Low-temperature heat capacities and standard molar enthalpy of formation of aspirin

Molar heat capacities (C-p,C-m) of aspirin were precisely measured with a small sample precision automated adiabatic calorimeter over the temperature range from 78 to 383 K. No phase transition was observed in this temperature region. The polynomial function of Cp, vs. T was established in the light of the low-temperature heat capacity measurements and least square fitting method. The corresponding function is as follows: for 78 Kless than or equal toTless than or equal to383 K, C-p,C-m/J mol(-1) K-1=19.086X(4)+15.951X(3)-5.2548X(2)+90.192X+176.65, [X=(T-230.50/152.5)]. The thermodynamic functions on the base of the reference temperature of 298.15 K, {DeltaH(T)-DeltaH(298.15)} and {S-T-S-298.15}, were derived.

Thermodynamic study of ibuprofen by adiabatic calorimetry and thermal analysis

Molar heat capacities of ibuprofen were precisely measured with a small sample precision automated adiabatic calorimeter over the temperature range from 80 to 400 K. The polynomial functions of C-p,C-m (J K-1 mol(-1)) versus T were established on the heat capacity measurements by means of the least fitting square method. The functions are as follows: for solid ibuprofen, at the temperature range of 79.105 K less than or equal to T less than or equal to 333.297 K, C-p,C-m = 144.27 + 77.046X + 3.5171X(2) + 10.925X(3) + 11.224X(4), where X = (T - 206.201)/127.096; for liquid ibuprofen, at the temperature range of 353.406 K less than or equal to T less than or equal to 378.785 K, C-p,C-m = 325.79 + 8.9696X - 1.6073X(2) - 1.5145 X-3, where X = (T - 366.095)/12.690. A fusion transition at T = 348.02 K was found from the C-p-T curve. The molar enthalpy and entropy of the fusion transition were determined to be 26.65 kJ mol(-1) and 76.58 J mol(-1) K-1, respectively. The thermodynamic functions on the base of the reference temperature of 298.15 K, (H-T - H-298.15) and (S-T - S-298.15), were derived. Thermal characteristic of ibuprofen was studied by thermo-gravimetric analysis (TG-DTG) and differential scanning calorimeter (DSC). The temperature of fusion, the molar enthalpy and entropy of fusion obtained by DSC were well consistent with those obtained by adiabatic calorimeter. The evaporation process of ibuprofen was investigated further by TG and DTG, and the activation energy of the evaporation process was determined to be 80.3 +/- 1.4 kJ mol(-1). (C) 2003 Elsevier B.V. All rights reserved.

Surface modelling of soil pH

In addition to classical methods, namely kriging, Inverse Distance Weighting (IDW) and splines, which have been frequently used for interpolating the spatial patterns of soil properties, a relatively more accurate surface modelling technique is being developed in recent years, namely high accuracy surface modelling (HASM). It has been used in the numerical tests, DEM construction and the interpolation of climate and ecosystem changes. In this paper, HASM was applied to interpolate soil pH for assessing its feasibility of soil property interpolation in a red soil region of Jiangxi Province, China. Soil pH was measured on 150 samples of topsoil (0-20 cm) for the interpolation and comparing the performance of HASM, kriging. IDW and splines. The mean errors (MEs) of interpolations indicate little bias of interpolation for soil pH by the four techniques. HASM has less mean absolute error (MAE) and root mean square error (RMSE) than kriging, IDW and splines. HASM is still the most accurate one when we use the mean rank and the standard deviation of the ranks to avoid the outlier effects in assessing the prediction performance of the four methods. Therefore, HASM can be considered as an alternative and accurate method for interpolating soil properties. Further researches of HASM are needed to combine HASM with ancillary variables to improve the interpolation performance and develop a user-friendly algorithm that can be implemented in a GIS package. (C) 2009 Elsevier B.V. All rights reserved.

Assignment of absolute configuration of cyclic secondary amines by NMR techniques using Mosher's method: a general procedure exemplified with (-)-isoanabasine

A general procedure to determine the absolute configuration of cyclic secondary amines with Mosher's NMR method is demonstrated, with assignment of absolute configuration of isoanabasine as an example. Each Mosher amide can adopt two stable conformations (named rotamers) caused by hindered rotation around amide C-N bond. Via a three-step structural analysis of four rotamers, the absolute configuration of (-)-isoanabasine is deduced to be (R) on the basis of Newman projections, which makes it easy to understand and clarify the application of Mosher's method to cyclic secondary amines. Furthermore, it was observed that there was an unexpected ratio of rotamers of Mosher amide derived from (R)-isoanabasine and (R)-Mosher acid. This phenomenon implied that it is necessary to distinguish the predominant rotamer from the minor one prior to determining the absolute configuration while using this technique.

