Discrimination of carbonyl groups of meso-α-diketones with Horner-Wadsworth-Emmons reagent of chiral binaphthyl esters

Asymmetric Horner-Wadsworth-Emmons reactions of selected meso-α-dicarbonyl compounds with chiral phosphonate reagents, which possessed axially dissymmetric 1,1′-bi-2- or 8-naphthol at the carboxylate moiety as a chiral auxiliary, were examined. The reactions proceeded smoothly with good chemical yields as well as with high diastereoselectivities. Z-olefins were preferentially formed, and it was found that the free hydroxy group at the 2′- or 8′-position on the naphthalene ring plays a crucial role in the high diastereoselectivity, probably due to a complex-induced proximity effect. Mechanistic considerations are also described.     

Numerical analysis of finite amplitude motion of waves and a moored floating body under severe storm conditions

The motion of a moored floating body under the action of wave forces, which is influenced by fluid forces, shape of the floating body and mooring forces, should be analysed as a complex coupled motion system. Especially under severe storm conditions or resonant motion of the floating body it is necessary to consider finite amplitude motions of the waves, the floating body and the mooring lines as well as non-linear interactions of these finite amplitude motions. The problem of a floating body has been studied on the basis of linear wave theory by many researchers. However, the finite amplitude motion under a correlated motion system has rarely been taken into account. This paper presents a numerical method for calculating the finite amplitude motion when a floating body is moored by non-linear mooring lines such as chains and cables under severe storm conditions.     

Phase Measurement Algorithm in Wavelength Scanned Fizeau Interferometer

Wavelength scanned interferometry allows the simultaneous measurement of top surface shape and optical thickness variation of a transparent object consisting of several parallel surfaces. Interference signals from these surfaces can be separated in frequency space, and their phases are detected by discrete Fourier analysis. However, these signal frequencies are shifted from the detection frequency by the refractive index dispersion of the object and a nonlinearity of the wavelength scanning. The Fourier analysis is sensitive to the detuning of the signal frequency and suffers from the multiple-beam interference noise. Conventional error-compensating algorithms cannot be applied to an object consisting of more than three reflecting surfaces. We derive a new 2N-1 sample error-compensating algorithm, which allows the phase detection of any order of harmonic frequency among the interference signals. The new algorithm suppresses the effect of signal frequency detuning as well as the multiple-beam interference noise and can be applied to the measurement of complex objects consisting of more than three reflecting surfaces.     

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%.     

Stable isotope dilution mass spectrometry for the simultaneous determination of cortisol, cortisone, prednisolone and prednisone in plasma.

A capillary gas chromatographic-mass spectrometric method for the simultaneous determination of cortisol, cortisone, prednisolone and prednisone in human plasma is described. [1,1,19,19,19-2H5]Cortisol, [1,1,19,19,19-2H5]cortisone, [1,19,19,19-2H4]prednisolone and [1,19,19,19-2H4]prednisone were used as internal standards. Formation of the bismethylenedioxy-3-heptafluoro-n-butyryl (BMD-HFB) derivatives made possible the separation of the four corticosteroids with good gas chromatographic behaviour. The new double derivatization has been demonstrated to be of value for sensitive and selective quantification by this technique. Detection was performed by monitoring the molecular ion (M+) of the BMD-HFB derivatives for cortisone and prednisolone, the [M - 18]+ ion for cortisol, and the [M - 30]+ ion for prednisone. The method requires no complex corrections for contributions and provides good accuracy and precision.     

THE CONFORMATIONAL ANALYSIS AND PHOTOISOMERIZATION OF RETINOCHROME ANALOGS WITH POLYENALS

Abstract— 3, 7-Dimethyl-2, 4, 6, 8, 10-dodecapentaenal was synthesized for reconstitution of the retinochrome analog. Its opsin shift was 1000 cm ¹ smaller than that of native retinochrome, whose chromophore contains the same number of double bonds. The conformational change from 6-s-trans to 6-s-cis , as figured in a retinal molecule, plays an important role in the formation of the retinochrome analog, based on the estimation of opsin shifts for retinal analogs locked in the 6-s conformation. Thus the conformation of the 6–7 single bond in the native retinochrome was suggested to be 6 -cis . Analysis of the circular dichroic spectra of retinochrome analogs revealed that the 6-s conformation is independent of the appearance of the β-band. The stereoselectivity in the photoisomerization of the retinal analogs by a retinochrome template depends on the hydrophobic binding in the region of the β-ionone ring.     

Determination of different oxidation states of arsenic and selenium by inductively coupled plasma-atomic emission spectrometry with ion chromatography

Recent regulation in Japan requires more sensitive trace analysis methods for the determination of arsenic and selenium and their oxidation states As(III) and (V), Se(IV) and (VI). The hydride generation (HG) technique is usually used in combination with AAS and ICP-AES to increase sensitivity. However, hydrochloric acid is mostly used to acidify the sample solution in HG. Isobaric interferences due to chlorine-related species cause mass spectral problems when the same solution is used for the determination of these elements by ICP-MS. In this study, different oxidation states of As and Se were determined by coupling ion chromatography (IC) to an ICP-AES instrument. An HG technique was used to introduce test samples into the ICP. Nitric acid was employed to acidify the samples for HG. The concentrations of acid and base were kept as low as possible to reduce contamination. The formation of As and Se hydrides could be achieved without HCl, if the concentrations of acid and alkaline solutions were optimized. However, HCl was necessary for additional reduction of Se(VI) to Se(IV).     

Determination of meropenem by capillary electrophoresis using direct injection of serum

Concentration determination of meropenem, a carbapenem antibiotic, using a capillary electrophoresis method by direct injection of serum samples without any pretreatment is described herein. Sodium tetraborate (25 mM)-sodium hydroxide (0.1 M) containing sodium dodecyl sulfate (90 mM) is used as a run buffer (pH 10.0). Meropenem is detected at its absorption maximum at 297 nm. Migration time of meropenem is approximately 7.2 min, and the detection limit of the assay is 2.0 mg/L at a signal-to-noise ratio of 3.0. The relative standard deviations of intra- and interassay accuracies are 3.43-8.87% and 4.28-8.54%, respectively, at a nominal concentration of 6.3-100.0 mg/L, and their recovery rates are 94-111% and 92-105%, respectively.