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Chinese Journal of Chromatography
2016, Vol. 34, No. 7
Online: 08 July 2016

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Special Column on Progress of Aptamers Selection against Multiscale Targets

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Review on application of mass spectrometry-based techniques in food allergen analysis GU Shuqing, ZHAO Chaomin, CHENG Jia, ZHAN Lina, DENG Xiaojun 2016, 34 (7):  639-646.  DOI: 10.3724/SP.J.1123.2016.03005 Abstract ( 667 )   [Full Text(HTML)] () PDF (983KB) ( 340 )   Food allergen analysis is of great significance in the field of food safety. As one of the most useful methods, mass spectrometry-based techniques can provide chemical structure information of the analytes and have been extensively applied in biological macromolecule analysis, such as food allergen detection. Mass spectrometry-based techniques possess many advantages, including reliability, high specificity, sensitivity, etc., and have attracted great attentions. This review summarizes the development of mass spectrometry-based techniques for food allergen analysis in recent years.

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Application of liquid chromatography-high resolution mass spectrometry in the identification and detection of food fraud SUN Xingquan, ZHAO Yu, YANG Chunguang, XU Jing, CAO Jijuan 2016, 34 (7):  647-656.  DOI: 10.3724/SP.J.1123.2016.04028 Abstract ( 584 )   [Full Text(HTML)] () PDF (959KB) ( 139 )   Food fraud, such as illegal use of pesticides and veterinary drugs, abuse of food additives, addition with inedible substances and food adulteration, is a prominent food safety problem in our country at present stage. The application of liquid chromatography coupled to high resolution mass spectrometry technology in the field is summarized over the last five years. The function of target screening and non-targeted screening of high resolution mass spectrometry, including flight of time mass spectrometry and electrostatic orbitrap mass spectrometry is introduced mainly. It is hoped to provide valuable support for the solution of food fraud.

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Progress on metabolomics for authenticity identification of food YU Qiuhao, ZHANG Jiukai, YE Xingqian, CHEN Ying 2016, 34 (7):  657-664.  DOI: 10.3724/SP.J.1123.2016.03040 Abstract ( 592 )   [Full Text(HTML)] () PDF (1102KB) ( 199 )   With the rapid developments of food industry and the improvement of living conditions, the phenomenon of economically motivated adulteration (EMA) is an extremely issue of concern due to people's increasing requirements for food safety. Nowadays, the major EMA incidents include substitution of varieties, mislabeling geographical origin, interfusion of poor quality, incorporation of inferiority, etc. Therefore, an efficient authentication technology needs to be established. Metabolomics is defined as the quantitative and qualitative analyses of large quantity of metabolites as a whole in a given sample, which has huge advantages in non-targeted analysis. Metabolomics has been adopted extensively by both domestic and abroad researchers to study the food safety problems, which provided an alternative research tool to identify the EMA incidents. In this paper, the progress and applications of metabolomics in identifying food varieties, geographical origin, quality and counterfeits have been reviewed, which provide technical support to ensure food quality and safety and protect the interests of consumers.

