Shusheng Zhang

A rapid, sensitive, and practical CE with C⁴D detection was developed for the analysis of three polyphenols (rutin, scopoletin, and chlorogenic acid) in tobacco samples. The constructed mini detection cell (12 mm × 10 mm × 10 mm) of C⁴D featured with small inner cell volume (∼2 nL), smaller noise (−1 2‐amino‐2‐methyl‐1‐propanol (pH 11.2), and the applied separation voltage of +20 kV over a capillary of 50 μm id × 375 μm od × 50 cm (38 cm to the C⁴D window, 41.5 cm to the UV detector window), which gave a baseline separation of three polyphenols within ca. 6 min. The method provided the limits of quantification (S/N = 10) at about 0.08–0.15 μg g⁻¹ for three polyphenols, whereas the overall recoveries ranged from 82% to 88%. The proposed method has been successfully applied to measure three polyphenols in the actual tobacco samples, and their contents were calculated and evaluated.

A heart-cutting two-dimensional gas chromatography (GC) method was developed for the determination of nitrobenzene compounds (NBCs) in mainstream cigarette smoke. For the method, the particulate matter of cigarette smoke was extracted with cyclohexane, purified with a silica solid-phase extraction (SPE) cartridge and analyzed by heart-cutting two-dimensional GC equipped with two electron capture detectors. The heart-cutting two-dimensional GC was achieved by a single-column GC oven equipped with a microfluidic pressure balanced device (Deans switch). Two-dimensional GC was compared to single-dimensional GC and found to be clearly better for the separation of seven NBCs from a complex smoke matrix. The limits of detection ranged from 1.28 to 9.83 ng/mL, spiked recoveries were between 88.3 and 106.8% and relative standard deviation ranged from 2.79 to 12.78%. The NBCs yields of six kinds of Chinese and international cigarettes brands, which were all smoked according to two smoking protocols (International Organization for Standardization and Health Canada Intense smoking regimens), were determined and compared.

A new para‐tert‐butylcalix[4]arene column containing thiadiazole functional groups was prepared and used for the separation of polycyclic aromatic hydrocarbons, phenolic compounds, aromatic amines, benzoic acid and its derivatives by high‐performance liquid chromatography (HPLC). The effect of organic modifier content in the mobile phase on retention and selectivity of these compounds were investigated. The results indicate that the stationary phase behaves like reversed‐phase packing. However, hydrogen bonding, π–π and inclusion interactions seem to be involved in the separation process. The column has been successfully employed for the analysis of clenbuterol in pork and pig casing; the limit of detection and the limit of quantitation for this method by HPLC‐UV detection was 0.03 and 0.097 μg/mL, respectively; the method is demonstrated to be suitable and a competitive alternative analytical method for the determination of clenbuterol.

The chromatographic behaviors of benzoic acid (BAH) were investigated on a self-made p-tert-butyl-calix [4] arene-1,2-crown-4 (Cx4-4) stationary phase by changing methanol content and pH value of the mobile phase. The results show that hydrophobic interaction is the main interaction in the separation of benzoic acid, moreover, inclusion interaction, pi-pi and hydrogen bonding interactions also play additional roles. A Density Functional Theory (DFT) method with the base set of B3LYP/STO-3G* was employed to explain the interaction between BAH and Cx4-4, and the optimized supramolecular structure (Cx4-4 and BAH), the Gibbs free energy change (delta G) and stabilization energy change (delta E) were obtained. With the assistance of quantum chemistry calculation, the separation mechanism is further discussed. The quantum chemical calculation results were consistent with the retention behavior of BAH on Cx4-4 stationary phase. Finally, by using the self-made Cx4-4 column, a high performance liquid chromatographic (HPLC) method for the analysis of BAH in tuber mustard and vinegar was developed.

