Ion-pair formation of a copper(II)-ammine complex with an anionic surfactant and the recovery of copper(II) from ammonia medium by the surfactant-gel extraction method.

The extraction and separation of copper(II), zinc(II), cobalt(II), and cadmium(II) were investigated. Both copper(II) and zinc(II) formed ammine-complexes, while cadmium(II) and cobalt(II) formed hydroxide precipitates in an ammonia medium. By the addition of sodium dodecylsulfate (SDS), a copper(II) complex formed an ion-pair (copper-ammine-DS), which was extracted into the SDS phase. However, a zinc(II) complex did not form an ion-pair, and was soluble in water. Copper(II) ion was recovered by stripping (back-extraction) after the addition of hydrochloric acid. This method was applied to the separation of copper(II) in a brass alloy.     

Application of total reflection X-ray fluorescence spectrometry to small glass fragments.

Total reflection X-ray fluorescence spectrometry (TXRF) has been applied for trace elemental analysis of small glass fragments. A small glass sample (a fragment with weight less than 0.5 mg) was decomposed by 100 microg of HF/HNO3 acid; the material was condensed to 10 microl and was dried on a Si wafer. Since the size of the dried residue on the Si wafer was less than 1 cm in diameter, an incident X-ray beam with about 1 cm in width could effectively excite elemental components in such a small glass fragment. The precision of the present technique was checked by analyzing the glass fragments (<0.5 mg) from NIST SRM612; the relative standard deviations (RSD) of less than 8.1% were achieved for elemental ratios that were normalized by Sr. Fragments (<0.5 mg) obtained from 23 figured sheet glasses were used as samples for estimating the utility of this technique to forensic discrimination. Comparison of five elemental ratios of Ti/Sr, Mn/Sr, Zn/Sr, Rb/Sr, and Pb/Sr calculated from X-ray fluorescence spectra was effective in distinguishing glass fragments that could not be differentiated by their refractive indexes (RI).     

Preparation and certification of the new reference materials; plastics (disk form, JSAC 0621-0625) for determination of mercury using x-ray fluorescent analysis.

The Japan Society for Analytical Chemistry has developed some new plastic certified reference materials (CRMs) for the analysis of mercury in polyester disks using XRF analysis. These CRMs (named as JSAC 0621-0625) were prepared by casting polyesters including a toluene solution of organometallic compounds as a standard. Concentrations of the five levels of mercury ranged from 0 to 250 mg/kg. Homogeneity tests of prepared disks had shown excellent results. Interlaboratory comparison study for the certification was performed by 15 laboratory participants. The z-scores in robust statistical method was applied for the evaluation of outliers. The certified values were assigned after discarding outliers. The uncertainties of certified values were determined as the confidence levels of 95%.     

Singular integral operators on 53-0153-0153-01-spaces

Summary It is shown that certain singular integral operators with variable kernels leave invariant theL ^v, -spaces studied by Campanato, Stampacchia, Peetre and others. Our results extend Peetre's work on convolution operators.     

Senecicannabine,a new pyrrolizidine alkaloid from senecio cannabifolius

The structure of senecicannabine($\text{1}$), a new mcrocyclic pyrrolizidine alkaloid isolated from $\text{Senecio cannabifolius}$, has been established by chemical study and X-ray analysis.     

Electrical conducting and magnetic properties of (ethylenedithiotetrathiafulvalenothioquinone-1,3-diselenolemethide)2.FeBr4 (GaBr4) crystals with two different interlayer arrangements of donor molecules

Two donor molecules newly synthesized, dimethylthio- and ethylenedithio-tetrathiafulvalenothioquinone-1,3-diselenolemethides (1 and 2), were used to prepare their charge-transfer (CT) salts with a magnetic FeBr(4)(-) counteranion. For 1, a low electrical conducting 1:1 salt (1.FeBr(4)) was obtained, in which molecules of 1 are tightly dimerized in a one-dimensional (1D) stacking column. On the other hand, 2 gave a 2:1 salt (2(2).FeBr(4)) as two different kinds of plate crystals (I and II). Both I and II possess similar stacking structures of molecules of 2 in each 1D column with a half-cut pipelike structure along the c axis. However, for I, the stacking columns are aligned in the same direction along the a and b axes, while for II they are in the same direction along the a axis, but in the reverse direction along the b axis, resulting in the difference in the relative arrangement of molecules of 2 and FeBr(4)(-) ions between the two crystals. The room-temperature electrical conductivities of the single crystals of I and II were 13.6 and 12.7 S cm(-)(1), respectively. The electrical conducting behavior in I was metallic above 170 K but changed to be semiconducting with a very small activation energy of 7.0 meV in the temperature range 4-170 K. In contrast, II showed the semiconducting behavior in the whole temperature range 77-285 K. The corresponding nonmagnetic GaBr(4)(-) salts with almost the same crystal structure as I and II showed definitively different electrical conducting properties in the metal to semiconductor transition temperature in I as well as in the magnitude of activation energy in the semiconducting region of I and II. The interaction between the d spins of FeBr(4)(-) ions was weak and antiferromagnetic in both I and II, but the magnitude of the spin interaction was unexpectedly larger compared with that in the FeBr(4)(-) salt of the corresponding sulfur derivative of 2 with closer contact between the neighboring FeBr(4)(-) ions. These electrical conducting and magnetic results suggest a significant interaction between the conducting pi electrons and the d spins of FeBr(4)(-) ions located near the columns or layers.     

Simultaneous assay of four stereoisomers of diltiazem hydrochloride. Application to in vitro chiral inversion studies

Summary The simultaneous stereospecific assay of four stereoisomers of diltiazem hydrochloride in bulk drug and aqueous solution was developed using HPLC on a Chiralcel OF column. The four isomers were quantitated with good precision by the internal standard method. The chiral inversion of (+)-cis-diltiazem hydrochloride in vitro, stability of its (2S, 3S) configuration in the solid and aqueous states was examined by HPLC. Chiral inversion of (+)-cis-diltiazem hydrochloride was not observed in the solid state, and its (2S, 3S) configuration was stable to heat, humidity and light. Chiral inversion of (+)-cis-diltiazem hydrochloride (2S, 3S) was observed in aqueous solution under UV, but not in aqueous solution stored at 80°C for 5h nor under visible light for 10 h. The (+)-cis-diltiazem hydrochloride (2S, 3S) epimerized to (+)-trans-diltiazem hydrochloride (2R, 3S) with a half-life of 5h in aqueous solution under UV but the reverse chiral inversion of (+)-trans-diltiazem hydrochloride (2R, 3S) to (+)-cis-diltiazem hydrochloride (2S, 3S) was not observed.