Combined vibrational,conformational and electron diffraction studies of 2,2,6-trimethylcyclohexanone

The molecular structure of 2,2,6-trimethylcyclohexanone was studied by electron diffraction in the vapor phase combined with auxiliary vibrational and conformational calculations, r_a = 1.535 ± 0.004 and r_a = 1.108 ± 0.015 were found for the average C-H and C-C bonds, respectively, from data taken at both the Oslo and Arkansas electron diffraction units. Five local conformational energy minima (2 rigid (chair) and 3 flexible (boat) ones) were found for the molecule. Data analysis revealed that, at 70° C, the vapors of the compound contained essentially one conformer in a chair form with two of the three methyl-substituents in equatorial positions. Molecular mechanics results based on different force fields taken from the literature were compared, and found to be in fair agreement.     

A selective membrane electrode for iodide ion based on a thiopyrilium ion derivative as a new ionophore

A highly selective electrode for iodide ion based on a thiopyrilium derivative as an excellent ionophore is described. At pH 5.5-8.0, the electrode responds to iodide ion in a linear range from 1.0×10⁻¹ to 8.0×10⁻⁷ M with a slope of 60.2 mV per decade, and a detection limit of 2.0×10⁻⁷ M. Selectivity coefficients determined with the match potential method (MPM) indicate that the interference from inorganic and organic anions is very small. The proposed sensor shows a fast response time of approximately 15 s. It was applied as an indicator electrode in titration of iodide with Ag⁺.     

The Lichtenbaum-Hartshorne theorem for modules which are finite over a ring homomorphism

Let φ:(R,m)→S be a flat ring homomorphism such that mS≠S. Assume that M is a finitely generated S-module with dim_R(M)=d. If the set of support of M has a special property, then it is shown that if and only if for each prime ideal satisfying , we have . This gives a generalization of the Lichtenbaum-Hartshorne vanishing theorem for modules which are finite over a ring homomorphism. Furthermore, we provide two extensions of Grothendieck’s non-vanishing theorem. Applications to connectedness properties of the support are given.     

Electron Transfer from Thioethers

Abstract

Oxidation of thioethers is greatly facilitated by neighboring group participation by carboxylate, alcohol, and thioether moieties.     

Polymerization of methyl acrylate and as comonomer with ethylene using a bis(imino)pyridine iron(II) chloride/methylaluminoxane catalyst

This article describes the homopolymerization of methyl acrylate (MA) and its attempted copolymerization with ethylene using three single‐site catalysts. The primary catalyst under investigation is formed from a bis(imino)pyridine iron(II) chloride with methylaluminoxane ( 1 ), which is compared with bis(4,5,6,7‐tetrahydro‐1‐indenyl)zirconium dimethyl/tris(pentafluorenyl)borane) ( 2 ), and a P,O‐chelated nickel(II) enolate catalyst ( 3 ). Catalyst ( 1 ) leads to the highest activities exceeding those of catalyst ( 2 ) by a magnitude, whereas catalyst ( 3 ) results in formation of no polymer. The kinetics of the polymerizations and the effect of the Al/Fe‐ratio and temperature on the activity and molecular weight of the polymers have been determined. In the ethylene/MA copolymerization trials, catalyst ( 1 ) produces a blend of the two homopolymers, polymethyl acrylate (PMA) and polyethylene. Remarkably, using catalyst ( 1 ) it is possible to produce polymer blends with up to 52% PMA at relatively high activities. The polymerization kinetics has been determined based on the directly measured uptake of ethylene during the runs. NMR spectroscopy, DSC and GPC measurements have been used as efficient methods to prove that polymer blends instead of true copolymers were formed. Finally, some conclusions about the polymerization mechanism will be drawn. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5542–5558, 2008     

One‐Pot Four‐Component Synthesis of N2‐Alkyl‐N3‐[2‐(1,3,4‐oxadiazol‐2‐yl)aryl]benzofuran‐2,3‐diamines

A simple synthesis of N²‐alkyl‐N³‐[2‐(1,3,4‐oxadiazol‐2‐yl)aryl]benzofuran‐2,3‐diamines 5 via a one‐pot four‐component reaction is described (Scheme 1). A mixture of N‐(isocyanoimino)triphenylphosphorane ( 1 ), a 2‐aminobenzoic acid 2 , a 2‐hydroxybenzaldehyde 3 , and an isocyanide 4 in absolute EtOH at room temperature undergoes a smooth reaction to afford 5 in excellent yields (Table).     

