Steric influence in the direction of elimination of gas-phase pyrolyses of several highly branched secondary acetates

The rate coefficients for the gas-phase pyrolyses of a series of structurally related secondary acetates have been measured in a static system over the temperature range of 289.1–359.5°C and the pressure range 50.0–203.0 torr. The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for 3-hexyl acetate, log k₁ (s^?) = (12.12 ± 0.33) ? (176.1 ± 3.9)kJ/mol/2.203RT; for 5-methyl-3-hexyl acetate, log k₁ (s^?) = (13.17 ± 0.20) ? (186.2 ± 2.3)kJ/mol/2.303RT; and for 5,5-dimethyl-3-hexyl acetate, log k₁ (s^?) = (12.70 ± 0.19) ? (177.4 ± 2.2)kJ/mol/2.303RT. The direction of elimination of these esters has shown from the invariability of olefin distributions at different temperatures and percentages of decomposition that steric hindrance is a determining factor in the eclipsed cis conformation. Moreover, a more detailed analysis indicates that the greater the alkyl–alkyl interaction, the less favored the elimination tends to be. Otherwise, an increase of alkyl–hydrogen interaction caused steric acceleration to be the determining factor.     

Synthesis and structural investigations of derivatives of 5-ethyl-2-styryl-pyridine

Because of their strongly delocalized electronic systems, polymeric and non-polymeric aromatic compounds show high nonlinear optical properties. The present work deals with the synthesis and structural characterization (including X-ray single crystal studies) of new picoline derivatives, 5-ethyl-2-(4-nitro-styryl)-pyridine, space group P a = 6.9505(7), b = 7.418(1), c = 13.877(2) Å, = 105.14(1), = 93.88(1), = 105.89(1)°, and 5-ethyl-2-(4-nitro-7-ol-styryl)-pyridine, space group Pcab, a = 8.628(2), b = 10.405(2), and c = 31.604(5) Å.     

Interplay between cation-pi, anion-pi and pi-pi interactions.

The interplay between three important noncovalent interactions involving aromatic rings is studied by means of high level ab initio calculations. They demonstrate that very strong synergic effects are present in complexes where either cation–π or anion–π and π‐‐π interactions coexist. These strong synergic effects have been studied using the “atoms in molecules” theory and the physical nature of the interactions investigated by means of the molecular interaction potential with polarization (MIPp).     

Preparation and crystal structure of the new ionic bis-[hydrazido]-molybdenum complex [Mo(NNPh2)2(acac)(PPh3)2]+OTf−

The title compound [Mo(NNPh₂)₂ (acac)(PPH₃)₂]⁺OTf^?, Mr=1233.1, crystallizes in the triclinic space group $P\bar 1$ , witha=12.881 (4),b=13.795(3),c=17.160(5)Å, α=90.95(1), β=91.31(1), ψ=103.53(1)°, andZ=2. The structure was solved by Patterson methods, and refined with some difficulties due to extensive disorder in the counterion. The Mo ion is hexacoordinated in an octahedral environment, with two O and two N defining the basal plane, and two P atoms in the apical sites.     

New palladium(II) complexes with pyrazole ligands

This study describes the synthesis, IR, ¹H, and ¹³C{¹H} NMR spectroscopic as well the thermal characterization of the new palladium(II) pyrazolyl complexes [PdCl₂(HmPz)₂] 1, [PdBr₂(HmPz)₂] 2, [PdI₂(HmPz)₂] 3, [Pd(SCN)₂(HmPz)₂] 4 {HmPz = 4-methylpyrazole}. The residues of the thermal decomposition were identified as Pd⁰ by X-ray powder diffraction. From the initial decomposition temperatures, the thermal stability of the complexes can be ordered in the sequence: 1 > 2 > 4 ≈ 3. The cytotoxic activities of the complexes and the ligand were investigated against two murine cancer cell lines: mammary adenocarcinoma (LM3) and lung adenocarcinoma (LP07) and compared to cisplatin under the same experimental conditions.     

Synthesis,characterization and X-ray crystal structure of an allyloxo functionalized nonsymmetric nickel coordination complex based on N2O2 chelating ferrocenyl ligand

The synthesis of the new air and thermally stable orange neutral dinuclear iron–nickel unsymmetrical Schiff base complex, [8-(2-oxo,5-allyloxo-phenyl)-4,7-diaza-3-methyl-1-ferrocenyl-1-one-octa-1,3,7-trienato]nickel(II) (2), was achieved via the Williamson coupling reaction between the 2-oxo,5-hydroxyphenyl precursor 1 and allyl chloride in the presence of base. Complex 2 was isolated in 68% yield and characterized by IR, UV–Vis, ¹H and ¹³C NMR spectroscopy, HRMS and authenticated by a single crystal X-ray diffraction analysis. The organometallic/inorganic hybrid complex 2 consists in a ferrocenyl fragment linked to a classical Werner-type complex made of an unsymmetrical quadridentate N₂O₂ Schiff base ligand with a pendant allyl ether functionality as a potential anchoring group. The Ni(II) center displays a square-planar geometry with the nitrogen and oxygen atoms occupying mutually trans positions. The structure of 2 · H₂O shows that the water crystallization molecule interacts through two distinct intermolecular hydrogen bonds with the two oxygen atoms of the tetradentate N₂O₂ acyclic chelating ligand, forming in the solid state, a distorted six-membered ring.     

Effect of dental finishing instruments on the surface roughness of composite resins as elucidated by atomic force microscopy

Roughness increases significantly after finishing procedures. The aim of this study was to assess by the atomic force microscope (AFM) the effect of finishing instruments on the surface roughness of composite resins. A nanofiller composite resin (Filtek Supreme, 3MP) were selected. The finishing procedures were done with a 30-blade carbide bur (C) and a 30-M), and (3) finishing instrument (FM, PM, FC, FD, PC, PD). The mean surface roughness was evaluated by AFM in the contact mode. FM and PM groups were assessed statistically by the Student's T test, and FC, FD, PC, PD groups were submitted to variance analysis (ANOVA), both at 5% significance. The mean surface roughness values, in nanometers, were FM, 23.63 (b); FC, 283.88 (c); FD, 510.55 (d); PM, 12.52 (a); PC, 343.98 (c); PD, 531.64 (d). Microhybrid composite displayed less roughness than nanofiller composite in the absence of finishing procedures. The 30-blade carbide bur produced less roughness compared to the extra fine diamond bur.     

Speckle time evolution characterization by the co-occurrence matrix analysis

We describe some aspects of the measurement of dynamic speckle activity. We propose the use of the co-occurrence matrix of the time history of the intensity of a speckle pattern. Then we suggest a measure of the activity based on the use of one of its second order moments. Some numerical simulations were performed for testing purposes. The method was applied to the study of the drying of paint and was compared with gravimetric measurements. Experimental results obtained are shown and a good correlation is obtained.