Thraustochytrid as a potential source of carotenoids

Thraustochytrids, marine protists whose dominant genera are Thraustochytrium and Schizochytrium, belong to the kingdom Chromista and are known as an industrial source of DHA. We describe here that thraustochytrid strain KH105, isolated as a DHA producer, also accumulates significant levels of β-carotene and xanthophylls including canthaxanthin and astaxanthin. A4-d cultivation using a medium composed of 10% glucose and less than 0.3% of nitrogen sources in a half-concentration of seawater gave an astaxanthin production up to 6.1 mg/L, and canthaxanthin content reached more than 10 mg/L under conditions where a higher concentration of nitrogen sources (6%) was employed. It might be advantageous in mass production systems for these carotenoids to be extracted readily by simply suspending the cells with organic solvents such as acetone and chloroform. Analyses on the morphological and life history features of the KH105 strain revealed that it belongs to the genus Schizochytrium. This particular species of thraustochytrids is thus considered to be a promising source of xanthophylls as well as DHA for use in the food industry.     

Evidence for the formation of interpenetrated spherulites in poly(butylene succinate-co-butylene carbonate)/poly(l-lactic acid) blends investigated by atomic force microscopy

The spherulitic morphology in poly(butylene succinate-co-butylene carbonate)/poly(l-lactic acid) (PEC/PLLA) blends was investigated by atomic force microscopy (AFM) to obtain direct evidence for the formation of interpenetrated spherulites (IPS), where the spherulites of PEC penetrate into PLLA spherulites. The observation actually revealed that PEC crystals penetrated into interfibrillar regions of edge-on lamellae in a PLLA spherulite. The penetration process was also investigated by AFM with a temperature controller. An edge-on PLLA lamella or a fibril that ran nearly perpendicular to the growth direction of a PEC spherulite obstructed the growth of PEC spherulite. The PEC crystals filled the blocked space after growing around the PLLA lamella. These results showed that the spherulites of PEC and PLLA grow on the same layer instead of forming a layered structure of two spherulites. All the results supported the formation of IPS.     

Interfacial shear strength of C/C composites

Fiber-bundle push-out, single-fiber push-in, and single-fiber push-out tests were conducted in order to examine the applicability of these methods for determining the interfacial shear strength of carbon-carbon composites. The fiber-bundle push-out test resulted mostly in fractures along the fiber/matrix interface but created a small amount of fractures in the matrix. Hence, the evaluated strength was regarded as an approximate value. In order to precisely evaluate the interfacial strength, push-in and push-out tests for a single fiber were performed using a micro-Vickers indentation tester. In these tests, the load has to be placed within a target fiber, and the indentation should not extend to the matrix. This condition restricted the load that could be applied to a carbon fiber. Within this limit, a single carbon fiber could not be pushed-in. For the sake of load reduction, single-fiber push-out tests were conducted using thin specimens. The thickness appropriate for a single-fiber push-out specimen was estimated based on the interfacial shear strength obtained by the bundle push-out tests. Below this thickness, single-fiber push-out tests could be successfully performed.     

Characterization and CO2 sorption properties of poly[methacryloxypropylheptacyclopentyl‐T8‐silsesquioxane‐ co‐3‐methacryloxypropyltris(trimethylsiloxy)silane]

Poly[methacryloxypropylheptacyclopentyl‐T8‐silsesquioxane (MAPOSS)‐co‐3‐methacryloxypropyltris(trimethylsiloxy)silane (SiMA)] was synthesized through free radical polymerization. The physical and carbon dioxide (CO₂) sorption properties of the copolymer membranes were investigated in terms of the MAPOSS content. As the MAPOSS content increases, the membrane density increased, suggesting a decrease in the fractional free volume. In addition, the thermal stability was improved with increasing the MAPOSS content. These are because of the polyhedraloligomericilsesquioxane (POSS) units that restrict the high mobility of poly(SiMA) segments. The glass transition temperature, T_g of the copolymers was single T_g based on the differential scanning calorimetry, suggesting that the copolymers were random and not phase separation. Based on the CO₂ sorption measurement, the POSS units play a role in reducing Henry's dissolution by suppressing the mobility of the poly(SiMA) component, while POSS units increase the nonequilibrium excess free volume, which contributes to the Langmuir dissolution. Based on these results, the introduction of MAPOSS unit is one of the effective ways to improved the thermal stability and CO₂ sorption property due to the enhancement of the polymer rigidity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

ADDUCT FORMATION OF β-DIKETONATO LANTHANOIDS(III) WITH CARBOXYLIC ACIDS HAVING HYDROXYL AND METHOXYL GROUPS

Adduct formation of 2-thenoyltrifluoroacetonato(tta) lantha-num(III), europium(III), and ytterbium(I II) with α-pheny 1 1 actic, α-methoxy phenyl acetic, salicylic, and o-methoxy benzoic acids in chloroform has been studied by solvent extraction technique. It has been found that 1anthanoid(111) chelates form more stable adducts with these carboxylic acids in the sequence: Yb(tta)₃ < Eu(tta) ₃ < La(tta) ₃. The adduct formation constants as well as the separation factors obtained as the ratio of the constants between a pair of metals are the largest for α-phenyl lactic acid among these acids. The characteristics with α-phenyl 1actic acid would be caused by the action as bidentate unlike benzoic acid derivatives which work as monodentates owing to the internal complexa-tion through hydrogen bonding.     

