Vaporization and thermal decomposition of transition metal salts in flameless atomic absorption spectrometry with a carbon tube atomizer

Vaporization and thermal decomposition of Cr, Mn, Fe, Co, Ni and Cu salts were investigated by measuring the absorption spectra observed when aqueous solutions of these salts were heated in the carbon tube atomizer. Gaseous metal halides are vaporized in the atomizer at temperatures above 300–500° C. SO₂ and NO are produced by thermal decomposition of metal sulfates and nitrates, respectively. The vaporization of metal halides is also confirmed by the spectra for solutions of metals in hydrochloric acid and for mixtures of metal nitrates and ammonium halides.     

Passivation of defect states in surface and edge regions on pn-junction Si solar cells by use of hydrogen cyanide solutions

The local photovoltage of the pn-junction single-crystalline silicon solar cells observed by spot light scanning gradually decreases in the vicinity of edges. The energy conversion efficiency is increased by shadowing the edge regions where the local photovoltage is lower, showing that the defect density is high in the edge regions. From the analysis of the local photovoltage, the spacial distribution of defect states is obtained. The cyanide method, i. e., immersion of solar cells in HCN solutions at room temperature, increases the local photovoltage and increases the energy conversion efficiency.      

A direct method for the separation and quantification of bile acid acyl glycosides by high-performance liquid chromatography with an evaporative light scattering detector

A direct method for the separation and quantification of a series of bile acid acyl glycosides using high-performance liquid chromatography coupled to an evaporative light scattering detector (HPLC-ELSD) is described. Complete separation of each of 15 bile acid acyl 24-alpha-glucosides and their 24-beta-anomers and 24-beta-galactosides was achieved by the stepwise gradient elution mode on a C18 column using a mixture of acetonitrile-methanol (8:2, v/v) and 1% aqueous acetic acid as the mobile phase. 24-beta-Galactosides were always eluted faster than the corresponding 24-beta-glucosides, which eluted after the corresponding 24-alpha-anomers. Calibration curves of different 24-beta-galactosides were linear over a range of 0.2-40 nmol of injected amount and the detection limits (S/N > 3) were from 0.08 to 0.1 nmol. The present HPLC-ELSD method may provide an insight into the separation and quantification of the biologically interesting neutral bile acids.     

Synthesis of 3alpha,7alpha,14alpha-trihydroxy-5beta-cholan-24-oic acid: a potential primary bile acid in vertebrates

A method for the synthesis of 3alpha,7alpha,14alpha-trihydroxy-5beta-cholan-24-oic acid which is a possible candidate of bile acid metabolite in vertebrates was developed. The principal reactions involved were 1). stereoselective remote-hydroxylation of methyl ursodeoxycholate diacetate with dimethyldioxirane, 2). site-selective protection at C-3 by tert-butyldimethylsilylation of the resulting 3alpha,7alpha,14alpha-trihydroxy ester, 3). oxidation of the diol with pyridinium dichromate adsorbed on activated alumina, 4). stereoselective reduction of the 7-ketone with zinc borohydride, and 5). cleavage of the protecting group at C-3 with p-toluenesulfonic acid. A facile elimination of the 14alpha-hydroxy group under an acidic or neutral condition is also described. The synthetic reference compound is now available for comparison with unidentified biliary bile acids detected in vertebrate bile.     

Reaction of cyanide ions with copper on Si surfaces and its use for Si cleaning

A Si cleaning method has been developed by use of potassium cyanide (KCN) dissolved in methanol. When silicon dioxide (SiO₂)/Si(1 0 0) specimens with 10¹⁴ atom/cm² order copper (Cu) contaminants are immersed in 0.1 M KCN solutions of methanol at 25 °C, the Cu concentration is reduced to below the detection limit of total X-ray fluorescence spectrometer of ∼3 × 10⁹ atoms/cm². X-ray photoelectron spectra show that the thickness of the SiO₂ layers is unchanged after cleaning with the KCN solutions. 10¹⁴ cm⁻² order Cu contaminants on the Si surface can also be removed below ∼3 × 10⁹ atoms/cm², without causing contamination by potassium ions. UV spectra show that Cu-cyano complex ions are formed in the KCN solutions after the cleaning. The main Cu species in the KCN solutions is ions with the concentration of []:[Cu⁺] = 1:1.6 × 10²³. Even when the KCN solutions are contaminated with 64 ppm Cu²⁺ ions in the solutions, which form ions, the cleaning ability does not decrease, showing that ions are not re-adsorbed. The KCN solutions can also passivate defect states such as Si/SiO₂ interface states, leading to the improvement of characteristics of Si devices.     

Vaporization of atoms and molecules during heating of cadmium,lead and zinc salts in a carbon tube atomizer

Vaporization characteristics of atoms and molecules produced during heating of aqueous solutions of Cd, Pb and Zn salts in the carbon tube atomizer are described. Sulfates, nitrates and fluorides are decomposed completely to free atoms without losses. When concentrated halide solutions are employed, gaseous metal chlorides, bromides and iodides are removed partly from the atomizer in the initial atomization phase, and the atomic absorption response is decreased. This loss can be suppressed effectively by adding nitric or sulfuric acid to the halide solutions.     

Capillary gas chromatographic separation of bile acid acyl glycosides without thermal decomposition and isomerization

A direct method for the capillary gas chromatographic (cGC) separation of the acyl glycosides of bile acids was successfully attained. The free acyl glycosides were derivatized to their complete trifluoroacetyl (TFA) derivatives with N-methyl-bis(trifluoroacetamide). The highly volatile TFA derivatives were chromatographed on a short-length (10 m), narrow-bore (0.1 mm) capillary column coated with a thin film (0.1 microm) of 5% phenyl polysilphenylene-siloxane at a column temperature below 280 degrees C. Each exhibited a single, well-separated peak of the theoretical shape without any accompanying peaks due to the thermal decomposition and isomerization. The bile acid 24alpha-glucosides were always eluted faster than the corresponding 24beta-glucosides, which eluted before the corresponding 24beta-galactosides. The method could be usefully applied to biosynthetic and metabolic studies of bile acid acyl glycosides in biological materials.     

Potential bile acid metabolites. 25. Synthesis and chemical properties of stereoisomeric 3alpha,7alpha,16- and 3alpha,7alpha,15-trihydroxy-5beta-cholan-24-oic acids

Epimeric 3alpha,7alpha,16- and 3alpha,7alpha,15-trihydroxy-5beta-cholan-24-oic acids and some related compounds were synthesized from chenodeoxycholic acid (CDCA) and ursodeoxycholic acid (UDCA), respectively. The key reaction involved one-step remote oxyfunctionalization of unactivated methine carbons at C-17 of CDCA and at C-14 of UDCA as their methyl ester-peracetate derivatives with dimethyldioxirane (DMDO). After dehydration of the resulting 17alpha- and 14alpha-hydroxy derivatives with POCl(3) or conc. H(2)SO(4), the respective Delta(16)- and Delta(14)-unsaturated products were subjected to hydration via hydroboration followed by oxidation to yield the 3,7,16- and 3,7,15-triketones, respectively. Stereoselective reduction of the respective triketones with tert-butylamine-borane complex afforded the epimeric 3alpha,7alpha,16- or 3alpha,7alpha,15-trihydroxy derivatives exclusively. A facile formation of the corresponding epsilon-lactones between the side chain carboxyl group at C-24 and the 16alpha- (or 16beta-) hydroxyl group in bile acids is also clarified.