Ultraviolet derivatization of steroidal saponin in garlic and commercial garlic products as p-nitrobenzoate for liquid chromatographic determination

A method is described for determination of the steroidal saponin, eruboside B, originating in garlic and garlic products as the p-nitrobenzoyl chloride (PNBC) derivative by reversed-phase liquid chromatography (with ultraviolet detection at 260 nm. Proto-eruboside B was extracted from garlic (Allium sativum L.); subjected to solid-phase extraction (SPE) with a C18 cartridge, Florisil column chromatography, and silica gel column chromatography; and then enzymatically converted to eruboside B, which was applied as an external standard. Steroidal saponins in garlic and commercial garlic products were extracted with methanol and purified by SPE cartridges, followed by enzymatic treatment. A frostanol saponin such as proto-eruboside B is enzymatically transformed to a spirostanol saponin, eruboside B. After the derivatization with PNBC, the saponin derivative was chromatographed on a C8 column with a gradient elution of (A) 80% aqueous acetonitrile and (B) 100% acetonitrile. The detection limit of the developed method was 1 microg/g for the samples. The method was applied to the analysis of garlic and garlic health food products available in Japan.     

Dehydrogenation versus oxygenation in two-electron and four-electron reduction of dioxygen by 9-alkyl-10-methyl-9,10-dihydroacridines catalyzed by monomeric cobalt porphyrins and cofacial dicobalt porphyrins in the presence of perchloric acid

Dehydrogenation of 10-methyl-9,10-dihydroacridine (AcrH(2)) by dioxygen (O(2)) proceeds efficiently, accompanied by the two-electron and four-electron reduction of O(2) to produce H(2)O(2) and H(2)O, which are effectively catalyzed by monomeric cobalt porphyrins and cofacial dicobalt porphyrins in the presence of perchloric acid (HClO(4)) in acetonitrile (MeCN) and benzonitrile (PhCN), respectively. The cobalt porphyrin catalyzed two-electron reduction of O(2) also occurs efficiently by 9-alkyl-10-methyl-9,10-dihydroacridines (AcrHR; R = Me, Et, and CH(2)COOEt) to yield 9-alkyl-10-methylacridinium ion (AcrR+) and H(2)O(2). In the case of R = Bu(t) and CMe(2)COOMe, however, the catalytic two-electron and four-electron reduction of O(2) by AcrHR results in oxygenation of the alkyl group of AcrHR rather than dehydrogenation to yield 10-methylacridinium ion (AcrH+) and the oxygenated products of the alkyl groups, i.e., the corresponding hydroperoxides (ROOH) and the alcohol (ROH), respectively. The catalytic mechanisms of the dehydrogenation vs the oxygenation of AcrHR in the two-electron and four-electron reduction of O(2), catalyzed by monomeric cobalt porphyrins and cofacial dicobalt porphyrins, respectively, are discussed in relation to the C(9)-H or C(9)-C bond cleavage of AcrHR radical cations produced in the electron-transfer oxidation of AcrHR.     

Temperature dependence of formation of nanorods and dots of iodine compounds on an H-terminated Si(111) surface in a concentrated HI solution

Immersion of atomically flat, H-terminated Si(111) surfaces in 7.6 M HI for 0.5 - 4 h caused spontaneous formation of nanosized clusters at the Si surface. X-ray photoelectron spectroscopy analysis suggested that the clusters were composed of silicon iodides (such as SiHxI4-x), produced most probably by Si etching with HI. Atomic force microscopy inspection revealed that the immersion at a low temperature below about 30 degrees C led to the formation of long rod-shaped clusters, oriented in the (112) direction or equivalents, whereas the immersion at a high temperature above 30 degrees C led to the formation of circular dot clusters, their size and shape changing abruptly at about 70 degrees C. It is shown experimentally that the formation of dot clusters at a high immersion temperature is explained on the basis of thermodynamics, whereas that of oriented rod clusters at a low temperature is explained by a kinetics-controlled mechanism.     

