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31.
32.
Srinivasachari Rajappa Kuppuswamy Nagarajan Kailasam Venkatesan Nirupa Kamath Vipanjeri Madabhusi Padmanabhan Wolfgang von Philipsborn Ban Chin Chen Raffaelo Müller 《Helvetica chimica acta》1984,67(7):1669-1680
The 1H-NMR spectra of 2-(nitromethylidene)pyrrolidine ( 7 ), 1-methyl-2-(nitromethylidene)imidazolidind ( 10 ) and 3-(nitromethylidene)tetrahydrothiazine ( 11 ) in CDCl3 and (CD3)2SO indicate that these compounds have the intramolecularly H-bonded structures (Z)- 7 , (E)- 10 and (Z)- 11 while the N-methyl derivative 8 of 7 is (E)-configurated in both solvents. 1-Benzylamino-1-(methyltio)-2-nitroehtylene ( 13 ), an acylic model, has the H-bonded configuration (E)- 13 in CDCl3 and in (CD3)2SO. 2-(Nitromethylidene)thiazolidine ( 3 ) has the (E)-configuration in CDCl3 but exists in (CD3)2SO as a mixture of (Z)- and (E)-isomers with the former predominating. Both species are detected to varying proportions in a mixture of the two solvents. 15N-NMR spectroscopy of 3 ruled out unambiguously the nitronic acid structure 6 and the nitromethyleimine structure 5 . The N-methyl derivative 4 of 3 is (Z)-configurated in (CD3)2SO. Comparison of the olefinic proton shifts of (Z)- 3 and (Z)- 4 with those of analogues and also of 1,1-bis(methylti)-2-nitroethylene ( 12 ) shows decreased conjugation of the lone pair of electrons of the ring N-atom in (Z)- 3 and (Z)- 4 . This is also supported by 13C-NMR studies. Plausible explanations for the phenomenon are offered by postulating that the ring N-atoms are pyramidal in (Z)- 3 and (Z)- 4 and planar in other cases or, alternatively, that the conjugated nitroenamine system gets twisted due to steric interaction between the NO2-group and the ring S-atom. Single-crystal X-ray studies of 3 and 8 show that the former exists in the (Z)-configuration and the latter in (E)-configuration; the ring N-atom in the former has slightly more pyramidal character than in the latter. 相似文献
33.
Chin‐Ping Yang Ruei‐Shin Chen Ming‐Jui Wang 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1092-1102
A novel tetraimide dicarboxylic acid was synthesized with the ring‐opening addition of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline, and trimellitic anhydride in a 1/2/2 molar ratio in N‐methyl‐2‐pyrrolidone followed by azeotropic condensation to tetraimide dicarboxylic acid. A series of poly(amide imide imide)s (PAIIs) with inherent viscosities of 0.8–1.1 dL/g were prepared from tetraimide dicarboxylic acid with various aromatic diamines by direct polycondensation. Most of the PAIIs were readily soluble in a variety of amide polar solvents and even in less polar m‐cresol and pyridine. Solvent‐cast films had tensile strengths ranging from 99 to 106 MPa, elongations at break ranging from 8 to 13%, and initial moduli ranging from 2.0 to 2.3 GPa. The glass‐transition temperatures of these PAIIs were recorded at 244–276 °C. They had 10% weight losses at temperatures above 520 °C in air or nitrogen atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1092–1102, 2002 相似文献
34.
Kim Y Choi YH Chin YW Jang YP Kim YC Kim J Kim JY Joung SN Noh MJ Yoo KP 《Journal of chromatographic science》1999,37(12):457-461
An investigation of the effect of plant matrix on the supercritical fluid extraction efficiency of five schisandrin derivatives is reported, exhibiting a great difference with respect to extraction efficiency depending on the matrix. Pure supercritical CO2 at 60 degrees C and 34.0 MPa cannot fully recover schisandrin derivatives from the leaves as much as from the other matrices. Only 36.9% of these compounds are extracted from leaves of Schisandra chinensis by supercritical CO2 in comparison with organic solvent extraction. However, more than 80% of schisandrin derivatives are obtained from both stem and fruit parts. Ethanol addition also shows a different effect depending on plant matrix; that is, CO2 modified with 10% ethanol could enhance the yield of schisandrin derivatives from leaves by four times when compared with that of pure CO2, but it has little effect on both stems and fruits. 相似文献
35.
Mian Chin Gregory L. Durst Simone R. Head Paul L. BockJohn A. Mosbo 《Journal of organometallic chemistry》1994,470(1-2):73-85
Molecular mechanics (MM2) calculations were performed on 54 conformations of 18 phosphines (PH3; PH3−nRn, where n = 1,…3, and R = Me and Et, n = 1 or 2 and R =iPr, and n = 1 and R =tBu, PMe2Et, PMeEt2, and PPhMe2, and PPh2R where R = Me, Et, iPr, tBu and Ph). The results are compared to those previously obtained from MINDO/3 and MNDO calculations, and to experimental data. Single conformer cone angles and weighted average cone angles were calculated from MM2 optimized geometries employing Tolman's general definition, and they are compared to Tolman's values, MINDO/3 results, and T.L. Brown's ER values. Of the cone angle definitions used, the weighted average values are suggested as the best single representation of phosphine ligand sizes. The steric parameters (cone angle and ER values) alone, and in conjunction with electronic parameters, are correlated with experimental data. 相似文献
36.
