Conductometric titration study of the reactions of some trialkylphosphines with bromine,iodine and iodine bromide

The reactions of tributyl-, trioctyl-, and tricyclohexyl-phosphine with bromine, iodine and iodine bromide have been studied by conductometric titration in acetonitrile. In general, evidence was obtained for the formation, in solution, of highly conducting 0.5 : 1, 1 : 1, and 2 : 1 adducts. The 1 : 1 and 2 : 1 adducts (R₃PX₂ and R₃PX₄) were isolated and the electrolytic conductivity of their acetonitrile solutions measured. Values of molar conductivity are reported; these point to strong electrolyte behaviour, hence the 1 : 1 and 2 : 1 adducts must be formulated as the phosphonium salts, R₃PX⁺X^? and R₃PX⁺X₃^? respectively.     

Intervals and the deduction of drug binding site models

In the search for new drugs, it often occurs that the binding affinities of several compounds to a common receptor macromolecule are known experimentally, but the structure of the receptor is not known. This article describes an extraordinarily objective computer algorithm for deducing the important geometric and energetic features of the common binding site, starting only from the chemical structures of the ligands and their observed binding. The user does not have to propose a pharmacophore, guess the bioactive conformations of the ligands, or suggest ways to superimpose the active compounds. The method takes into account conformational flexibility of the ligands, stereospecific binding, diverse or unrelated chemical structures, inaccurate or qualitative binding data, and the possibility that chemically similar ligands may or may not bind to the receptor in similar orientations. The resulting model can be viewed graphically and interpreted in terms of one or more binding regions of the receptor, each preferring to be occupied by various sorts of chemical groups. The model always fits the given data completely and can predict the binding of any other ligand, regardless of chemical structure. The method is an outgrowth of distance geometry and Voronoi polyhedra site modeling but incorporates several novel features. The geometry of the ligand molecules and the site is described in terms of intervals of internal distances. Determining the site model consists of reducing the uncertainty in the interregion distance intervals, and this uncertainty is described as intervals of intervals. Similarly, the given binding affinities and their experimental uncertainties are treated as intervals in the affinity scale. The final site model specifies an entire region of interaction energy parameters that satisfy the training set rather than a single set of parameters. Predicted binding for test compounds results in an interval which, when compared to the experimental interval, may be correct, incorrect, or vague. There is a pervasive ternary logic involved in the assessment of predictions, in the search for a satisfactory model, and in judging whether a given molecule may bind in a particular orientation: true, false, or maybe. The approach is illustrated on an extremely simple artificial example and on a real data set of cocaine analogues binding to a nerve membrane receptor in vitro. © 1995 by John Wiley & Sons, Inc.     

Boolean Orthogonalities For Near-rings

Cornish has developed a theory of Boolean orthogonalities for sets with an associated algebraic closure system of “ideals”, and applied it to reduced rings and semiprime rings. In this paper we apply the theory to near-rings and in particular to 3-somiprime near-rings. As one consequence, we identify some near-rings whose 3-semiprime ideals are intersections of 3-prime ideals. In the final section, we discuss local ideals and normality conditions for near-rings with a. Boolean orthogonality.     

Chow–Künneth projectors for modular varietiesProjecteurs de Chow–Künneth pour des variétés modulaires

We show the existence of the Chow–Künneth projectors for certain varieties, including Kuga–Shimura varieties of Hilbert modular varieties. The Chow–Künneth projectors of a smooth projective variety are, by definition, mutually orthogonal idempotents of the Chow ring of self-correspondences which give decomposition of the total cohomology of the variety into degree pieces. To cite this article: B.B. Gordon et al., C. R. Acad. Sci. Paris, Ser. I 335 (2002) 745–750.     

The growth and interaction of conjugated polymer chains,the unpaired electron localization

An ESR method was used to study the structure of the macroradical of the propagating chain R_p in the low-temperature, solid-phase polymerization of p-diethynylbenzene (DEB). The ESR spectra for γ-irradiated DEB samples and those of DEB deuterated in the ethynyl group showed that in the range 77–230 K, the unpaired electron of the macroradical was localized on one of the monomer links. At 230–310 K, its delocalization in a polyconjugated system took place because of addition of a linear macroradical to a double bond of a polymer molecule. The encounter of the macroradical with double bond probably occurs as polymer chain propagation. © 1994 John Wiley & Sons, Inc.     

CHLOROPHYLL PHOTOSENSITIZED ELECTRON TRANSFER REACTIONS IN LIPID BILAYER VESICLES: GENERATION OF PROTON GRADIENTS ACROSS THE BILAYER COUPLED TO QUINONE REDUCTION AND HYDROQUINONE OXIDATION

Abstract— A chlorophyll-containing small unilamellar lipid bilayer vesicle system with a sulfonated quinone molecule (MQS) in one aqueous compartment and a sulfonated hydroquinone molecule (H₂QS) in the other has been investigated, using laser flash photolysis and steady-state irradiation, as a means of storing light energy in the form of a proton gradient across the lipid bilayer. Under optimal conditions, an efficiency of 39% based on the chlorophyll triplet state quenched has been achieved for vectorial electron transfer across the bilayer; this corresponds to a quantum yield of 23% based on absorbed photons. As a consequence of irradiation by a single laser flash, 0.2 μ M of protons were taken up by quinone reduction (MQS → H₂MQS) in the outer compartment. The same number of protons were released in the inner compartment by hydroquinone oxidation (H₂QS → QS). Since the volume occupied by the vesicles was only 1/1000 of the total volume of the sample, the local concentration of protons in the inner compartment was 1000 times larger ( i.e. ≅ 200 μ M ), resulting in the generation of an appreciable proton gradient across the bilayer.     

Absorption of H and D Ly-α radiation by O2 molecules at high temperatures

Absorption cross sections of molecular oxygen were measured at the H and D Ly-α wavelengths (1215.67 and 1215.34 Å) between 800 and 1700°K, the cross sections being given by the equation σ (cm²) = 4.2E-18 exp(-3070/T) (4.2E-18 = 4.2 × 10^-18). The absorption cross section for v = 1 is (9±2)E-19 cm² and that for v = 2 is (7±3)E-18 cm², compared to 1.E-20 cm² for v = 0. Vibrational relaxation times were found to be in agreement with literature data over the range of common temperatures.     

An improved technique for the spectrophotometric determination of nitrate with 2,4-xylenol

An improved method is proposed for the spectrophotometric determination of nitrate with 2,4-xylenol. The sample in aqueous (1.7 + 1 ) sulfuric acid is treated with 2,4-xylenol to produce 6-nitro-2,4-xylenol which is distilled into an ammoniacal water—isopropanol mixture. The intense yellow color of the ammonium salt of 6-nitro-2,4-xylenol is measured at 455 nm. The distillation is done in a Parnas—Wagner Kjeldahl Semimicro distillation apparatus. The isopropanol keeps the excess of 2,4-xylenol in solution. Two procedures are described. In the first (applicable to samples containing alkali nitrates but no chloride, alkaline earth, or ammonium salts), the solution is evaporated to dryness, and (1.7 + 1) sulfuric acid and 2,4-xylenol in acetone are added. In the second (applicable to samples containing chloride, alkaline earth, or ammonium salts), concentrated sulfuric acid is added dropwise to a cooled aliquot and the 2,4-xylenol reagent is then added; if chloride is present, it must be removed by prior precipitation with silver sulfate. Nitrite shows a slight interference which depends on the amount of nitrate and nitrite present.