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    Chinese Journal of Chromatography
    2014, Vol. 32, No. 12
    Online: 08 December 2014

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    Preparation of new solid-phase microextraction fiber based on cucurbit[7]uril coordination polymers and its application in determination of polycyclic aromatic hydrocarbons from environmental water samples
    YAN Lifen, LÜ Yan, SHAO Lin, ZHOU Qingdi, DONG Nan
    2014, 32 (12):  1295-1300.  DOI: 10.3724/SP.J.1123.2014.09015
    Abstract ( 585 )   [Full Text(HTML)] () PDF (2992KB) ( 224 )  

    A novel solid-phase microextraction fiber was prepared via simple adhesion process. Fused-silica fiber was used as supporting substrate and the cucurbit[7]uril/Eu coordination polymers induced by [CdCl4]2- anion was affixed onto the surface of fused-silica fiber with high-temperature epoxy resin as a sorbent coating. The SPME coating was characterized by scanning electron microscopy and thermal analysis. Coupled to gas chromatography, the fiber was used to extract polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Analytical performances of the proposed method were investigated under the optimum extraction conditions (extraction temperature, 75 ℃; mass concentration of NaCl, 200 g/L; extraction time, 40 min; desorption time, 2 min; desorption temperature, 250 ℃) compared with commercial fibers for the same analytes. For the seven PAHs (naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene), good linearity was obtained ranging from 1 μg/L to 1000 μg/L. Limits of detection were 0.29-2.09 μg/L with the RSDs no more than 8.6%. The established SPME-GC method was applied to determine the spiked PAHs in real river water samples and satisfactory results were obtained with recoveries between 97.2% and 109.0%. Under the optimal conditions, the extraction effect of home-made coating was similar to the commercial PDMS (polydimethylsiloxane) coating, which further confirmed its potential in the solid-phase microextraction.

    Serum metabolomics analysis on benign prostate hyperplasia in mice based on liquid chromatography-mass spectrometry
    GENG Yue, SUN Fengxia, MA Yu, DENG Ligang, LÜ Jianyun, LI Teng, WANG Congcong
    2014, 32 (12):  1301-1305.  DOI: 10.3724/SP.J.1123.2014.08005
    Abstract ( 743 )   [Full Text(HTML)] () PDF (834KB) ( 367 )  

    Benign prostatic hyperplasia (BPH) increasingly becomes a common factor affecting the quality of life of aging men. Its pathogenesis has not yet been fully elucidated. Ultra-high pressure liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) was employed to detect the changes of serum metabolites in normal mice, benign prostatic hyperplasia model mice and BPH model mice with finasteride intervention. The serum metabolite profiles of the three groups of mice were analyzed. Partial least squares-discriminant analysis (PLS-DA) was used for group differentiation and biomarker selection. The results showed good distinction among the three groups of mice serum metabolite spectra. Three potential biomarkers, 1-hexadecanoyl-SN-glycero-3-phosphocholine, 1-O-hexadecyl-2-O-acetyl-sn-glyceryl-3-phosphorylcholine and (Z)-13-docosenamide, were discovered and identified. They all indicated the occurrence of benign prostatic hypertrophy is closely related to the disorders of lipid metabolism. Compared with the control group, the contents of the first two substances were significantly increased in the serum of BPH model mice, and significantly decreased after intervened by finasteride. The contents of (Z)-13-docosenamide decreased significantly in the serum of model group, and increased after intervened by finasteride. Compared with the control group, the contents of three biomarkers in finasteride group did not recover completely and had significant differences. This study is conductive to open new avenues of diagnosis and medical treatment for BPH.