BACKGROUND: Practical methods for the analysis of fenoxycarb residues in wheat samples were developed using high‐performance liquid chromatography (HPLC) and non‐aqueous capillary electrophoresis (NACE).RESULTS: Fenoxycarb residues in wheat were extracted with acetone by ultrasonication, followed by a clean‐up procedure with liquid–liquid extraction with 5% NaCl/dichloromethane. The HPLC was developed using C18 as column, MeOH/water (6:4, v/v) as the mobile phase and 199 nm as the detection wavelength. The optimal NACE condition was established with the running buffer of 20.0 mmol L⁻¹ NH₄Ac in 95% MeOH (pH* 9.0), and the applied voltage of 30 kV over a capillary of 50 µm i.d. × 48.5 cm × 40 cm effective length. Both methods gave the relatively lower limits of detection (0.008 mg kg⁻¹ for HPLC and 0.024 mg kg⁻¹ for NACE) and the higher recoveries (>85.0%). They were successfully applied to the determination of fenoxycarb in wheat samples.CONCLUSION: The results showed that the fenoxycarb residue gradually reduced to trace amounts after about 3 years, which implied that the pharmacological actions of fenoxycarb could last for about 3 years. Meanwhile, more effort should be made to control and reduce fenoxycarb residues because of its potential health risks to consumers. Copyright © 2007 Society of Chemical Industry

A practical method for residue analysis of 2,4‐D, dicamba and 2,4,5‐T in baked tobacco leaves has been developed using nonaqueous CE (NACE). The herbicide residues of 2,4‐D, dicamba and 2,4,5‐T in tobaccos were extracted by ultrasonication with ethyl acetate, followed by a cleanup procedure with gel permeation chromatography. The separation of 2,4‐D, dicamba and 2,4,5‐T by NACE was optimized based on orthogonal experiment design with four factors at three levels. The optimal NACE condition was established with the running buffer of 40.0 mmol/L ammonium acetate in 90% CH₃CN (apparent pH 10.2), and the applied voltage of –25 kV over a capillary of 50 μm id×46 cm (37.5 cm to the detector window), which gave a baseline separation of 2,4‐D, dicamba and 2,4,5‐T within 15 min. The LOD were ca. 0.4–0.6 μg/mL for the three herbicides, whereas the overall recovery ranged from 80.8 to 84.1%. The proposed method has been successfully applied to measure 300 real tobacco samples, and the residue profiles of the three herbicides in tobacco samples were obtained and evaluated.

Diphenamide, napropamide and metolachlor (FIG. 1) are selective, pre-emergence arylamide herbicides used to control the growth of annual grasses and broadleaf weeds in a variety of fields, e.g. fruit trees, nuts, corns, green crops, etc. They possess high activity and moderate toxicity. For food and environment safety, the detailed investigations on their residues and metabolism are very important. Diphenamide, napropamide and metolachlor in the pesticide products, serum, urine, soil, environmental water, fruits and wine have been widely analyzed by ELISA, fluorescence, phosphorescence, capillary electrophoresis, high performance liquid chromatography (HPLC), gas chromatography(GC) and GC mass spectrometry (GC-MS). However, to our knowledge, simultaneous residue analysis of diphenamide, napropamide and metolachlor in tobacco samples has not been extensively documented. Tobacco is greatly consumed by smokers throughout the world. The pesticide residue in tobaccos might be potentially harmful to smokers' health. With this in mind the residue determination and control of diphenamide, napropamide and metolachlor in the tobacco leaves are very important for tobacco products and consumers. For these three herbicides, the tolerable maximum residue limits (MRLs) have been limited ranging from 0.05 (for tobacco products) to 5 mg/kg (for tobacco leaves) in different European countries. For the complex tobacco samples, the GC and HPLC with UV detection suffer from matrix interference making quantification and identification of these herbicides difficult. In such cases the removal of the matrix effects and identification of the target compounds are of great importance. The present work reports the extraction and clean up procedures, as well as, the chromatographic conditions developed for the simultaneous determination of diphenamide, napropamide and metolachlor residues in the fluecured tobacco leaves, from the different sources using HPLC-UV method.