Pd-catalyzed hydrosilylation polymerization of a dihydrosilane with diyne/triyne mixed systems affording crosslinked silylene-divinylene polymers and their properties

Treatment of a dihydrosilane (methylphenylsilane, 1) with mixtures of a diyne (p- or m-diethynylbenzene, 2a or 2b) and a triyne (1,3,5-triethynylbenzene, 3a or B,B′,B″-triethynyl-N,N′,N″-trimethylborazine, 3b; 1:2:3=100:95:5, 100:90:10, 100:80:20) in the presence of Pd-PCy₃ (Cy=cyclohexyl) catalyst gave new crosslinked silylenedivinylene polycarbosilanes. In TGA the resulting crosslinked polymers tended to show higher Td₅ values and higher char yields than the corresponding linear polymers. On the other hand, UV/vis absorption spectra of the crosslinked polymers obtained in the reactions of 2a or 2b with 3a exhibited increased broad peaks around 390 nm for 2a or 360 nm for 2b. Coincidently, their fluorescence spectra showed significant increase of the emission peaks in 400-550 nm. The crosslinked polymer derived from 2a and 3b, however, showed decrease of the absorption peak around 390 nm and profound depression of fluorescence peaks in 400-550 nm.     

Alteration of substrate specificity of cholesterol oxidase from Streptomyces sp. by site-directed mutagenesis

Despite the structural similarities between cholesterol oxidasefrom Streptomyces and that from Brevibacterium, both enzymesexhibit different characteristics, such as catalytic activity,optimum pH and temperature. In attempts to define the molecularbasis of differences in catalytic activity or stability, substitutionsat six amino acid residues were introduced into cholesteroloxidase using site-directed mutagenesis of its gene. The aminoacid substitutions chosen were based on structural comparisonsof cholesterol oxidases from Streptomyces and Brevibacterium.Seven mutant enzymes were constructed with the following aminoacid substitutions: L117P, L119A, L119F, V145Q, Q286R, P357Nand S379T. All the mutant enzymes exhibited activity with theexception of that with the L117P mutation. The resulting V145Qmutant enzyme has low activities for all substrates examinedand the S379T mutant enzyme showed markedly altered substratespecificity compared with the wild-type enzyme. To evaluatethe role of V145 and S379 residues in the reaction, mutantswith two additional substitutions in V145 and four in S379 wereconstructed. The mutant enzymes created by the replacement ofV145 by Asp and Glu had much lower catalytic efficiency forcholesterol and pregnenolone as substrates than the wild-typeenzyme. From previous studies and this study, the V145 residueseems to be important for the stability and substrate bindingof the cholesterol oxidase. In contrast, the catalytic efficiencies(k_cat/K_m) of the S379T mutant enzyme for cholesterol and pregnenolonewere 1.8- and 6.0-fold higher, respectively, than those of thewild-type enzyme. The enhanced catalytic efficiency of the S379Tmutant enzyme for pregnenolone was due to a slightly high k_catvalue and a low K_m value. These findings will provide severalideas for the design of more powerful enzymes that can be appliedto clinical determination of serum cholesterol levels and assterol probes.     

Synthesis of geranyl acetate by lipase entrap-immobilized in cellulose acetate-TiO2 gel fiber

Lipase from Candida antarctica was entrap-immobilized in cellulose acetate-TiO₂ gel fiber (fiber-immobilized lipase) by the sol-gel method. Syntheses of geranyl acetate and citronellyl acetate catalyzed by the fiber-immobilized lipase were studied in heptane solution. Conversions reached 85% for geranyl acetate after 100 h, and 75% for citronellyl acetate after 80 h, and these values were almost identical to those for syntheses catalyzed by nonimmobilized lipase, although the reaction rate was decreased by immobilization. Compared to those of the non-immobilized lipase and commercially available immobilized lipase (Novozyme 435), the activity of the fiber-immobilized lipase was not particularly affected by changes in reaction conditions, such as bulk water content or substrate concentration. The fiber-immobilized lipase retained a high level of activity after six repeated uses, and almost no enzyme leakage from fiber was observed. However, the reactivity of the fiber-immobilized lipase was depressed at higher temperature, presumably due to dehydration by thermal contraction of the gel fiber.     

Acid-dyeable acrylic fibres copolymerised with amino alkyl methacrylates for differential cross-dyeing

The equilibrium adsorption of acid dyes on acrylic fibres copolymerised with dimethyl amino ethyl methacrylate has been investigated. A typical characteristic of this type of fibre is its excellent stable dyeability over a wide pH range. This is due to the strong basicity of alkylamino groups in the copolymerised component, which makes it possible to dye the fibre thoroughly even in a weakly acidic dyebath using a normal dyeing processes of acrylic fibre with cationic dye. Consequently it is useful for differential cross-dyeing in a single dyebath.