    Structural characterization of Astragalus polysaccharides using partial acid hydrolysis-hydrophilic interaction liquid chromatography-mass spectrometry
    LIANG Tu, FU Qing, XIN Huaxia, LI Fangbing, JIN Yu, LIANG Xinmiao
    2014, 32 (12):  1306-1312.  DOI: 10.3724/SP.J.1123.2014.08023
    Abstract ( 766 )   [Full Text(HTML)] () PDF (951KB) ( 475 )  

    Water-soluble polysaccharides from traditional Chinese medicine (TCM) have properties of broad-spectrum treatment and low toxicity, making them as important components in natural medicines and health products. In order to solve the problem of polysaccharides characterization caused by their complex structures, a "bottom-up" approach was developed to complete the characterization of polysaccharides from Astragalus. Firstly, Astragalus pieces were extracted with hot water and then were precipitated by ethanol to obtain Astragalus polysaccharides. Secondly, a partial acid hydrolysis method was carried out and the effects of time, acid concentration and temperature on hydrolysis were investigated. The degree of hydrolysis increased along with the increase of hydrolysis time and acid concentration. The temperature played a great role in the hydrolysis process. No hydrolysis of the polysaccharides occurred at low temperature, while the polysaccharides were almost hydrolyzed to monosaccharide at high temperature. Under the optimum hydrolysis conditions (4 h, 1.5 mol/L trifluoroacetic acid, and 80 ℃), Astragalus polysaccharides were hydrolyzed to characteristic oligosaccharide fragments. At last, a hydrophilic liquid chromatography-mass spectrometry method was used for the separation and structural characterization of the polysaccharide hydrolysates. The results showed that the resulting polysaccharides were mainly 1→4 linear glucan, and gluco-oligosaccharides with the degrees of polymerization (DP) of 4-11 were obtained after partial acid hydrolysis. The significance of this study is that it is the guidance for the characterization of other TCM polysaccharides.

    Simultaneous determination of 4 kinds of 29 banned and restricted veterinary drugs in animal-derived foods by ultra performance liquid chromatography- tandem mass spectrometry and modified QuEChERS for sample preparation
    LI Na, ZHANG Yuting, LIU Lei, SHAO Hui, LI Hui, LI Jing, GUO Yongze
    2014, 32 (12):  1313-1319.  DOI: 10.3724/SP.J.1123.2014.07044
    Abstract ( 648 )   [Full Text(HTML)] () PDF (846KB) ( 483 )  

    An ultra performance liquid chromatography-tandem mass spectrometric method, with modified QuEChERS method for sample preparation, was developed for the determination of the 4 kinds of 29 banned and restricted veterinary drugs in chicken muscle, chicken liver, porcine muscle and porcine liver samples. The drugs were extracted with McIlvaine buffer solution and acetonitrile, then cleaned-up by modified QuEChERS method, and finally analyzed by ultra performance liquid chromatography-tandem mass spectrometry in multiple reaction monitoring mode via positive electrospray ionization. The method was validated at three fortification levels (LOQ level, 20 μg/kg and 50 μg/kg) in chicken muscle, chicken liver, porcine muscle and porcine liver samples. The validation results were as follows. The correlation coefficients of the standard calibration curves for the 29 veterinary drugs were all between 0.993 and 0.999 over their own concentration ranges. The average recoveries of the 29 drugs were between 71.5% and 93.2%, with the relative standard deviations (RSDs) between 0.8% and 7.7%. The limits of determination (S/N=3) of the drugs were between 0.3 and 3.0 μg/kg. The limits of quantification (S/N≥10) were 1.0 μg/kg for amantadine, 10.0 μg/kg for the tetracycline drugs, and 5.0 μg/kg for all the other drugs. It was indicated that the method developed is easy, sensitive, and has a good purification effect. The sensitivity, accuracy and precision of the method were all acceptable, and it can meet the requirements of the multiple residue analysis. So, this method can be further applied to investigate the veterinary drug residues in animal derived foods.