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Chemometric approach based on liquid chromatography- quadrupole/time of flight high resolution mass spectrometry to screen chemical hazards in infant formula ZHANG Hongwei, XU Hui, ZHANG Xiaomei, BAO Lei, WANG Fengmei, CHEN Liangzhen, LIANG Chengzhu, WANG Yanting, QIN Liangyong 2016, 34 (7):  665-672.  DOI: 10.3724/SP.J.1123.2015.11031 Abstract ( 556 )   [Full Text(HTML)] () PDF (938KB) ( 121 )   A chemometric model for screening chemical hazards in infant formula has been built based on liquid chromatography coupled to quadrupole/time of flight (Triple TOF®) mass spectrometry. Six chemicals, naming as salbutamol, lincomycin, sulfadiazine, spiramycin and megestrol acetate, were deliberately selected as the representatives of unknown chemical hazards to be spiked into infant formula. Fifteen different infant formula samples, with equal amount, were dissolved into water and mixed homogeneously to prepare test samples representing typical infant formula matrices. All test samples were divided into reference group (free from spiked chemicals) and spiked group. The test samples were extracted with acetonitrile, and then cleaned-up with Captiva NDLipids filtering solid phase extraction column. The liquid chromatographic separation was made on a CORTECSTM C18+column using mobile phases of 0.3%(v/v) formic acid-5%(v/v) water in acetonitrile and 0.3%(v/v) formic acid-5%(v/v) acetonitrile in water with gradient elution. Mass spectrometric analysis was conducted by a mixed acquisition mode of TOF full mass scan-information dependent acquisition (IDA)-product ion scan. Acquired data were exported to MarkerViewTM software (version 1.2.1.1, SCIEX, USA) for peak finding, alignment and filtering. Then the preprocessed data were subject to SIMCA-P software (version 14.0, Umetrics AB, Sweden) for discriminant analysis. An orthogonal partial least squares-discriminant analysis (OPLS-DA) model was built with good fitness and good prediction ability (R2X(cum)=0.742, R2Y(cum)=0.997, Q2Y(cum)=0.905). The reference and spiked samples were well grouped and the six chemicals (spiking level down to 50 μg/kg, based on weight of infant formula) were reliably identified by S-Plot of OPLS-DA model. The technological system for monitoring quality and safety of infant formula could be benefited from the proposed approach.

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Simultaneous determination of 24 phthalates in liquors using front adsorption technology and ultra performance liquid chromatography-tandem mass spectrometry WU Min, ZHENG Xianghua, ZHANG Zhigang, CHEN Yan, LIN Liyi, HUANG Zhiqiang 2016, 34 (7):  673-680.  DOI: 10.3724/SP.J.1123.2016.03001 Abstract ( 424 )   [Full Text(HTML)] () PDF (955KB) ( 94 )   A method for the simultaneous determination of 24 phthalates in liquors was developed by using front adsorption technology and ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The samples were diluted and cleaned-up by an HLB solid phase extraction cartridge. The front adsorption technology was used to suppress the interferences which came from plastic pipes in the UPLC-MS/MS. And then the targets were analyzed by UPLC-MS/MS under the positive ion mode using multiple reaction monitoring (MRM) mode. The calibration curves showed a good linearity in the range of 0.005-2.00 mg/L with r>0.99. The limits of detections (S/N=3) were 0.003-0.05 mg/kg. The average recoveries of the spiked samples were between 75.4% and 118.2% with the relative standard deviations (RSDs) of 4.0%-11.2%. The method could be used to simultaneously confirm the multi-residue of the 24 phthalates in liquors. And the method is simple, sensitive and stable.

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Determination of β-methylphenethylamine and picamilon in health products by ultra performance liquid chromatography-multiple reaction monitoring and online full scan mass spectrometry ZHU Weixia, ZHANG Li, LI Sui, ZHANG Li, LIU Yafeng, YANG Jizhou 2016, 34 (7):  681-685.  DOI: 10.3724/SP.J.1123.2016.03029 Abstract ( 507 )   [Full Text(HTML)] () PDF (1602KB) ( 114 )   A confirmative method was developed for determining β-methylphenethylamine (BMPEA) and picamilon in health products by ultra performance liquid chromatography-triple quadrupole linear ion trap mass spectrometry (UPLC-Q Trap MS). The sample was ultrasonically extracted with methanol. The purification was carried out on a new reversed phase solid-phase extraction column (PRiME HLB). The detection of compounds was in the positive mode. Multiple technologies were applied to solve the identification and quantification for the two compounds, such as multiple reaction monitoring (MRM), online enhanced product ion full scan (EPI) and library search. Methanol and 0.1% (v/v) formic acid aqueous solution were used as the mobile phases with gradient elution. A SHISEIDO CAPCELL MG Ⅱ C18 column was used to separate the analytes. The LODs and LOQs for BMPEA and picamilon in liquid, table and capsule samples were 0. 2-0.5 μg/kg and 0.5-2.0 μg/kg, respectively. The average spiked recoveries of the method varied from 79.5% to 103.8% and the RSDs were between 3.6% and 15.4%. In the range of 0.2-200.0 μg/kg, the peak areas and concentrations of matrix standard solution showed good linear relationship (r≥0.9969). The qualitative confirmation results were required based on the search-match MRM and EPI mass spectra simultaneously. The method is simple and accurate for the determination of BMPEA and picamilon in imported and commercial health products.

