IR-spectroscopic study of the structures of matrix-isolated complexes of amines with HCl and DCl

Conclusions It has been demonstrated experimentally that small N-heterocyclic compounds interact with HCl (DCl) to form various stoichiometric types of H-complexes: type II, R₃N(HCl)₂; and type III, R₃N(HCl)₃.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 947–952, May, 1981.     

CHARGE TRANSFER ACROSS PIGMENTED BILAYER LIPID MEMBRANE AND ITS INTERFACES

Abstract— The technique of forming bilayer lipid membranes (BLM) has made it possible to study photoreactions of pigments in an environment that is much closer to those in photosynthetic and visual membranes. A pigmented BLM system with Mg²⁺-porphyrins as membrane-bound pigments and with ferricyanide and ferrocyanide as the aqueous electron acceptor and donor, respectively, was used to illustrate the photoelectric effects due to coupled interfacial charge transfer reactions.
The steady-state continuous photoresponse was studied by means of the voltage clamp method and a null current method. The independence of the pigment conductance channel and the ionic conductance channel was demonstrated. A tunable voltage clamp method was used to study the transient pulsed photoresponses. Such a measurement permits us to characterize the photosystem in terms of an equivalent circuit model which contains a novel chemical capacitance. Molecular interpretation of this equivalent circuit model was given.
A microscopic model based on the Gouy–Chapman theory and chemical kinetics calculation leads to an equivalent circuit which is also equivalent to the previous one. Generalization of this microscopic model further leads to a physical mechanism of the generation of the early receptor potential (ERP) in visual membranes. Relevance of pigmented BLM research to photosynthesis and other disciplines was also discussed.     

Intramolecular metal—double bond interactions : VII. Intramolecular cyclization of alkenyl derivatives of lithium,aluminum, gallium and indium

The intramolecular cyclization reactions of tri-1-hex-5-enyl Group III derivatives and of 1-hex-5-enyllithium have been investigated and it is proposed that the reactions may be depicted as internal addition across the terminal double bonds of the alkenyl species. The cyclization reaction proceeds more readily for the 1-hex-5-enyl derivatives than for any other chain length and is dependent on temperature, concentration and solvent. ¹H NMR data and cryoscopic molecular weight data are presented for several diisobutyialkenyl- and diisobutylalkyl-aluminum derivatives. These data have been interpreted in terms of a direct intramolecular interaction between the metal center and the π-electron system of the olefinic site. The intramolecular cyclization reactions for the 1-hept-6-enyl, 1-oct-7-enyl- and 1-undec-10-enylaluminum derivatives also were investigated and it was found that cyclization occurred only for the 1-hept-6-enyl derivative.     

NMR studies on the stereospecific polymerization of methyl vinyl ether. Part I. Polymerization by metal halides: Penultimate effect

Methyl vinyl ether (MVE) was polymerized under various conditions by BF₃·O(C₂H₅)₂ and SnCl₄·CCl₃CO₂H catalysts. The effect of polymerization conditions on the steric structure of poly(methyl vinyl ether) (PMVE) was studied by NMR spectra. It was found that the triad isotacticity of PMVE decreased and the syndiotacticity and heterotacticity increased with increasing polarity of the solvent and increasing polymerization temperature. This result coincided with the qualitative conclusion estimated from softening point and infrared spectra. However, the variation of tacticity by the change of the polarity of a solvent was not so large as expected. There was no large difference between the behavior of BF₃·O(C₂H₅)₂ and SnCl₄·CCl₃CO₂H as catalysts. From the relation between the difference of free energy of monomer addition due to the steric structure of the polymer and the polymerization temperature, it was concluded that the penultimate effect really existed and was due to only the difference in enthalpy in the MVE–BF₃. O(C₂H₅)₂ or MVE–SnCl₄·CCl₃CO₂H systems. The penultimate effect was not greatly changed by the polymerization conditions in these systems.     

Skeletal reactions of perfluoromethylethyl- and perfluorodiethylbenzocyclobutenes with 1,1- and 1,2-alkyl groups in SbF5

