Role of carbon clusters in pyrolysis of iodomethanes

Molecular parameters and thermodynamic functions of the carbon cluster cyclo-C₁₂ were calculated by the B3LYP method in the aug-cc-pVDZ basis. The composition of products of iodomethane pyrolysis in the range 500–1000 K was calculated from the data obtained in combination with published data on thermodynamic function of other molecules. High experimental yield of methane and carbon (carbyne) in the iodomethane pyrolysis and the absence of even traces of ethane, 1-iodoethane, and 1,2-diiodoethane were accounted for.     

Selectivity of the stationary phase in gas-liquid chromatography

The use of molar refractions is insufficient to describe the retention volumes and thermodynamic functions of solutions in nonpolar stationary phases. The heats of dissolution of monofunctional derivatives of the alkanes are proportional to the polarizability and inversely proportional to the sixth power of the van der Waals' radius of the interacting particles. The heat of dissolution of substances being analyzed, with the same number of carbon atoms, in aromatic solvents depends on the conditions of contact between the molecules of the substances being analyzed and the benzene rings of the solvent. The order of the heats of dissolution of substances being analyzed in different nonpolar solvents does not remain the same, indicating that the theory of regular solutions cannot be applied to these systems. To determine the order of the heats of dissolution of isomers in nonpolar stationary phases it is necessary to take account of the electron density distribution in the molecules of the reacting substances and the probability of molecular arrangement for the most favorable interaction.     

In vivo optical analysis of quantitative changes in collagen and elastin during arterial remodeling

Altered collagen and elastin content correlates closely with remodeling of the arterial wall after injury. Optical analytical approaches have been shown to detect qualitative changes in plaque composition, but the capacity for detection of quantitative changes in arterial collagen and elastin content in vivo is not known. We have assessed fluorescence spectroscopy for detection of quantitative changes in arterial composition in situ, in rabbit models of angioplasty and stent implant. Fluorescence emission intensity (FEI) recorded at sites remote from the primary implant site was correlated with immunohistochemical (IH) analysis and extracted elastin and collagen. FEI was significantly decreased (P<0.05) after treatment with anti-inflammatory agents, and plaque area decreased on comparison with saline-treated rabbits after stent implant or angioplasty (Por=0.961) analysis were detected by multiple regression (MR) analysis. Good correlations also were found for FEI with elastin and collagen measured by high-performance liquid chromatography; MR analysis provided highly predictive values for collagen and elastin (R2>or=0.994). Fluorescence spectroscopic analysis detects quantitative compositional changes in arterial connective tissue in vivo, demonstrating changes at sites remote from primary angioplasty and stent implant sites.     

Selectivity of stationary phases for the resolution of polycyclic aromatic hydrocarbons

Summary Relative retentions, heats and entropies of solution for 16 PAH in seven different stationary phases were measured under standard isobaric conditions using GC. The experimental conditions to obtain reproducible retention data at non-linear adsorption isotherms are discussed and standard conditions are recommended using the linear relationship between retention time and 1/log h (where h is the peak height). A linear relationship was established between the relative molar heats of solution and the number of carbon atoms in the PAH-molecule. This relationship is valid only for non-polar stationary phases. Certain effects of the isomeric structures of PAH are studied using the relative molar heats and entropies of solution. The latter function is very sensitive to the spherical form of a molecule. Different aspects of isomeric selectivity are discussed and it is concluded that the better way for resolving complex PAH-mixtures is rather an improvement in column efficiency than searching for new stationary phases.     

Synthesis of non-equilibrium PtxOs1−x Solid solutions. Crystal structure of [Pt(NH3)4][OsCl6]

Several non-equilibrium solid solutions belonging to the platinum-osmium systems Os_0.9Pt_0.1, Os_0.8Pt_0.2, Os_0.5Pt_0.5, Os_0.7Pt_0.3, Os_0.75Pt_0.25 are prepared and studied. The thermal decomposition of [Pt(NH₃)₄][OsCl₆] in the hydrogen and helium atmosphere is investigated. It is found that the Pt_0.5Os_0.5 solid solution develops through the formation of (NH₄)₂[OsCl₆] and a metallic phase based on Pt. The crystal structure of a double complex salt [Pt(NH₃)₄][OsCl₆] is studied (X8-APEX Bruker, 1508 independent reflections, R = 2.04%). Crystal data for PtOsN₄Cl₆H₁₂ are: a = 11.6216(5) Å, b = 11.0016(5) Å, c = 10.3819(5) Å, V = 1327.4(1) ų, space group Cmca, Z = 4, d _x = 3.333 g/cm₃. The coordination polyhedron around Os is octahedral: 〈Os-Cl〉 2.357 Å, ∠Cl-Os-Cl 89.5–90.5°, while around Pt it is square-planar: Pt-N 2.046 Å, ∠ N-Pt-N 89.59° and 90.41°.     

Thermal Decomposition in Systems of Acid Zn(II), Co(II), and Ni(II) Maleates with the Formation of Metallic Nanoparticles

Russian Journal of Physical Chemistry A - Conditions of synthesis are optimized and XRD and thermoanalytical studies are performed for normal maleate [Zn(H2O)2(C4H2O4)] and acid maleate...     

Regularities of thermolysis for the Fe(II), Co(II), and Ni(II) salts of maleic and ortho-phthalic acids with the formation of metal/polymer composites

Russian Journal of Coordination Chemistry - Regularities of the thermolysis of acidic salts of unsaturated (maleic) [M(H2O)4(C4H3O4)2] and aromatic (ortho-phthalic) [M(H2O)6](C8H5O4)2 (M = Fe(II),...     

Complexes of PdCl2 with chiral oximes of α-(o-anisidino)caranone and α-(o-anisidino)pinanone: synthesis and crystal structures

3-(2-Methoxyphenylamino)caran-4-one and 2-(2-methoxyphenylamino)pinan-3-one E-oximes obtained from appropriate natural terpenes were transformed into 1: 1 complexes with PdCl₂. The structures of the complexes were examined by X-ray diffraction.     

Synthesis and structure of palladium(II) and copper(II) complexes with chiral bis-α-aminooximes containing (+)-3-carene or (+)-limonene fragments and 4,4′-methylenedianiline linker. Crystal structure of the complex [Cu(i-PrOH)Cl2(μ-H2L3)CuCl2·H2O]

Coordination compounds Pd₂(H₂L²)Cl⁴ (I), Cu₂(H₂L²)Cl₄ (II), Pd₂(H₂L³)Cl₄ (III), and Cu₂(H₂L³)Cl₄ (IV), where H₂L² and H₂L³ are chiral bis-α-aminooxime ligands consisting of (+)-3-carene or (+)-limonene fragments and 4,4′-methylenedianiline linker, were synthesized and examined by NMR, ESR, and IR spectroscopy. The structure of [Cu(i-PrOH)CL₂(μ-H₂L³)CuCL₂·H₂O] (V) was determined by X-ray analysis.