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Determination of six pesticide residues including diquat in crude palm oil by QuEChERS-liquid chromatography- tandem mass spectrometry WANG Lianzhu, LI Xiaolian, FANG Enhua, CHEN Yong, WANG Dengfei, XU Dunming 2016, 34 (7):  686-691.  DOI: 10.3724/SP.J.1123.2016.04017 Abstract ( 728 )   [Full Text(HTML)] () PDF (1500KB) ( 312 )   A fast method based on QuEChERS methodology was developed for the simultaneous determination of diquat, dimethoate, fenthion, fenthion-sulfoxide, fenthion-sulfone, haloxyfop-methyl in crude palm oil using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The clean-up effects of four dispersive sorbents were evaluated in terms of recoveries and matrix effects. The four sorbents were the mixture of primary secondary amine (PSA) and C18, a mixture of two sorbents a bonded C18 zirconia-coated silica (Z-Sep+) and C18, Z-Sep+, C18. As a result, the best effects were obtained from using the mixture of Z-Sep+ and C18 sorbents. The samples were extracted with methanol containing 1%(v/v) acetic acid. The extracts were cleaned up with dispersive solid phase extraction using Z-Sep+/C18 sorbents. Chromatographic analysis was carried out on an Atlantis T3 column with gradient elution. The pesticides were analyzed by positive electrospray ionization-tandem mass spectrometry under multiple reaction monitoring mode. The quantification was achieved using matrix-matched standard calibrations as external standard. The recoveries at the fortification levels of 10, 20 and 250 μg/kg in crude palm oil ranged from 70.0% to 97.9% with the relative standard deviations of 2.6%-10.2%. The limits of quantification (S/N≥10) were 0.1-2.5 μg/kg. The method has been proven to be simple, sensitive, accurate and environmental and thus suitable for the determination of the six pesticide residues above in crude palm oil.

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Simultaneous determination of eight vitamin E isomers and vitamin A in foods by normal-phase high performance liquid chromatography ZHENG Yibin, HUANG Baifen, REN Yiping 2016, 34 (7):  692-696.  DOI: 10.3724/SP.J.1123.2016.02011 Abstract ( 626 )   [Full Text(HTML)] () PDF (867KB) ( 138 )   A synchronous detection method was established by normal-phase (NP)-HPLC to separate and determine eight vitamin E isomers and vitamin A in foods. The sample was pretreated and then separated on a Waters ACQUITYTM UPLC BEH Amide column (150 mm×3.0 mm, 1.7 μm). The mobile phase consisted of hexane (A, 90%) and tert-butyl methyl ether-tetrahydrofuran-methanol (20 : 10 : 1, v/v/v) (B, 10%). The analytes were detected by UV and fluorescence detectors, identified and quantified with external standards. The linear ranges of tocopherols were from 5.0 mg/L to 60.0 mg/L (r2≥0.9999), and those of tocotrienols and vitamin A were from 0.5 mg/L to 6.0 mg/L (r2≥0.9996), while the LODs of vitamin E isomers and vitamin A were from 20 μg/kg to 60 μg/kg. The method is of high precision, stability and repeatability, and the recoveries were from 79.2% to 114.2%. This method is simple, accurate and suitable for the analysis of vitamin E isomers and vitamin A in foods.

