Isolation and structures of new cyclomyltaylane and ent-chamigrane-type sesquiterpenoids from the liverwort Reboulia hemishaerica and their biotransformation by the fungus Aspergillus niger

Reboulia hemisphaerica, the thalloid liverwort, contained four new cyclomyltaylane- and two new ent-beta-chamigrane-type sesquiterpenoids of which the absolute stereostructures were established by a combination of two-dimensional NMR spectroscopy, X-ray crystallographic analysis, and the modified Mosher's method. Cyclomyltaylan-5alpha-ol and ent-beta-chamigren-1alpha-ol were biotransformed by the fungus Aspergillus niger to afford new oxygenated matabolites. Their structures were also elucidated in the same manner as described above.     

2R-regenerative all-optical switch based on a highly nonlinear holey fiber

We report the fabrication of a highly nonlinear holey fiber made from pure silica with an effective area of just ~2.8mu;m(2) at 1550 nm. We believe this to be the smallest effective area yet measured for a holey fiber at 1550 nm. We also report the operation of a 2R regenerative optical switch based on just 3.3 m of the fiber that is shown to have 30 times the nonlinear figure of merit of previous devices based on dispersion-shifted fiber.     

On central critical values of the degree four L-functions for {\text {GSp}}\left( 4\right) : a simple trace formula

We establish a simple relative trace formula for ${\text {GSp}}(4)$ and inner forms with respect to Bessel subgroups to obtain a certain Bessel identity. From such an identity, one can hope to prove a formula relating central values of degree four spinor $L$ -functions to squares of Bessel periods as conjectured by Böcherer. Under some local assumptions, we obtain nonvanishing results, i.e., a global Gross–Prasad conjecture for $(\text {SO}(5),\text {SO}(2))$ .     

Dose distribution of carbon ions in air assessed using imaging plates and ionization chamber

A system to expose biological specimens to medium-energy (2.6–6.0  MeV/u) irradiation has been developed at the NIRS-HIMAC. In order to determine the beam energy or LET at the irradiation position in air, the dose distribution for 6.0  MeV/u carbon beam has been obtained using a secondary electron monitor and a flat-type ionization chamber by using air as the energy absorber. Imaging plates were applied to assess the beam profile distribution. The intensity of photo-stimulated luminescence (PSL) was found to be almost proportional to the energy deposited within the sensitive layer of the imaging plate. It has been confirmed that a uniform irradiation field can be produced (about ±5% within 20 mm in diameter) at low-intensity exposure from 10¹ to . Long-term beam stability in the low-intensity condition has also been demonstrated. As a consequence, the methodology for uniform, stable and low-intensity beam exposure has been established, and the continuously variable linear energy transfer (LET) values have also been obtained by changing the distance from the endcap of beamport, for biological studies.     

Determining sulfamonomethoxine and its acetyl/hydroxyl metabolites in chicken plasma under organic solvent-free conditions

A quantitative technique is described for a sample preparation followed by high performance liquid chromatography method for the simultaneous determination of sulfamonomethoxine and its metabolites, N ⁴-acetyl SMM and 2,6-dihydroxy SMM, in chicken plasma. The average recoveries, analytical total time, and limits of quantitation were ≥80% (relative standard deviations (SD) ≤6%), <30 min sample-1 (12 samples in 2 h), and ≤0.09 μg ml⁻¹, respectively. The procedure, performed under 100% aqueous conditions, uses no organic solvents and toxic reagents at all and is, therefore, harmless to the environment and humans.      

Fast and facile synthesis of silica coated silver nanoparticles by microwave irradiation

