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Chinese Journal of Chromatography
2017, Vol. 35, No. 5
Online: 08 May 2017

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Synthesis of AAPBA@KCC-1 and its application in the analysis of sialic acid and gangliosides in serum TIAN Huajun, XUE Yun, CHEN Qiaomei, WANG Yan, YAN Chao 2017, 35 (5):  473-481.  DOI: 10.3724/SP.J.1123.2017.01025 Abstract ( 761 )   [Full Text(HTML)] () PDF (3822KB) ( 116 )   A new material AAPBA@KCC-1 was synthesized by using 3-acrylamidophenylboronic acid (AAPBA) modified on mesoporous silica KCC-1. First, AAPBA was modified on the surface of KCC-1 by three-step synthesis method. Then, AAPBA@KCC-1 was characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), N2 adsorption-desorption isotherm and X-ray photoelectron spectroscopy (XPS). AAPBA@KCC-1 was used as the dispersive solid-phase extraction (dSPE) adsorbent to extract and enrich sialic acid and ganglioside (GLS) from serum samples. Finally, Fourier transform ion cyclotron resonance mass spectrometry (FT-MS) and ultra performance liquid chromatography-ion mobility spectrometry-quadrupole time of flight mass spectrometry (UPLC-IMS-QTOF MS) were used to evaluated the adsorption ability of AAPBA@KCC-1 to sialic acid and GLS, respectively. The results showed that AAPBA@KCC-1 can effectively adsorb sialic acid and GLS, and can be used for further studies of sialic acid and GLS in biological samples.

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Rapid determination of rotenone in whole blood and urine by two-dimensional ultra performance liquid chromatography- triple quadrupole/linear ion trap mass spectrometry ZHANG Xiaoyi, ZHANG Xiuyao, CAI Xinxin, LI Ruifen, LIN Xueyao, LIN Jie 2017, 35 (5):  482-486.  DOI: 10.3724/SP.J.1123.2016.12023 Abstract ( 481 )   [Full Text(HTML)] () PDF (1034KB) ( 75 )   The two-dimensional ultra performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry (2D-UPLC-QTRAP MS) method has been developed for the determination of rotenone in whole blood and urine. This method is based on the use of two columns of different stationary phases (Kinetex Biphenyl and Acquity BEH C8) connected through two six-port two-position switching valves. Urine samples were diluted with equal quantity of water and then directly injected into the separation system. Blood samples were prepared by precipitation of proteins with acetonitrile, and then the supernatants were diluted with water and injected into the system. The samples were loaded onto the Cyclone column at high flow-rates, allowing the excluded proteinaceous material to flow through to waste. Then the retained rotenone was eluted into the Kinetex Biphenyl column, and the first dimension separation was completed. The fraction containing rotenone was switched into a trap column (XBridge C8 Direct Connect HP). After the rotenone was retained completely by trap column, the valve switched it into the stream of the second dimension. The rotenone was separated on the Acquity BEH C8 column with gradient elution of mobile phases of acetonitrile-H2O containing 0.2% (v/v) formic acid, detected by positive electrospray ionization tandem mass spectrometry in the multiple reaction monitoring-information-dependent acquisition-enhanced product ion (MRM-IDA-EPI) mode, and quantified by solvent standard solutions. The average recoveries were 84.6%-94.3% and 88.4%-95.7% for rotenone in blood and urine with relative standard deviations of 2.6%-7.3% and 2.8%-6.8% (n=6). The limits of detection were 0.2 and 0.03 μg/L for blood and urine, respectively. The method is sensitive, selective, and has been successfully applied to the detection of rotenone in the samples resulting in food poisoning.

