Novel,biodegradable, functional poly(ester‐carbonate)s by copolymerization of trans‐4‐hydroxy‐L‐proline with cyclic carbonate bearing a pendent carboxylic group

Water‐soluble poly(ester‐carbonate) having pendent amino and carboxylic groups on the main‐chain carbon is reported for the first time. This article describes the melt ring‐opening/condensation reaction of trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) with 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) at a wide range of molar fractions. The influence of reaction conditions such as catalyst concentration, polymerization time, and temperature on the number average molecular weight (M_n) and molecular weight distribution (M_w/M_n) of the copolymers was investigated. The polymerizations were carried out in bulk at 110 °C with 3 wt % stannous octoate as a catalyst for 16 h. The poly(ester‐carbonate)s obtained were characterized by Fourier transform infrared spectroscopy, ¹H NMR, differential scanning calorimetry, and gel permeation chromatography. The copolymers synthesized exhibited moderate molecular weights (M_n = 6000–14,700 g mol^?1) with reasonable molecular weight distributions (M_w/M_n = 1.11–2.23). The values of the glass‐transition temperature (T_g) of the copolymers depended on the molar fractions of cyclic carbonate. When the MBC content decreased from 76 to 12 mol %, the T_g increased from 16 to 48 °C. The relationship between the poly(N‐CBz‐Hpr‐co‐MBC) T_g and the compositions was in approximation with the Fox equation. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐MBC)s was evaluated from weight‐loss measurements and the change of M_n and M_w/M_n. Debenzylation of 3 by catalytic hydrogenation led to the corresponding linear poly(ester‐carbonate), 4 , with pendent amino and carboxylic groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2303–2312, 2004     

Stereological simulations of asymmetric polymerization in channels of bile acid inclusion compounds: A detailed analysis of the monomer arrangements in the channels

We studied simulations by computer graphics to estimate the steric mechanism of the asymmetric polymerization of prochiral diene monomers in channels of inclusion compounds of steroidal bile acids, such as deoxycholic acid (DCA) and cholic acid. We applied a hierarchization method to interpret the crystal structures of bile acids, clarifying that the chiral host molecules associated to form characteristic 2₁-helical assemblies with uneven surfaces. A detailed analysis of the uneven channels in a close-packing state indicated that there were many possible arrangements of the monomers in the channels. The plausible arrangements in the channel could explain a previous study, which showed that the polymerization in the DCA channel yielded chiral polymers with a predominant configuration from prochiral diene monomers, such as 2-methyl-trans-1,3-pentadiene. On the basis of such simulation studies of the arrangements of guest monomers in the channel, we examined a plausible steric mechanism for asymmetric inclusion polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4648–4655, 2004     

Thermoplastic poly(ester‐imide)s derived from anhydride‐terminated polyester prepolymer and diisocyanate

The phase‐separation behavior of thermoplastic poly(ester‐imide) [P(E‐I)] multiblock copolymers, (A‐B)_n, was investigated by a stepwise variation of the imide content. All the multiblock copolymers were synthesized by solution polycondensation with dimethylformamide as a solvent. P(E‐I)s were prepared with anhydride‐terminated polyester prepolymer and diisocyanates. Polyester prepolymers were prepared by the reaction of pyromellitic dianhydride and two different polyols [poly(tetramethylene oxide glycol) (PTMG) and polycaprolactone diol (PCL)]. Structural determination was done with Fourier transform infrared spectroscopy and Fourier transform NMR, and the molecular weight was determined by gel permeation chromatography. The effect of the imide content on the thermal properties of the synthesized P(E‐I)s was investigated by thermogravimetric analysis and differential scanning calorimetry. The polymers were also characterized for static and dynamic mechanical properties. Thermal analysis data indicated that the polymers based on PTMG were stable up to 330 °C in nitrogen atmosphere and exhibited phase‐separated morphology. Polymers based on PCL showed multistage decomposition, and the films derived from them were too fragile to be characterized for static and dynamic mechanical properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 341–350, 2004     

New liquid‐crystalline poly(ester amide)s: The role of nitro groups in the phase behavior