    Determination of 19 antibiotic and 2 sulfonamide metabolite residues in wild fish muscle in mariculture areas of Laizhou Bay using accelerated solvent extraction and high performance liquid chromatography-tandem mass spectrometry
    LIU Sisi, DU Juan, CHEN Jingwen, ZHAO Hongxia
    2014, 32 (12):  1320-1325.  DOI: 10.3724/SP.J.1123.2014.08032
    Abstract ( 886 )   [Full Text(HTML)] () PDF (818KB) ( 430 )  

    A sample preparation and analytical method with accelerated solvent extraction (ASE) and high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed to detect 19 antibiotic (9 sulfonamides, 4 quinolones, 3 macrolides and 3 others) and 2 sulfonamide metabolite residues in fish muscle. The target compounds were extracted using ASE and purified simultaneously by a C18 resin in the extraction cell. The extracts were evaporated to dryness, and redissolved with the initial mobile phase for HPLC-MS/MS analysis after freezing centrifugation (10000 r/min, -4 ℃) to remove the fat and other matrix compounds further. The separation of the analytes was carried out on an Xterra MS C18 column with methanol-acetonitrile (1:1, v/v) as mobile phase A and 0.1% formic acid (containing 0.1% ammonium formate) as mobile phase B. The spiked recoveries of the method were 55.2%-113.3%, with the relative standard deviations of 0.1%-17.6%(n=6). The limits of detection ranged from 0.003 to 0.6 ng/g. The method was applied to two fish (Synechogobius hasta and Liza haematocheilus) collected in mariculture areas of Laizhou Bay and six antibiotics were detected, in which the mass concentrations of norfloxacin were highest with mean values of 67.01 and 27.58 ng/g, respectively. The method is simple, rapid, highly sensitive, and useful in the study on exposure levels and environmental behavior of the antibiotics.

    Qualitative and quantitative analysis of the amino acids in Rhizoma Arisaematis by ultra high performance liquid chromatography-tandem mass spectrometry and high performance liquid chromatography
    WANG Xing, CHI Yumei, KANG An
    2014, 32 (12):  1326-1332.  DOI: 10.3724/SP.J.1123.2014.08025
    Abstract ( 617 )   [Full Text(HTML)] () PDF (869KB) ( 265 )  

    A method for the identification and determination of the polar amino components without ultraviolet activity in traditional Chinese medicines was developed. With Rhizoma Arisaematis as the object of this study, using pre-column derivatization with phenyl isothiocyanate (PITC) as the derivatization reagent, compounds were separated and identified on a C18 column (100 mm×2.1 mm, 3.5 μm) by ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). A total of 20 components, including 18 amino acids and 2 amine compounds were identified. Furthermore, after the optimization of the derivatization conditions, 15 amino acids were determined by high performance liquid chromatography (HPLC) on Diamonsil C18 column (250 mm×4.6 mm, 5 μm), detected at 254 nm and gradiently eluted by acetonitrile and 0.05 mol/L ammonium acetate-acetic acid (pH 6.5) as the mobile phases. The results of methodological study demonstrated that the method can meet the requirements of the determination. All calibration curves expressed good linearity: Glu, Try in the range of 2-100 mg/L, Arg in the range of 6-300 mg/L, others in the range of 0.8-40 mg/L, with the correlation coefficients ≥ 0.9995. The average recovery of this method was among 95%-105% and the RSD was less than 3%. The developed method was successfully applied to quantitative determination of amino compounds in 12 batches of Rhizoma Arisaematis samples. The method is simple, sensitive, accurate, and can be used for rapid identification and determination of amino components in traditional Chinese medicines.

