Effects of pressure and temperature on dyeing acrylic fibres with basic dyes in supercritical carbon dioxide

The dyeing of acrylic fibre with CI Basic Blue 47 has been investigated using an ammonium carboxylate perfluoropolyether as an auxiliary in order to perform the reverse micellar system in supercritical carbon dioxide media. The basic dye was satisfactorily solubilised in the interior of the reverse micelle in the system, and dyeability in the supercritical carbon dioxide media was excellent, even in the absence of a retardant and/or an acid. The optimum proton-rich condition for dyeing of acrylic fabric is performed in reverse micelle aggregates and the proton-rich water pool is suitable for dye uptake by the fibre even without the presence of additives. Changes in glass transition temperature of acrylic fibre in the carbon dioxide media also influence the dyeing behaviour of acrylic fabric.     

Carbon nanotubes prepared from three-layered copolymer microspheres of acrylonitrile and methylmethacrylate

Carbon nanotubes (CNTs) were synthesized from fine three-layered copolymer microspheres using the polymer blend technique. Diameter of PMMA core/Poly(AN-co-MMA) shell-1/PMMA shell-2 microspheres, prepared by a radical soap-free emulsion polymerization of methylmethacrylate (MMA) and acrylonitrile (AN), was between 400 nm and 500 nm. Microspheres were subjected to melt-spinning at 305 °C, stabilizing in oxygen at 220 °C for 4 h, and finally carbonizing at 1000 °C for 30 min. FE-SEM study of carbonized sample revealed the presence of CNTs arrays on carbon blocks. Similar arrays were observed in a comparative CNTs sample prepared from three-layered microspheres with the pure PAN shells-1 layers. HRTEM showed that the CNTs derived from copolymer microspheres had different structure when compared to the control sample, i.e. CNTs often adhered to each other and contained the internal compartments. The insufficient PMMA shell-2 coating of copolymer microspheres is believed to be a reason for CNTs adhesion. The possible mechanisms of the carbon block formation and the adhesion of CNTs are introduced.     

Production of FAME from acid oil model using immobilized <Emphasis Type="Italic">Candida antarctica</Emphasis> lipase

Acid oil is a by-product in the neutralization step of vegetable oil refining and is an alternative source of biodiesel fuel. A model substrate of acid oil, which is composed of TAG and FFA, was used in experiments on the conversion to FAME by immobilized Candida antarctica lipase. FFA in the mixture of TAG/FFA were efficiently esterified with methanol (MeOH), but the water generated by the esterification significantly inhibited methanolysis of TAG. We thus attempted to convert a mixture of TAG/FFA to FAME by a two-step process comprising methyl esterification of FFA and methanolysis of TAG by immobilized C. antarctica lipase. The first reaction was conducted at 30°C in a mixture of TAG/FFA (1∶1, wt/wt) and 10 wt% MeOH using 0.5 wt% immobilized lipase, resulting in efficient esterification of FFA. The reaction mixture after 24 h was composed of 49.1 wt% TAG, 1.3 wt% FFA, 49.1 wt% FAME, and negligible amounts of DAG and MAG (<0.5 wt%). The reaction mixture was then dehydrated and used as a substrate for the second reaction, which was conducted at 30°C in a solution of the dehydrated mixture and 5.5 wt% MeOH using 6 wt% immobilized lipase. The activity of the lipase increased gradually when the reaction was repeated by transferring the enzyme to a fresh substrate mixture. The activity reached a maximum after 6 cycles, and the content of FAME achieved was >98.5 wt% after a 24-h reaction. The immobilized lipase was very stable in the first-and second-step reactions and could be used for >100 d without significant loss of activity.     

Synthesis of polychloroprene–silica composites by sol‐gel method in the presence of modified polychloroprene containing triethoxysilyl group

Triethoxysilyl‐modified polychloroprene (CR) latex was synthesized by the emulsion copolymerization of 2‐(3‐triethoxysilylpropyl)‐1,3‐butadiene with chloroprene. This latex was mixed with unmodified CR latex and tetraethoxysilane to obtain CR–silica composites by sol‐gel reaction in the latex. SEM observation showed that the silica particles in unvulcanized composites have various diameters ranging from 0.1 to 0.6 μ m, and their size became larger with the decrease of the silica content. Vulcanized CR–silica composites showed that the tensile modulus and tear strength improved with an increase of the amount of modified CR. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1545–1552, 2005     

Design of a Full-Consensus Glutamate Decarboxylase and Its Application to GABA Biosynthesis

Glutamate decarboxylase (GAD) catalyses the decarboxylation of L-glutamate to gamma-aminobutyric acid (GABA). Improvement of the enzymatic properties of GAD is important for the low-cost synthesis of GABA. In this study, utilizing sequences of enzymes homologous with GAD from lactic acid bacteria, highly mutated GADs were designed using sequence-based protein design methods. Two mutated GADs, FcGAD and AncGAD, generated by full-consensus design and ancestral sequence reconstruction, had more desirable properties than native GADs. With respect to thermal stability, the half-life of the designed GADs was about 10 °C higher than that of native GAD. The productivity of FcGAD was considerably higher than those of known GADs; more than 250 mg/L of purified enzyme could be produced in the E. coli expression system. In a production test using 26.4 g of l -glutamate and 3.0 g of resting cells, 17.2 g of GABA could be prepared within one hour, without purification, in a one-pot synthesis.     

