Kinetic study on the radical polymerization of 2‐methacryloyloxyethyl phosphorylcholine

Polymerization of 2‐methacryloyloxyethyl phosphorylcholine (MPC) was kinetically investigated in ethanol using dimethyl 2,2′‐azobisisobutyrate (MAIB) as initiator. The overall activation energy of the homogeneous polymerization was calculated to be 71 kJ/mol. The polymerization rate (R_p) was expressed by R_p = k[MAIB]^0.54±0.05 [MPC]^1.8±0.1. The higher dependence of R_p on the monomer concentration comes from acceleration of propagation due to monomer aggregation and also from retardation of termination due to viscosity effect of the MPC monomer. Rate constants of propagation (k_p) and termination (k_t) of MPC were estimated by means of ESR to be k_p = 180 L/mol · s and k_t = 2.8 × 10⁴ L/mol · s at 60 °C, respectively. Because of much slower termination, R_p of MPC in ethanol was found at 60 °C to be 8 times that of methyl methacrylate (MMA) in benzene, though the different solvents were used for MPC and MMA. Polymerization of MPC with MAIB in ethanol was accelerated by the presence of water and retarded by the presence of benzene or acetonitrile. Poly(MPC) showed a peculiar solubility behavior; although poly(MPC) was highly soluble in ethanol and in water, it was insoluble in aqueous ethanol of water content of 7.4–39.8 vol %. The radical copolymerization of MPC (M₁) and styrene (St) (M₂) in ethanol at 50 °C gave the following copolymerization parameters similar to those of the copolymerization of MMA and St; r₁ = 0.39, r₂ = 0.46, Q₁ = 0.76, and e₁ = +0.51. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 509–515, 2000     

Candicanoside A,a Novel Cytotoxic Rearranged Cholestane Glycoside from Galtonia candicans

A novel cholestane diglycoside, named candicanoside A ( 1 ), was isolated from the bulbs of Galtonia candicans by monitoring the cytotoxic activity on HL‐60 leukemia cells. Candicanoside A ( 1 ) is very unique in structure, having two epoxy functionalities in its rearranged cholestane skeleton, and showed differential cytotoxicity in the Japanese Foundation for Cancer Research 38 cell‐line assay.     

Shear flow effect on phase behavior and morphology in polymer blends

The effect of simple shear flow on the phase behavior and morphology was investigated for both polystyrene/poly(vinyl methyl ether) (PS/PVME) and poly(methyl methacrylate)/poly(styrene‐co‐acrylonitrile) (PMMA /SAN‐29.5) blends, which have LCST (lower critical solution temperature)‐type phase diagram. The measurements were carried out using a special shear apparatus of two parallel glass plates type. The PS/PVME blends showed shear‐induced demixing and shear‐induced mixing at low and high shear rate values, respectively. In addition, the rotation speed and the sample thickness were found to have a pronounced effect on the phase behavior under shear flow. On the‐other hand, PMMA/SAN blend showed only shear‐induced mixing and the magnitudes of the elevation of the cloud points were found to be composition and molecular weight dependent. The morphology of the PMMA/SAN=75/25 blend indicated that shear‐induced mixing occurred at a critical shear rate value, below which the two phases were highly oriented and elongated in the flow direction.     

Synthesis of Immobilized CMP-Sialic Acids and Their Enzymatic Transfer with Sialyltransferase

A novel immobilization procedure for glycoproteins is based on the reacion of immobilized CMP-NeuAc (CMP-sialic acids) with sialyltransferase (see scheme). The transfer ability was tested under various conditions; a corresponding oligosaccharide or asialoglycoprotein acted as sialyl acceptor. The solid-phase synthesis of CMP-NeuAc is also described.     

Synthesis of regiocontrolled poly(4,6-di-n-butoxy-1,3-phenylene) by oxidative coupling polymerization

Poly(4,6-di-n-butoxy-1,3-phenylene) ( 6 ) was prepared by oxidative coupling polymerization of 1,3-di-n-butoxybenzene ( 1 ) or 2,2′,4,4′-tetra-n-butoxy biphenyl (3). Polymerizations were conducted in nitrobenzene in the presence of FeCl₃ at room temperature and produced polymers with number-average molecular weights up to 42,000. The effects of various factors, such as amount of FeCl₃ and reaction temperature and time were studied. The structure of polymer 6 was characterized by 270 MHz ¹H- and 68.5 MHz ¹³C-NMR spectroscopies and was estimated to consist of almost completely 1,3-linkage. The regiocontrolled polymer was readily soluble in common organic solvents. Thermogravimetric analysis of polymer 6 showed 10% weight loss at 390°C in nitrogen. © 1997 John Wiley & Sons, Inc. J Polym Chem 35 : 2259–2266, 1997