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1.
G. A. Skorobogatov D. V. Korol’kov A. G. Rebrova V. I. Baranovskii 《Russian Journal of General Chemistry》2006,76(2):245-250
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. 相似文献
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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. 相似文献
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Christov A Korol RM Dai E Liu L Guan H Bernards MA Cavers PB Susko D Lucas A 《Photochemistry and photobiology》2005,81(2):457-466
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. 相似文献
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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. 相似文献
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I. V. Korol’kov A. I. Gubanov K. V. Yusenko I. A. Baidina S. A. Gromilov 《Journal of Structural Chemistry》2007,48(3):486-493
Several non-equilibrium solid solutions belonging to the platinum-osmium systems Os0.9Pt0.1, Os0.8Pt0.2, Os0.5Pt0.5, Os0.7Pt0.3, Os0.75Pt0.25 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 Pt0.5Os0.5 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) Å3, 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°. 相似文献
8.
Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献
9.
Yudanova L. I. Logvinenko V. A. Korol’kov I. V. Ishchenko A. V. Rudina N. A. 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2018,92(11):2247-2252
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... 相似文献
10.
EI Rodriguez Martinez CI Barriga-Paulino MI Zapata CC Chinchilla AM López-Jiménez CM Gómez 《BMC neuroscience》2012,13(1):104-23
ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages. 相似文献