The effect of high electric fields on the structure and dielectric properties of the B2 phase

Dielectric studies are presented of a banana-shaped compound that exhibits the antiferroelectric B₂ phase. Upon application and subsequent removal of strong electric fields the textures and dielectric properties of the phase drastically change. Most notable is the huge increase of the low frequency permittivity. This behaviour would suggest the induction of ferroelectricity by the electric field.     

New pi-extended water-soluble squaraines as singlet oxygen generators

[graph: see text] Condensation of squaric acid with a number of differently substituted 2-pyrrolyl derivatives afforded three new classes of squaraines. Their sharp and intense absorption bands in the biological window (700-900 nm), inherent singlet oxygen generation capabilities, together with proper functionalization allowing good water solubility make them suitable candidates as new non-porphyrinic singlet oxygen photosensitizers for photodynamic therapy (PDT).     

Die Kristallstruktur des l, 6-8, 13-Bis-oxido-[14]-annulens

Crystals of 1,6-8, 13-bis-oxido-[14]-annulene are monoclinic, a = 9,29, b = 9,74, c = 11,46 Å, β = 90,0°, space group P 2₁/c, with 4 molecules in the unit cell. The structure has been solved by direct methods and refined by full-matrix least-squares analysis of three-dimensional intensity data. The cis-configuration of the two oxygen bridges is confirmed, and the observed molecular parameters are in full accord with the aromatic properties of the molecule.     

5-vinylisoxazole

Cycloaddition of fulminic acid to 1-butyn-3-ol gave a mixture of 5-α-hydroxyethylisoxazole (I) and 4-α-hydroxyethylisoxazole (II) in the ratio 9:1. By the dehydration of 1, 5-vinylisoxazole (III) was obtained. Compound III has also been prepared by cyclization of 4-penten-2-ynal as well as its diethylacetal with hydroxylamine hydrochloride; in both instances no isomers have been obtained. Compound III spontaneously polymerizes even at room temperature yielding a polymer still containing isoxazole rings.     

The reactivity of the A-CH=N-NR-CX-B system. 1,3,4-Oxadiazoles and 2,3,4,5-tetrahydro-1,2,4-triazin-3-ones through the 1–5 and 1–6 cyclization reactions of α-thienylglyoxal monosemicarbazones

The factors influencing the reactivity of α-thienylglyoxal monosemicarbazones when treated with cyclizing reagents (bromine/sodium acetate and hydrobromic acid in acetic acid) were investigated. Depending on the experimental conditions, on the position of the substituent on the semicarbazide residue, and on the cyclizing agent, the substrates 1a-e give the semicarbazone bromides 2a-b, 5 , the 1,3,4-oxadiazoles 3a-c , the 1,2,4-triazine 11 and the 2,3,4,5-tetrahydro-1,2,4-triazine-3-ones 6, 8 and 9 . Compound 6 by thermolysis undergoes ring contraction in the Δ²-1,3,4-oxadiazoline 12 , while treatment with base involves the conversion of 6 into 1,2,4-triazol-5-one 13 . Ir, nmr and mass spectra support the reported structures.     

Use of a55Fe radioisotope for the determination of titanium in laterite samples via energy dispersive X-ray fluorescence

A rapid method for the determination of titanium in geochemical samples using a⁵⁵Fe radioisotope as the extraction source coupled to a Si(Li) detector and a PDP-11.05 computer is described. The relative standard deviation for a thin sample about 100 mg in weight is less than 4% and it is achieved in a fluorescent time of 100 sec. Data are given for the use of two different internal standards, KBrO₃ and K₂Cr₂O₇, the latter being more precise. The values for five international reference standards are in agreement for this method with the reported values. Finally, besides being rapid, no hydrofluoric acid dissolution of fusion is necessary as in atomic absorption and classical methods. This paper was presented at the XX Colloquium Spectroscopium Internationale, 8 Aug.–7. Sept. 1977, Prague, Czechoslovakia.     

NMR stereospecific long-range coupling and preferred conformations in some (E)- and (Z)-α-phenyl-β-[2-(N-methyl)nitropyrrolyl] acrylic acids

NMR data have been used to assign the stereochemistry to some new (E)- and (Z)-α-phenyl-β-[2-(N-methyl)nitropyrrolyl]acrylic acids. The (E)-molecules are biased in the s-cis conformation showing NMR spectroscopic features strictly depending on the conformation.The analysis of the NMR spectra reveals that the (Z)-isomers exist also in the s-cis conformation.     

Bioelectrochemical determination of lactic and malic acids in wine

Electroanalytical methods based on biosensor technology and differential pH measurement for the determination of l-lactic and l-malic acids in wine were developed. Lactic acid was determined according to two procedures consisting of the use of two lactate electrochemical biosensors, one based on a Clark O(2) probe and the other based on the H(2)O(2) probe. The two probes were assembled employing a polymeric membrane where the enzyme lactate oxidase was previously immobilized. Both sensors exhibited high storage and operational stabilities, and good reproducibility when used in wine matrix. Measurement of lactate was carried out using two different flow-through cells assembled with the lactate probes. The low detection limit of these probes and the relatively high concentration of lactate in wine samples required a serial dilution in the range 1:100 to 1:200, thus eliminating all potential electrochemical or enzyme interferences present in the sample. Malic acid was determined using a differential commercially available pH-meter and an enzymatic procedure. For this analysis, we employed the malic enzyme (EC 1.1.1.40) and the NADP(+) cofactor. The pH variation due to the action of this enzyme on malic acid was found to be proportional to the malic acid present in the sample. Experimental parameters such as pH, temperature, and co-factor concentration were optimized, resulting in malate determination in less than 1 min with good reproducibility. Various samples of wine and wine musts were assayed for lactate with the two biosensor procedures, and for malate with differential pH-metry. The results when compared with those obtained with the commonly used spectrophotometric procedure correlated well.