Authors:X. Zeng, Y. Chen, S. Cheng, X. Meng, and Q. Wang
A novel method for the determination of rate constants of reactions, the time-variable method, is proposed in this paper. The method needs only three time points (t), peak heights () and pre-peak areas (), obtained from the measured thermoanalytical curve. It does not require the thermokinetic reaction to be completed. It utilizes data-processing on a computer to give the rate constants. Four reaction systems, including a first-order reaction, second-order reactions (with equal concentrations and with unequal concentrations) and a third-order reaction, were studied with this method. The method was validated and its theoretical basis was verified by the experimental results.
Authors:Y. Chen, H. Wang, X. Meng, X. Zeng, and J. Xie
A novel thermokinetic research method for determination of the rate constant of a reaction taking place in a batch conduction
calorimeter under isothermal conditions is proposed: the double-thermoanalytical curve method. The method needs only the characteristic
time parameter tm, the peak height Δm at time tm and the peak area a*m after time tm for two thermoanalytical curves measured with different initial concentrations of the reactants: it conveniently calculates
the rate constants. The thermokinetics of four reaction systems were studied with this method, and its validity was verified
by the experimental results.
Authors:W. Huang, Y. Xu, X. Chen, X. Gao, and Y. Fu
The radiation effect of γ-ray on polyether-urethane foam was studied. The gas products from irradiated samples were analyzed
quantitatively and qualitatively by gas chromatography, the thermal property and radical intensity were determined by differential
thermal gravimetry and electron spin resonance. The dynamic mechanical property, compression and tensile properties were analyzed.
Positron annihilation lifetime of irradiated samples was also measured at room temperature in vacuum. The results show that
the general mechanical properties of ETPU sample irradiated by γ-rays at a dose of 8.0·105 Gy is excellent, but there are considerable gas products and a great deal of radicals created, which indicates that the sample
has been damaged by radiation. Relatively, the thermal stability of the sample remained fine.
The thermal and structural properties of binary blends of Nylon-6 (N6) and a chemically related biopolymer, Bombyx mori silk fibroin (SF), are reported in this work. Homopolymers and blends, in composition ratios of N6/SF ranging from 95/05
to 70/30, were investigated by thermogravimetric (TG) analysis, differential scanning calorimetry (DSC), Fourier transform
infrared (FTIR) spectroscopy and wide angle X-ray scattering (WAXS). Silk fibroin typically degrades at temperatures just
above 210°C, which occurs within the melting endotherm of N6. In TG studies, the measured mass remaining was slightly greater
than expected, indicating the blends had improved thermal stability. No beta sheet crystals of SF were detected by FTIR analysis
of the Amide I region.
Strong interaction between N6 and SF chains was observed, possibly as a result of formation of hydrogen bonds between N6 and
SF chains. DSC analysis showed that the addition of SF to N6 caused a decrease in the crystallization temperature, the melting
temperature of the lowest melting crystals and the crystallinity of N6. Furthermore, the α-crystallographic phase dominates
and the γ-crystallographic phase was not observed in N6/SF blends, in contrast to the homopolymer N6, which contains both
phases. We suggest that the addition of SF might result in changes of the chain extension of N6, which lead to the appearance
of α-rather than γ-phase crystals.
Yanghuo Sanqi tablet (YST), combined prescription mainly derived from the leaves of herba epimedii and the roots of Panax notoginseng, is a traditional Chinese medicine (TCM). Flavonoids (icarrin, epimedin A, epimedin B, epimedin C, and baohuoside I) and saponins (notoginsenoside R1, ginsenoside Rgl, and ginsenoside Rbl) are considered as the main bioactive compounds of YST. However, there is no report on quality control of TCMs by simultaneous determination of above-mentioned flavonoids and saponins so far. In this work, for the first time, a high-performance liquid chromatography-diode array detector-evaporative light-scattering detector (HPLC-DAD-ELSD) method was developed to evaluate the quality of YST through a simultaneous determination of five major active flavonoids and three main saponins. Optimum separations were obtained with a Zorbax SB-C18 column by gradient elution with acetonitrile-water as the mobile phase. The drift tube temperature of ELSD was set at 105 °C, and the nebulizing gas flow rate was 2.5 L min−1. The fully validated method was successfully applied to quantify the eight bioactive components in three lot products. This simple, low-cost, and reliable HPLC-DAD-ELSD method provided a new basis for assessing the quality of traditional Chinese medicinal compound preparations (TCMCPs) consisting of many bioactive components.
