Stereocontrolled synthesis of 8,11-dideoxytetrodotoxin,unnatural analogue of puffer fish toxin

[structure: see text] 8,11-Dideoxytetrodotoxin, an unnatural tetrodotoxin analogue, was synthesized in a highly stereoselective manner from a common intermediate in our synthetic studies on tetrodotoxin. The synthesis features neighboring group participation of trichloroacetamide for stereoselective hydroxylation, protection of ortho ester, and guanidine installation with Boc-protected isothiourea.     

Isolation and structure elucidation of genuine oat phytoalexin,avenalumin I

The major phytoalexin from oat leaves has been identified as 2-[2-(4-hydroxyphenyDethenyl] -6-hydroxy-4H-3,1-benzoxazin-4-one ($\text{A}$).     

Homogeneity of a Distance-Regular Graph Which Supports a Spin Model

A spin model is a square matrix that encodes the basic data for a statistical mechanical construction of link invariants due to V.F.R. Jones. Every spin model W is contained in a canonical Bose-Mesner algebra (W). In this paper we study the distance-regular graphs whose Bose-Mesner algebra satisfies W (W). Suppose W has at least three distinct entries. We show that is 1-homogeneous and that the first and the last subconstituents of are strongly regular and distance-regular, respectively.     

Emulsion Combustion and Flame Spray Synthesis of Zinc Oxide/Silica Particles

Two flame spray methods, emulsion combustion method (ECM) and flame spray pyrolysis (FSP), were compared for synthesis of pure and mixed SiO₂ and ZnO nanoparticles. The effect of silicon precursor was investigated using liquid hexamethyldisiloxane (HMDSO) or SiO₂ sol, while for ZnO zinc acetate (ZA) was used. Gas phase reaction took place when using HMDSO as Si precursor, forming nanoparticles, whereas the SiO₂ sol used as Si source was not evaporated in the flame, creating large aggregates of the sol particles (e.g. 1 m). The FSP of ZA produced ZnO homogeneous nanoparticles. Lower flame temperatures in ECM than in FSP resulted in mixed gas and liquid phase reaction, forming ZnO particles with inhomogeneous sizes. The FSP of HMDSO and ZA led to intimate gas-phase mixing of Zn and Si, suppressing each other's particle growth, forming nanoparticles of 19 nm in BET-equivalent average primary particle diameter. Nucleation of ZnO and SiO₂ occurred independently by ECM of HMDSO and ZA as well as by FSP of the SiO₂ sol and ZA, creating a ZnO and SiO₂ mixture. The reaction of ZnO with SiO₂ was likely to be enhanced by ECM of the SiO₂ sol and ZA where both Zn and Si species were not evaporated completely, resulting in ZnO, -willemite and Zn_1.7SiO₄ mixed phase.     

Improved surface morphology of flow-modulated MOVPE grown AIN on sapphire using thin medium-temperature AIN buffer layer

High-temperature (HT) AIN films were grown on (0 0 0 1) sapphire by low-pressure flow-modulated (FM) metal organic vapor phase epitaxy (MOVPE) with and without inserting a thin medium-temperature (MT) AIN layer. To suppress parasitic reactions between the sources of trimethylaluminum (TMA) and ammonia (NH₃), TMA and NH₃ was introduced to the reactor of MOVPE by alternating supply way. Surface morphology and crystalline quality were characterized by a scanning electronic microscopy (SEM), atomic force microscopy (AFM) and X-ray rocking curve (XRC) measurements of (0 0 0 2) and (10-12) diffractions. The AFM and SEM measurements indicated that the thin MT-AIN layer had a strong influence on the surface morphology of the HT-AIN films. The surface morphology became quite smooth by inserting the thin MT-AIN layer and surface RMS roughness values were 0.84 nm and 13.4 nm for the HT-AIN films with and without inserting the thin MT-AIN buffer layer, respectively. By etching the samples in aqueous KOH solution, it was found that the polarity of AIN films was different, the HT-AIN film with the thin MT-AIN layer could not be etched, indicating that the film had an Al-polar surface; however, the film without the MT-AIN layer was etched, which was explained that that film had a N- or mixed-polar surface. The mechanism for the origin of the different polarity of HT-AIN with and without the thin MT-AIN layer was proposed and discussed in detail.     