    Determination of poppy ingredients in chafing dish materials by isotopic internal standard coupled with multiple reaction monitoring and online full scan mass spectrometry
    ZHU Weixia, SUN Zhuanlian, YUAN Ping, YANG Jizhou, LIU Yafeng, SUN Wuyong
    2014, 32 (12):  1333-1339.  DOI: 10.3724/SP.J.1123.2014.09012
    Abstract ( 514 )   [Full Text(HTML)] () PDF (855KB) ( 197 )  

    A confirmative method was developed for determining five poppy alkaloids including morphine, codeine, papaverine, tibane, noscapine in chafing dish ingredients by high performance liquid chromatography coupled with triple quadrupole linear ion trap mass spectrometry (HPLC-Q Trap MS). The sample was extracted with dilute HCl solution under heating condition. The removal of lipid procedure was performed with hexane. The purification was carried out on a mixed-cation solid-phase extraction column (MCX) and ethyl acetate-methanol containing 5% aqueous ammonia was used for elution. A PAK ST column was used to separate the analytes, and 5 mmol/L ammonium acetate methanol and 10 mmol/L ammonium acetate (pH 3.6) were used as mobile phases. The five alkaloids was detected in the positive mode simultaneously by multiple reaction monitoring (MRM) and online enhanced product ion full scan (EPI). The LODs were 0.05-0.5 μg/kg and the LOQs were 0.2-2 μg/kg for the five poppy alkaloids. The overall recoveries of the method varied from 64.2% to 110.6%, and the RSD were between 4.2% and 12.5%. The EPI mass spectra of positive samples were searched through standard library for qualitative confirmation. The detection of real hot pot material samples showed this method can be used for the simple and accurate determination of the five poppy alkaloid residues in chafing dish.

    Simultaneous determination of 33 primary aromatic amines of free state in fine pigments by ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry
    MAN Zhengyin, WANG Quanlin, LI Hesheng, ZHANG Aizhi
    2014, 32 (12):  1340-1348.  DOI: 10.3724/SP.J.1123.2014.07049
    Abstract ( 521 )   [Full Text(HTML)] () PDF (883KB) ( 197 )  

    A comprehensive analytical method based on ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry (UPLC-MS/MS) has been developed for the simultaneous determination of 33 primary aromatic amines (PAAs) in fine pigments such as gouache paint, oil painting pigment and acrylic paint. The primary aromatic amines in samples were extracted with acetonitrile. Then the extract was concentrated by centrifugation and nitrogen blow, finally diluted to 2 mL with methanol-water (1:9, v/v) and filtered through 0.22 μm membrane before UPLC-MS/MS analysis. The analytes were separated on a BEH Phenyl column (100 mm×2.1 mm, 1.7 μm) with 0.07% (v/v) formic acid in methanol-water as mobile phases in gradient elution. The PAAs were detected by UPLC-MS/MS under multiple reaction monitoring (MRM) mode and quantified by the internal standard method. The separation conditions, fragment voltages and collision energies were optimized. The impacts of extraction times, extraction solvents and concentration methods on recoveries were studied. The limits of detection and limits of quantitation for the 33 primary aromatic amines were 5-50 μg/kg and 15-150 μg/kg respectively. The mean recoveries of three different dye products at three spiked levels were 70.1%-115.8%. The relative standard deviations were 2.1%-15%. The experimental results indicated that the method is simple, rapid, sensitive, accurate and can meet the requirements for the determination.

    Kinetic migration of 4-cumylphenol and 4-tert-butylphenyl salicylate from paper packaging to dry food simulant Tenax TA
    HAN Wei, YU Yanjun, LI Ningtao, WANG Libing
    2014, 32 (12):  1349-1355.  DOI: 10.3724/SP.J.1123.2014.08031
    Abstract ( 686 )   [Full Text(HTML)] () PDF (1026KB) ( 286 )  

