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991.
The neutral, cationic, and anionic structures of both prototropic tautomers oftrans- andcis-urocanic acid [(E)- and (Z)-3-(1H-imidazol-4(5)-yl)propenoic acid, respectively] were studied by using semiempirical andab initio gas-phase calculations. Potential energy surfaces of the structures were calculated by using the semiempirical AM1 method, and the geometries corresponding to global minima on these surfaces were optimized up to the MP2/6-31G* level of theory. The calculated protonation forms of each urocanic acid isomer have a planar molecular structure due to a delocalized -electron system, and all of them prefer thes-trans conformation with respect to the bond between the imidazole and the propenoic acid moieties. Thecis-urocanic acid structures are stabilized by an intramolecular hydrogen bond. The chargedcis-urocanic acid isomers have a lower molecular energy than the correspondingtrans-isomers, whereas the neutral molecules have, after inclusion of thermodynamic corrections, approximately the same energy. The cationic urocanic acid structures have about 2500 kJ mol–1 lower energy than the anionic ones and about 1000 kJ mol–1 lower energy than the neutral ones. The nonzwitterionic forms of the neutral urocanic acid isomers have about 200 kJ mol–1 lower energy than the zwitterionic ones. These energy differences are explained by the proton affinities of the imidazole and the propenoic acid moieties of the urocanic acid structures. 相似文献
992.
Marina Lulla Jelena Asari Jaan Aarik Kaupo Kukli Raul Rammula Unto Tapper Eero Kauppinen Väino Sammelselg 《Mikrochimica acta》2006,155(1-2):195-198
Quantitative electron probe microanalysis of highly insulating materials is a complicated problem, partially solved by coating
samples with grounded thin conductive layers or using novel scanning electron microscopy (SEM) techniques, such as low-voltage
and/or variable pressure SEM. In this work, some problems of quantitative X-ray microanalysis of thin HfO2 films, in particular the possibility to determine mass thickness correlated to the density of the layer material, are discussed.
For comparison, Al2O3, Ta2O5 and TiO2 films grown onto both semiconductive Si and insulating quartz substrates were also analysed. All the films studied were synthesized
by atomic layer deposition method. 相似文献
993.
The stability of spontaneous thin layers and thin layers formed upon cathodical polarization of Ti in KOH solutions have been
studied by potentiostatic and ellipsometric methods. At open circuit potential (OCP) the strongly adherent films, whose thickness
depends on the concentration of the KOH solution, were formed. During the cathodic polarization the transformation of these
films to weakly adsorbed precipitated layers on the electrode surface was observed. Comparing the theoretically computed curves
with the experimental Ψ vs Δ loci measured ellipsometrically, the complex indices of refraction and the thickness of the generated films, from 3.6
to 60 nm in 1 M KOH and from 36 to 105 nm in 5 M KOH (adherent to the electrode surface), were determined. At OCP the rate
of film growth increases with increasing the concentration of KOH solution. Cathodic polarizations change the chemical composition
and retard the rate of film growth. Based on the ellipsometric and electrochemical data the chemical compositions of the formed
films consisted of TiO2, Ti2O3, TiO2·H2O, Ti(OH)3 and TiOOH·nH2O. 相似文献
994.
Xiufang Xu Guichang Wang Xuezhuang Zhao Yinming Pan Yunxiao Liang Zhenfeng Shang 《Journal of mathematical chemistry》2007,41(2):143-160
In this paper, the fuzzy symmetry of some prototypical linear molecules has been analyzed. The results show that some molecular
orbitals (MOs) are less symmetrical but some others are more symmetrical than the molecular skeleton, which the MOs correspond
to. The membership functions of space inversion for MOs are closely related to the chemical characteristics of the MOs. Sometimes,
although the symmetry of a molecular skeleton is not obvious, however that of some MO is quite obvious. The membership functions
of the fuzzy inversion symmetry depend on the choice of the position of the center of inversion. As compared to those of diatomic
molecules and linear tri-atomic molecules, the linear polyatomic molecules in which a distinctive fuzzy symmetry of space
translation may exist, and thus a significant effect on their properties can be expected. 相似文献
995.