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Determination of L-carnitine in dairy products by high performance liquid chromatography coupled with pre-column derivatization WANG Qiaoling, YU Yue, XU Dunming, ZHANG Zhigang, FANG Enhua, FENG Feng, ZHANG Feng, CHU Xiaogang 2016, 34 (7):  697-702.  DOI: 10.3724/SP.J.1123.2016.03027 Abstract ( 642 )   [Full Text(HTML)] () PDF (885KB) ( 100 )   A method has been established for the determination of L-carnitine in dairy products by high performance liquid chromatography (HPLC) coupled with pre-column derivatization. The samples were extracted by ultrasonator with 0.1 mol/L HCl as extraction solvent, and purified by a cation exchange solid phase extraction column, undergone a substitution reaction with L-propionamide-β-naphthylamine catalyzed by triethylamine and butyl chlorocarbonate. Then, the compound was detected by HPLC, with a diode array detection (DAD) as quantitative method. A linear calibration curve was obtained in the mass concentration range of 0.250-50.0 mg/L. The linear equation was y=164.4x-11.3 with the correlation coefficient of 0.9998, and the recoveries were 84.3%~86.0% with the relative standard deviations (RSDs) of 1.93%~3.18%. The limit of detection (LOD) was 10 mg/kg, and the limit of quantification (LOQ) was 25 mg/kg. The proposed procedure was then applied to the analysis of 20 real samples collected from China, and the contents of L-carnitine were 53-163 mg/kg. This method is rapid, simple, accurate and suitable for the determination of L-carnitine in dairy products.

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Determination of estradiol in table sugar by auto-solid-phase extraction-high performance liquid chromatography-tandem mass spectrometry ZENG Sanmei, XU Dunming, WEI Yiting, ZHONG Liping 2016, 34 (7):  703-707.  DOI: 10.3724/SP.J.1123.2016.03011 Abstract ( 365 )   [Full Text(HTML)] () PDF (1136KB) ( 85 )   A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was established for the determination of estradiol in table sugar. Sugar samples were dissolved in water, and extracted by alkaline acetonitrile, then cleaned-up using an HLB column. The resulting samples were detected under negative multiple reactions monitoring (MRM) mode, and quantified by the internal standard method. As the results showed, the matrix effects were depressed obviously after the purification. The limit of determination and the limit of quantification of the method were 0.1 μg/kg and 0.5 μg/kg, respectively. For all the tested samples, the average spiked recoveries ranged from 83.9% to 95.1%, and the relative standard deviations (RSDs, n=6) were lower than 10%. The method is quick, easy, effective, sensitive and accurate, and can meet the requirements of the determination of estradiol in table sugar.

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Determination of 16 perfluorinated alkyl substances in food packaging materials by solid phase extraction-liquid chromatography-tandem mass spectrometry HE Jianli, PENG Tao, XIE Jie, HU Xueyan, CHANG Qiaoying, CHEN Hui, FAN Chunlin, LI Cun 2016, 34 (7):  708-714.  DOI: 10.3724/SP.J.1123.2016.01012 Abstract ( 600 )   [Full Text(HTML)] () PDF (907KB) ( 237 )   A method for the simultaneous determination of 16 perfluorinated alkyl substances (PFAS) in food packaging materials by solid phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) was developed. Comparison and optimization of the sample pretreatment methods, mass spectrometry and other conditions were carried out. The samples were ultrasonically extracted with methanol, followed by clean-up using an Oasis WAX SPE column. The analytes were separated on a reversed phase Atlantis T3 C18 column and eluted gradiently with acetonitrile and 5 mmol/L ammonium acetate. The analytes were quantified using isotope internal standard and isotope external standard calibration curve method. The linear calibration curves were obtained in the range of 0.5-20.0 μg/L with the linear relative coefficients more than 0.99. The recoveries were in the range of 68.6%-109.2% and the relative standard deviations (RSDs) were ranged from 2.5% to 18.1% (n=6). The limits of detection (LODs) and the limits of quantification (LOQs) for the PFAS were 0.2-0.5 μg/kg and 0.5-1.0 μg/kg, respectively. This method is simple, rapid, accurate and can be used in the determination of PFAS in food packaging materials.

