A mild and highly efficient protocol for the one-pot synthesis of primary α-amino phosphonates under solvent-free conditions

Under solvent-free reaction conditions and in the presence of solid LiClO₄ a novel and mild protocol for the one-pot, three-component synthesis of primary α-amino phosphonates from an aldehyde, hexamethyldisilazane and a trialkyl phosphite is described giving high yields and having short reaction times. The same products are obtained in very low yields, when the three-component reaction is carried out under microwave irradiation and in the absence of solid LiClO₄. Examples of some prepared 1-aryl-N,N′-bis(arylidene)methanediamines are also described.     

One-pot diastereoselective synthesis of α-aminonitriles from aldehydes, chiral amines, and trimethylsilyl cyanide under solvent-free conditions

Treatment of aliphatic and aromatic aldehydes with chiral amines and trimethylsilyl cyanide in the absence or in the presence of Lewis acids (including lithium perchlorate) under solvent-free conditions afforded the corresponding α-aminonitriles in good yields and with a diastereoselectivity of 68 to 86%. Published in Russian in Zhurnal Organicheskoi Khimii, 2006, Vol. 42, No. 1, pp. 56–59. The text was submitted by the authors in English.     

Silicon-29 diffusion-ordered NMR spectroscopy (DOSY) as a tool for studying aqueous silicates

The first use of silicon-29 diffusion-ordered NMR spectroscopy (DOSY) is reported, in a study of the speciation of aqueous silicates.     

Application of thermal analysis to carbon black-elastomer systems

In this study a relationship between the surface and textural properties of carbon blacks and the gasification process induced thermally in air is noted. A temperature jump method was used to follow the gasification in air and to establish the relevant Arrhenius parameters. This can be associated with the activity of ‘basal’ plane carbon atoms as well as ‘edge’ carbon atoms at the surface. This is based on a model of carbon black structure consisting of the irregular packing of small graphite carbon structures. The carbon black surface was measured using a single measurement of adsorption based essentially on the BET volumetric method. The carbon black surface had a rate of oxidation per unit are which clearly indicated that the lower area carbon blacks had a predominately active area of ‘edge’ atoms at the surface while the surface of the higher area carbon blacks had a predominate amount of ‘basal’ plane graphite carbon atoms.     

SUPPRESSION OF THE INDUCTION OF DELAYED-TYPE HYPERSENSITIVITY REACTIONS IN MICE BY A SINGLE EXPOSURE TO ULTRAVIOLET RADIATION

Abstract— After a single exposure of mice to UV radiation, their ability to generate a contact hypersensitivity (CHS) response to contact sensitizers applied epicutaneously to distant, unirradiated skin is severely impaired. It is not clear, however, if the classic delayed type hypersensitivity (DTH) reponse to exogenous antigens, injected into the subcutaneous (s.c.) space, can also be modulated by UV radiation. We report here that a single exposure of mice to UV radiation suppressed the induction of DTH to both erythrocyte and soluble protein antigens injected s.c., but did not suppress the elicitation of the response. The suppressive effect was abrogated by cyclophosphamide treatment. In addition, antigen-specific suppressor cells were found in the spleens of the mice with a decreased DTH response. Since the ability to mount a DTH response has been linked with the resistance to certain pathogenic microorganisms, we suggest that the suppression of DTH by UV radiation may have the potential to compromise host resistance to such infectious agents.     

In Silico Analysis of PORD Mutations on the 3D Structure of P450 Oxidoreductase

Cytochrome P450 oxidoreductase (POR) is a membrane-bound flavoprotein that helps in transferring electrons from its NADPH domain to all cytochrome P450 (CYP450) enzymes. Mutations in the POR gene could severely affect the metabolism of steroid hormones and the development of skeletal muscles, a condition known as Cytochrome P450 oxidoreductase deficiency (PORD). PORD is associated with clinical presentations of disorders of sex development, Antley and Bixler’s syndrome (ABS), as well as an abnormal steroid hormone profile. We have performed an in silico analysis of POR 3D X-ray protein crystal structure to study the effects of reported mutations on the POR enzyme structure. A total of 32 missense mutations were identified, from 170 PORD patients, and mapped on the 3D crystal structure of the POR enzyme. In addition, five of the missense mutations (R457H, A287P, D210G, Y181D and Y607C) were further selected for an in-depth in silico analysis to correlate the observed changes in POR protein structure with the clinical phenotypes observed in PORD patients. Overall, missense mutations found in the binding sites of POR cofactors could lead to a severe form of PORD, emphasizing the importance of POR cofactor binding domains in transferring electrons to the CYP450 enzyme family.     

Rotating Bose-Einstein condensate in an optical lattice: Formulation of vortex configuration for the ground state

We consider a rotating Bose-Einstein condensate in an optical lattice in the regime in which the system Hamiltonian can be mapped onto a Josephson junction array. In an approximate scheme where the couplings are assumed uniform, the ground state energy is formulated in terms of the vortex configuration. Application of the method for the ladder case presented and the results are compared with Monte-Carlo method.     

An efficient four-component synthesis of dithiocarbamate derivatives

An environmentally benign, one-pot, four-component synthesis of chemically and pharmaceutically interesting dithiocarbamate derivatives is reported. The one-pot reaction of various aromatic aldehydes, ketones, aliphatic amines, and carbon disulfide, in the presence of potassium hydroxide in urea-choline chloride deep eutectic solvent or ethanol, leads to the corresponding dithiocarbamates in good to excellent yields. This method provides a convenient and time-saving strategy, with a simple work-up procedure.     

Mild,four-component synthesis of 6-amino-4-aryl-3-methyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitriles catalyzed by titanium dioxide nano-sized particles

A convenient and efficient solvent-free procedure is described for preparation of 6-amino-4-aryl-3-methyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitriles by four-component reaction of hydrazine hydrate, ethyl acetoacetate, aryl aldehyde, and malononitrile in the presence of a catalytic amount of titanium dioxide nano-sized particles. Short reaction times, high yields under ambient conditions, simple reaction, clean work-up, and reusability of the nano heterogeneous catalyst are the advantages of this method.     

Behavior of magnetocrystalline anisotropy constants of [Co3,2nmPt1,5nm]6 multilayer observed by torque magnetometer

The presence of the magnetic anisotropy is clearly intimately related to the anisotropy nature of the artificial multilayer structure itself. We present here the behavior of magnetocrystalline anisotropy constants of the [Co_3,2nmPt_1,5nm]₆ multilayer, as a function of the temperature and the external magnetic field observed by means of a torque magnetometer in an in-plane configuration. We have determined the magnetocrystalline anisotropy constants from the magnetic torque curves for different temperatures and in different magnetic fields, taking into account the angle difference between the directions of the external field and the magnetization. The most prominent result in this work consists in the need to introduce the anisotropy constant of third order in the analysis.