A highly stereoselective synthesis of 11Z-retinal using tricarbonyliron complex

A stereoselective synthesis of 11Z-retinal 2, which is the chromophore of visual pigment (rhodopsin), was accomplished from the beta-ionylideneacetaldehyde-tricarbonyliron complex 3. The Peterson reaction of 3 using ethyl trimethylsilylacetate smoothly proceeded to afford predominantly the Z-ester 6. Transformation of the Z-ester 6 to the methyl ketone 19, followed by the Emmons-Horner reaction of 19 with C2-cyanophosphonate, produced ethyl 11Z, 13E-retinonitrile-tricarbonyliron complex 21 as the only product. Decomplexation of 21 with CuCl2 and subsequent DIBAL reduction gave 11Z-retinal 2 in excellent yield. Mechanistic consideration of Z-selectivity in the Peterson reaction of the aldehyde-tricarbonyliron complex is also discussed.     

A reversed-phase high-performance liquid chromatographic method to analyze retinal isomers

A high-performance liquid chromatographic (HPLC) procedure was developed to separate all-trans-, 13-cis-, 11-cis- and 9-cis-retinal isomers. Two reversed-phase Vydac C18 columns in series were used with an isocratic solvent system of 0.1 M ammonium acetate-acetonitrile (40:60, v/v) as mobile phase and all-trans-9-(4-methoxy-2,3,6-trimethylphenyl)-3,7-dimethyl-2,4,6,8-no natetraene-1-ol (TMMP) as internal standard. Prior to HPLC, the retinal isomers were efficiently extracted in their original isomeric conformation using dichloromethane-n-hexane in the presence of formaldehyde. This technique is suitable for the assay of 11-cis- and all-trans-retinal isomers in retina.     

Difference-frequency terahertz-wave generation from 4-dimethylamino-N-methyl-4-stilbazolium-tosylate by use of an electronically tuned Ti:sapphire laser

Among nonlinear materials, the organic ionic salt crystal 4-dimethylamino- N -methyl-4-stilbazolium-tosylate (DAST) is known for its large nonlinearity. We generated a coherent terahertz (THz) wave, using DAST, from the difference frequency between two oscillating wavelengths of an electronically tuned Ti:sapphire laser. In LiNbO(3), LiTaO(3), KTiOPO(4), and GaP crystals, THz-wave generation was not observed under the same experimental conditions. This result proves the high efficiency of DAST crystals for generation of difference-frequency THz waves.     

Low-frequency and high-frequency relaxations in dynamic electric birefringence of poly(γ-benzyl-L-glutamate) in m-cresol

The dc component Δn of the electric birefringence of poly(γ-benzyl-L -glutamate) in m-cresol is measured under an ac electric field at frequencies from 0.5 Hz to 200 kHz for solutions covering the dilute and semidilute regions. The dispersion curve indicates that at low frequencies Δn decreases with increasing frequency (low-frequency relaxation). For high-molecular-weight polymers at high concentration, Δn becomes negative at high frequency and its absolute value decreases with further increase in frequency (high-frequency relaxation). A unified theory for the two relaxations is developed on the basis of a model in which, in the semidilute regime, the rodlike polymer is confined in a cage formed by neighboring polymers and the lifetime of the cage lies between relaxation times of the two relaxations. The low-frequency relaxation is ascribed to end-over-end rotation of the polymer and the high-frequency relaxation to the rotation within a limited angle in the cage. The dependences of relaxation parameters on polymer concentration and molecular weight are reasonably explained by the theory.     

Dispersion relation approach to the anomalous magnetic moment in gauge theories

The reason why the dispersion relations for the anomalous magnetic moment are not valid in gauge theories is explained. New sum rules are derived based on unitary bounds of scattering amplitudes. In gauge theories these sum rules give the correct values for the anomalous magnetic moment, while, in the case of conventional renormalizable theories which contain no massive vector bosons, they are identical with the usual dispersion relations for the anomalous magnetic moment.     

Neutralization of static electricity charged on running vinyl chloride sheet by the use of soft beta-ray sources (author's transl)

The feasibility of 147Pm and 3H beta-ray sources as static eliminator was experimentally investigated. A sheet of vinyl chloride of 0.1 mm in thickness was used as an example of electrified materials. Its surface charge densities before and after beta-ray neutralization were measured as the function of electrostatic charge changing the speed of the sheet and the distance between the beta-ray source and the sheet. With a 147Pm beta-ray source of 200mCi in effective activity, almost complete neutralization was found for the sheet with the charge density less than 6 X 10(-6) C/m2 running at the speed of 0.18 m/s. In the case of the running speed of 0.5 m/s frequently used in industry, the electrostatic charge below 3 X 10(6) C/m2, where corona discharger is not so effective, was also perfectly eliminated. It was found that the optimal distance between the beta-ray source and the sheet was 10 cm in the case of 147Pm. The use of 3H beta-ray source of 1 Ci was not satisfactory. These results demonstrate that 147 Pm beta-ray source operates most efficiently as static eliminator when the charge density of material and/or its moving speed is not high.     

Synthesis of DTPA-conjugated (1,4)-linked 2-aminoglycosides varying in the anomeric configuration and their MRI contrast effect

We describe the efficient synthesis of DTPA-conjugated oligosaccharides composed of alpha- and/or beta-linked tri to monoglucosamines. Gd(iii) complex with DTPA-conjugated chitotriitol has been reported to be an effective MRI contrast agent. In order to elucidate the structure-property relationships, we planned to synthesize the DTPA-conjugated 2-amino-tri-, di-, and monosaccharides varying in configuration at the anomeric positions and the C2 position on the reducing end. Our strategy for the synthesis of the DTPA-conjugated oligosaccharides involves O-perbenzyl protected 2-amino-tri-, di-, and monosaccharides as key intermediates. The 2-aminoglycosides were prepared by non-selective glycosidation of 2-azido-2-deoxyglycosyl donors, followed by separation of two anomeric isomers. Although the synthesis involves separation of the stereoisomers, it circumvents not only the careful tuning of reaction conditions, but also the time-consuming preparation of glycosyl donors attached to different protecting groups. The protected 2-aminoglycosides were converted to the fully deprotected DTPA-conjugated tri- to monosaccharides by the same operation. MRI phantom study using the Gd(III) complexes of DTPA-conjugated oligosaccharides indicates that the number of the monosaccharide units was critical for enhancing the relative signal intensity of water protons per Gd, and various stereoisomers would be candidate scaffolds for MRI contrast agents.     

Possible one-dimensional 3He quantum fluid formed in nanopores

Heat capacity measurements have been made down to 5 mK for 3He fluid films adsorbed in one-dimensional (1D) nanometer-scale pores, 28 A in diameter, preplated with 4He of 1.47 atomic layers. At low 3He density, the heat capacity shows a density-dependent, Schottky-like peak near 150 mK asymptoting to the value corresponding to a 2D Boltzmann gas at high temperatures. The peak behavior is attributed to the crossover from a 2D gas to a 1D state at low temperatures. The degenerate state of the 1D 3He fluid is indicated by a predominantly linear temperature dependence below about 30 mK.