Orientation of Rod-Shape Molecule, 2,2′-Bis[4-(Trifluoromethyl)Phenyl]-5,5′-Bithiazole in Films Deposited in a Vacuum on Oriented α-Sexithiophene Films

We demonstrated orientation control of n-type rod-shape, 2,2′-Bis[4-(trifluoromethyl)phenyl]-5,5′-bithiazole (BTMPB) molecules when deposited on the in-plane oriented polythiophene (PT) and α-sexithiophene (6T)/PT films in vacuum. The results showed that the π-π stacking direction of BTMPB molecules on the PT and 6T/PT films is perpendicular to the substrate plane. In addition, a molecular long axis of BTMPB oriented parallel to the friction direction of the PT. Moreover, in-plane orientation of BTMPB was more enhanced by in-plane oriented 6T molecules than in-plane oriented PT underneath. On the other hand, the molecular long axis of BTMPB deposited on the substrates stood on the substrates.     

Role of bis(monoacylglycero)phosphate in propranolol binding to phospholipid membranes under acidic conditions as measured by high‐performance frontal analysis/capillary electrophoresis

Bis(monoacylglycero)phosphate (BMP) is localized in acidic organelles such as late endosomes or lysosomes. It has been reported that BMP levels increase under phospholipidosis induced by cationic amphiphilic drugs. In the present study, the effect of BMP on the binding of propranolol (PRO) to phospholipid liposomes under acidic conditions was investigated. Binding experiments were conducted by high‐performance frontal analysis/capillary electrophoresis. PRO showed nonspecific binding to BMP‐containing liposomes (BMP:phosphatidylcholine = 1:4), when numbers of bound drug molecules per lipid molecule (r) ranged 0.01–0.06. Total binding affinity increased depending on the BMP content. Binding affinity was decreased by low ionic strength, or by substitution of BMP with diacylglycerol, suggesting that electrostatic interactions were involved. The binding‐enhancement effect of BMP was almost equivalent to that of phosphatidylglycerol, and slightly larger than that of phosphatidylserine. An acidic environment (pH 5.0) decreased total binding affinity to BMP‐containing liposomes. This could be explained by the pH‐partition theory (i.e., the loss in affinity was caused by a decrease in the neutral form of the drug accessible to the membrane core). These results suggest that PRO binding is enhanced by BMP in late endosomes or lysosomes, whereas an acidic environment weakens such binding.     

Studies on isoindoline derivatives and related compounds. I Synthesis and reduction of 1,3-dicarboethoxymethyleneisoindoline

The reaction of iminoether III with benzyl cyanoacetate gave ethyl 1-(α-cyanocarbobenzyl-oxymethylene)isoindoline-3-acetate (V) in a 26% yield. Decarboxylation of ethyl 1-(α-cyanocarboxymethylene)isoindoline-3-acetate (VI), obtained by hydrogenolysis of V, gave a mixture of 1-carboethoxymethyleneisoindoline-3-acetonitrile (VII) as major component and 1-carboethoxymethylene-3-cyanomethyleneisoindoline (VIII) as minor component, which were reconvertible into each other. On the other hand, decarboxylation of VI was successfully carried out to give VII as a single product under a nitrogen atmosphere. Ethanolysis and autoxidation of VII gave crystalline diethyl 1,3-dicarboethoxymethyleneisoindoline (XIII). Catalytic hydrogenation of of XIII over platinum oxide gave diethyl isoindoline-cis-1,3-diacetate (XIV) in a yield of 92%. The uv spectra of these 1,3-disubstituted isoindoline derivatives are summarized in Table I.     

Relation between dielectric and low-frequency Raman spectra of hydrogen-bond liquids

We analyzed the complex dielectric and Raman spectra of hydrogen-bond liquids in the microwave to terahertz frequency range. As for water and methanol, the high-frequency component of the dielectric spectrum, i.e., the small deviation from the principal Debye relaxation, clearly corresponds to the Raman spectrum. This indicates that the cooperative relaxation, accompanied by huge polarization fluctuation, is virtually not Raman active, whereas the faster processes reflect common microscopic dynamics. For ethylene glycol, the shape of the Raman spectrum also resembles that of the high-frequency deviation of the dielectric spectrum, but, additionally, a weak manifestation of the cooperative relaxation arising from quadrupolar conformers is detected.     

Coulomb- and antiferromagnetic-induced fission in doubly charged cubelike fe-s clusters

We report the observation of symmetric fission in doubly charged Fe-S cluster anions, [Fe(4)S(4)X(4)](2-)-->2[Fe(2)S(2)X(2)](-) (X=Cl,Br), owing to both Coulomb repulsion and antiferromagnetic coupling. Photoelectron spectroscopy shows that both the parent and the fission fragments have similar electronic structures and confirms the inverted energy schemes due to the strong spin polarization of the Fe 3d levels. The current observation provides direct confirmation for the unusual spin couplings in the [Fe(4)S(4)X(4)](2-) clusters, which contain two valent-delocalized and ferromagnetically coupled Fe2S2 subunits.     

The crystal structure of Rb-β-alumina

The crystal structure of Rb₂O·11Al₂O₃ has been determined from three-dimensional X-ray data. The compound forms hexagonal crystals with a = 5.600, c = 22.87 Å, and Z = 1 in space group $\text{P6}{}_3\text{mmc}$. The structure has been refined by least-squares methods with anisotropic temperature factors to an R value of 0.079 for 331 independent reflections collected by diffractometry. The mobile ion sites and their occupation percentages are discussed in relation to other β-alumina compounds. The covalently bonded corner-sharing O₃AlOAlO₃ tetrahedra are discussed in relation to the ionic conduction phenomena.     

Synthesis of a 2-Methyl-4-sulfanilamido-s-triazine derivative

An attempt to obtain 2-methyl-4-sulfanilamido-s-triazine (XXI) by condensation of 2-amino-4-methyl-s-triazine (II) with p-acetamidobenzenesulfonyl chloride (III) in pyridine and in benzene containing trimethylamine gave instead the unexpected products, guanidine N-acetylsulfanilate (IV) (after hydrolysis) and N¹,N¹-dimethylsulfanilamide (V), respectively. On the other hand, 2-methyl-4-methylthio-6-sulfanilamido-s-triazine (XIX) was obtained from 4,6-dimethylthio-s-triazine (XVII), but the reduction of XIX with Raney nickel in aqueous sodium hydroxide solution also gave an unexpected compound, sulfaguanidine (XX).