Structural characterization of five-coordinate copper(II), nickel(II), and cobalt(II) thiocyanato complexes derived from bis(2-(3,5-dimethyl-1-pyrazolyl)ethyl)amine

The reaction of M(ClO₄)₂·6H₂O with NH₄NCS in presence of the organic sterically hindered bis(2-(di-3,5-dimethyl-1-pyrazolyl)ethyl)amine (bedmpza) afforded the five-coordinate mononuclear dithiocyanato-M(II) complexes [M(bedmpza)(NCS)₂]·xMeOH (1: M = Cu²⁺, x = 0; 2: M = Ni²⁺, x = 0; 3: M = Co²⁺, x = 0.84). The compounds which proved to be non-electrolytes were characterized by IR and UV-Vis spectroscopy and their molecular structures were determined by single-crystal X-ray crystallography. In these complexes, the five-coordinate geometry was achieved by the three N-donors of the ligand bedmpza and two N atoms of the terminal thiocyanato ligands. The Cu(II) complex exists in two polymorphs 1-I and 1-II: an intermediate five-coordinate geometry with the two thiocyanato ligands are arranged as cisoid in 1-I and distorted square pyramidal geometry with the thiocyanato ligands are in transoid orientation in 1-II. Although the later geometry was also observed in the nickel complex 2, distorted trigonal bipyramidal geometry was found in 3. Each complex forms hydrogen bonds of type N-H?S from the secondary amine N(3) donor atoms to the adjacent terminal S(1) acceptor atoms of the thiocyanate group. The thermal behavior of the two polymorphs 1-I and 1-II were similar and no significant differences were observed between the two complexes.     

Gold nanoparticle shape effects on human serum albumin corona interface: a molecular dynamic study

Three-dimensional (3D) hierarchical rutile TiO₂ microspheres composed of nanorods with diameter of several-tens of nanometers, with different morphologies and with average size ranging from 1.3 to 1.8 μm, were successfully synthesized through a surfactant-free solvothermal route. The effects of the solvents n-hexane, chloroform, and cyclohexane on the microstructures of 3D hierarchical TiO₂ nanostructures were investigated. Results of scanning electron microscopy showed that 3D sea-urchin like hierarchical TiO₂ composed of nanorods with a diameter of ~10 nm can only be prepared in the cyclohexane-water system. The growth mechanism of 3D sea-urchin like hierarchical TiO₂ composed of numerous nanorods was further examined and found to differ from the well-known “growth → assembly” mode. The effects of surface tension and polarity of solvents on the morphology and crystal strength of 3D hierarchical TiO₂ nanostructure were also investigated. In addition, the prepared 3D sea-urchin like hierarchical TiO₂ showed highest photocatalytic activity compared with other 3D hierarchical TiO₂ nanostructures in this study and Degussa P25 for the degradation of Rhodamine B solution under UV light irradiation, which could be attributed to its special hierarchical superstructure, the increase of surface catalytic sites and its special composition units.     

Imprinted polymer particles for iron uptake: Synthesis, characterization and analytical applications

This work reports the preparation of molecularly imprinted polymer particles for selective extraction and determination of iron ions from aqueous media. The polymer particles were synthesized from Fe(NO₃)₃, morin, 4-vinylpyridine, ethyleneglycoldimethacrylate, and 2,2′-azobisisobutyronitrile and characterized by IR and DSC both prior to and after removing the Fe-morin complex by leaching with HCl. The effect of different parameters, such as pH, adsorption and desorption time, type and minimum amount of eluent for removing the complex from polymer was evaluated and optimized. The proposed method is characterized by the detection limit of 3.1 µg l^?1 anddynamic linear range of 25 to 200 µg l^?1, with the relative standard deviation less than 8.8%. The method was applied to the recovery and determination of iron ions in a few real samples.     

Module derivation problem for inverse semigroups

The derivation problem for a locally compact group G asserts that each bounded derivation from L ¹(G) to L ¹(G) is implemented by an element of M(G). Recently a simple proof of this result was announced. We show that basically the same argument with some extra manipulations with idempotents solves the module derivation problem for inverse semigroups, asserting that for an inverse semigroup S with set of idempotents E and maximal group homomorphic image G _S , if E acts on S trivially from the left and by multiplication from the right, any bounded module derivation from ? ¹(S) to ? ¹(G _S ) is inner.