Polyglycidols are flexible hydrophilic polyethers that are potentially biocompatible polymers based on their similarities to the well-studied poly(ethyleneglycol). Polyglycidols can be prepared as branched or linear polymers by suitable synthetic methods. Biocompatibility testing of these polymers conducted in vitro as well as in vivo are reported here. The in vitro studies included hemocompatibility testing for effects on coagulation (PT and APTT), complement activation, red blood cell aggregation, and whole blood viscosity measurements. In vitro cytotoxicity experiments were also conducted. The results were compared with some of the common biocompatible polymers already in human use. Results from these studies show that polyglycidols are highly biocompatible. Hyperbranched polyglycidols were found to be well tolerated by mice even when injected in high doses.

No abstract

Very high molecular weight (M n up to 700 000) and narrowly polydispersed (PDI = 1.1−1.4) hyperbranched polyglycerols (HPG) were synthesized by ring-opening multibranching polymerization of glycidol using dioxane as an emulsifying agent. Broader molecular weight distributions with low molecular weight fractions were obtained when diglyme was used as the emulsifying agent. But the low molecular weight fractions could be removed by dialysis. Isolated yields in both the cases were 70−90%. The different result in the case of dioxane may be due to faster cation exchange which leads to low polydispersites. HPGs of various molecular weights were characterized by a GPC system coupled with a multiangle laser light scattering detector and a triple detector array. The intrinsic viscosities were low for these polymers and did not increase with molecular weight. The dimensions of these polymers (R g, R h, R η) and their dependence on molecular weights are described. The hydrodynamic radii were very small with dimensions similar to those of dendrimers. Our results show that these polymers are very compact and have spherical conformations in water with no indications of aggregate formation. The melt viscoelastic properties were also studied. Despite their self-similar structures, depending on the type of solvent used to synthesize them (diglyme vs dioxane), topologically restricted configurations are produced that result in completely different entanglement dynamics.

Functionalized anionic polystyrene latex particles with ATRP initiators were synthesized by surfactant-free shell-growth emulsion polymerization of styrene and 2-(2′-chloropropionato)ethyl acrylate (HEA-Cl). N-Isopropylacrylamide (NIPAM) was polymerized from these particles by surfaceinitiated aqueous ATRP using PMDETA/CuCl and HMTETA/CuCl catalysts to synthesize poly(Nisopropylacrylamide) (PNIPAM) brushes. The grafted latexes were characterized for molecular weight of the PNIPAM chains, grafting density, and hydrodynamic thickness of the grafted polymer layer. Molecular weights of the grafted PNIPAM chains depended on the monomer concentration, concentration of copper(II) complex, and the presence of external initiator in the reaction medium. M n of the grafted chains increases with increase in the monomer concentration and decreases with addition of copper(II) complex and external initiator. The HMTETA/CuCl catalyst produces higher molecular weight chains than PMDETA/CuCl. Molecular weights from ∼50 000 to 800 000 with low polydispersities, between 1.25 and 1.4, were achieved. The grafting density of PNIPAM on the surface increases with increasing monomer concentration and decreases with addition of copper(II) catalyst and external initiator. Block copolymerization of N,Ndimethylacrylamide from PNIPAM-grafted latex demonstrated that the chains are terminated with a chlorine atom, and the grafting reactions are taking place by the ATRP mechanism. The hydrodynamic thickness (HT) of the grafted PNIPAM layer scales as DP 0.66 (where DP ) degree of polymerization) at constant grafting density (chains/nm 2 ). The HT values for PNIPAM brushes are sensitive to temperature and salt concentration. Since the transition from extended coil to collapsed structure occurs over a range of temperature and salt concentration, it follows a second-order transition, as predicted by theory. The thickness of the collapsed brush is sensitive to the type of stimulus used to induce the phase transition.

We develop a theory of electrophoresis of human erythrocytes that predicts mobilities significantly smaller than those based on the classical Smoluchowski relation. In the classical treatment the charge is assumed to be spread uniformly on the hydrodynamic surface. The present model takes into account that most of the charge, due mainly to sialic acid, is contained in the glycocalyx. The glycocalyx is modeled as a permeable layer of polyelectrolyte molecules anchored to the cell membrane. The charge is assumed to be uniformly distributed throughout this layer. The fluid flow in the layer is treated as being dominated by Stokes friction arising from idealized polymer segments. The Navier-Stokes equations are solved to give the dependence of electroosomotic velocity with distance from the cell surface. An expression for the electrophoretic mobility is obtained which contains two parameters (a) the thickness of the glycocalyx and (b) the mean polymer segment radius. The best fit to experimental data is obtained if these are given the values 75 A and 7 A, respectively. Deviation from experimental data at low ionic strength (less than 0.05 M) occurs. However, this deviation is in the direction one would expect if at low ionic strength the polyelectrolyte layer expands slightly due to decreased charge shielding.