Reaction of 3,3,3-trifluoropropene-1 with bromoform and methylene bromide

The radical telomerization of 3,3,3-trifluoropropene with bromoform and methylens bromide has been studied. The nature of the products with bromoform depends substantially on the method of initiation. In the presence of Fe(CO)₅ + DMF, telomers of CHBr₂(CH₅₂CHCF₃)_nBr are formed, while with initiation with benzoyl peroxide other compounds are also formed that contain two, three, or four bromine atoms per molecule. To elucidate the formation of these products a reaction scheme is proposed that involves rearrangement of CHBr₂CH₂CH(CF₃)CH₃CHCF₃ radicals to CBr₂CH₂CH(CF₃)CH₂CH₂CF₃ radicals.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2558–2562, November, 1989.     

Electrohydrodynamic instability in some nematic cyanobiphenyls in an a.c. electric field

Electrohydrodynamic instability in homeotropically oriented nematic samples of 4'-n-octyl-4-cyano-biphenyl and 4'n-alkyloxy-4-cyanobiphenyl, (n = 8.9) have been studied in an a.c. electric field. The domain patterns during the instability in these compounds in a very low frequency a.c. field are very similar to those in a d.c. field. The domain patterns observed at higher frequencies have been identified as 'maltese crosses' or 'crossed isogyres'. The electro-convective 'isotropic' flows near the electrode play an important role in the observed instability.     

Combined supercritical-fluid chromatography/mass spectrometry in the analysis of diuron in plasma using on-line phase-system switching

On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL.     

An interpretation of cortical maps in echolocating bats

Target parameters such as reflectivity, range, velocity, and angular position are represented by ordered maps of tuned cortical neurons in insectivorous bats. It is suggested that the response of each neuron in such a map is determined by a hypothesis test conditioned on a particular value of the mapped parameter. The excitation of each neuron is then interpreted as a sample value of a conditional log-likelihood ratio or a log-likelihood function. Interpolation between the samples, which is needed to find the parameter that maximizes the mapped function (e.g., the maximum likelihood parameter estimate), can be accomplished with overlapped tuning curves. An attempt to portray a sharp peak by a weighted sum of relatively broad neuronal tuning curves or interpolation functions results in excitatory center/inhibitory surround behavior. Facilitation or antifacilitation of neurons that are likely to be excited by succeeding observations can be used for sequential detection and tracking. Interpolation and pulse-to-pulse data storage capability are required to explain range jitter sensitivity and to allow for moving target indication in bat sonar. If a cortical map represents an ordered array of hypothesis tests, then many such tests are implemented in parallel when target parameters are unknown. Detection performance is then degraded relative to the idealized situation in which all parameters are specified. Performance in noise may thus appear to be much worse than that of an ideal detector, even if each hypothesis test is optimally implemented.     

Binary quantum logic and generating semigroups

A refined definition of basic concepts for logic describing physical systems is proposed. Within the suggested formalism of generating semigroups the active logic of questions and passive logic of answers are introduced. The objects for which both logics are isomorphic are called self-adequate. It is shown that the assumption of self-adequacy implies that the object is either quantum or classical. The possibility of application of the theory to non-self-adequate objects is discussed.     

Nonlinear effects of electrical transport in crystals with orbital degeneration

The influence of an electrical field on the charge transfer in crystals with orbital degeneration is investigated. An expression is obtained for the current density in crystals with narrow d-conduction bands in transition metal compounds. As the electrical field intensity increases, a current density maximum is observed with a subsequent section of negative differential conductivity. The results of the investigation agree qualitatively with experimental data.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 14–18, February, 1989.     

Conservation de la charge dans les codes PIC

This Note introduces a new integral form of the charge and current deposition scheme given in 1992 by Villasenor and Buneman, which permits the conservation of charge in PIC codes. This integral form extends directly to higher order spline shape factors, whose use produces less numerical noise. We thus get a discrete charge conserving method for high order shape factors. This method extends easily to nonuniform Cartesian grids for first order shape factors. To cite this article: R. Barthelmé, C. R. Acad. Sci. Paris, Ser. I 341 (2005).     

Spectrofluorimetric Method for the Determination of Aluminum with Alizarin Red PS

 A simple and direct spectrofluorimetric method has been developed for the determination of aluminum using alizarin red PS (1,2,4-trihydroxy 9,10-anthraquinone-3-sulfonic acid). The method is based on the strong fluorescence (480/564 nm) of Al³⁺ and alizarin red. Experimental parameters such as pH, concentration of the ligand, ionic strength of the solution, reaction time and temperature were optimized in order to maximize the analytical signal. Interferences of several ions (anions and cations) were studied and evaluated. The linear range of the method extends from 3 to 100 μg L⁻¹. Limit of detection (3s_b) was 0.9 μg L⁻¹. The method was tested with a silicate certified reference material. Interferences were eliminated by a liquid extraction with cupferron. Author for correspondence. E-mail: aucelior@rdc.puc-rio.br Received September 10, 2002; accepted January 15, 2003 Published online May 5, 2003     

Photochemistry of trifluromethyl substituted 1‐methylpyrazoles

Trifluromethyl substitution on the pyrazole ring was found to enhance photoreactivity via the P₄ pathway which involves interchange of the N2‐C3 ring atoms. Thus, 1‐methyl‐3‐(trifluromethyl)pyrazole (1) and 1‐methyl‐5‐(trifluromethyl)pyrazole (3) transposed with a P₄/P₆ or P₄/P₆+P₇ ratio of 2.1:1. 1‐methyl‐4‐(trifluromethyl)pyrazole (2) transposed regiospecifically by the P₄ transposition pathway. Compounds 2 and 3 were also observed to undergo photocleavage to yield enaminonitrile and enaminoisocyanide products.     

Effect of Conditions of Electric-Spark Dispersion of Zinc on the Quality of the Product Obtained

Influence exerted by additives introduced into the working solution, by iron or copper formedin electric-spark dispersion of these metals and zinc, on the quality of the products obtained in electric erosionwas studied.