Melt rheological properties of polypropylene-polyarnide6 blends compatibilized with maleic anhydride-grafted polypropylene

The melt rheological properties of binary uncompatibilized polypropylene -polyamide6 (PP-PA6) blends and ternary blends compatibilized with maleic anhydride-grafted PP (PP-PP-g-MAH-PA6) were studied using a capillary rheometer. The experimental shear viscosities of blends were compared with those calculated from Utracki's relation. The deviation value delta between these two series of data was obtained. In binary PP-PA6 blends, when the compatibility between PP and PA6 was poor, the deformation recovery of dispersed PA6 particles played the dominant role during the capillary flow, the experimental values were smaller than those calculated, and delta was negative. The higher the dispersed phase content, the more deformed the droplets were and the lower the apparent shear viscosity. Also, the absolute value of delta increased with the dispersed phase composition. In ternary PP-PP-g-MAH-PA6 systems, when the compatibility between PP and PA6 was enhanced by PP-g-MAH, the elongation and break-up of the dispersed particles played the dominant role, and the experimental values were higher than calculated. It was observed that the higher the dispersion of the PA6 phase, the higher the delta values of the ternary blends and the larger the positive deviation.

Determination of ethenzamide and acetoaminophen in quaternary powdered samples by near infrared spectroscopy and searching combination moving window partial least squares algorithm: effects of spectral resolution and signal-to-noise ratio

The present study reports an application of the searching combination moving window partial least squares (SCMWPLS) algorithm to the determination of ethenzamide and acetoaminophen in quaternary powdered samples by near infrared (NIR) spectroscopy. Another purpose of the study was to examine the instrumentation effects of spectral resolution and signal-to-noise ratio of the Buchi NIRLab N-200 FT-NIR spectrometer equipped with an InGaAs detector. The informative spectral intervals of NIR spectra of a series of quaternary powdered mixture samples were first located for ethenzamide and acetoaminophen by use of moving window partial least squares regression (MWPLSR). Then, these located spectral intervals were further optimised by SCMWPLS for subsequent partial least squares (PLS) model development. The improved results are attributed to both the less complex PLS models and to higher accuracy of predicted concentrations of ethenzamide and acetoaminophen in the optimised informative spectral intervals that are featured by NIR bands. At the same time, SCMWPLS is also demonstrated as a viable route for wavelength selection.

Three-dimensional quantitative structure-activity relationship of the opioid antagonist with potent anorectant activity of 3,4-dimethyl-4-(3-hydroxyphenyl) piperidine

A series of 3,4-dimethyl-4-(3-hydroxyphenyl) piperidine opioid antagonists with varying substituents on the nitrogen were evaluated for their effect on food consumption in obese Zucker rats. In developing three-dimensional quantitative structure-activity relationship (3D-QSAR) studies for this series of opioid antagonists, different structure alignments have been tested to predict the anorectant activities. The interaction energies between molecules and the probe atom were then correlated with anorectant activity using partial least squares (PLS) method. The steric and electrostatic features of the 3D-QSAR were presented in the form of standard deviation coefficient contour maps of steric and electrostatic fields. The results showed that 3D-QSAR results are much better than the results obtained by 2D-QSAR.

Decomposition of circular dichroism of norepinephrine by singular value decomposition-least square method

Singular value decomposition - least squares (SVDLS), a new method for processing the multiple spectra with multiple wavelengths and multiple components in thin layer spectroelectrochemistry has been developed. The CD spectra of three components, norepinephrine reduced form of norepinephrinechrome and norepinephrinequinone, and their fraction distributions with applied potential were obtained in three redox processes of norepinephrine from 30 experimental CD spectra, which well explains electrochemical mechanism of norepinephrine as well as the changes in the CD spectrum during the electrochemical processes.

The glass transition temperatures of PS/PPO blends: Couchman volume-based equation and its verification

The glass transition temperatures (T-g) of PS/PPO blends with different compositions were studied under various pressures by means of a PVT-100 analyzer. A general relation of T-g and pressure of the PS/PPO system was deduced by fitting the experimental T-g's. Couchman volume-based equation was testified with the aid of those data. It was found that the experimental T-g's do not obey the Couchman equation of glass transition temperature based on thermodynamic theory. According to our studies, the major reason of the deviation is caused by the neglect of DeltaV(mix). (C) 2001 Published by Elsevier Science Ltd.

Charge transport of indigo-carmine doped polypyrrole

Charge transport in polypyrrole doped with indigo-carmine was investigated by the method of electrochemical alternating current impedance. By the nonlinear least square fitting, the equivalent circuit and parameter of each component are obtained. The apparent diffusion coefficients and heterogeneous electron transfer constants are given. It is found that, along with the increasing of film thickness, D-app and k(0) increase also.

LEAST-SQUARES POLYNOMIAL SMOOTHING FOR INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTRA

The use of least-squres polynomial smoothing in ICP-AES is discussed and a method of points insertion into spectral scanning intervals is proposed in the present paper. Optimal FWHM/SR ratio can be obtained, and distortion of smoothed spectra can be avoided by use of the recommended method.

A METHOD OF FITTING TO MOSSBAUER SPECTRUM OF EU-151 AND ITS APPLICATION TO EUROPIUM COMPOUNDS

A method of fitting to Mossbauer spectrum of 151Eu has been proposed. The intensities and the positions of all the possible transitions between the sublevels of the ground state and those of the excited state of nucleus with spin I> 3/2 can be considered at one time in fitting to experimental Mossbauer spectra by this method. The method has been used to fit to the experimental Mossbauer spectra of europium orthophosphate crystal and of europium pentaphosphate crystal, and to derive Mossbauer parameters from...