A novel, fast and facile microwave technique has been developed for preparing monodispersed silica coated silver (Ag@SiO(2)) nanoparticles. Without using any other surface coupling agents such as 3-aminopropyltrimethoxysilane (APS) or polymer such as polyvinyl pyrrolidone (PVP), Ag@SiO(2) nanoparticles could be easily prepared by microwave irradiation of a mixture of colloidal silver nanoparticles, tetraethoxysilane (TEOS) and catalyst for only 2 min. The thickness of silica shell could be conveniently controlled in the range of few nanometers (nm) to 80 nm by changing the concentration of TEOS. Transmission electron microscopy (TEM) and UV-visible spectroscopy were employed to characterize the morphology and optical properties of the prepared Ag@SiO(2) nanoparticles, respectively. The prepared Ag@SiO(2) nanoparticles exhibited a change in surface plasmon absorption depending on the silica thickness. Compared to the conventional techniques based on St?ber method, which need 4-24 h for silica coating of Ag nanoparticles, this new technique is capable of synthesizing monodispersed, uniform and single core containing Ag@SiO(2) nanoparticles within very short reaction time. In addition, straightforward surface functionalization of the prepared Ag@SiO(2) nanoparticles with desired functional groups was performed to make the particles useful for many applications. The components of surface functionalized nanoparticles were examined by Fourier transform infrared (FT-IR) spectroscopy, zeta potential measurements and X-ray photoelectron spectroscopy (XPS).     

On the Dual Mode of Aldol Cyclization of Bicyclo-[4.3.1] Decane-3,8-Dione: A Novel,Efficient Entry into the Isotwistanone System

Isotwistanones have been highlighted since their use in the sesquiterpene syntheses.¹ Begley and coworkers reported a new access to this system via the postulated aldol cyclization of bicyclo [4.3.1]decane-2, 7-dione.² We have found another novel path of a similar mode.     

Biotransformation of aristolane- and 2,3-secoaromadendrane-type sesquiterpenoids having a 1,1-dimethylcyclopropane ring by Chlorella fusca var. vacuolata, mucor species, and Aspergillus niger

Biotransformation of the aristolane-type sesquiterpene hydrocarbon (+)-1(10)-aristolene (1) from the crude drug Nardostachys chinensis and of the 2,3-secoaromadendrane-type sesquiterpene lactone plagiochilide (2) from the liverwort Plagiochila fruticosa by three microorganisms, Chlorella fusca var. vacuolata, Mucor species, and Aspergillus niger was investigated. C. fusca var. vacuolata and Mucor sp. introduced oxygen function into the cyclohexane ring of aristolene while A. niger oxidized stereoselectively one methyl of the 1,1-dimethyl group on the cyclopropane ring of aristolanes and 2,3-secoaromadendrane to give C-12 primary alcohol and C-12 carboxylic acid. The possible metabolic pathway of the formation of new metabolites is discussed. The stereostructures of new metabolites were established by a combination of NMR spectroscopy including HMBC and NOESY, X-ray crystallographic analysis, and chemical reaction.     

Efficient stereocontrolled synthesis of sphingadienine derivatives

Sphinga-4,8-dienines, principal long-chain bases of glycolipids in plants and fungi, were efficiently synthesized from l-serine. Hydrozirconation of pentadec-5-en-1-ynes followed by ZnBr₂-catalyzed addition to Garner's aldehyde afforded protected sphinga-4,8-dienines stereoselectively. The (2S,3R,4E,8E)-9-methyl-sphingadienine derivative was then coupled with 2(R)-acetoxypalmitic acid derivative prepared via asymmetric dihydroxylation to give a protected ceramide, which was converted into the corresponding glucocerebroside in two steps.     

Polymer adsorption on fine particles; the effects of particle size and its stability

The effects of particle size on polyacrylamide (PAAm,M _w =59×10⁴, 500×10⁴) adsorption were investigated using a series of well-characterized hematite (-Fe₂O₃) dispersions. The -Fe₂O₃ particles with highly monodisperse and nearly spherical shape ranged in radius from 23 nm to 300 nm. the maximum amount of PAAm adsorption (M _m ) in each system, showed a steady increase with decreasing particle radius and was influenced strongly by particle concentrations in the medium. Furthermore, it was realized that the diameter of -Fe₂O₃ particles after treatment with PAAm under different particle concentrations decreased with increasing particle concentration. The relation between particle concentration in the medium and particle size after treatment was also influenced by the medium pH, i.e., at the medium pH close to the isoelectric point of -Fe₂O₃ particles (pH^o=9.2), the particle size after treatment increased with increasing particle concentration. All these results suggest that in the system of ultra-fine particles, the mixing process between particle-particle and polymerparticle will play an important role on the conformation of adsorbed polymer layer.