Ate complexes of Ge(II) and Sn(II) with bidentate ligands [LiE(OCH2CH2NMe2)3]2 (E=Ge, Sn): synthesis and structure

The reaction of equimolar quantities of LiOCH₂CH₂NMe₂ and E¹⁴(OCH₂CH₂NMe₂)₂ (E¹⁴=Ge, Sn) in ether yielded new ate complexes [LiE¹⁴(OCH₂CH₂NMe₂)₃]₂ (E¹⁴=Ge (1), Sn (2)) with bidentate ligands. The compounds 1 and 2 are white crystalline substances which are highly soluble in THF and pyridine and very sensitive to the traces of oxygen and moisture. The structures of these compounds are studied by X-ray diffraction analysis. The ate complexes 1 and 2 are powerful nucleophiles and may be employed as ligands (neutral) in the coordination chemistry of the transition metals. The electronegative O-substituents at the divalent E¹⁴ atoms render them less oxidizable than alkyl- or aryl-substituted derivatives, and the bidentate ligands, owing to intramolecular donor-acceptor interactions, make them more thermodynamically stable compared to monodentate ligands.     

Wetting films of lipids in the development of sensitive interfaces. An electrochemical approach

Solid-supported thin liquid films of lipids, contacting an electrolyte phase, turned out to be a dependable system in the field of bosensors. The investigations of these objects during the past decade reveal some of their intriguing features enabling the application in constructions of receptor part with 'two-dimensional' arrangement. As a model system, complementary to the other artificial analogs of biomembranes, the wetting films of lipids offer certain advantages concerning the compromise between the stability and flexibility of the molecular structures involved in sensing. The basic principles underlaying the techniques of formation, as well as the conditions of the films stability are emphasized in the present consized review. While no limitations are imposed by the way of preparation, the films seem especially profitable in conjunction with methods for electrochemical signal transduction. In this regard some prominent examples are discussed.     

The endocannabinoid anandamide is a precursor for the signaling lipid N-arachidonoyl glycine by two distinct pathways

Background  

N-arachidonoyl glycine (NAGly) is an endogenous signaling lipid with a wide variety of biological activity whose biosynthesis is poorly understood. Two primary biosynthetic pathways have been proposed. One suggests that NAGly is formed via an enzymatically regulated conjugation of arachidonic acid (AA) and glycine. The other suggests that NAGly is an oxidative metabolite of the endogenous cannabinoid, anandamide (AEA), through an alcohol dehydrogenase. Here using both in vitro and in vivo assays measuring metabolites with LC/MS/MS we test the hypothesis that both pathways are present in mammalian cells.     

Critical Points in a Crystal and Procrystal

The critical points in the model electron density distributions of LiF, NaF, NaCl, and MgO crystals, constructed from accurate X-ray diffraction data, are determined. For LiF and MgO they are compared with those obtained from a Hartree–Fock electron density calculation. Both experiment and theory show the same type of critical points on the bond lines. The topological features in areas between structural units, where the electron density is low and near-uniform, turn out to be model dependent and cannot be established well with the data available. Topological analysis of procrystals (hypothetical systems consisting of spherical atoms or ions placed on the same sites as atoms in real crystal) show that (3, –1) critical points, usually connected with bonding interaction, are observed on interatomic lines in these nonbonded systems as well.     

Acylative kinetic resolution of racemic amines using N-phthaloyl-(S)-amino acyl chlorides

A comparative study of the kinetic resolution of racemic 2-methyl-1,2,3,4-tetrahydroquinoline and 2,3-dihydro-3-methyl-4H-1,4-benzoxazine using N-phthaloyl-(S)-amino acyl chlorides as chiral acylating agents is described. Temperature and solvent effects on the stereochemical features have been examined. It has been found that N-phthaloyl-(S)-phenylalanyl and N-phthaloyl-(S)-2-phenylglycyl chlorides bearing aromatic substituents close to the stereogenic centre are more stereoselective acylating agents than N-phthaloyl-(S)-alanyl chloride. For the preparative kinetic resolution of racemic amines N-phthaloyl-(S)-phenylalanyl chloride proved to be the most appropriate chiral acylating agent.     

Synthesis of new organophosphorus‐substituted mono‐ and bis(trimethylsilyl)amines with PCH2N fragments and their derivatives

Convenient procedures for the synthesis of new organophosphorus‐substituted mono‐ and bis(trimethylsilyl)amines with PCH₂N moiety are proposed, starting from trimethylsilyl esters of organophosphorus acids, as well as 1,3,5‐trialkylhexahydro‐1,3,5‐triazines and N‐alkoxymethyl bis(trimethylsilyl)amines as aminomethylating reagents. Certain properties of the resulting compounds are presented. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:71–77, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20580     

Synthesis of bis‐ and tris‐organophosphorus substituted amines and amino acids with PCH2N Fragments

The aminomethylation of the derivatives of trivalent organophosphorus acids, containing PH and POSiMe₃ fragments with various bis‐ and tris(alkoxymethyl)amines and bis(alkoxymethyl)amino acids, is proposed as a convenient method for the synthesis of new bis‐ and trisphosphorylated amines and amino acids as well as their derivatives with four and five coordinated phosphorus. Also the three‐components systems of phosphorous acid, paraformaldehyde, and amines are thoroughly investigated via the treatment of reaction mixtures with bis(trimethylsilyl)amine. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:430–440, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20616     

IR and NMR spectra,intramolecular hydrogen bonding and conformations of para-tert-butyl-aminothiacalix[4]arene in solid state and chloroform solution

It is demonstrated that dissolution of aminothiacalix[4]arene in chloroform results in transformation of 1,3-alternate conformation, adopted in single-crystal and bulk polycrystalline solids, to the pinched-cone form. This conformer is stabilised by the intramolecular hydrogen bonds of two distal amino-groups acting as H-donors with another two amino moieties that appear as H-acceptors. The H-bonds cause quite small (ca. 10–20 cm^?1) red shift of the IR bands of the NH₂ stretching vibrations, which suggests rather weak NH?N hydrogen bonding. This latter is sufficient to stabilize the pinched-cone conformation in the chloroform solution, but the energy gap between the pinched-cone and other conformations is small, and solid-state intermolecular forces easily overcome it, leading to realisation of the 1,3-alternate conformer. The comparison of the DFT computed and experimental vibrational and NMR spectra demonstrates good quality of present quantum-chemical computations, allows complete interpretation of the spectra and reveals simple IR and NMR spectroscopic markers of the conformers of aminothiacalix[4]arenes.