Taking perfluoro-1,1-dialkylbenzocyclobutenes as examples, it has been shown to be possible to enlarge the four-membered ring in polyfluorobenzocyclobutenes to five-membered in the presence of SbF₅, by cleavage of the four-membered ring followed by cyclization of the resulting polyfluorostyrene to the polyfluoroindane, which then undergoes further reactions. Perfluoro-1-methyl-1-ethylbenzocyclobutene isomerizes at 50°C in the presence of SbF₅ to perfluoro-,-o -trimethylstyrene, which is reversibly converted at 130°C into perfluoro-1,2-dimethylindane. Perfluoro-l,l-diethylbenzocyclobutene isomerizes at 130°C in the presence of SbF₅ to give perfluoro- -ethyl-,o -dimethylstyrene, which at 170°C gives perfluoro-2-methyl-3-ethylindene- and perfluoro-2-methyl-3-ethyl-4,5,6,7-tetrahydroindene. The last two compounds, together with perfluoro-o-dipropylbenzene, are obtained from per fluoro-1,2-diethylbenzocyclobutene-with SbF₅ at 170°C. From perfluoro-1-methyl-2-ethylbenzocyclobutene with SbF₅ at 95°C there is obtained perfluoro-1-ethylindane, while at 130°C, in addition to the latter compound, there are obtained perfluorinated 1,1-dimethylindane, 1,2-dimethylindane, ,,o-trimethylstyrene, 2,3-dimethylindene, and 2,3-dimethyl-4,5,6,7-tetrahydroindene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1114–1120, May, 1990.     

Isolation of a urease from watermelon seeds and the study of its properties

The enzyme urease has been isolated from the seeds of the watermelon of the Ogonek variety and has been characterized. The molecular weight of a rechromatographed sample of the enzyme has been determined as 480,000. The pH dependence of the activity of the urease and the kinetic parameters of the enzyme have been studied.All-Union Scientific-Research Institute of the Chemistry and Technology of Drugs, Khar'kov. Vitaminy Scientific-Production Amalgamation, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 624–628, September–October, 1983.     

Kinetic study of copper(II) complexation with 9-ethyl-3-carbazolecarboxaldehyde-thiosemicarbazone and kinetic-spectrophotometric determination of copper(II)

The kinetics of complexation reaction of Cu(II) with 9-ethyl-3-carbazolecarboxaldehyde-thiosemicarbazone (ECCAT) has been examined spectrophotometrically. The ligand was synthesized for the first time. The complexation reaction was carried out in a DMF-water medium at 35°C. The complex has maximum absorbance at 393 nm. Kinetic and activation parameters of the complexation reaction were calculated by the Arrhenius and Eyring equations using the data obtained from investigating the effect of temperature on reaction rates under the specified conditions. We also proposed reaction rate equations. Based on the studied complexation reaction, a simple kinetic method for the spectrophotometric determination of copper(II) has been developed. The calibration graphs are linear in the concentration range 0.2–1.9 μg/mL. The species that caused interference were investigated. The text was submitted by the authors in English.     

Evidence for yellow light suppression of lettuce growth

Researchers studying plant growth under different lamp types often attribute differences in growth to a blue light response. Lettuce plants were grown in six blue light treatments comprising five blue light fractions (0, 2, 6% from high-pressure sodium [HPS] lamps and 6, 12, 26% from metal halide [MH] lamps). Lettuce chlorophyll concentration, dry mass, leaf area and specific leaf area under the HPS and MH 6% blue were significantly different, suggesting wavelengths other than blue and red affected plant growth. Results were reproducible in two replicate studies at each of two photosynthetic photon fluxes, 200 and 500 mumol m-2 s-1. We graphed the data against absolute blue light, phytochrome photoequilibrium, phototropic blue, UV, red:far red, blue:red, blue: far red and 'yellow' light fraction. Only the 'yellow' wavelength range (580-600 nm) explained the differences between the two lamp types.     

PHYTOCHROME-MEDIATED GERMINATION: EFFECTS OF BRIEF HIGH TEMPERATURE TREATMENTS

Abstract— Brief high temperature treatments, applied early in the pregerminative period to radiation-requiring seeds of lettuce, inhibited both dark and radiation-induced germination. The inhibition increased with increasing incubation temperature. There was little difference in the germination percentage whether the inductive irradiation was applied before or after the high temperature treatment. When the high temperature treatment preceded induction, there was an increase in the radiation dosage required for maximum germination. These findings are interpreted in terms of lability of physiologically active phytochrome to higher temperatures.     

A field theoretical approach to calculate electronic Born-Oppenheimer coupling terms

In this paper we suggest to consider the spatial distribution of the Born-Oppenheimer nonadiabatic coupling terms as fields which are created by sources, located at degeneracy points, and which can be derived using the ordinary mathematical tools of field theory. It is shown that the curl-divergence equations as formed within a given Hilbert space [M. Baer, Chem. Phys. Lett. 35, 112 (1975)] can be converted into a set of inhomogeneous coupled Poisson equations which are solved for a given set of boundary conditions. The method is applied to the three-state Hilbert subspace of the H(3) system. The numerical results are compared with ab initio calculations for which a very encouraging fit is found.