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Determination of 27 new fungicides in cereals, vegetables and fruits by dispersive solid phase extraction and liquid chromatography-tandem mass spectrometry CUI Chunyan, ZHANG Hongyi, WU Xingqiang, FAN Chunlin, LI Shuai, CHEN Hui, CHANG Qiaoying, PANG Guofang 2017, 35 (5):  487-494.  DOI: 10.3724/SP.J.1123.2016.12040 Abstract ( 653 )   [Full Text(HTML)] () PDF (1731KB) ( 134 )   A method for simultaneous determination of 27 new fungicides in cereals, vegetables and fruits using dispersive solid phase extraction and liquid chromatography-tandem mass spectrometry (DSPE-LC-MS/MS) was developed. Samples were extracted with acetone containing 1% (v/v) acetic acid, purified by a mixed sorbent of ethylenediamine-N-propylsilane (PSA), C18, anhydrous magnesium sulfate (MgSO4) and multi-walled carbon nanotubes (MWCNT), separated by a reversed phase C18 column, and gradiently eluted with acetonitrile and 0.1% (v/v) formic acid solution (containing 5 mmol/L ammonium acetate). Anhydrous magnesium sulfate was used as a dewatering agent. The positive ion mode and multiple reaction monitoring (MRM) mode were used in the analysis, and the analytes were quantified by external standard method. Thifluzamide and triclopyricarbe showed good linearities in the range of 20.47-200 μg/kg, and the limits of detection (LODs) and the limits of quantification (LOQs) were 6.15-16.67 and 20.47-55.5 μg/kg, respectively. The other 25 new fungicides showed good linearities in the range of 0.02-100 μg/kg, and the LODs and LOQs were 0.006-4.44 and 0.02-14.79 μg/kg, respectively. The linear relative coefficients were not less than 0.9950. The recoveries were in the range of 70.02%-117.6% and the relative standard deviations (RSDs) ranged from 0.01% to 19.62% (n=3). The method has the advantages of simplicity, rapidity, high sensitivity and better purification effect. It is suitable for the rapid determination of the 27 new fungicides in cereals, vegetables and fruits.

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Determination of 20 perfluorinated alkyl substances in honey by high performance liquid chromatography- tandem mass spectrometry LI Shuai, CHEN Hui, JIN Linghe, PENG Tao, FAN Chunlin, WANG Minglin 2017, 35 (5):  495-501.  DOI: 10.3724/SP.J.1123.2016.12016 Abstract ( 573 )   [Full Text(HTML)] () PDF (1373KB) ( 302 )   A sensitive method for simultaneous determination of 20 perfluorinated alkyl substances (PFASs) in honey was developed by QuEChERS-high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The samples were extracted by acetonitrile with 1.5% (v/v) formic acid, and purified by C18 and N-propylethylenediamine (PSA) adsorbents. The separation of the 20 PFASs was performed on an Atlantis T3 C18 column using gradient elution with methanol containing 5 mmol/L ammonium acetate and 5 mmol/L ammonium acetate as mobile phases within 16 min. The PFASs were analyzed under the multiple reaction monitoring (MRM) mode with negative electrospray ionization (ESI-). Under the optimal conditions, the isotope internal standard method was used to quantify the contents of the 20 PFASs. The calibration curves were acquired in the concentration range of 0.2-10 μg/L with correlation coefficients (r) greater than 0.99. The limits of detection (LODs) and limits of quantitation (LOQs) ranged from 0.04 to 0.10 μg/kg and 0.10 to 0.20 μg/kg, respectively. The recoveries of the 20 PFASs spiked in blank honey samples were between 72.6% and 113.0% with relative standard derivations (RSDs) of 0.4%-15.9% (n=6). The developed method is rapid, efficient and accurate, and suitable for the simultaneous analysis of the 20 PFASs in honey samples.

