Withasteroids of Physalis. IX. Physangulide — The first natural 22S-withasteroid

A new withasteroid — physangulide — has been isolated from the leaves ofPhysalis angulata L. It has been shown that physangulide is the first natural 22S-withanolide. Its structure has been determined as 3β,4β,20,24,25-pentahydroxy-1-oxo-5β,6β-epoxy-20R,22S,24S,25R-withanolide. Its¹H and¹³C NMR spectra, confirming this interpretation, are given. Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 366–371, May–June, 1990.     

n-Butane isomerization in the gas phase and under supercritical conditions

The aromatization of n-butane under supercritical conditions on gallium-, zinc-, and platinum-modified high-silica zeolites with a modulus of 30–70 was first studied, and the experimental data were compared to the results of a study of this process in the gas phase. It was found that the operational efficiency of catalysts for n-butane conversion under supercritical conditions was much higher than that for the gas-phase reaction in terms of activity, productivity, and resistance to poisoning by condensation products. The aromatization of gaseous n-butane at 530°C and 1 atm was characterized by rapid catalyst deactivation. The selectivity for the benzene-toluene-xylene (BTX) fraction was higher than 50%. Under supercritical conditions at 430–560°C and 100–200 atm, the selectivity of formation of aromatic compounds decreased by a factor of 2, whereas the yield of C₁-C₃ cracking products increased by the above factor. On the other hand, it was found that an increase in the productivity of catalysts by a factor of 20–50 with the retention of almost 100% activity for several days of operation is an advantage of the process performed under supercritical conditions. The almost complete conversion of butane under supercritical conditions was found on promoted HZSM-5 zeolite samples. The thermogravimetric analysis of spent samples suggested a higher degree of catalyst carbonization under supercritical conditions, as compared with that in the reaction performed in the gas phase. However, the deposition of 20–30 wt % condensation products on the catalysts had no detectable effect on the high activity of the catalysts in the reaction performed under supercritical conditions.     

Streaming potential in cylindrical pores of poly(ethylene terephthalate) track-etched membranes: variation of apparent zeta potential with pore radius

Streaming potential variation with pressure measured through poly(ethylene terephthalate) track-etched membranes of different pore sizes led to the determination of an apparent interfacial potential zetaa in the presence of 10-2 M KCl. The variation of zetaa with the pore radius r0 is interpreted by (i) the electric double layer overlap effect and (ii) the presence of a conductive gel layer. We propose a method which integrates both effects by assuming a simple model for the conductive gel at the pore wall. We observed the following three domains of pore size: (i) r0 > 70 nm, where surface effects are negligible; (ii) approximately 17 nm < r0 < 70 nm, where the pore/solution interface could be described as a conductive gel of thickness around 1 nm; (iii) r0 < approximately 17 nm, which corresponds to the region strongly damaged by the ion beam and is not analyzed here. The first one (zeta = -36.2 mV) corresponds to the raw material when etching has completely removed the ion beam predamaged region, which corresponds to the second intermediate domain (zeta = -47.3 mV). There the conductance of the gel layer deduced from the treatment of streaming potential data was found to be compatible with the number of ionic sites independently determined by the electron spin resonance technique.     

Water soluble chromone Schiff base derivatives as fluorescence receptor for aluminium(III)

A novel water-soluble chromone Schiff base derivatives bearing polyhydroxylated moiety were prepared and applied for specific recognition of metal ions in aqueous medium. Their selective fluorescence response to Al(III) over a variety of other biologically important metal ions were demonstrated. Electronic parameters of the sensors were also studied by quantum chemical computations.     

X-ray powder diffraction and electron microscopic studies of the ZnTe-CdSe system

Substitutional solid solutions in the ZnTe-CdSe system were synthesized by isothermal diffusion. Within the composition range 100-68 mol % ZnTe, they crystallize in the cubic sphalerite structure; and at ZnTe contents below 26 mol %, in the wurtzite hexagonal structure. The cubic-to-hexagonal structure transition occurs within the composition range 26–68 mol % ZnTe. The atomic concentrations of chemical elements on the oxidized surface of grains of the solid solutions and in their bulk differ. X-ray powder diffraction and electron microscopic studies showed that, with decreasing specific geometric surface area of grains, the average sizes of coherent scattering regions increase.     

Kinetics of thermal decomposition of sulfur-containing amino acids

Rates of thermal decomposition of sulfur-containing amino acids such as D,L-methionine, L-cysteine, and L-cystine are studied. It is established that the amino acids decompose at 190–240°C to give the gaseous and liquid decomposition products in the polyphasic system formed. The rate of summary process is described by the first order kinetic equation up to 30–50% conversion. In spite of close values of the effective activation energies of thermal decomposition of D,L-methionine, L-cysteine, and L-cystine (195, 193, and 184 kJ mol^?1 respectively) the effective rate constants at one and the the same temperature differ by one or two orders of magnitude in the above-mentioned series. Sulfur-containing compounds prevail in the gaseous decomposition products, while in the liquid phase the nitrogen-containing ones are accumulated.     

Design of energy band alignment at the Zn(1-x)Mg(x)O/Cu(In,Ga)Se2 interface for Cd-free Cu(In,Ga)Se2 solar cells

The electronic band structure at the Zn(1-x)Mg(x)O/Cu(In(0.7)Ga(0.3))Se(2) interface was investigated for its potential application in Cd-free Cu(In,Ga)Se(2) thin film solar cells. Zn(1-x)Mg(x)O thin films with various Mg contents were grown by atomic layer deposition on Cu(In(0.7)Ga(0.3))Se(2) absorbers, which were deposited by the co-evaporation of Cu, In, Ga, and Se elemental sources. The electron emissions from the valence band and core levels were measured by a depth profile technique using X-ray and ultraviolet photoelectron spectroscopy. The valence band maximum positions are around 3.17 eV for both Zn(0.9)Mg(0.1)O and Zn(0.8)Mg(0.2)O films, while the valence band maximum value for CIGS is 0.48 eV. As a result, the valence band offset value between the bulk Zn(1-x)Mg(x)O (x = 0.1 and x = 0.2) region and the bulk CIGS region was 2.69 eV. The valence band offset value at the Zn(1-x)Mg(x)O/CIGS interface was found to be 2.55 eV after considering a small band bending in the interface region. The bandgap energy of Zn(1-x)Mg(x)O films increased from 3.25 to 3.76 eV as the Mg content increased from 0% to 25%. The combination of the valence band offset values and the bandgap energy of Zn(1-x)Mg(x)O films results in the flat (0 eV) and cliff (-0.23 eV) conduction band alignments at the Zn(0.8)Mg(0.2)O/Cu(In(0.7)Ga(0.3))Se(2) and Zn(0.9)Mg(0.1)O/Cu(In(0.7)Ga(0.3))Se(2) interfaces, respectively. The experimental results suggest that the bandgap energy of Zn(1-x)Mg(x)O films is the main factor that determines the conduction band offset at the Zn(1-x)Mg(x)O/Cu(In(0.7)Ga(0.3))Se(2) interface. Based on these results, we conclude that a Zn(1-x)Mg(x)O film with a relatively high bandgap energy is necessary to create a suitable conduction band offset at the Zn(1-x)Mg(x)O/CIGS interface to obtain a robust heterojunction. Also, ALD Zn(1-x)Mg(x)O films can be considered as a promising alternative buffer material to replace the toxic CdS for environmental safety.