Persistence of nonprotein seed amino acid s-(β-carboxyethyl)-cysteine in young leaves ofCalliandra rubescens Ecological implications

The insecticidal nonprotein amino acid S-(-carboxyethyl)-cysteine (S-CEC) is the major free amino acid in the seeds of severalCalliandra spp. where it accounts for up to 2.9 % of dry weight. Lesser amounts of other related S-containing amino acids and an array of nonprotein imino acids derived from pipecolic acid are other constituents. High concentrations of imino acids, which also show insecticidal activity, are maintained in the mature leaves, but sulfur compounds are lacking. In this study the disappearance of S-CEC from the germinating seeds and young seedlings ofC. rubescens was monitored over time. After 10 weeks, S-CEC continues to be found in high concentrations in the stems and new leaves. As young leaves mature, sulfur compounds quickly decrease in concentration. Traces of S-CEC are found in new leaves of plants up to nine months after germination. Whether high concentration of S-CEC in young leaves is due to transportation from the seed or de novo synthesis is unclear. The ecological implications are discussed.     

Preparation of stable polyurethane-polystyrene copolymer emulsions via RAFT polymerization process

Stable polyurethane-polystyrene (PU-PS) copolymer emulsions were prepared by the polymerization of 2-hydroxyethyl acrylate (HEA)-capped PU macromonomer and styrene, using azobis(isobutyronitrile) (AIBN), a radical initiator, and 4-((benzodithioyl)methyl)benzoic acid, a reversible addition-fragmentation chain transfer (RAFT) agent. As the molar ratio of the RAFT agent to AIBN increased, the zeta potential of the resulting copolymer emulsion increased, but the average size and size distribution of the emulsion droplets decreased. A living polymerization of HEA end-capped PU macromonomer and styrene was characterized by a linear increase in the molecular weight and decrease in the molecular weight distribution with consumption of monomers. The tensile strength, hardness and water-resistance of the copolymer films, prepared from the PU-PS copolymer emulsions, were much greater than those of the films prepared from the pure PU emulsion. The copolymer emulsions, prepared via the RAFT polymerization process, are expected to exhibit better storage stability than those prepared via the conventional free radical polymerization process, due to the presence of carboxyl groups derived from the RAFT agent at the PS block termini.     

Effects of preparation conditions on the surface modification and performance of polyethersulfone ultrafiltration membranes

The impact that some membrane preparation steps had on ultrafiltration (UF) membrane characteristics and performance was studied. Polyethersulfone (PES) was employed as base polymer, while N‐methyl pyrrolidone (NMP) was used as a solvent, and polyvinylpyrrolidone (PVP) was used as a nonsolvent pore‐forming additive. The manufacturing variables studied were solvent evaporation time and membrane surface modification, using a fluorine‐based copolymer referred to as surface‐modifying macromolecule (SMM). The flat sheet membranes, prepared via phase inversion, were characterized using solute transport data, X‐ray photoelectron spectroscopy (XPS), and contact angle measurements. Membrane performance was evaluated via filtration test protocol that included a 6‐day filtration of concentrated river water. The flux reduction with time was modeled using single and dual mechanisms of fouling. The pore blockage/cake filtration model described better the behavior of the permeation rate along the experiments. Increasing the solvent evaporation time decreased the size of the pores and the permeation rate. However, it did not significantly affect the removal of the organic compounds naturally present in the river water used as feed. XPS and contact angle measurements proved that the short evaporation periods did not allow enough SMM migration to the surface to provoke a significant effect on the membrane performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Molecular weight distribution of polyethylene catalyzed by Ziegler–Natta catalyst supported on MgCl2 doped with AlCl3

Ti‐based Ziegler–Natta catalysts supported on MgCl₂ doped with AlCl₃ were prepared by the reaction of MgCl₂/AlCl₃–ethanol adduct with TiCl₄. No AlCl₃ crystallites were found in the AlCl₃‐doped catalysts by WAXD analysis, suggesting that AlCl₃/MgCl₂ solid solution was formed. The effect of doping on the catalyst performance in ethylene polymerization was investigated. The results showed that the catalysts based on AlCl₃‐doped MgCl₂ support exhibited a slightly higher activity than did the MgCl₂‐supported catalyst and the molecular weight distribution (MWD) of polyethylene (PE) markedly increased (from 10.8 to 47.9) with the increase of AlCl₃ content in catalysts. The changes in catalyst's active center distribution were studied based on nonlinear fitting of the polymer GPC curves by multiple Flory functions. It was found that increase of types of active centers by introducing AlCl₃ into the support should be responsible for the broadening of MWD of PE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1768–1772, 2006     

Physical properties of polycaproamide/cationic dyeable poly(ethylene terephthalate) polyblended fibers

