Osmium tetroxide-promoted catalytic oxidative cleavage of olefins: an organometallic ozonolysis

A mild, organometallic alternative to ozonolysis utilizing oxone and OsO(4) is presented. This is a direct oxidation of olefins via the carbon-carbon cleavage of an osmate ester by the action of oxone. Twenty-four different olefins were converted to their corresponding ketones or carboxylic acids in high yields (>80%). Free alcohols, acetate- and benzyl-protected alcohols, and 1,2-diols were stable under these conditions. This method should be applicable for traditional organic synthesis.     

Prompt determination of absolute configuration for epoxy alcohols via exciton chirality protocol

A microscale protocol for determination of absolute configurations of 2,3-epoxy alcohols is described. 2,3-Disubstituted (cis and trans), 2,2-disubstituted, 2,2,3-trisubstituted, and 2,3,3-trisubstituted epoxy alcohols rendered prominent ECCD signals upon complexing with a Lewis acidic porphyrin tweezer and consequently provide straightforward assignment of chirality for epoxy alcohols. This method proved to be rapid, simple, sensitive, and reliable for the class of molecules listed above.     

Dilational viscoelasticity and relaxation properties of interfacial electrostatic complexes between oppositely charged hydrophobic and hydrophilic polyelectrolytes

Strongly adsorbing hydrophobic cationic polyelectrolyte, Eudragit RS, containing approximately 2.5 mol% of pendent hydrophilic trimethylammonium (TMA) groups irreversibly adsorbs from its methylene chloride (MCl) solution at the MCl/water interface and forms solid-like adsorption layers (ALs). Submitted to periodic dilational deformations with the standard radial frequency omega(0)=0.63 rad/s, these ALs exhibit relatively high dilational storage modulus E' approximately 20 mN/m and practically zero loss modulus E' at the bulk concentration C(Eud)=4 x 10(-3)g/L. The frequency scanning of these ALs in the diapason omega=0.01-0.63rad/s and the approximation of the experimental dependences E'(omega) and E'(omega) by two relaxation times rheological model makes it possible to estimate the crossing frequency of these ALs determined from the condition E'(omega(c))=E'(omega(c)) as omega(c) approximately 5 x 10(-4)rad/s. Upon dissolving the hydrophilic anionic polyelectrolyte, chitosan sulfate (ChS), in the water phase (C(ChS)=3 x 10(-2)g/L) the electrostatic interpolyelectrolyte complexes form at the MCl/water interface. The elasticity moduli E' and E' of these mixed AL did not undergo remarkable variations, but the crossing frequency is sharply increased by approximately 10 times becoming equal to omega(c) congruent with 3 x 10(-3)rad/s. The increase of omega(c) certifies for the liquefaction of mixed Eudragit RS/ChS adsorption layers. A remarkable decrease of the storage modulus down to E'=8 mN/m and simultaneous increase of the crossing frequency up to omega(c) congruent with 10(-2)rad/s occurs upon increasing the concentrations of both components, Eudragit RS and ChS, up to 0.1g/L. The liquefaction effect in the mixed ALs of oppositely charged polyelectrolytes was explained on the basis of the proposed relaxation mechanism. The effect of the liquefaction of adsorption layers of strongly adsorbing hydrophobic polyelectrolytes by formation of interpolyelectrolyte complexes with hydrophilic polyelectrolytes must be taken into account in the production of nano-capsules and nano-fibers.     

New synthetic route towards 2,2‐dimethylchromene and synthesis of substituted 7‐(dimethylpropargyl)chromene

Trifluoromethansufonic acid (TFA) was found a proper reagent for regioselectively ring closure of resorcinol to afford 7‐hydroxy‐2,2‐dimethyl‐2,3‐dihydrochromen‐4‐one 3 . The propargylation of 3 gave rise to 2,2‐dimethyl‐7‐(2‐methylbut‐3‐yn‐2‐yloxy)‐2,3‐dihydrochromen‐4‐one 4 . Condensation of 4 with substituted phenyl or benzyl Grignard reagents afforded substituted phenyl or benzylidene chromenes 6a‐d and 4‐(substitutedbenzylidene)‐3,4‐dihydro chromenes 8a‐e , respectively.     

Modulated large-pore mesoporous silica as an efficient base catalyst for the Henry reaction

In this study, mesoporous silica materials with tuned pores and surface areas were successfully synthesized by adjusting the amount of applied hexane and controlling the hydrothermal temperature. The synthesized silica materials were then functionalized by an amine group to produce solid base catalysts and be applicable as efficient heterogeneous base catalysts for the Henry reaction. The mesoporous silica catalysts possessing large-pores and surface area expose their active catalytic sites and thereby improve contacts with reactants fulfilling the reactions expeditiously in comparison with solid base catalysts possessing small-pores and surface area. The results indicated that the yield of the products is significantly dependent on the structure of the applied solid base catalysts. The modulated large-pore solid base catalysts presented high catalytic activity in Henry reactions and could be reused for five consecutive cycles.     

A CONVENIENT METHOD FOR THE SYNTHESIS OF PHOSPHOROTHIOATES AND THEIR ANTICHOLINESTERASE ACTIVITIES

A simple, efficient, and general method has been developed for the synthesis of phosphorothioates through a one-pot reaction of alkyl halides with the mixture of diethyl phosphite in the presence of NH ₄ OAc/S/CaO under solvent–free conditions. The anticholinesterase activities of eight different phosphorothioates were investigated on acetylcholinesterase from electric eel.     

Measure preserving homomorphisms and independent sets in tensor graph powers

In this note, we study the behavior of independent sets of maximum probability measure in tensor graph powers. To do this, we introduce an upper bound using measure preserving homomorphisms. This work extends some previous results concerning independence ratios of tensor graph powers.     

Regularization of backward heat conduction problem

We study the backward heat conduction problem in an unbounded region. The problem is ill-posed, in the sense that the solution if it exists, does not depend continuously on the data. Continuous dependence of the data is restored by cutting-off high frequencies in Fourier domain. The cut-off parameter acts as a regularization parameter. The discrepancy principle, for choosing the regularization parameter and double exponential transformation methods for numerical implementation of regularization method have been used. An example is presented to illustrate applicability and accuracy of the proposed method.     

M(H) shape reconstruction using magnetic spectroscopy

Knowledge about the magnetization behavior M(H) is crucial for the use of magnetic materials in engineering applications. To date many systems exist that are able to measure the magnetization behavior, e.g. VSM, VCM, MOKE. In addition to their huge costs, complex and space-consuming measurement setup, large amount of preparatory work and restricted surface measurements are handicaps which restrict their field of application. Furthermore, the influence of additional physical quantities such as temperature, strain or pressure can only be investigated with great efforts. These influences are, however, of major importance in the development of magnetic sensor systems that are based on the change in magnetic properties.In this paper, a new measurement principle based on a frequency mixing technique is introduced for investigation of the shape of the magnetization curve of soft non-hysteretic magnetic materials. Based on the Taylor expansion of the magnetization curve and the spectral investigation of the inductively detected signal, a mathematical model for the reconstruction of M(H) is proposed. The model is both numerically and experimentally verified. It is shown that the magnetization curve of a nanocrystalline soft magnetic material used in this study can be reconstructed very accurately and the influence of an additional parameter, i.e. strain, can be investigated in detail as well.