vitro. The cell viability showed an increase with increasing concentration of H‐GP from 0.1 to 1 µmol L^?1 and then decreased with further increase in its concentration (10–1000 µmol L^?1). PEO‐GP did not show a significant variation in cell viability on variation of its concentration from 0.1 to 1000 µmol L^?1. The significant improvement in biocompatibility with osteoblast cells in the presence of PEO‐GP was considered as due to the covalently bonded PEO segment of the methacrylate glycopolymer block. © 2014 Society of Chemical Industry     

Synthesis of PEO-based di-block glycopolymers at various pendant spacer lengths of glucose moiety and their in-vitro biocompatibility with MC3T3 osteoblast cells

Di-block copolymers of poly(ethylene oxide) (PEO) and glycopolymers at three different pendant spacer lengths of glucose moiety were synthesized by deacetylation of pendant moieties of 2,3,4,6-tetra-O-acetyl-d-glucopyranosides which were prepared by reversible addition-fragmentation chain-transfer (RAFT) process. The water soluble deacetylated copolymers, PEO-b-poly(acryl-d-glucopyranoside) (PEO-b-PAG, 2a), PEO-b-poly[4′-(acryloxy)butyl-d-glucopyranoside] (PEO-b-PABG, 2b), and PEO-b-poly[6′-(acryloxy)hexyl-d-glucopyranoside] (PEO-b-PAHG, 2c) were characterized in comparison with acetylated copolymers by spectroscopic and gel permeation chromatography methods. In order to assess the biocompatibility of these three di-block copolymers, the adhesion (%), viability (%), and proliferation assays were carried out in MC3T3 cells in-vitro at different concentrations from 10 nM to 1000 μM. Qualitative analysis of cell cytoskeletal organization was obtained by immunostaining with talin and integrin α5. It was clearly indicative of well spreading of cells in the presence of all glycopolymers at lower concentrations but with an increase in the concentration (10 and 100 μM) showed significant change in the cell surface morphologies, despite having good cell adhesion and viability as compared to the control conditions. The use of di-block glycolpolymers at?≤?100 μM of the concentration showed very good osteoblast cells adhesion and viability response; however at higher concentrations (1000 μM) of glycopolymers > 80% of cells lost their viability.     

Solvent‐free cyanoethylation of selected alcohols using amberlyst A‐21 polymer resin

Solvent‐free cyanoethylation of selected alcohols with acrylonitrile (AN) using a weakly basic polymer resin, Amberlyst A‐21 (AA‐21) was studied at 75°C. The conversion of primary alcohols, 1‐octadecanol, hexane‐1,6‐diol, pentaerythritol, but‐2‐yne‐1,4‐diol, N‐methyldiethanolamine, triethanolamine and diethanolamine is higher than secondary alcohols, isopropanol and glycerol in the presence of polymer resin. Of various alcohols, but‐2‐yne‐1,4‐diol gave the product in high conversion (87%) in cyanoethylation with a polymer resin/AN weight ratio of 0.04. The polymer resin showed recycling ability only in two cycles to produce cyanoethylated product from diethanolamine. In case of 1‐octadecanol, hexane‐1,6‐diol, and N‐methyldiethanolamine with AN under similar conditions, no recycling ability was observed. Thermally treated polymer resin at 75°C afforded the product in lower conversion (55%) whereas the same product was obtained in 69% when fresh polymer resin was used in cyanoethylation of 1‐octadecanol. No catalytic effect was observed for polymer resin treated at 100°C. Fourier transform infrared (FTIR) spectra showed CN stretching at 2248 cm^?1 for the polymer resin collected after the reaction which was caused by the AN binding on polymer resin during the reaction. As per thermogravimetric curves, 5% weight loss was observed at 201°C for recovered resin and at 161°C for polymer resin treated at 100°C. Scanning electron microscope images confirmed the AN binding on polymer beads after catalytic activity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Emission (Gd3+ and Sm3+) and ESR (Gd3+) studies of La1−xLnxB3O6 (Ln = Gd,Sm; 0 ≤ x ≤ 0.2 for Gd; 0 ≤ x ≤ 0.1 for Sm) phosphors

Polycrystalline powders of rare-earth doped La_1?xGd_xB₃O₆ (0?≤?x?≤?0.2) and La_1?xSm_xB₃O₆ (0.0?≤?x?≤?0.1) phosphors were successfully prepared by a B₂O₃ flux method. All the phosphor samples are well characterized by powder X-ray diffraction (XRD), infrared (IR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) methods and fluorescence lifetime of Sm³⁺ ion. The XRD patterns show that La_1?xM_xB₃O₆ (M?=?Gd and Sm) adopt monoclinic with the I2/a space group. The SEM–EDS results confirmed the doping of Gd and Sm into LaB₃O₆ lattice. The IR and Raman spectra of these solid solutions gave distinctive bands corresponding to planar BO₃ and tetrahedral BO₄ groups. The photoluminescence (PL) spectra of La_1?xGd_xB₃O₆ gave a strong emission band, ⁶P_J?→?⁸S_7/2, at 310 nm. The PL spectra of La_1?xSm_xB₃O₆ phosphor showed orange-red emission at 598 nm when excited using light of wavelength of 402 nm. The results were obtained by the transition ⁴G_5/2?→?⁶H_7/2 of Sm³⁺ ions. The influence of dopant concentration on the emission profiles was studied. The ESR spectra of La_1?xGd_xB₃O₆ (x?=?0.02) gave a typical U-spectrum and spin-Hamiltonian parameters are deduced.