Reviews

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Research methods and approach for Composing Prescription fingerprints of traditional Chinese medicine YANG Fangliang, ZHANG Jing, SUN Guoxiang, SUN Wanyang 2016, 34 (7):  715-725.  DOI: 10.3724/SP.J.1123.2016.02022 Abstract ( 456 )   [Full Text(HTML)] () PDF (1079KB) ( 134 )   Traditional Chinese medicine (TCM) Composing Prescription is the compatible prescription of Chinese medicinal materials according to certain rules. The differences of its dosage compatibility can often lead to the changes of physical and chemical properties, so that it can change the effects and natures of Composing Prescription and even produce new chemical compositions. So far the identification and quality control of TCM Composing Prescription has been a difficult problem to the medical workers for these reasons. By recent years' development, fingerprint technology has been widely used in TCM research field for having a lot of advantages such as holistic view, accuracy and stability. Composing Prescription fingerprint of TCM is also the most effective control method on solving the problem of the reasonable prescription compatibility of TCM. Now its quality control ability has received wide-spread attention. Fingerprint has both the holistic quantitative function and the characteristic identifiable effects. With these advantages, it could qualitatively, quantitatively and comprehensively evaluate the complicated components of Composing Prescriptions of TCM. In this paper, we review the subject significance and purpose of Composing Prescription fingerprints of TCM, in which we elaborate the study methods and research approach in detail. The main purpose of this paper is to provide a certain reference for TCM and research of the Composing Prescription fingerprints.

Articles

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Fingerprint profiling of Astragalus polysaccharides based on partial acid hydrolysis-hydrophilic interaction chromatography analysis and comprehensive quality evaluation of Astragalus membranaceus combined with reversed-phase liquid chromatography fingerprint analysis WANG Hui, XIN Huaxia, CAI Jianfeng, LI Fangbing, JIN Yu, FU Qing 2016, 34 (7):  726-736.  DOI: 10.3724/SP.J.1123.2016.03006 Abstract ( 612 )   [Full Text(HTML)] () PDF (1177KB) ( 122 )   Astragalus polysaccharides (APS) are important components in Astragalus membranaceus (A. membranaceus). However, for the huge relative molecular mass, strong polarity, and difficulty in chromatographic separation, there's a lack of quality control finely reflecting the composition of APS up to now. To solve the problems, the key lies in degradation of polysaccharides and analysis of the hydrolyzates. A partial acid hydrolysis-hydrophilic interaction liquid chromatography (HILIC) fingerprint for APS and a comprehensive quality evaluation method for A. membranaceus combining with the traditional RPLC fingerprint were developed. Orthogonal experiments were designed to investigate the influencing factors of partial hydrolysis and the conditions were optimized based on HILIC analysis. The hydrolyzates were successfully separated using HILIC-evaporative light scattering detection (ELSD) method and the optimal conditions of hydrolysis were selected as 80℃, 1.5 mol/L trifluoroacetic acid and 4 h, which proved to be stable and repeatable after the validation. This method was applied for the fingerprint analysis of 20 batches of A. membranaceus. Cosine method was used for similarity calculation using the average of samples Nos. 1-10 as reference. Moreover, RPLC fingerprint analysis was processed on other components and the data were compared for comprehensive evaluation. The similarities of ten samples with the reference ranged from 0.258 to 0.949, which were consistent with the chromatograms reflecting the apparent disparity in APS, and could be as a supplement of the RPLC fingerprint. The new method, with the advantages of intuition, convenience, and quantifiable in similarity, could reflect the differences of the composition of polysaccharides after degradation and was successfully applied in profiling of APS, contributing to the quality control together with the RPLC fingerprint.