Water activity-adjusted enzymatic partial hydrolysis of phospholipids to concentrate polyunsaturated fatty acids

Selective partial hydrolyses of egg yolk phospholipid and squid skin phospholipid were carried out. By keeping the water activity (a _w) of Lipozyme IM at an intermediate level, it was easy to concentrate docosahexaenoic acid (DHA). It was also possible to concentrate both DHA and arachidonic acid (AA) simultaneously to a certain level under this a _w range. However, it was impossible to concentrate AA alone when DHA was present. Though there is a limitation in concentrating AA exclusively, the proposed a _w-adjusted hydrolytic reaction is a promising way for preparing phospholipids rich in DHA.     

Synthesis and Characterization of Cellulose Carbamates Having α-Amino Acid Moieties

Summary The reaction of cellulose with N-carbonyl α-amino acid ester 1 leading to cellulose carbamate 2 was carried out in N,N-dimethylacetamide at 100 °C. For N-carbonyl L-leucine ethyl ester (1a), the degree of the carbamate substituent (DS) in 2a was 2.5 for [1a]/[glucose units in cellulose] = 3.0 and reached ca. 3.0 for [1a]/[glucose units in cellulose] = 4.0. Cellulose carbamate 2a was highly soluble in not only aprotic polar solvents but also other organic solvents such as ethyl ether and methyl alcohol. The chiral discrimination ability of 2a was higher than those of the cellulose carbamates having L-phenylalanine and L-aspartic acid moieties.     

Preparation and Properties of Carbon/Zeolite Composites with Corrugated Structure

Composites of carbon/zeolite with corrugated structures were prepared by carbonization, steam activation and/or hydrothermal treatment of corrugated paper. No zeolite formation resulted from conventional hydrothermal treatment of the carbonized and activated samples in NaOH solution but zeolite Na P1 was formed by addition of silica to the solution. By contrast, zeolites Na P1 and Na A were formed by the in-situ crystallization method (hydrothermal treatment of solid samples impregnated with NaOH solution). With higher impregnating NaOH concentrations, longer reaction times and higher reaction temperatures, the products changed to sodalite- and cancrinite-type compounds. Hydrothermal treatment was effective in increasing the specific surface area of the products by the formation of zeolite from amorphous calcium aluminosilicate, and also increased the mechanical strength by gluing together the carbon fibers in the samples. The resulting samples showed enhanced adsorption for polar molecules such as ammonia, water vapor and methanol due to the formation of composites of activated carbon with hydrophilic zeolites.     

Manipulation of single-walled carbon nanotubes with a tweezers tip

We demonstrate that a tweezers tip can be directly used to manipulate single-walled carbon nanotube (SWCNT) films and individual SWCNTs (or bundles). Specifically, we can align, bend, and even cut SWCNTs on the substrates where they are grown. With this manipulation technique, we are able to control the position, direction, and length of SWCNTs and fabricate complex patterns. Because of the large size of the tweezers tip, long SWCNTs (hundreds of micrometers in length) are found to be critical for the realization of such manipulations. This finding would contribute to the property studies on nanotubes and the fabrication of nanodevices.     

Comparing guiding track requirements for myosin- and kinesin-powered molecular shuttles

The design of nanoscale transport systems utilizing motor proteins as engines has advanced rapidly. Here, actin/myosin- and microtubule/kinesin-based molecular shuttles are compared with respect to their requirements for track designs. To this end, the trajectory persistence length of actin filaments gliding on myosin-coated surfaces has been experimentally determined to be equal to 8.8 +/- 2 microm. This measurement complements an earlier determination of the trajectory persistence length of microtubules gliding on kinesin-coated surfaces and enables a comparison of the accessible track designs for kinesin and myosin motor-powered systems. Despite the 200-fold smaller stiffness of actin filaments compared to that of microtubules, the dimensions of myosin tracks for actin filaments have to be quite similar to the dimensions of kinesin tracks for microtubules (radii larger than 200 nm and widths smaller than 0.9 microm compared to 600 nm and 19 microm). The difference in gliding speed is shown to require additional consideration in the design of track modules.     

Earth‐Abundant and Durable Nanoporous Catalyst for Exhaust‐Gas Conversion

Precious metals (Pt and Pd) and rare earth elements (Ce in the form of CeO₂) are typical materials for heterogeneous exhaust‐gas catalysts in automotive systems. However, their limited resources and high market‐driven prices are principal issues in realizing the path toward a more sustainable society. In this regard, herein, a nanoporous NiCuMnO catalyst, which is both abundant and durable, is synthesized by one‐step free dealloying. The catalyst thus developed exhibits catalytic activity and durability for NO reduction and CO oxidation. Microstructure characterization indicates a distinct structural feature: catalytically active Cu/CuO regions are tangled with a stable nanoporous NiMnO network after activation. The results obtained by in situ transmission electron microscopy during NO reduction clearly capture the unique reaction‐induced self‐transformation of the nanostructure. This finding can possibly pave the way for the design of new catalysts for the conversion of exhaust gas based on the element strategy.     

