BINOL-derived diphosphoramidites bearing unsymmetrical 1,2-diamine link and their application in asymmetric catalysis

New P,P-bidentate diastereomeric diphosphoramidite chiral ligands with mixed stereogenic elements and a C₁ backbone symmetry have been prepared from (S_a)- and (R_a)-1,1′-binaphthyl-2,2′-diol (BINOL) and (S)-N-benzyl-1-(pyrrolidin-2-yl)methanamine and are fully characterized. The use of these ligands provides up to 84% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate and up to 95% ee in the Rh-catalyzed asymmetric hydrogenation of α-dehydrocarboxylic acid esters. The results indicate that the catalytic performance is highly affected by the axial chirality of the binaphthyl moieties of the ligand and the nature of the solvent.     

Solid support flame synthesis of 1-D and 3-D tungsten-oxide nanostructures

In this paper we report the growth of 1-D and 3-D tungsten-oxide nanostructures on tungsten wire probes inserted in an opposed-flow oxy-fuel flame. The probe diameter and oxygen content in the oxidizer were varied to study their influence on the growth of tungsten-oxide nanostructures. The introduction of a 1-mm diameter W probe into the flame environment with an oxidizer composition of 50%O₂ + 50%N₂, resulted in the formation of 1-D nanorods on the upper surface of the probe. The formation of triangular, rectangular, square, and cylindrical 3-D channels with completely hollow or semi-hollow morphology was achieved by reducing the probe diameter to 0.5 mm. Whereas, the increase of the O₂ content to 100% and the employment of a 1-mm probe resulted in the growth of ribbon-like micron-sized structures. The lattice spacing of ∼0.38 nm measured for the 1-D W-oxides closely matches a monoclinic WO₃ structure. X-ray photoelectron spectroscopy analysis revealed that the larger 3-D structures also consist of WO₃ confirming that the chemical composition of the structures remains the same while varying the probe and flame parameters. The proposed growth mechanism states that the 3-D WO₃ structures are formed through the lateral coalescence of 1-D W-oxide nanorods.     

Synthesis and Reaction Peculiarities of Phosphorylated Trifluoroethane Imines

Abstract

Convenient methods for C,N - mono- and biphosphorylated trifluoroethane imines have been developed. These are reactive synthons allowing important derivatives of aminophosphonic acids, fluorine- and phosphorus-containing heterocycles, vinylamides, etc. A rare example of a Perkov-type reaction involving trifluoromethyl group has been discovered.     

Competition of Different Addition and Cycloaddition Processes During Reaction of Phosphorus(II) and (III) Halides with Alkynes

Abstract

Addition of P-halogenophosphaalkenes to I-alkoxyalkynes provides either 2-phosphabutadienes 2 or P(II1)-substituted allenes 3. The reaction o f P-halogenophosphaalkenes I with I-aminoalkynes leads to the phosphetines 4 wa 5 - the product of 1,2-addition reaction.     

Gravitational states of antihydrogen near material surface

We present a theoretical study of the motion of antihydrogen atoms in the Earth??s gravitational field near a material surface. We predict the existence of long-living quasistationary states of antihydrogen in a superposition of the gravitational and Casimir-van der Waals potentials of the surface. We suggest an interferometric method of measuring the energy difference between such gravitational states, hence the gravitational mass of antihydrogen.     

Chitosan nanostructures deposited from solutions in carbonic acid on a model substrate as resolved by AFM

Chitosan macromolecules can be dissolved in water saturated with CO₂ under high pressure, i.e. in carbonic acid. This unique biocompatible solvent with acidity regulated by the variation of applied CO₂ pressure is rather promising for biomedical applications. In this work the main features of deposition of chitosan structures on the model substrate from solutions in this media were examined. After deposition on the mica surface, the obtained structures have been successfully visualised by atomic force microscopy (AFM). It has been found out that they adsorb as rather peculiar elongated objects with an average length of about 70?nm. Such conformations are believed to appear due to amphiphilic nature of chitosan semiflexible chains in agreement with recent theoretical findings. The well-defined geometry of the elongated monodispersed structures allows them to demonstrate some elements of liquid crystalline-like ordering.     

Biochemical and Structural Studies of Conserved Maf Proteins Revealed Nucleotide Pyrophosphatases with a Preference for Modified Nucleotides

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D-scan measurement of nonlinear refractive index in fibers heavily doped with GeO2

Concentration dependence of nonlinear refractive index n2 in fibers heavily doped with GeO2 is studied by using the D-scan method. Good agreement with an empirical dependence established earlier with lower GeO2 concentrations by the cw dual-frequency beat signal technique is shown for GeO2 concentrations up to approximately 100 mol.%. The highest values of the nonlinear coefficient gamma at 1.25 microm of 47.9, 57.7, and 70.9 W(-1) km(-1) were obtained in fibers doped with 67, 75, and 97 mol.% GeO2, respectively.