Dietary supplementation of gamma-linolenic acid improves skin parameters in subjects with dry skin and mild atopic dermatitis

Disruption of the skin barrier function caused by epidermal hyper-proliferation, results in the skin becoming dry and showing high transepidermal water loss (TEWL). Gamma linolenic acid (GLA) is reportedly efficacious for treating TEWL and epidermal hyper-proliferation. In this study, to elucidate the effect of GLA-rich oil on skin function, GLA-containing food was given to adults with dry skin or mild atopic dermatitis and skin parameters were evaluated. In the results, we recognized beneficial effects on the TEWL index. The efficacy of GLA was also demonstrated to be statistically significant especially in subjects with pro-inflammatory features. The results suggest that the mechanism of improvement of skin barrier has been associated with possible generation of anti-inflammatory metabolites from GLA. The clinical physician also confirmed that none of the subjects showed any noteworthy side effects. GLA-enriched food appears to be safe and to improve skin barrier function in subjects with dry skin conditions and mild atopic dermatitis.     

Preparation of avidin-containing polyelectrolyte microcapsules and their uptake and release properties

Avidin-containing polyelectrolyte microcapsules were prepared by a layer-by-layer deposition technique and uptake and release of biotin-labelled fluorescein (b-FITC) was studied. The polyelectrolyte microcapsules were prepared by coating the surface of calcium carbonate (CaCO₃) microparticles containing avidin-poly(styrene sulfonate) (PSS) conjugate, followed by dissolution of CaCO₃ core in an ethylenediaminetetraacetic acid solution. Release of avidin from the microcapsules was markedly suppressed due to formation of a high molecular weight of avidin-PSS conjugate in the microcapsules. The uptake of b-FITC into the microcapsules was highly enhanced through a strong binding of b-FITC to avidin, as compared to the uptake into avidin-free microcapsules. Release of b-FITC from the microcapsules was accelerated upon addition of biotin, 2-iminobiotin, or lipoic acid in the solution due to the competitive binding of the additives to the binding site of avidin.     

In situ binary sol–gel reaction of various trifunctional alkoxysilane in the silane‐grafted polyolefin matrix and its effect upon the mechanical properties

The vinyltrimethoxysilane‐grafted ethylene‐propylene copolymer/trifunctional methoxysilane (EPR‐g‐VTMS/RTMS) composites were prepared via in situ silica sol–gel reactions. Five trifunctional methoxysilane compounds (n‐hexyltrimethoxysilane, n‐decyltrimethoxysilane, n‐tetradecyltrimethoxysilane, n‐octadecyltrimethoxysilane, and phenyltrimethoxysilane) have been selected for this study. The water‐cross‐linked EPR‐g‐VTMS/RTMS composites were characterized by attenuated total reflectance‐Fourier transform infrared spectroscopy, gel content, solid‐state ²⁹Si CP/MAS NMR, wide‐angle x‐ray scattering, tensile strength, and field emission scanning electron microscopy measurements. The type of RTMS additive has a substantial influence on the nature of siloxane band networks and eventually the mechanical tensile properties. This finding suggests that the interaction and/or entanglement between the EPR‐g‐VTMS matrix and the substituent of the RTMS additives are crucial for the modifying mechanical properties. Moreover, for the water‐cross‐linked EPR‐g‐VTMS/CnTMS (n = 6, 10, 14, and 18) composites, the joint evidence provided by attenuated total reflectance‐Fourier transform infrared spectroscopy, ²⁹Si CP/MAS NMR, and wide‐angle x‐ray scattering results suggested the formation of ladder‐type poly(n‐alkyl silsesquioxane)s and the presence of the highly ordered structure with a thickness equal to the length of two n‐alkyl groups in all‐trans conformation. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Potential bile acid metabolites. 24. An efficient synthesis of carboxyl-linked glucosides and their chemical properties

A facile and efficient synthesis of the carboxyl-linked glucosides of bile acids is described. Direct esterification of unprotected bile acids with 2,3,4,6-tetra-O-benzyl-d-glucopyranose in pyridine in the presence of 2-chloro-1,3,5-trinitrobenzene as a coupling agent afforded a mixture of the α- and β-anomers (ca. 1∶3) of the 1-O-acyl-d-glucoside benzyl ethers of bile acids, which was separated effectively on a C₁₈ reversedphase chromatography column (isolated yields of α- and β-anomers are 4–9% and 12–19%, respectively). Subsequent hydrogenolysis of the α- and β-acyl glucoside benzyl ethers on a 10% Pd−C catalyst in acetic acid/methanol/EtOAc (1∶2∶2, by vol) at 35°C under atmospheric pressure gave the corresponding free esters in good yields (79–89%). Chemical specificities such as facile hydrolysis and transesterification of the acyl glucosides in various solvents were also discussed.     

deNOx Performance and Reaction Mechanism of the Di-Air System

The detailed reaction mechanism of Di-Air, which showed the unprecedented high deNO_x performance at high temperature conditions, was studied in this work. Since the Di-Air phenomenon occurs with continuous short pulse injections of hydrocarbons over NSR (NO_x storage and reduction) catalyst, this study focused on the specific function of HC as an effective reductant for NO_x reduction reaction. As a first step, the deNO_x performance was compared with three different reductant gases including CO, H₂ and C₃H₆ in a modified synthetic gas bench equipped with a gas injector which enables continuous small amount of injections. At inlet gas temperature of 450 °C C₃H₆ showed the best deNO_x performance whereas H₂ was the best at 150 °C. Moreover the result of temperature programmed desorption showed that intermediate species represented by –NCO (isocyanates) produced from C₃H₆ was thermally more stable than that produced from CO. These results confirmed that the injected HC reacts with adsorbed NO_x on NSR catalyst generating thermally stable intermediates, which could contribute the high deNO_x performance at high temperature conditions.