    Migration investigations were carried out on paper food packaging in contact with dry food simulant Tenax TA. The aim was to explore the migration behaviours of 4-cumylphenol (CP) and 4-tert-butylphenyl salicylate (TBS) as potential contaminants, from paper materials to Tenax TA at different migration temperatures for variant migration times. A method based on ultrahigh performance liquid chromatography coupled with fluorescence detection (UPLC-FLR) was developed to determine CP and TBS migrated into the simulant. Two independent migration tests performed under open system and closed system were contrastively studied. At the same time, a series of migration tests by using different masses of Tenax TA to contact round paper samples with the diameter of 3.5 cm was conducted to explore the proper ratio between the mass of Tenax TA and the area of food packaging sample. Based on the analytical results, high temperature and long contact time had positive effect on the migration rate of the contaminants. However, persistent high migration temperature would lead to decrease the migration rate due to desorption of CP and TBS from Tenax TA. Migration rate in closed system was higher than that in open system. In the process of migration test, a ratio of 4.16 g/dm2 was an appropriate experimental condition to conduct the migration test. All of the migration results revealed that the proper ratio of mass of Tenax TA to area of paper sample was the key to conduct the exposure assessment of food contact materials.

    Rapid determination of eight organic acids in plant tissue by sequential extraction and high performance liquid chromatography
    HUANG Tianzhi, WANG Shijie, LIU Xiuming, LIU Hong, WU Yanyou, LUO Xuqiang
    2014, 32 (12):  1356-1361.  DOI: 10.3724/SP.J.1123.2014.09016
    Abstract ( 689 )   [Full Text(HTML)] () PDF (835KB) ( 394 )  

    A sequential extraction method was developed to determine different forms of oxalate and seven oxalate-metabolism-related organic acids (glyoxylic acid, tartaric acid, glycolic acid, malic acid, acetic acid, citric acid, succinic acid) in plant tissue. The ultra-pure water was used as the extraction medium to obtain water-soluble oxalic acid and the other seven water-soluble organic acids. After the extraction of the water-soluble organic acids, the residues were extracted by dilute hydrochloric acid successively to get the acid-soluble oxalate which entered the liquid phase. A Hypersil ODS column was used with 5 mmol/L potassium dihydrogen phosphate buffer solution (pH 2.8) as the mobile phase. The diode array detector was set at 210 nm and the column temperature at 30 ℃ with the injection volume of 5 μL. The flow rate was controlled at different times which allowed a good and rapid separation of the organic acids and hydrochloric acid. Under these conditions, the linear ranges of the method were 1-2000 mg/L for oxalic acid, 25-2000 mg/L for acetic acid, and 10-2000 mg/L for glyoxylic acid, tartaric acid, glycolic acid, malic acid, citric acid and succinic acid, with the correlation coefficients of the eight organic acids ≥ 0.9996. The average recoveries of the eight organic acids in leaves and roots were 93.5%-104.4% and 85.3%-105.4% with RSDs of 0.15%-2.43% and 0.31%-2.9% (n=7), respectively. The limits of detection ranged from 1 to 10 ng (S/N=3). The results indicated that the method is accurate, rapid and reproducible for the determination of organic acids in plant samples.

    Combination of dispersive liquid-liquid microextraction based on ionic liquid and pre-column fluorescence derivatization-high performance liquid chromatography for determination of eight sulfonamides in water samples
    WU Cuiqin, LEI Jinmei, LI Yunling, WANG Yunliang, CHEN Diyun, GONG Jian
    2014, 32 (12):  1362-1367.  DOI: 10.3724/SP.J.1123.2014.08006
    Abstract ( 476 )   [Full Text(HTML)] () PDF (875KB) ( 170 )  

    Dispersive liquid-liquid microextraction based on ionic liquid coupled with high performance liquid chromatography (HPLC) and pre-column fluorescent derivatization method (IL-DLLME-HPLC-FL) was developed for the determination of eight sulfonamides (SAs). The influence of IL-DLLME parameters on extraction efficiency and the stability of derivatives of the eight SAs were investigated. The optimized experimental conditions were as follows: 40 μL [C6MIM]PF6] as extraction solvent, 0.1 mL acetone as dispersion solvents; water sample with 0% NaCl (pH 4) was extracted by dispersive liquid-liquid microextraction without ultrasonic-assistance and then derivatized for 6 h. Under the optimized experimental conditions, the results indicated that the eight sulfanilamides showed good linearities when their mass concentrations were in 0.2-10 μg/L and 10-500 μg/L, and the linear correlation coefficients were no less than 0.9989. The detection limits ranged from 0.08 μg/L to 0.5 μg/L (S/N=3). The proposed method was applied to the analysis of four water samples from different sources (tap water, lake water, Pearl River water and pond water). The relative recoveries of the SAs spiked in water samples were 87.2%-101.4% with the relative standard deviations of 3.7%-6.2% at three different concentration levels of 5, 50 and 200 μg/L. It is a convenient, environmental friendly method for the routine analysis of SAs in water samples.