Polycaproamide (PCA) and cationic dyeable poly(ethylene terephthalate) (CDP) polymers were blended mechanically (in ratios of 75/25, 50/50, and 25/75) in a melt twin‐screw extruder to prepare three PCA/CDP polyblended materials. The blends of PCA and CDP were spun into fibers. The molar ratio of dimethyl 5‐sulfoisophthalate sodium salt for CDP was 2%. This study investigated the physical properties of PCA/CDP polyblended fibers with nuclear magnetic resonance, gel permeation chromatography, gas chromatography, potentiometer, differential scanning calorimetry (DSC), thermogravimetric analysis, scanning electron microscopy (SEM), extension stress–strain measurements, density gradient analysis, and rheometry. The experimental results of DSC proved that PCA and CDP formed an immiscible system. In an SEM image of a 50/50 PCA/CDP blend, the morphological aggregation of a larger size, from 3 to 5 μm in diameter, was observed. The rheological behavior of the PCA/CDP polyblended materials exhibited negative‐deviation blends, and the 50/50 blend of the PCA/CDP polyblended fibers showed a minimum tenacity value. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1710–1715, 2004     

Effect of Twin-Plane Reentrant Edge on the Coarsening Behavior of Barium Titanate Grains

When BaTiO₃ ceramics were sintered at relatively low temperatures (≤1250°C), the grains with reentrant edges caused by a (111) double twin grew exclusively. As a result, a microstructure with a bimodal grain-size distribution composed of platelike large grains and fine matrix grains was obtained. In contrast, at the usual sintering temperature between 1250° and 1350°C, grains containing a (111) double twin did not exhibit any growth advantage. In this case, a coarse and uniform microstructure was obtained. When this coarse-grained specimen was further heat-treated at 1365°C, the grains possessing a double twin were observed to grow exclusively again. The results were explained in terms of a coarsening process controlled by two-dimensional nucleation.     

Enhanced surface morphologies of screen-printed carbon nanotube films by heat treatment and their field-emission properties

A heating process for obtaining free-standing carbon nanotube emitters is presented with the aim of improving field-emission properties from the screen-printed multiwalled carbon nanotube (MWCNT) films. Using an atmosphere with an optimum combination of nitrogen and air for heat treatment of CNT films, the CNT emitters can be made to protrude from the surface. This allows for a high emission current and the formation of very uniform emission sites without special surface treatment. The morphological change of the CNT film by this technique has eliminated additional processing steps, such as surface treatment which may result in secondary contamination and damage to the film. Despite its simplicity the process provides a high reproducibility in emission current density which makes the films suitable for practical applications.     

Syndiotactic Polystyrene/Organoclay Nanocomposites: Synthesis via In Situ Coordination‐Insertion Polymerization and Preliminary Characterization

Summary: Syndiotactic polystyrene (sPS)/organophilic clay nanocomposites were obtained by in situ coordination‐insertion polymerization of styrene. Two cationic surfactants (alkylammonium and alkylphosphonium) were used for the intercalation of montmorillonite (MMT). For each organically modified clay, three protocols were performed using an MAO‐activated hemi‐metallocene catalyst, in order to compare the influence of experimental conditions on the composite microstructure and on its thermal stability. The microstructures of nanocomposites were investigated by wide angle X‐ray scattering and DSC. Partially exfoliated or intercalated materials were obtained in all cases and a decrease of crystallinity is observed. Thermal properties were also studied by DSC and thermogravimetric analysis. The presence of clay does not have a strong influence on the sPS thermal transitions but the thermal decomposition process of the material was slowed down in the presence of few organoclay percents, particularly in the degradation beginning. The influence of these two organically modified clays on the thermal stability of the material is discussed.

Gel and suspension formed from the combination of cloisite with toluene (left) and styrene (right), respectively.     

Synthesis of 2‐monoglycerides by alcoholysis of palm oil and tuna oil using immobilized lipases

Commercial immobilized lipases were used for the synthesis of 2‐monoglycerides (2‐MG) by alcoholysis of palm and tuna oils with ethanol in organic solvents. Several parameters were studied, i.e., the type of immobilized lipases, water activity, type of solvents and temperatures. The optimum conditions for alcoholysis of tuna oil were at a water activity of 0.43 and a temperature of 60 °C in methyl‐tert‐butyl ether for ～12 h. Although immobilized lipase preparations from Pseudomonas sp. and Candida antarctica fraction B are not 1, 3‐regiospecific enzymes, they were considered to be more suitable for the production of 2‐MG by the alcoholysis of tuna oil than the 1, 3‐regiospecific lipases (Lipozyme RM IM from Rhizomucor miehei and lipase D from Rhizopus delemar). With Pseudomonas sp. lipase a yield of up to 81% 2‐MG containing 80% PUFA (poly‐unsaturated fatty acids) from tuna oil was achieved. The optimum conditions for alcoholysis of palm oil were similar as these of tuna oil alcoholysis. However, lipase D immobilized on Accurel EP100 was used as catalyst at 40 °C with shorter reaction times (<12 h). This lead to a yield of ～60% 2‐MG containing 55.0‐55.7% oleic acid and 18.7‐21.0% linoleic acid.     

THERMODYNAMIC PERFORMANCE PREDICTION FOR NON-CFC MIXTURES

The ideal thermodynamic performances of a variety of non-CFC refrigerants and their mixtures were calculated by using the Patel-Teja equation of state. The results indicated that the preferable non-CFC refrigerant mixtures could be HCFC-I24 +HFC-152a, HFC-152a + HFC-134, dimethyl ether + HCFC-22, and dimethyl ether + HCFC-124 for air-conditioning systems, and binary mixtures of HCFC-22 + HFC-125, and HCFC-22 + HFC-143a for low-temperature applications. Those potential non-CFC mixtures were suggested for further investigations.