Preconcentration of silver(I), gold(III) and palladium(II) in sea water with p-dimethylaminobenzylidenerhodanine supported on silica gel

A water-insoluble chelating material, p-dimethylaminobenzylidenerhodanine on silica gel (DMABR—SG) is described for preconcentration of trace amounts of silver(I), gold(III) and palladium(II) from water samples. Radioactive tracers (^110mAg and ¹⁹⁵Au) were used to study the behavior of silver and gold; palladium was monitored spectrophotometrically as its 1-(2-pyridylazo)naphthol complex in chloroform. In batch experiments, silver was quantitatively retained on the DMABR—SG at acidities ranging from 1.7 M to pH 5, and gold from 3 M to pH 5; equilibrium was achieved within 1 min for both elements. From sea water, silver ion was completely retained at pH 1.0–6.5 and gold ion at pH 1.0–3.5. In the case of palladium, shaking for about 20 min was required for quantitative retention at pH 1.0–5.0 for aqueous solution and at pH 1.0–7.0 for sea water. The chelating capacity of the DMABR—SG was 23 μmol Ag, 11 μmol Au and 11 μmol Pd per g. Quantitative recovery of silver and gold on DMABR—SG columns from sea water was achieved at higher flow rates (1–2 l h^-1 and 2–3 l h^-1, respectively) than with other chelating resins, e.g., Chelex 100, palladium required slower flow rate (150 ml h^-1). Silver retained on the DMABR—SG column was completely eluted with 20 ml of 2.5% sodium thiosulfate solution but palladium remained on the column. Silver, gold and palladium were quantitatively eluted with 20 ml of 0.1% thiourea in 0.1 M hydrochloric acid.     

Validation of the CALUX bioassay for the screening of PCDD/Fs and dioxin-like PCBs in retail fish

The chemical-activated luciferase expression (CALUX) assay is a reporter gene assay that detects dioxin-like compounds based on their ability to activate the aryl hydrocarbon receptor (AhR) and thus expression of the reporter gene. In this paper, the CALUX assay was examined for its application in the screening of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in retail fish. The sample extracts were cleaned up on a sulfuric acid-silica gel column followed by an activated carbon column, and the AhR activity of the separated PCDD/F and dioxin-like PCB fractions was determined using the assay. The quantitative limit for 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was 0.98 pg ml(-1) (0.19 pg assay(-1) in the standard curve, corresponding to 0.16 pg g(-1) of CALUX-based toxic equivalency (2,3,7,8-TCDD equivalents) in the tested sample. Recovery tests in which dioxins were added to fish samples resulted in acceptable recoveries (77-117%). The CALUX assay performed well in the analysis of dioxins in fish samples and a comparative study revealed a strong correlation between the CALUX assay and high-resolution gas chromatography-high-resolution mass spectrometry analysis for the determination of PCDD/Fs (r = 0.89) and dioxin-like PCBs (r = 0.91) in retail fish (n = 22). These data revealed that the CALUX assay would be a useful screening method for PCDD/Fs and dioxin-like PCBs in retail fish.     

Metal-to-Oxide Charge Transfer Observed by a Kelvin Probe Force Microscope

The charge transfer from a nanometer-sized transition metal particle to a catalyst support is thought to affect reactions over the metal surface. We propose the application of Kelvin probe force microscope, which is an extension of the atomic force microscope, to observe the charge transfer particle-by-particle. Our recent results on Na adatoms, Cl adatoms, Pt adatoms and particles, and Ni particles evaporated on TiO₂(110) are reviewed.     

Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure study on oxidative etching of diamond-like carbon films by hyperthermal atomic oxygen

Surface structural changes of a hydrogenated diamond-like carbon (DLC) film exposed to a hyperthermal atomic oxygen beam were investigated by Rutherford backscattering spectroscopy (RBS), synchrotron radiation photoelectron spectroscopy (SR-PES), and near-edge X-ray absorption fine structure (NEXAFS). It was confirmed that the DLC surface was oxidized and etched by high-energy collisions of atomic oxygen. RBS and real-time mass-loss data showed a linear relationship between etching and atomic oxygen fluence. SR-PES data suggested that the oxide layer was restricted to the topmost surface of the DLC film. NEXAFS data were interpreted to mean that the sp² structure at the DLC surface was selectively etched by collisions with hyperthermal atomic oxygen, and an sp³-rich region remained at the topmost DLC surface. The formation of an sp³-rich layer at the DLC surface led to surface roughening and a reduced erosion yield relative to the pristine DLC surface.     