Alexeev OS Chin SY Engelhard MH Ortiz-Soto L Amiridis MD 《The journal of physical chemistry. B》2005,109(49):23430-23443
TiO2- and gamma-Al2O3-supported Pt catalysts were characterized by HRTEM, XPS, EXAFS, and in situ FTIR spectroscopy after activation at various conditions, and their catalytic properties were examined for the oxidation of CO in the absence and presence of H2 (PROX). When gamma-Al2O3 was used as the support, the catalytic, electronic, and structural properties of the Pt particles formed were not affected substantially by the pretreatment conditions. In contrast, the surface properties and catalytic activity of Pt/TiO2 were strongly influenced by the pretreatment conditions. In this case, an increase in the reduction temperature led to higher electron density on Pt, altering its chemisorptive properties, weakening the Pt-CO bonds, and increasing its activity for the oxidation of CO. The in situ FTIR data suggest that both the terminal and bridging CO species adsorbed on fully reduced Pt are active for this reaction. The high activity of Pt/TiO2 for the oxidation of CO can also be attributed to the ability of TiO2 to provide or stabilize highly reactive oxygen species at the metal-support interface. However, such species appear to be more reactive toward H2 than CO. Consequently, Pt/TiO2 shows substantially lower selectivities toward CO oxidation under PROX conditions than Pt/gamma-Al2O3. 相似文献
37.
Tan BJ Sow CH Koh TS Chin KC Wee AT Ong CK 《The journal of physical chemistry. B》2005,109(22):11100-11109
Two-dimensional ordered arrays of gold (Au) nanoparticles were fabricated using two different variants of the nanosphere lithography technique. First, ordered arrays of polystyrene nanospheres on Si substrate were used as deposition masks through which gold films were deposited by electron beam evaporation. After the removal of the nanospheres, an array of triangular Au nanodisks was left on the Si substrate. After thermal annealing at increasing temperature, systematic shape transition of the nanostructures from original triangular Au nanodisks to rounded nanoparticles was observed. This approach allows us to systematically vary the size and morphology of the particles. In the second and novel technique, we made use of reactive ion etching to simultaneously reduce the dimension of the masking nanospheres and create arrays of nanopores on the substrate prior to the deposition of the Au films. These samples were subsequently annealed, which resulted in size-tunable and ordered Au nanoparticle arrays with the nanoparticles nested in the nanopores of the templated substrate. With the nanoparticles anchored in the nanopores, the substrate could be useful as a template for growth of other nanomaterials. 相似文献
38.
39.
Seow Jecg Chin Peter Hornsby Damjan Vengust Dragan Mihailović J. Mitra Paul Dawson Tony McNally 《先进技术聚合物》2012,23(2):149-160
Composites of poly(ε‐caprolactone) (PCL) and molybdenum sulfur iodine (MoSI) nanowires were prepared using twin‐screw extrusion. Extensive microscopic examination of the composites revealed the nanowires were well dispersed in the PCL matrix, although bundles of Mo6S3I6 ropes were evident at higher loadings. Secondary electron imaging (SEI) showed the nanowires had formed an extensive network throughout the PCL matrix, resulting in increased electrical conductivity of PCL, by eight orders of magnitude, and an electrical percolation threshold of 6.5 × 10?3 vol%. Thermal analysis (DSC), WAXD, and hot stage polarized optical microscopy (HSPOM) experiments revealed Mo6S3I6 addition altered PCL crystallization kinetics, nucleation density, and crystalline content. A greater number of smaller spherulites were formed via heterogeneous nucleation. The onset of thermal decomposition (TGA) of PCL decreased by 70°C, a consequence of the thermal degradation of Mo6S3I6 to MoO3, which in turn accelerates the formation of volatile gases during the first stage of PCL decomposition. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
40.
Isotactic polypropylene (PP) composites filled with hydroxyapatite nanorods (nHAs) were fabricated using a melt compounding process. The effects of nHA additions on the structure, thermal, and mechanical properties as well as bioactivity of PP were investigated. Wide-angle X-ray diffraction and differential scanning calorimetry results showed that PP crystallized exclusively in the α-form when adding nHAs. Dynamic mechanical analysis showed that nHAs enhanced the storage modulus of PP. Mechanical measurements showed that nHAs stiffened and reinforced PP but reduced its tensile ductility and impact strength considerably. Furthermore, the PP/nHA nanocomposites were found to exhibit excellent bioactivity upon immersion in a simulated body fluid solution. This was attributed to the formation of apatite mineral crystals on the nanocomposite surfaces as revealed by scanning electron microscopy and energy dispersive X-ray analysis. 相似文献