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81.
Enol and keto tautomers of methyl 3-oxo pentanoate could be separated on a HP-5 capillary column. The chromatographic peaks
were identified by examining characteristic mass ions arose from the corresponding enol and keto molecular ions. The study
showed that the area percentage of enol tautomer is a function of temperature of the column. Treating the column as a reactor,
the energy of activation for the on-column tautomerization could be extracted (35.1 kJ mol−1) by monitoring the loss of the enol tautomer, because the reaction is found to obey pseudo first-order kinetics. The enthalpy
and the entropy changes (ΔH = −3.98 kJ mol−1, ΔS = −7.89 J K−1mol−1) for the enol-to-keto reaction in the stationary phase were also obtained. 相似文献
82.
A series of vinylidene dichloride (VDC) copolymers with methyl acrylate (MA) ascomonomer (3--12wt%), was prepared by free-radical suspension copolymerization. Thepermeability coefficients of the copolymers to oxygen and carbon dioxide were measured at1.0 MPa and at 30℃, and those to water vapor were measured at 30℃ and 100% relativehumidity All the VDC/MA copolymers studied are semicrystalline. As the MA contentincreases, the permeability coefficients of the copolymers to oxygen, carbon dioxide, andwater vapor are progressively increased, caused by decrease in crystalline fraction andincrease in free volume of VDC/MA copolymers. 相似文献
83.
84.
W. Ren 《Colloid and polymer science》1992,270(10):990-998
Inverse relaxation is studied for hard elastic polypropylene (HEPP), rubber and non-elastic polypropylene. The results show that contractive stress, stress, and internal friction are three essential factors related to the phenomenon. A three-element model in which each element has a definite meaning is proposed to describe this phenomenon. The results also show that, in the first cyclic deformation, relaxation time increases with the increase of recovery for all the materials, which indicates that recovery viscosity increases with the increase of recovery, but the stress rising amplitude (SRA) of inverse relaxation has a maximum in the recovery range. Analysis indicates that SRA equals recovery internal friction (RIF) for ideal material in which stress is solely a function of strain, independent of paths, and approximately equals RIF for non-ideal material at a given strain. From this principle it is found that the order of the work counteracted by RIF for the four materials is the same as that of their second hysteresis loop, and the RIF of HEPP has a sudden increase at the later recovery range. 相似文献
85.
《Electroanalysis》2006,18(2):127-130
The voltammetric behavior of 2‐methyl‐4,6‐dinitrophenol was investigated by differential pulse voltammetry (DPV) at a nontoxic mercury meniscus‐modified silver solid amalgam electrode (m‐AgSAE). Conditions have been found for its determination by DPV at m‐AgSAE in the concentration range of 0.2 to 1 μmol L?1. 相似文献
86.
Hans Günther Wahl Silke-Yvonne Habel Norbert Schmieder Hartmut M. Liebich 《Journal of separation science》1994,17(7):543-548
Identification of cis/trans isomers of unsaturated fatty acids cannot usually be achieved by GC-MS (gas chromatography-mass spectrometry) without reference substances. In this study a GC-FTIR-MS system (gas chromatography-Fourier transform-mass spectrometry) was used to identify fatty acid methyl esters (FAMEs) and differentiate between the cis/trans isomers. Besides methyl esters, 2-alkenyl-4,4-dimethyloxazoline derivatives (DMOX), which have been used to locate double bond positions of unsaturated fatty acids, were examined with respect to their suitability for cis/trans differentiation. A combined GC-FTIR-MS system with a wide band (4000–550 cm?1) mercury cadmium telluride (MCT) detector was used in series and parallel to identify 31 reference unsaturated fatty acids, including 7 pairs of cis/trans isomers. Serum samples of healthy persons and commercially available fish oil were analyzed as examples of complex mixtures. Using splitless injection the detection limit for the less sensitive IR detector was 25 ng/μl in case of the weak cis and trans bands. In the FTIR spectra cis/trans isomers were identified by analysis of bands arising from C? H out-of-plane (oop) bending: for both the FAME and DMOX derivatives cis-1,2-disubstituted double bonds give a strong band near 720 cm?1 and the corresponding trans isomers near 967 cm?1. cis Isomers could be identified further by a band at 3012 cm?1. With the combined data of the GC-FTIR-MS system it is now possible to identify polyunsaturated fatty acids with regard to the discrimination of cis/trans isomers. 相似文献
87.
