Investigation on the influence of methanol on adsorption and leaching of pesticides with soil column liquid chromatography

The effect of methanol of low concentration on adsorption and leaching of atrazine and tebuconazole was studied in this paper. The adsorption coefficients and the retardation factors (R-m) of pesticides on EUROSOIL 3# log-linearly decreased as volumetric fraction of methanol (f(c)) was increased in the binary solvent mixtures of methanol and water. These data are consistent with solvophobic theory formerly outlined for describing the adsorption and transport of hydrophobic organic chemicals from mixed solvents. Nevertheless, the adsorption of these pesticides in soil-water system slightly increased when the soil was pre-washed with methanol in comparison with that pre-washed with water (pure water system). Furthermore, their adsorption coefficients were still higher in binary solvent systems with methanol of very low concentrations, i.e. f(c) < 0.03 for atrazine and f(c) < 0.01 for tebuconazole, than those in pure water system. The adsorption coefficients (logK(w)) of atrazine and tebuconazole predicted by solvophobic theory were 0.5792 and 1.6525, respectively, and their experimental logK(w) were 0.3701 and 1.6275 in pure water system. Obviously, the predicted log K-w of the two pesticides was higher than the experimental log K-w in pure water system. The predicted K-w and the retardation factor (R-w) in pure water system by solvophobic theory are thus possibly inaccurate. (C) 2004 Elsevier Ltd. All rights reserved.

Study on conical columns with different conical angles for semi-preparative liquid chromatography

The dynamic flow profiles and separation performances in conically shaped preparative liquid chromatographic columns (inlet i.d. larger than outlet i.d.) with three different angles (7, 10 and 15degrees) were studied and compared with cylindrical column of the same length and internal volume. The shapes of dynamic flow profiles were studied by on-column visualization method. The transparent chromatographic columns made of polymethyl methacrylate (PMMA), packed with C-18 bonded silica, were immerged into a cubic pool filled with glycerol to eliminate the cylindrical and conical lens effect. The flow profiles of colored iodine solution in the columns were observed clearly using cyclohexane as mobile phase since the refractive indices of C-18, column wall and the mobile phase are very close. In the conical column of 15degrees (20-7 mm i.d.) the mobile phase in the central region migrated slower than in wall region as it moved toward the column outlet, while in the conical column of 7degrees (17-11 mm i.d.) the mobile phase in the central region migrated faster than in wall region just like in cylindrical column. We found that a plug-like flow profile was generated in the conical column of 10degrees (18-9 mm i.d.) during the whole migration process. A carmine and brilliant blue mixture was used as a probe to test the separation ability of the columns. The resolutions of the two compounds on the conical column of 7, 10, 15degrees and on the cylindrical column were 0.6, 1.57, 1.29 and 0.8, respectively. (C) 2003 Elsevier B.V. All rights reserved.

Separation and identification of compounds in Rhizoma chuanxiong by comprehensive two-dimensional liquid chromatography coupled to mass spectrometry

A comprehensive two-dimensional liquid chromatographic separation system based on the combination of a CN column and an ODS column is developed for the separation of components in a traditional Chinese medicine (TCM) Rhizoma chuanxiong. Two columns are coupled by a two-position, eight-port valve equipped with two storage loops and controlled by a computer. The effluent is detected by both the diode array detector and atmospheric pressure chemical ionization (APCI) mass spectrometer. More than 52 components in the methanol extract of R. chuanxiong were resolved and 11 of them were preliminary identified according to their UV and mass spectra. (C) 2004 Elsevier B.V. All rights reserved.

Study on conical columns for semi-preparative liquid chromatography

The dynamic flow profiles and column efficiencies in conically shaped semi-preparative liquid chromatographic columns (inlet ID larger than outlet ID) with two different conical angles (7degrees and 15degrees) were studied. The dynamic flow profiles were studied by an on-column visualization method. Conical columns were compared with cylindrical column of the same length and internal volume. The results showed that the flow profile of a sample band in the conical column of 7degrees (50 mm x 17 mm --> 11 mm ID) was parabolic in shape. The sample band migrated slower in the wall region than in the central region, as in the cylindrical column (50 mm x 14 mm ID). However, the sample band in the conical column of 15degrees (50 mm x 20 mm --> 7 mm ID) migrated slower in the central region than in the wall region, resulting in a reverse parabolic flow profile, in contrast to that in cylindrical column. This indicated that a flat flow profile might be realized in a conical column with a conical angle between 7degrees and 15degrees. The conical column of 15degrees had the highest column efficiency among the three columns under the same conditions. Compared with the cylindrical column packed with identical packing material, the conical column of 15degrees had 22%-45% higher column efficiency and 11%-27% higher peak height.