New hydrogen‐bonded liquid‐crystalline poly(ester amide)s (PEA)s were obtained from 1,4‐terephthaloyl[bis‐(3‐nitro‐N‐anthranilic acid)] (5) or 1,4‐terephthaloyl[bis‐(N‐anthranilic acid)] (6), with or without nitro groups, respectively, through the separate condensation of each with hydroquinone or dihydroxynaphthalene. The dicarboxylic monomers were synthesized from 2‐aminobenzoic acid. The phase behavior of the monomers and polymers were studied with differential scanning calorimetry, polarized light microscopy, and wide‐angle X‐ray diffraction methods. Monomer 5, containing nitro groups, exhibited a smectic liquid‐crystalline phase, whereas the texture of monomer 6 without nitro groups appeared to be nematic. The PEAs containing nitro groups exhibited polymorphism (smectic and nematic), whereas those without nitro groups exhibited only one phase transition (a nematic threaded texture). The changes occurring in the phase behavior of the polymers were explained by the introduction of nitro groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1289–1298, 2004     

Plasticized microporous poly(vinylidene fluoride) separators for lithium-ion batteries. III. Gel properties and irreversible modifications of poly(vinylidene fluoride) membranes under swelling in liquid electrolytes

Microporous poly(vinylidene fluoride) (PVdF) separators for lithium-ion batteries, used in liquid organic electrolytes, have been characterized with respect to the swelling phenomena on dense PVdF membranes (obtained through hot pressing). In the first and second parts of this study, we have described the swelling equilibria and swelling kinetics of dense PVdF. Here the thermal properties of PVdF gels and their irreversible modifications induced by swelling are characterized. Particular attention is paid to crystallinity modifications, polymer plasticization, and membrane degradation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2308–2317, 2004     

PURIFICATION OF L-METHIONINE AND N-ACETYL-D-METHIONINE FROM THE MIXTURE OF ENZYMATICALLY DEACYLATED N-ACETYL-DL-METHIONINE

1. INTRODUCTION Methionine, namely 2-amido-4-thiomethyl butyric acid with a structure of CH3SCH2CH2CHCOOH, is one of the essential amino acids and has two natural enantionmers, D and L-methionine. The mixture of L- and D-isomers can be used as analeptics or nutritive additives to maintain the equilibrium of amino acids of feed [1,2]. L-methionine can release active methyl and accelerate the synthesis of choline, which further speeds up the conversion of the lipid accumulated in liv…     

Self-assembly of Carboxyl Functionalized Polystyrene Nanospheres into Close-packed Monolayers via Chemical Adsorption

The polyacrylic acid functionalized polystyrene nanospheres were synthesized and self-assembled into irregular, densely packed monolayers in non-aqueous media. The polymer nanoparticles were chemically adhered to substrates. The morphologies of the resulting films were investigated. The impact of the volume fraction of alcohol in the mixed solvents on the particle adsorption and fabrication of nanosphere assembled films was examined.     

Solid Phase Synthesis of 2-Substituted 1,3-Oxazin-6-ones Using Resin-bound Cyclic Malonic Acid Ester

A facile solid phase synthesis of 2-substituted 1,3-oxazin-6-ones using polymer-supported Meldrum‘s acid has been reported. Reaction of the resin-bound cyclic malonic acid ester with triethyl orthoformate and subsequent double substitution with amide, afforded the corresponding polymer-supported acylaminomethylene cyclic malonic acid ester, which upon thermal treatment led to 1, 3-oxazin-6-ones in good yields and with high purity.     

Synthesis of Novel Monomeric Dyes with Anthraquinone Residue

Two novel polymerizable dyes with anthraquinone residue have been prepared, and their structures were characterized by FTIR, ^1HNMR and EA.     

Synthesis and Photocytotoxicity of Mono-functionalised Porphyrin with Valine Moiety

A mono-funtionalised tetraphenylporphyrin (TPP) bearing valine moiety at the phenyl ring was synthesized for photocytotoxicity examination in four steps, starting from regiospecific mono-nitration of TPP at the phenyl ring. The in vitro photocytotoxicitic effect against SPC-Al adenocarcinona cell line was tested.