Microcapsules containing healing agents have been used to develop the self-healing polymeric composites. These microcapsules
must possess special properties such as appropriate strength and stability in surrounding medium. A new series of microcapsules
containing dicyclopentadiene (DCPD) with melamine–formaldehyde (MF) resin as shell material were synthesized by in situ polymerization
technology. These microcapsules may satisfy the requirements for self-healing polymeric composites. The chemical structure
of microcapsule was identified by using Fourier transform infrared (FTIR) spectrometer. The morphology of microcapsule was
observed by using optical microscope (OM) and scanning electron microscope. Size distribution and mean diameter of microcapsules
were determined with OM. The thermal properties of microcapsules were investigated by using thermogravimetric analysis and
differential scanning calorimetry. Additionally, the self-healing efficiency was evaluated. The results indicate that the
poly(melamine–formaldehyde) (PMF) microcapsules containing DCPD have been synthesized successfully, and their mean diameters
fall in the range of 65.2∼202.0 μm when the adjusting agitation rate varies from 150 to 500 rpm. Increasing the surfactant
concentration can decrease the diameters of microcapsules. The prepared microcapsules are thermally stable up to 69 °C. The
PMF microcapsules containing DCPD can be applied to polymeric composites to fabricate the self-healing composites. 相似文献
996.
Xu-Chun Wang Jian-Feng Li He-Ping Chen Jie-Ying Wu Hong-Ping Zhou Jia-Xiang Yang Bao-Kang Jin Yu-Peng Tian 《Transition Metal Chemistry》2007,32(5):551-557
The novel compound, 3-(E)-ferrocenyl-vinyl-N-hexylcarbazole (FVHC) was first synthesized and fully characterized by elemental analysis, IR, 1H-NMR, single-crystal X-ray diffraction, ultraviolet (UV) absorption, cyclic voltammograms (CV) and optical limiting (OL)
measurements. The result of single crystal X-ray diffraction for the compound reveals that the ferrocenyl and carbazole groups
are approximately coplanar, and bridged by double-bond with E configuration, showing that there is a well-delocalized π-electron
system in the molecule. The electrochemical investigation indicated that the electron in the FVHC may partially be delocalized
over the π-conjugated system and CT process in functionalized carbazole systems. Besides, the compound exhibited strong UV
absorption and large optical limiting effect, indicating promising potential applications as useful OL materials. 相似文献
997.
Emilie Barriau Holger Frey Anton Kiry Manfred Stamm Franziska Gröhn 《Colloid and polymer science》2006,284(11):1293-1301
The preparation of carboxylated hyperbranched polyglycerols of narrow polydispersity was achieved by modification (78–90%) of the hydroxyl end groups via Michael addition of acrylonitrile, followed by hydrolysis. High conversion could only be achieved for low molecular weight starting materials (520 and 1,030 g mol−1). The solution properties of the resulting materials were investigated by dynamic light scattering (DLS), showing the formation of large aggregates with size depending on the pH value. After deposition on a negatively charged mica surface, the structures observed by atomic force microscope (AFM) show the coexistence of aggregates and single macromolecules. Most interesting, in the case of the lower molecular weight sample (PG 520 g mol−1), extended and ordered terrace structures were formed, which are unprecedented for hyperbranched polymers and are of interest for surface modification in general. 相似文献
998.
Lämmerhofer M 《Journal of chromatography. A》2005,1068(1):31-57
A review on the advantages, peculiarities, and the potential of enantioselective capillary electrochromatography (CEC) in nonaqueous media is presented. Some fundamentals on CEC with particular focus on enantioselective CEC are discussed. The strategies, concepts, preferentially utilized chiral selectors and column technologies that have been utilized to succeed in highly efficient enantiomer separations by nonaqueous CEC are described thoroughly. 相似文献
999.
Optimisation of Supercritical Carbon Dioxide Systems for Complexation of Naproxen : Beta-Cyclodextrin 总被引:1,自引:0,他引:1
Susana Junco Teresa Casimiro Nuno Ribeiro Manuel Nunes Da Ponte Helena M. Cabral Marques 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):69-73
Supercritical carbon dioxide (scCO2)offers several attractive scenarios for thepharmaceutical processing as an alternativeto aqueous and organic solvents. In thiswork naproxen, a widely used non steroidalanti-inflammatory drug with analgesic andanti-inflammatory properties, was chosenas a model drug. Its complexation with cyclodextrinsimproves the rate and extent of dissolutionof the drug, increase its rate of absorption and mayreduce the unpleasant side-effects of the drug.The interest in using this supercritical technologyled us to develop an experimental unit for the useof supercritical CO2 as a processing medium forthe complexation of naproxen with beta cyclodextrin (CD). 相似文献
1000.
Carbon nanotube array-based biosensor 总被引:8,自引:0,他引:8
Aligned multi-wall carbon nanotubes (MWNT) grown on platinum substrate are used for the development of an amperometric biosensor. The opening and functionalization by oxidation of the nanotube array allows for the efficient immobilization of the model enzyme, glucose oxidase. The carboxylated open-ends of nanotubes are used for the immobilization of the enzymes, while the platinum substrate provides the direct transduction platform for signal monitoring. It is also shown that carbon nanotubes can play a dual role, both as immobilization matrices and as mediators, allowing for the development of a third generation of biosensor systems, with good overall analytical characteristics. 相似文献