Yanghuo Sanqi tablet (YST), combined prescription mainly derived from the leaves of Herba epimedii and the roots of Panax notoginseng, is a traditional Chinese medicine (TCM). Flavonoids (icarrin, epimedin A, epimedin B, epimedin C, and baohuoside I) and saponins (notoginsenoside R1, ginsenoside Rgl, and ginsenoside Rbl) are considered as the main bioactive compounds of YST. However, there is no report on quality control of TCMs by simultaneous determination of above-mentioned flavonoids and saponins so far. In this work, for the first time, a high-performance liquid chromatography-diode array detector-evaporative light scattering detector (HPLC-DAD-ELSD) method was developed to evaluate the quality of YST through a simultaneous determination of five major active flavonoids and three main saponins. Optimum separations were obtained with a Zorbax SB-C18 column by gradient elution with acetonitrile-water as the mobile phase. The drift tube temperature of ELSD was set at 105 °C, and the nebulizing gas flow rate was 2.5 L min−1. The fully validated method was successfully applied to quantify the eight bioactive components in three lot products. This simple, low-cost, and reliable HPLC-DAD-ELSD method provided a new basis for assessing the quality of traditional Chinese medicinal compound preparations (TCMCPs) consisting of many bioactive components.
Authors:Y. Chen, X. Li, F. Chen, Q. Zhu, and J. Luo
A rapid, simple, and practical high-performance liquid chromatographic method (HPLC) was developed and validated for the simultaneous determination of norephedrine (NME), norpseudoephedrine (NMP), ephedrine (E), pseudoephedrine (PE), and methylephedrine (ME) in traditional Chinese medicines (TCM) which contained Ephedrae Herba (Ephedra). This analysis could be accomplished within 12.5 min with an Alltima Phenyl Column by isocratic elution using a mixture of KH2PO4 (20 mM)-acetonitrile (96:4, v/v) as the mobile phase at a flow-rate of 0.6 mL min−1 and a wavelength of 210 nm. This method was successfully applied to quantify ephedra alkaloids in both Ma-xing-gan-shi decoction and Ephedra decoction. The concentration of total ephedra alkaloids (4.62 mg mL−1) in Ma-xing-gan-shi decoction was much lower than that (7.10 mg mL−1) in Ephedra decoction. Furthermore, the concentration of NME, NMP, E, PE, and ME was significantly lower in Ma-xing-gan-shi decoction than that in Ephedra decoction, respectively. The method was easily acceptable and would be popular with most analytical laboratories.
Authors:Y. Q. Cheng, Y. X. Zhang, S. D. Qi, H. L. Chen, and X. G. Chen
1,7-Dihydroxy-3,8-dimethoxyxanthone (X1) and 1,8-dihydroxy-3,7-dimethoxyxanthone (X2) are two important xanthones of the Tibetan medicinal plant Gentianopsis paludosa (Hook. f.) Ma. They are very similar in structure, the only difference being exchange of OH and OCH3 at the 7 and 8 positions. By calculations based on the geometry of the molecules using the MM+ force field, the different distances between the hydroxyl groups of the two xanthones were obtained (4.64774 Å for X2 and 7.19412 Å for X1), therefore, the two hydroxyl groups of X1 should freely interact with more water molecules than those of X2 in aqueous solution. In other words, X2 is more hydrophobic than X1. Micellar electrokinetic capillary chromatography (MEKC) was therefore chosen for separation of the compounds. The optimum separation conditions were: 20 mm borate + 20 mm SDS (pH 9.8) as running buffer, 17.5 kV applied potential, and detection wavelength 260 nm. The two xanthones were well separated in 9.0 min, with Gaussian peak shapes. The repeatability of the MEKC method (expressed as RSD) for X1 and X2 was 0.9 and 1.1%, respectively, for migration time, and 3.1 and 1.4% for peak area. The limits of detection (S/N = 3) were 0.41 μg mL−1 for X1 and 0.82 μg mL−1 for X2. The recovery of the MEKC method for the two xanthones was also satisfactory.
According to the theoretical basis of thermokinetics, the integral and differential thermokinetic equations of opposing reactions have been derived, and a novel thermokinetic research method, the characteristic parameter method for opposing reactions which taking place in a batch conduction calorimeter under isothermal condition, has been proposed in this paper. Only needing the characteristic thermoanalytical data corresponding to tm and 2tm from the same curve, the rate constants of forward and backward reactions and equilibrium constant can be calculated simultaneously with this method. In order to test the validity of this method, the proton-transfer reactions of nitroethane with ammonia at 15 and 25°C, and with trihydroxymethyl aminomethane (Tris) at 15 and 30°C have been studied, respectively. The results of rate constants and equilibrium constants calculated with this method are in agreement with those in the literature. Therefore, the characteristic parameter method for opposing reaction is believed to be correct.
In order to enrich the thermokinetic research methods and enlarge the applicable range of the thermokinetic time-parameter
method, the integral and differential thermokinetic equations of consecutive first-order reaction have been deduced, and the
mathematical models of the time-parameter method for consecutive first-order reactions have been proposed in this paper. The
rate constants of two steps can be calculated from the same thermoanalytical curve measured in a batch conduction calorimeter
simultaneously with this method. The thermokinetics of saponifications of diester in aqueoushanol solvent has been studied.
The experimental results indicate that the time-parameter method for the consecutive first-order reaction is correct.