    Determination of phenol in water by electrochemical tyrosinase biosensor based on ordered graphitized mesoporous carbon and evaluated by high performance liquid chromatography
    WU Lidong, LIU Huan, LI Jincheng, FU Xiaochen, SONG Yi
    2014, 32 (12):  1368-1372.  DOI: 10.3724/SP.J.1123.2014.09008
    Abstract ( 457 )   [Full Text(HTML)] () PDF (2512KB) ( 194 )  

    A novel electrochemical tyrosinase biosensor based on ordered graphitized mesoporous carbon (GMC) was obtained, which was used as a platform for phenol detection. The accuracy of tyrosinase biosensor method was comparatively evaluated by high performance liquid chromatography (HPLC). By entrapping tyrosinase molecules (6.5 nm×9.8 nm×5.5 nm) into the mesopores of GMC (diameter 10 nm, GMC10), the "interspace confinement effect" of GMC10 may improve the stability of tyrosinase in vitro. After 21-day storage, the GMC10-based tyrosinase biosensor retained more than 85% of its initial response. It is indicated that GMC10 with "interspace confinement effect" can significantly prolong the life of tyrosinase molecules in vitro. Furthermore, the GMC-based tyrosinase biosensor displayed excellent analytical performances for phenol detection, such as stability, repeatability, selectivity, sensitivity and limit of detection. The GMC-based tyrosinase biosensor demonstrated a linear response for phenol from 0.1 to 10 μmol/L with a low detection limit of 20 nmol/L. The comparative study between HPLC and GMC-based tyrosinase biosensor showed that the detection of phenol in water sample by the GMC-based tyrosinase biosensor method is reliable, accurate and effective. The proposed GMC-based tyrosinase biosensor proved to be a very promising "pre-alarm" tool for rapid detecting phenol pollution in emergency accidents.

    Chromatographic separation of inorganic ions on thin layers of titanium phosphate ion-exchanger
    Vanik GHOULIPOUR, Moharram SAFARI
    2014, 32 (12):  1373-1379.  DOI: 10.3724/SP.J.1123.2014.06031
    Abstract ( 421 )   [Full Text(HTML)] () PDF (668KB) ( 201 )  

    The chromatographic behavior of 30 inorganic cations has been studied on thin layers of titanium phosphate ion-exchanger using several aqueous, organic and mixed mobile phases. The separation of one ion from several other ions and also ternary and binary separations have been developed. Some important analytical separations are reported. The effect of pH of the mobile phase on retention factor (Rf) values of the cations in the presence of complex-forming anion along with the separation power of the ion-exchanger were studied. This ion-exchanger exhibits high sorption capacity and varying selectivity towards metal ions and makes it a suitable stationary phase in thin layer chromatography.

    Determination of fructooligosaccharides in milk powder using high performance anion-exchange chromatography coupled with pulsed amperometric detection
    GENG Lijuan, HUANG Junrong, FENG Feng, JIANG Pingping, CHU Xiaogang, ZHANG Feng, LING Yun
    2014, 32 (12):  1380-1384.  DOI: 10.3724/SP.J.1123.2014.07052
    Abstract ( 694 )   [Full Text(HTML)] () PDF (826KB) ( 251 )  