Bioactivity of CaSiO<Subscript>3</Subscript>/poly-lactic acid (PLA) composites prepared by various surface loading methods of CaSiO<Subscript>3</Subscript> powder

Mixing bioactive ceramic powders with polymers is an effective method for generating bioactivity to the polymer-matrix composites but it is necessary to incorporate up to 40 vol% of bioactive ceramic powder. However, such a high mixing ratio offsets the advantages of the flexibility and formability of polymer matrix and it would be highly advantageous to lower the mixing ratio. Since surface loading of ceramic powders in the polymer is thought to be an effective way of reducing the mixing ratio of the ceramic powder while maintaining bioactive activity, CaSiO₃/poly-lactic acid (PLA) composites were prepared by three methods; (1) casting, (2) spin coating and (3) hot pressing. In methods (1) and (2), a suspension was prepared by dissolving PLA in chloroform and dispersing CaSiO₃ powder in it. The suspension was cast and dried to form a film in the case of method (1) while it was spin-coated on a PLA substrate in method (2). In method (3), CaSiO₃ powder was surface loaded on to a PLA substrate by hot pressing. The bioactivity of these samples was investigated in vitro using simulated body fluid (SBF). Apatite formation was not observed in the samples prepared by method (1) but some apatite formation was achieved by mixing polyethylene glycol (PEG) with the PLA, producing a porous polymer matrix. In method (2), apatite was clearly observed after soaking for 7 days. Enhanced apatite formation was observed in method (3), the thickness of the resulting apatite layers becoming about 20 μm after soaking for 14 days. Since the amount of CaSiO₃ powder used in these samples was only ≤0.4 vol%, it is concluded that this preparation method is very effective in generating bioactivity in polymer-matrix composites by loading with only very small amounts of ceramic powder.     

Encapsulation-release property of amphiphilic hyperbranched d-glucan as a unimolecular reverse micelle

The synthesis of a novel unimolecular reverse micelle, the hyperbranched d-glucan carbamate (3), was accomplished through the carbamation reaction of the hyperbranched d-glucan (1) with the N-carbonyl l-leucine ethyl ester (2) in pyridine at 100 °C. Polymer 3 was soluble in a large variety of organic solvents, such as methanol, acetone, chloroform, and ethyl acetate, and insoluble in water, which remarkably differed from the solubility of 1. The degree of carbamate substitution (DS) for 3 was controlled by the feed rate of 2, and the DS values were in the range of 46.0-93.7%. Polymer 3 possessed the encapsulation ability for water-soluble molecules, such as rose bengal, thymol blue, and alizarin yellow in chloroform, and the encapsulation ability depended on the hydrophilicity of 3 and the molecular size of the dye. The rose bengal (RB) encapsulated polymer (RB/3) showed a slow release from the RB/3 system into water at neutral pH, while the release rate was significantly accelerated by the hydrolysis of the hydrophobic polymer shell under basic conditions.     

A unimolecular nanocapsule: Encapsulation property of amphiphilic polymer based on hyperbranched polythreitol

Hyperbranched polythreitol (1) with different molecular weights (M_w,SLS: 1.18 × 10⁴ and 4.79 × 10⁴) was reacted with trityl chloride in DMF to afford a novel amphiphilic polymer (2) consisting of 1 as the hydrophilic core and the trityl groups as the hydrophobic shell. Compound 2 was tested for its ability to act as a unimolecular nanocapsule toward the water-soluble dye, rose bengal (RB). Their encapsulation and release properties were also evaluated by comparison with the degree of substitution (DS) of the trityl groups, i.e., the hydrophobic shell density. The polymers were found to have very good unimolecular nanocapsule characteristics even at extremely low concentrations. The average number of RBs per polymer molecule depended on the hydrophilic core size and the hydrophobic shell density. The increasing DS value led to a decrease in the encapsulated amount due to the decrease in the hydrophilic core space, while the low DS value (less than ca. 20 mol%) led to a destabilization as a unimolecular nanocapsule and a lower encapsulation ability. In particular, 2 with ca. 23% DS value showed an efficient encapsulation. Based on a release test of the RB-loaded unimolecular nanocapsules, the polymers showed a high RB-holding ability in water.     

Carbon nanotube growth from semiconductor nanoparticles

Nanoscale metal catalysts have been indispensable for carbon nanotube (CNT) synthesis by chemical vapor deposition (CVD). We show that even semiconductor nanoparicles of SiC, Ge, and Si produce single-walled and double-walled CNTs in CVD with ethanol. This implies that nanosize structures might act as a template for the formation of CNT caps composed of five- and six-membered rings. Providing a template for cap formation is the essential role of the catalysts.