Growth of undoped and Zn-doped GaN nanowires

Undoped and Zn-doped GaN nanowires were synthesized by chemical vapor deposition (CVD), and the effects of substrates, catalysts and precursors were studied. A high density of GaN nanowires was obtained. The diameter of GaN nanowires ranged from 20 nm to several hundreds of nm, and their length was about several tens of μm. The growth mechanism of GaN nanowires was discussed using a vapor–liquid–solid (VLS) model. Furthermore, room-temperature cathodoluminescence spectra of undoped and Zn-doped GaN nanowires showed emission peaks at 364 and 420 nm, respectively.     

Chelation of cadmium ions by phytochelatin synthase: role of the cysteine-rich C-terminal.

The interactions between Cd(2+) and the C-terminal region of phytochelatin (PC) synthase using recombinant wild-type and mutant PC synthase were studied. We show that site-directed mutagenesis of Cys residues at C(358)C(359)XXXC(363)XXC(366) motif decreases the number of Cd(2+) and other heavy metal ions interacting with the enzyme, and that the motif binds the metals discriminatingly. The optimum binding ratio of PC synthase to Cd(2+) was also determined. The findings indicate that Cys exists as a free SH residue and that it is involved in the regulation of PC enzyme activity by transferring the metals into closer proximity with the catalytic domain. These results are important in understanding heavy metal detoxification mechanisms in higher plants, a step towards phytoremediated-applications.     

Deracemization of 1,2-diol monotosylate derivatives by a combination of enzymatic hydrolysis with the Mitsunobu inversion using polymer-bound triphenylphosphine

The deracemization of 1,2-diol monotosylate derivatives is achieved by the sequential combination of enzymatic hydrolysis and Mitsunobu inversion using a polymer-bound triphenylphosphine. After the lipase-catalysed hydrolysis of the racemic 2-acetoxyhexyl tosylate, the subsequent Mitsunobu reaction without separation causes an inversion of the resulting (R)-alcohol to give the (S)-enantiomer of the acetate as a single product. In particular, the reaction using the polymer-bound triphenylphosphine also proceeds smoothly, and the product is easily separated by filtration from the polymer-bound reagent and its by-products. This deracemization process is applicable to the preparation of several optically active 1,2-diol monotosylates.     

Synthesis and characterization of transparent silica-based aerogels using methyltrimethoxysilane precursor

Silica-based aerogels with high transparency and high bending strength were prepared using methyltrimethoxysilane and non-ionic surfactant under supercritical drying condition of CO₂. Non-ionic surfactant, ethylene oxide/propylene oxide block copolymer, was appropriate to form the three dimensional-connected thinner fibers of silica skeletons, which was extruded by soaking the wet gel in hot water at 50 °C, resulting in the formation of porous materials having small pores with narrow size distribution. The transparency of aerogels increased with decreasing the pore size, reaching to higher than 65 and 88% at 400 and 600 nm wavelength, respectively, for 10 mm thickness of sample. The formation of fiber skeletons were discussed using small angle X-ray scattering experiments.     

Determination of Cu, Pb, Fe, and Zn in plant component polymers of a hyperaccumulating plant.

Phytoremediation is an innovative technology that utilizes the natural properties of plants to remediate hazardous waste sites. For more cost-effective phytoremediation, it is important to utilize a hyperaccumulating plant after phytoremediation, i.e. the recovery of valuable metals and the production of useful materials. In this work, the determination of metals in plant component polymers in a fern, Athyrium yokoscense, as a hyper-accumulating plant was established using steam explosion, Wayman's extraction method, and ICP emission spectrometry. After A. yokoscense plants were treated by steam explosion, the steam-exploded A. yokoscense were separated into four plant component polymers, ie. water-soluble material fraction, holocellulose fraction, methanol-soluble lignin fraction, and residual lignin fraction. The concentrations of Cu, Pb, Fe, and Zn in these plant component polymers and the dry weights of plant component polymers were measured. These analytical process determining metals in the plants will contribute to not only the evaluation and the efforts of phytoremediation using a hyperaccumulating plant, but also to the development of more effective phytoremediation.