Hole Burning and Fluorescence Spectra of Sol-Gel Derived Sm2+-Doped Glasses

Sm2+-doped glasses in the system of Al2O3-SiO2 were prepared by sol-gel processing of metal alkoxides and reacting with H2 gas at 800°C. The hole burning properties of these glasses were investigated. The holes were burned in the 7F0 5D0 line of the Sm2+ ions using a DCM dye laser at 77 K. The hole depth increased with increasing the laser irradiation time, reaching up to 15% of the total intensity within a few hundred seconds. The hole width was 3 cm–1 full width at half maximum. Fluorescence line narrowing spectra of the 5D0 7 F1 transition were analyzed to study the local structure surrounding the Sm2+ ion. It is concluded that the Sm2+ ions are closely coordinated with nine oxygens of the AlO6 group in aluminosilicate glasses and that the addition of Al3+ ions into glass induces an increase in the coordination number of the Sm2+.     

Rational synthesis of Pt spheres with hollow interior and nanosponge shell using silica particles as template

Here we report a facile and efficient method to prepare Pt spheres with hollow interior and nanosponge shell with high surface area. Such a unique Pt nanostructure can effectively improve the electrocatalytic performance of Pt catalysts by facilitating the access of electroactive species to the full-extent Pt surface.     

Facile Synthesis of Free‐Standing Polymer Brush Films Based on a Colorless Polydopamine Thin Layer

A free‐standing polymer brush film with tailored thicknesses based on a colorless polydopamine (PDA) thin layer is prepared and characterized. The surface‐initiated atom transfer radical polymerization (ATRP) of 2‐hydroxyethyl methacrylate (HEMA) is performed on a PDA layer with thickness of ca. 6 nm, which generated an optically transparent and colorless free‐standing PHEMA brush film (1.5 cm × 1.5 cm). Because the cross‐linked PDA layer is used as the base for the polymer brushes, the reported method does not require cross‐linking the polymer brushes. The free‐standing film thicknesses of ≈16–75 nm are controlled by simply changing the ATRP reaction time. The results show that the free‐standing PHEMA brush film transferred onto a plate exhibits a relatively smooth surface and is stable in any solvent.

     

Synthesis of chiral 3,3′-disubstituted 1,1′-binaphthyl-2,2′-disulfonic acids

A convenient synthesis of chiral 3,3′-disubstituted 1,1′-binaphthyl-2,2′-disulfonic acids (BINSA, 1) was developed. The key was directed ortho-lithiation of BINSA methyl ester 2 with n-BuLi and subsequent reaction with an electrophile. Electrophiles such as Br₂, I₂, Me₃SiOTf, and i-PrOB(Pin) reacted smoothly with 3,3′-dilithiated BINSA methyl ester, and the corresponding 3,3′-dihalo-, 3,3′-bis(trimethylsilyl)-, and 3,3′-diboryl-BINSA derivatives were obtained in yields of 21–78%. This simple synthetic method is highly attractive since the ability to prepare 3,3′-disubstituted BINOLs in advance can be useful.     

Two chitinase-like proteins abundantly accumulated in latex of mulberry show insecticidal activity

Background  

Plant latex is the cytoplasm of highly specialized cells known as laticifers, and is thought to have a critical role in defense against herbivorous insects. Proteins abundantly accumulated in latex might therefore be involved in the defense system.     

Effects of oligoDNA template length and sequence on binary self-assembly of a nucleotide bolaamphiphile

Templated self-assembly of nucleotide bolaamphiphile 1 (in which a 3'-phosphorylated thymidine moiety is connected to each end of a long oligomethylene chain) with a 10-, 20-, 30-, or 40-meric single-stranded oligoadenylic acid (2, 3, 4, or 5) led to the formation of right-handed helical nanofibers in 0.1x Tris/EDTA (TE) buffer solutions. The helical pitch increased as the length of the oligoadenylic acid template increased. DNA composed of oligoadenylic and oligocytidylic acid sequences (6, 7, and 8) also acted as templates to induce the formation of helical nanofiber structures. The diameter of the nanofibers remained constant (6-6.6 nm) irrespective of the template used. The binary self-assembly of 1 with 4 also produced higher-order, double-stranded nanofibers.