Antonio Fernández-Ramos Benjamin A. Ellingson Rubén Meana-Pañeda Jorge M. C. Marques Donald G. Truhlar 《Theoretical chemistry accounts》2007,118(4):813-826
This article shows how to evaluate rotational symmetry numbers for different molecular configurations and how to apply them
to transition state theory. In general, the symmetry number is given by the ratio of the reactant and transition state rotational
symmetry numbers. However, special care is advised in the evaluation of symmetry numbers in the following situations: (i)
if the reaction is symmetric, (ii) if reactants and/or transition states are chiral, (iii) if the reaction has multiple conformers
for reactants and/or transition states and, (iv) if there is an internal rotation of part of the molecular system. All these
four situations are treated systematically and analyzed in detail in the present article. We also include a large number of
examples to clarify some complicated situations, and in the last section we discuss an example involving an achiral diasteroisomer. 相似文献
88.
A novel transesterification reaction between acetylated maritime pine sapwood (Pinus pinaster Soland) and methyl benzoate (MB), in the presence of dibutyltin oxide (DBTO) as a catalyst, was performed. Reaction was confirmed by Fourier-transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance cross-polarisation with magic-angle spinning (NMR CP MAS) analysis: signals corresponding to benzoylated wood were identified and, when transesterification was performed with ethyl trimethylsilylacetate (ETMSA), characteristic trimethylsilyl groups were detected. The acetyl/benzoyl exchange rate was found to increase with increasing amount of DBTO, temperature and reaction time and a concurrent deterioration of the woody material was evidenced. 相似文献
89.
Inversion of the temperature coefficient of internal pressure in liquid phase systems is considered. Both temperature and concentration inversions of the coefficient are shown to be possible. Details of the temperature inversion are discussed. This type of inversion is characteristic of only associated hydrogen-bonded liquids and is due to weaker association of molecules. 相似文献
90.
Novel HPLC methods were developed for the analytical and semipreparative resolution of new antidepressant drug mirtazapine enantiomers. At analytical scale, the separation of the mirtazapine enantiomers was investigated using both cellulose and amylose tris(3,5-dimethylphenylcarbamate) (CDMPC and ADMPC) chiral stationary phases under normal-phases and polar organic modes. Good baseline enantioseparation was achieved using cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phases under both normal-phases and polar organic modes. Furthermore, the elution order of mirtazapine enantiomic pairs was found reversed by changing the stationary phase from the amylose-based ADMPC–CSPs to its cellulose-based counterpart, CDMPC–CSPs. The validation of the analytical methods including linearity, limit of detection (LOD), limit of quantification (LOQ), recovery and precision, together with the semipreparative resolution of mirtazapine racemate were carried out using cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phases and methanol as mobile phase without any basic additives under polar organic mode. At analytical scale, the elution times of both enantiomers were less than 6 min at normal temperature and 1.0 ml/min, with the separation factor () 1.99 and the resolution factor (Rs) 3.56. Then, the analytical methods were scaled up to semipreparative loading to obtain small quantities of both mirtazapine enantiomers. At semipreparative scale, about 16 mg/h enantiomers could be isolated and elution times of both enantiomers were less than 10 min at 2.0 ml/min. To increase the throughput, the technique of boxcar injections was used. One enantiomer ((−)-(R)-mirtazapine) was isolated with purity of >99.9% e.e. and >98.0% yield and another ((+)-(S)-mirtazapine) was isolated with purity of >97.0% e.e. and >99.0% yield. In addition, optical rotation and circular dichroism (CD) spectroscopy of both mirtazapine enantiomers isolated were also investigated. 相似文献