Simultaneous speciation of selenium and sulfur species in selenized odorless garlic (Allium sativum L. Shiro) and shallot (Allium ascalonicum) by HPLC-inductively coupled plasma-(octopole reaction system)-mass spectrometry and electrospray ionization-tandem mass spectrometry

The simultaneous speciation of selenium and sulfur in selenized odorless garlic (Allium sativum L. Shiro) and a weakly odorous Allium plant, shallot (Allium ascalonicum), was performed by means of a hyphenated technique, a HPLC coupled with an inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) equipped with an octopole reaction system (ORS). The aqueous extracts of them contained the common seleno compound that was identified as gamma-glutamylmethylselenocysteine by an electrospray ionization-tandem mass spectrometry (ESI-MS/MS). Normal garlic contains alliin as the major sulfur-containing compound, which is the biological precursor of the garlic odorant, allicin. Alliin, however, was not detected in the extracts of the selenized odorless garlic. At least, four unidentified sulfur-containing compounds were detected in odorless garlic and shallot. Moreover, these Allium plants showed chemopreventive effects against human leukemia cells.     

Calcium-Mediated Adsorption of Neutral Amino Acids to Carboxymethylated Chitin

Among various divalent metal ions, calcium has been found to be adsorbed tightly onto carboxymethylated chitin. The adsorption was completed not only by induced carboxyl groups but also by the support of acetamide, as well as primary and secondary hydroxyl groups. Although the adsorption capacity for transition metal ions was enhanced appreciably by regeneration into fibrous form, only that of calcium ion, among alkali-earth metals, was at the same level as that of transition metals. Since little effect was shown on the adsorption of phenylalanine by the blocking of α-amino and α-carboxyl groups of L-Phe, and since D-Phe was so a little adsorbed, the chiral specific adsorption of phenylalanine might be supported by mediation of calcium ion and by the contribution of hydrophobicity of the β-phenyl group.     

RAMA stain: A fast,sensitive and less protein‐modifying CBB R250 stain

SDS‐PAGE and CBB staining are two of the most popular methods used for protein analysis. Although many reports that describe such staining methods have been published, these conventional protocols require several hours or days for staining and de‐staining. In this study we describe a recently developed, fast and sensitive CBB staining method that utilizes the staining solution of RAMA that consists of the low‐cost reagents: CBB R250, acetic acid, methanol and ammonium sulfate, and the destaining solution of water. Our method dose dependently detects 12 nanograms protein within 60 min and with a wide protein spectrum. Although the features of the dose‐dependent relationship depend upon protein amounts and protein types, for most of the protein samples tested, a linear relationship was observed in the region from 12 to 330 ng. Moreover, through further washing, the detection sensitivity of protein is enhanced and reaches a maximum at 1.4 ng and then gradually decreases in the de‐staining process. It has been shown recently through MS analyses that the sensitive colloidal CBB staining methods frequently result in artifactual methylations due to the strong acid and long contact during staining and the destaining processes. Such artifacts were reported to be reduced by the replacement of strong inorganic acid with acetic acid and because RAMA utilizes acetic acid and is in contact with the proteins for a short time during staining and de‐staining, it is expected that in vitro artifacts will be reduced. Finally, MS analyses of RAMA‐stained protein bands were revealed not to have been methylated.     

Anthracyclinone syntheses using strong base induced cycloaddition of homophthalic anhydrides and related compounds

The strong base induced cycloaddition of homophthalic anhydrides and related compounds to halo- 1,4-naphthoquinone derivatives has been shown to provide short convergent syntheses of anthracyclinones, 4-demethoxydaunomycinone (1), daunomycinone (2), 11-deoxydaunomycinone (3), and 11-deoxycarminomycinone (4).     

Annelation of α,β-unsaturated esters to thian-3-one 1-oxides using dianion of ω-(methylsulfinyl)acetophenone

β-Monosubstituted α,β-unsaturated esters undergo an annelation with dilithio salt of ω-(methylsulfinyl)-acetophenone to produce 5-substituted 6-benzoylthian-3-one 1-oxides.     

Optical Properties and Photopolymerization of Liquid Crystalline (Acetyl) (Ethyl) Cellulose/Acrylic Acid System

The structure and properties of a chiral nematic phase, which reflects one hand of circularly polarized light in a narrow region of wavelength, of fully acetylated (ethyl) cellulose [(acetyl) (ethyl) cellulose, AEC] in acrylic acid (AA) were studied in comparison with (ethyl) cellulose (EC). AEC mesophase formed right-handed chiral nematic structure while EC formed left-handed one. AEC mesophase showed higher birefringence and reflection intensity. The relationship between the reflection wavelength and the polymer concentration was negatively correlated for both AEC and EC mesophases. The relationship between the reflection wavelength and the molecular weight was also negative for AEC mesophase whereas positive for EC mesophase. AEC mesophase was solidified by photopolymerization of AA moiety. It was revealed that the optical properties of AEC mesophase could be preserved by photopolymerization, since the resulting solid material reflects selectively one hand of circularly polarized light.     

Confined water inside single-walled carbon nanotubes: global phase diagram and effect of finite length

Studies on confined water are important not only from the viewpoint of scientific interest but also for the development of new nanoscale devices. In this work, we aimed to clarify the properties of confined water in the cylindrical pores of single-walled carbon nanotubes (SWCNTs) that had diameters in the range of 1.46 to 2.40 nm. A combination of x-ray diffraction (XRD), nuclear magnetic resonance, and electrical resistance measurements revealed that water inside SWCNTs with diameters between 1.68 and 2.40 nm undergoes a wet-dry type transition with the lowering of temperature; below the transition temperature T(wd), water was ejected from the SWCNTs. T(wd) increased with increasing SWCNT diameter D. For the SWCNTs with D = 1.68, 2.00, 2.18, and 2.40 nm, T(wd) obtained by the XRD measurements were 218, 225, 236, and 237 K, respectively. We performed a systematic study on finite length SWCNT systems using classical molecular dynamics calculations to clarify the effect of open ends of the SWCNTs and water content on the water structure. It was found that ice structures that were formed at low temperatures were strongly affected by the bore diameter, a = D - σ(OC), where σ(OC) is gap distance between the SWCNT and oxygen atom in water, and the number of water molecules in the system. In small pores (a < 1.02 nm), tubule ices or the so-called ice nanotubes (ice NTs) were formed irrespective of the water content. On the other hand, in larger pores (a > 1.10 nm) with small water content, filled water clusters were formed leaving some empty space in the SWCNT pore, which grew to fill the pore with increasing water content. For pores with sizes in between these two regimes (1.02 < a < 1.10 nm), tubule ice also appeared with small water content and grew with increasing water content. However, once the tubule ice filled the entire SWCNT pore, further increase in the water content resulted in encapsulation of the additional water molecules inside the tubule ice. Corresponding XRD measurements on SWCNTs with a mean diameter of 1.46 nm strongly suggested the presence of such a filled structure.