Peptidehelicenes in solution and gel: chiral discrimination through interactions between two types of helixes

Helical [5]thiaheterohelicene 5HM, which rapidly interconverts between P and M enantiomers in solution, was connected to helical l-phenylalanine oligomers with an ester linkage to give peptidehelicenes (5Fn, where n: number of bonded phenylalanines). The characteristics of 5F4 and 5F5 with two types of helixes in a molecule were investigated, particularly in comparison with those of 5F1–5F3 with an incomplete coil of a peptide moiety. l-Phenylalanine peptide chains induced a shift in the equilibrium between the P and M helixes of 5HM toward the P side for all the 5Fns examined. The enantiomeric excess (ee) of the P form increased with a decrease in temperature, together with an elongation of the peptide chains. 5F4 and 5F5 in hot solutions of some solvents formed a gel at room temperature, whereas 5F1–5F3 showed no such behavior. In this gel, the stable helical form of the 5HM moiety in 5F4 and 5F5 was observed to be the M form in contrast to that in their solutions.     

The Biological Effects of Forsythia Leaves Containing the Cyclic AMP Phosphodiesterase 4 Inhibitor Phillyrin

Forsythia fruit (Forsythia suspensa Vahl (Oleaceae)) is a common component of Kampo medicines for treating the common cold, influenza, and allergies. The main polyphenolic compounds in the leaves of F. suspensa are pinoresinol β-d-glucoside, phillyrin and forsythiaside, and their levels are higher in the leaves of the plant than in the fruit. It is known that polyphenolic compounds stimulate lipid catabolism in the liver and suppress dyslipidemia, thereby attenuating diet-induced obesity and polyphenolic anti-oxidants might attenuate obesity in animals consuming high-fat diets. Recently, phillyrin was reported as a novel cyclic AMP phosphodiesterase 4 (PDE4) inhibitor derived from forsythia fruit. It was expected that the leaves of F. suspensa might display anti-obesity effects and serve as a health food material. In this review, we summarized our studies on the biological effects of forsythia leaves containing phillyrin and other polyphenolic compounds, particularly against obesity, atopic dermatitis, and influenza A virus infection, and its potential as a phytoestrogen.     

Convergent synthesis of polycyclic ethers via the intramolecular allylation of alpha-acetoxy ethers and subsequent ring-closing metathesis

The Lewis acid mediated reaction of alpha-acetoxy ethers 15-22 gave the corresponding cyclized products 23, 25, 27, 29, 31, 32, 34, and 36 in good yields with high stereoselectivities. Those cyclized products were subjected to ring-closing metathesis to afford the polycyclic ethers 38-42, 44, and 45 in good yields. The usefulness of the present methodology was demonstrated by the convergent synthesis of the CDEF ring system of brevetoxin B (1) and the CDEFG ring system of gambierol (2).     

Clove oil prevents glycyrrhizin gel formation in aqueous solution

One persistent problem with using therapeutic concentrations of glycyrrhizin (GZ) is that, at these high concentrations, it forms a gel in an aqueous solution. We previously solved this problem by dissolving GZ in a highly concentrated phosphate buffer. Unfortunately, the resulting GZ solution has a hyperosmotic pressure that renders it unsuitable for use in patients. The aim of this study was to prepare a highly concentrated GZ solution having an osmotic pressure ratio of 1 and a pH of 7.4. By adding small amounts of oil and using a 100 mM phosphate buffer, we achieved an emulsified GZ solution that is stable at room temperature and has a physiological osmotic pressure and pH. When clove oil was used as an emulsifier, the gel formation temperature of GZ solution decreased appreciably compared to that of GZ solution without clove oil. Using scanning electron microscopy (SEM), we examined the detailed characteristics of GZ gels prepared from solutions with or without clove oil. SEM of cross sections of GZ gels revealed an irregular structure in gels prepared with clove oil, indicating that clove oil prevented the formation of the intermolecular GZ networks typically characterized by gels derived from pure GZ solutions.