    Fructooligosaccharides (FOS) are usually added in milk powder as a kind of prebiotic. Thus, quantitative analysis of the FOS is very important for the quality control of milk powder. In this study, a simple method for the simultaneous determination of three FOS components with degrees of polymerization (DP) 3-5 in milk powder was developed by high performance anion-exchange chromatography coupled with pulsed amperometric detection (HPAEC-PAD). The samples were extracted with 50%(v/v) ethanol aqueous solution and defatted by an On Guard RP pretreatment column. The separation was performed on a CarboPac PA200 column by gradient elution using deionized water, 0.2 mol/L NaOH solution and 0.4 mol/L NaAc solution as the mobile phases. The flow rate was 0.4 mL/min. The column temperature was 30 ℃; and the injection volume was 25 μL. Good linear response was observed in the concentration range of 0.05-10 mg/L (r2>0.9993). The limits of quantification were 0.02, 0.005 and 0.02 mg/L for 1-kestose, nystose and fructofuranosyl-nystose, respectively. The mean recoveries varied from 86.0% to 114.0% at three spiked levels of 0.5, 1.0 and 5.0 mg/L. The short-chain fructooligosaccharides from inulooligosaccharides (IOS) were successfully separated by the developed HPAEC-PAD method. The method is simple, accurate, sensitive, and helpful for the quality control of milk powder.

    Gas chromatography-mass spectrometry/selected ion monitoring for screening asymmetric epoxidation of styrene
    MU Yao, WEI Siping, XU Min, CHEN Ping, WANG Qin, DU Xi
    2014, 32 (12):  1385-1389.  DOI: 10.3724/SP.J.1123.2014.09001
    Abstract ( 539 )   [Full Text(HTML)] () PDF (811KB) ( 182 )  

    A screening method by gas chromatography-mass spectrometry (GC-MS) with selected ion monitoring (SIM) has been developed for asymmetric epoxidation of styrene. All samples were analyzed by GC-MS with the mode of SIM by using ethylbenzene as the internal standard, by which styrene and styrene epoxide enantiomers were completely separated and their concentrations were accurately determined. Furthermore, this method was used to evaluate the epoxidation reaction of styrene, which was optimized by orthogonal experiment. The advantages of the method are as follows: excellent precision (RSD in the range of 1.2%-5.2%, n=5), good linearity (the correlation coefficients for styrene, (R)/(S)-styrene oxide were 0.9997, 0.9932 and 0.9963, respectively), low limits of quantitation (LOQs of styrene, (R)/(S)-styrene oxide were 1.3, 1.1 and 0.7 mg/L, respectively) and reasonable recoveries (98.2%-108.2%). All in all, the method provided a new way to determine the asymmetric epoxidation mixture of styrene and its homologs.

    Combination of programmable temperature vaporizer-large volume injection gas chromatography-mass spectrometry and automated mass spectral deconvolution and identification system for the determination of 32 pesticides in fruits and vegetables
    CAO Zhaoyun, MOU Renxiang, WU Li, LIN Xiaoyan, ZHU Zhiwei, CHEN Mingxue
    2014, 32 (12):  1390-1399.  DOI: 10.3724/SP.J.1123.2014.09005
    Abstract ( 616 )   [Full Text(HTML)] () PDF (1622KB) ( 174 )  

    An analytical method was developed for the simultaneous determination of 32 pesticides including organophosphorus, organochlorine, pyrethroid and carbamate pesticides in fruits and vegetables using gas chromatography-mass spectrometry (GC-MS). The sample was extracted with acetonitrile, and the organic layer was cleaned up with ENVI-Carb and LC-NH2 cartridges. A large volume of 20 μL purified solution was injected into the GC system using programmable temperature vaporizer (PTV). The mass spectrometric detection was operated with full scan mode. The automated mass spectral deconvolution and identfication system (AMDIS) and an isotopic internal standard were used for the qualitative and quantitative determination of the 32 pesticides, respectively. The conditions for PTV-large volume injection were studied. Furthermore, the selectivity and durability of the method were also assessed. Under the optimized conditions, the experimental results showed that all the linearities were good within their test ranges, with correlation coefficients more than 0.995, and the method detection limits of the pesticides were 2.0-5.0 μg/kg. The spiked recoveries (n=6) at three levels in the 0.010-0.50 mg/kg using spinach, snap bean and cucumber samples as blank matrices were in the range of 65.2%-120.3% with the relative standard deviations (RSDs) varying from 4.1% to 22.3%, showing good accuracy of the method. The advantages of the proposed method include high throughput, high sensitivity, reliability, robustness, and the ability to meet the demand of multi-residue pesticide analysis in fruits and vegetables.