Unilamellar liposomes covalently coupled on silica gel for liquid chromatography

Silica gel was used as a support for the covalent coupling of liposomes, which could overcome drawbacks of soft gel beads in column efficiency and separation speed. The influences of the concentration of added dimethylaminopyridine and reaction time on the chloroformate activation reaction of silica gel were investigated. Temperature and pH for covalent coupling of liposomes on the activated silica gel were also optimized. Experimental results indicated that the stability of the covalently coupled liposome columns was obviously superior to that of the noncovalently coated liposome columns but the selectivity of both columns was basically identical. Separation and analysis of a crude extract of a traditional Chinese medicine Ligusticum Wallichii and a mixture of small peptides on both columns further support this conclusion.

Determination of 1-phenyl-3-methyl-5-pyrazolone-labeled carbohydrates by liquid chromatography and micellar electrokinetic chromatography

In this paper, the method for the derivatization of carbohydrates with 1-phenyl-3-methyl-5-pyrazolone (PMP) was simplified. One-third of the derivatization time was saved. Five monosaccharide derivatives have been well separated by MEKC and HPLC under optimized conditions. Good reproducibility could be obtained with relative standard deviation (RSD) values of the migration times within 5.0 and 2.3%, respectively. Furthermore, the developed methods have been successfully applied to the analysis of carbohydrates in Aloe powder and food. These methods are quite useful for routine analysis of monosaccharides and oligosaccharides in real samples. (C) 2003 Elsevier B.V. All rights reserved.

Binding of metal ions with protein studied by a combined technique of microdialysis with liquid chromatography

A method has been developed for the determination of interactions of metal ions and protein by using microdialysis sampling technique combined with pre-column derivation and reversed-phase ion-pair liquid chromatographic (HPLC analysis. Cu(II), Zn(II) and human serum albumin (HSA) were chosen as model metal ions and protein, respectively. The mixed solutions of metal ions and HSA with different molar ratios buffered with 0.1 M Tris-HCl containing 0.1 M NaCl at pH 7.43 were sampled with a mirodialysis probe by keeping perfusion rate at 1 mul/min and the temperature at 37 degreesC. The free concentrations of metal ions in microdialysates were assayed by precolumn derivatization with meso-tetra(4-sulfophenyl)-porphyrin (TPPS4) followed ion-pair HPLC analysis. The recovery (R) of microdialysis sampling was measured in vitro under similar conditions as 65.74% for Cu(II), 70.45% for Zn(II) with R.S.D. below 3.2%. The primary binding constants and number of binding site estimated by the Scatchard plot analysis are 5.04 x 10(6) M-1 and 0.85 for Cu(II), and 9.87 x 10(6) M-1 and 1.10 for Zn(II), respectively. The competition of Cu(II) and Zn(II) at the second binding site on HSA was investigated, and it was observed that there is a second site on HSA to bind Cu(II) and Zn(II), the affinity of Cu(II) is stronger than that of Zn(II) to this second site of HSA. (C) 2001 Elsevier Science B.V. All rights reserved.

Multivariate optimization in micellar electrokinetic capillary chromatography

The optimization of the organic modifier concentration in micellar electrokinetic capillary chromatography (MECC) has been achieved by a uniform design and iterative optimization method, which has been developed for the optimization of composition of the mobile phase in high performance liquid chromatography. According to the proposed method, the uniform design technique has been applied to design the starting experiments, which can reduce the number of experiments compared with traditional simultaneous methods, such as the orthano design. The hierarchical chromatographic response function has been modified to evaluate the separation quality of a chromatogram in MECC. An iterative procedure has been adopted to search the optimal concentration of organic modifiers for improving the accuracy of retention predicted and the quality of the chromatogram. Validity of the optimization method has been proved by the separation of 31 aromatic compounds in MECC. (C) 2000 John Wiley & Sons, Inc.