VISUAL PIGMENTS—10. SPECTROSCOPY AND PHOTOPHYSICAL DYNAMICS OF RETINOL AND RETINYL ETHER

Abstract— The absorption and emission spectra, lifetimes and quantum yields of all-trans retinol have been examined as a function of solvent and temperature. In addition, the spectroscopy of retinyl ether and 2 other polyene alcohols have been determined. Based on the results obtained, we conclude that the singlet excited state of retinol and retinyl cther is of a forbidden character and of the type loosely called ¹A^-_g. Retinol forms a dimer in an alkane solvent when cooling from 298 to 77 K. A general structure for the dimer is proposed.     

Regional cerebral blood flow measurement in brain tumors

The regional cerebral blood flow (CBF) was determined on seventeen patients with brain tumors. Ring type single photon emission CT (SPECT) was used following intravenous injection of 133Xe. Case materials included eleven meningiomas and six malignant gliomas. Evaluation was performed with emphasis on the following points; Correlation of the flow data within tumors to the angiographic tumor stains, Influence of tumors on the cerebral blood flow of the normal brain tissue, Correlation between degree of peripheral edema and the flow data of the affected hemispheres. There was significant correlation between flow data within tumors and angiographic tumor stains in meningiomas. Influence of tumors on cerebral blood flow of the normal tissue was greater in meningiomas than in gliomas. There was negative correlation between the degree of peripheral edema and the flow data of the affected hemisphere. It has been concluded that the measurement of CBF in brain tumors is a valuable method in evaluation of brain tumors.     

Enantiomeric purity determination of malic acid in apple juices by multi-beam circular dichroism detection

A multi-beam circular dichroism (CD) detector which is easily constructed by inserting inexpensive optics into a conventional photo-diode array detector has an advantage of simultaneous detection of the absorbance and CD. The enantiomeric purity determination of malic acid in beverages was performed by this detection system. Malic acid when complexed with Cu(II) was found to have an absorbance maximum at around 750 nm. The L-malic acid-Cu(II) complex showed a positive Cotton effect in its absorbance band and its anisotropy factor (delta epsilon/epsilon) was relatively large at about 1/170. This complex was retained on a reversed-phase column with the addition of racemic 2-hydroxy-3-methylbutyric acid to the mobile phase as the ligand. A plot of the relative peak areas between the CD and the absorption (delta abs/abs) versus optical purity showed good linearity with a correlation coefficient of 0.999, and the precision expressed as the relative standard deviation of the errors from the regression line was +/-2.7% (2sigma). The accuracy of the proposed method was assessed by capillary electrophoresis. Eight commercially available juice products were analyzed using this method. Five of them were thought to be adulterated with synthetic malic acid.     

Polymerization of vinyl acetate in fatty acids and properties of poly (vinyl alcohols) derived from the poly (vinyl acetates)

Polymerization of vinyl acetate (VAc) in various fatty acids (carbon numbers 4–18) was carried out. Chain transfer constants to the acids were determined to be 20–35×10^–4, from which the constant to a methylene group was obtained to be 0.73×10^–4. Viscometry in aqueous solution of derived poly (vinyl alcohol) (PVA) showed the usual behavior in terms of Huggins constant obtained by the Schulz–Blaschkes equation for PVAs derived from fatty acid systems lower than hexadecanoic acid. PVA derived from octadecanoic acid system showed abnormality, indicating association of alkyl groups. Contact angles on surfaces of PVAs cast from aqueous solutions were measured. While those of PVA derived from lower acid systems were 62°, those of PVAs derived from higher aids were higher and increased to 92° with increase in carbon number to octadecanoic acid. Alkyl groups in the PVAs were estimated to appear on the surfaces. Surface tension of aqueous solution of the PVA derived from octadecanoic acid showed high surface activity, and depended on pH of the solution, indicating the presence and cleavage of lactone ring at the combined portion between PVA and the acid.     

Synthesis of stereocontrolled α,α-difluoro-β-hydroxycarbonyl materials

Synthesis and synthetic utilities of stereocontrolled α,α-difluoro-β-hydroxy-γ,δ-unsaturated carbonyl compounds via enzymatic resolution with lipase PS (Pseudomonas cepacia, Amano Pharmaceutical Co. Ltd.) or lipase MY (Candida rugosa, Meito Sangyo Co. Ltd.) were described, and then the absolute configuration of obtained chiral materials was determined by the modified Mosher's method.     

Isotachophoretic determination of mobility and pKa by means of computer simulation : V. Evaluation of mo and pKa of twenty-eight dipeptides and assessment of separability

Isotachophoretic qualitative indices, R_E, for twenty-eight dipeptides were measured in the range pH 7.4–9.6. The absolute mobility, m_o, and pK_a values were evaluated by the use of the least-squares method, utilizing a simulation of the isotachophoretic steady state. The m_o values were newly evaluated and the pK_a values were in good agreement with literature values. By comparison of the evaluated m_o and pK_a values of the dipeptides with those of the constituent amino acids, simple relationships were found which may be used to estimate the m_o and pK_a values of other dipeptides. The separability of the dipeptides was also evaluated by considering the differences between their simulated effective mobilities. It is concluded that isotachophoresis is very convenient for the separation of dipeptides and their constituent amino acids.     

Total synthesis of (+)-pederine. A simple synthetic method for N-(1-methoxyalkyl)amides

A mild one-pot method for the synthesis of acyclic N-(1-methoxyalkyl)amides starting from carboxylic acids and methyl imidates had been developed and applied to the total synthesis of the insect poison pederine $\text{1}$.     

Novel Z-selective head-to-head dimerization of terminal alkynes catalyzed by lanthanide half-metallocene complexes

Various terminal alkynes have been cleanly dimerized into the corresponding head-to-head (Z)-enynes by use of the half-metallocene lutetium alkyl complexes Me2Si(C5Me4)(NAr)Lu(CH2SiMe3)(THF) (Ar = Ph, C6H3Me2-2,6, C6H2Me3-2,4,6) as catalysts. Aromatic C-Cl, C-Br, and C-I bonds, which are known to be extremely susceptible to reductive cleavage by transition metals, survived in the present reactions. The corresponding dimeric alkynide species [Me2Si(C5Me4)(NAr)Lu(mu-CCR)]2 are thought to be the true catalysts, some of which have been isolated and structurally characterized. These alkynide species were thermally stable and soluble at the reaction temperatures (80-110 degrees C), but they precipitated upon cooling to room temperature after completion of the reaction. Therefore, this catalyst system works homogeneously but can be separated and reused, thus constituting the first example of a recyclable catalyst system for the dimerization of terminal alkynes and also the first example of (Z)-selective head-to-head dimerization of aromatic terminal alkynes.