    Simultaneous analysis of trehalose, glucose and maltose in biotransformation samples by high performance anion exchange chromatography with pulsed ampere detection
    XU Ying, ZANG Ying, JIANG Ting, ZHENG Zhaojuan, OUYANG Jia
    2014, 32 (12):  1400-1403.  DOI: 10.3724/SP.J.1123.2014.07037
    Abstract ( 710 )   [Full Text(HTML)] () PDF (797KB) ( 246 )  

    An analytical method for the determination of trehalose, maltose, and glucose in biotransformation samples was developed by using high performance anion exchange chromatography coupled with pulsed ampere detection (HPAEC-PAD). The analysis was performed on a CarboPacTM10 column (250 mm×2 mm) with the gradient elution of NaOH-NaAc as the mobile phase. The column temperature was set at 30 ℃, the flow rate was 0.30 mL/min. The results showed that trehalose, maltose, and glucose in biotransformation system were completely separated and determined in 15 min. The linear ranges and the working curves were determined by using standard samples. The correlation coefficients of three kinds of carbohydrates were over 0.9998 . The detection limits (LODs) were 0.010-0.100 mg/L. Under the optimized separation conditions, the recoveries of saccharides in the transformation system at three different spiked levels ranged from 89.4% to 103.2%. In biotransformation system, 50 IU trehalose synthase were added into 200 g/L maltose for reaction of 8 h at 37 ℃, pH 8.0. Under the above conditions, the concentration of trehalose in biotransformation sample was 101.084 g/L, and the conversion rate of trehalose reached 50.5%. The method can be applied to determine the composition in the transformation system with the advantages of simplicity and convenience.

    Isolation and preparation of gallic acid from Terminalia chebula Retz. with high-speed counter-current chromatography
    LI Zhongqin, LI Qiuyun, JIANG Xinglong, ZHANG Kun, GUAN Ruizhang
    2014, 32 (12):  1404-1408.  DOI: 10.3724/SP.J.1123.2014.07025
    Abstract ( 553 )   [Full Text(HTML)] () PDF (938KB) ( 252 )  

    A separation method based on high-speed counter-current chromatography (HSCCC) has been established for the isolation and preparation of gallic acid from the ethanol extract of Terminalia chebula Retz. After comparing five kinds of solvent protocols of HSCCC, the two-phase system of n-hexane-ethyl acetate-methanol-water (1:5:1:5, v/v/v/v) was finally chosen as the operating solvent of HSCCC for the separation of gallic acid, in which the lower phase was used as the mobile phase and the upper phase as stationary phase. The detection in the experiments was performed with an ultraviolet detector at 254 nm. Under the conditions of rotation speed of 850 r/min, lower phase flow rate of 2 mL/min, four peaks (Ⅰ/Ⅱ/Ⅲ/Ⅳ) were displayed on HSCCC chromatogram. Among them, only peak Ⅲ contained a large amount of gallic acid (about 96.40%), which was confirmed by electrospray ionization mass spectrometry (ESI-MS) and high performance liquid chromatographic (HPLC) analysis. As much as 8.6 mg of gallic acid was obtained from 100 mg of the ethanol extract of Terminalia chebula Retz., indicating the method is simple, robust and efficient for the preparation of gallic acid.