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Qualitative analysis of phenolic compounds in Camellia Sinensis seeds by ultra-high performance liquid chromatography combined with quadrupole time-of-flight mass spectrometry LAI Guoyin, WANG Lijuan, LU He, ZENG Qiumei, XU Dunming, WANG Xiaoqin, LIN Liyi, ZHANG Zhigang, LÜ Meiling 2017, 35 (5):  502-508.  DOI: 10.3724/SP.J.1123.2016.11010 Abstract ( 624 )   [Full Text(HTML)] () PDF (1208KB) ( 110 )   Phenol compounds from some plants are considered as the natural anti-oxidants and have been demonstrated with the beneficial biological activities. In this work, the ultra-high performance liquid chromatography (UHPLC) combined with quadrupole time-of-flight mass spectrometry (Q-TOF/MS) was applied to qualitatively determine the phenolic compounds in Camellia Sinensis seeds. The seed sample was extracted using ethanol aqueous solution and further subjected to the UHPLC separation with the reversed phase C18 column as the stationary phase and the acidified acetonitrile/water as the binary mobile phases. The eluent from the column was directed to Q-TOF/MS for compound identification. Based on a number of reports on the chemical components in Camellia Sinensis and the related plants, a customized compound database was initially created including the name and formula of the previously reported 106 phenol compounds. The acquired MS scan data were searched against the customized phenol compound database. The retrieved compounds were then subjected to MS/MS scan, and the obtained fragment ions were applied to further determine the possible structures. A total of 24 phenolic compounds were tentatively identified, including 13 phenolic acids, 4 catechins, and 7 flavonoids, which were characteristic in the ethanol extract according to the available references and the relevant structural information of the molecular and fragment ions. These compounds were further confirmed by matching against the standard compounds in retention times and fragment ions. The results demonstrated that the UHPLC-Q-TOF/MS with the high mass accuracy and the high resolution is a reliable technology for rapid qualitative identification of the phenolic compounds in Camellia Sinensis seeds, promoting the discovery and identification of the new compounds.

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Simultaneous determination of the specific migration amounts of light stabilizers and antioxidants in plastic materials in contact with foodstuffs by ultra-high performance liquid chromatography/orbitrap high resolution mass spectrometry WANG Chengyun, LI Chengfa, LIN Junfeng, XIE Tangtang, CHU Naiqing 2017, 35 (5):  509-519.  DOI: 10.3724/SP.J.1123.2016.11014 Abstract ( 576 )   [Full Text(HTML)] () PDF (886KB) ( 162 )   An effective method was established for the simultaneous determination of the specific migration amounts of light stabilizers and antioxidants in plastic materials in contact with foodstuffs using ultra-high performance liquid chromatography/orbitrap high resolution mass spectrometry (UPLC/Orbitrap HRMS). Plastic materials in contact with foodstuffs were treated by five food simulants:30 g/L acetic acid, 10% (v/v) ethanol, 20% (v/v) ethanol, 50% (v/v) ethanol and fatty food simulant (isooctane). The treated solution was analyzed by UPLC/Orbitrap HRMS. The concentrations of each analyte were calculated by the external standard method. The proposed method showed good linearities with the correlation coefficients above 0.998 for all the 40 target compounds. The limits of quantification (LOQs) varied from 0.01 to 1.00 μg/L for the 40 target compounds. The five food simulants mentioned above were investigated. The average spiked recoveries varied from 81.46% to 94.53% while the relative standard deviations (RSDs) varied from 3.25% to 9.99%. The proposed method was applied to determine the specific migration levels in different simulants of light stabilizers and antioxidants in plastic materials in contact with foodstuffs commercially available. Light stabilizers and antioxidants at various content levels were detected in some samples. The proposed method is sensitive and can meet the requirements of the specific migration limits (SML) of light stabilizers and antioxidants in plastic materials in contact with foodstuffs.

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Qualitative and quantitative analysis of unknown additives in sulfachlorpyrazine sodium soluble powder BAO Aiqing, CHEN Huihua, LU Chunbo, ZHOU Wei, WANG Bin, CHEN Xiaolin, LIN Xianjun 2017, 35 (5):  520-525.  DOI: 10.3724/SP.J.1123.2016.12004 Abstract ( 524 )   [Full Text(HTML)] () PDF (931KB) ( 98 )   A qualitative and quantitative analysis of unknown additives in a batch of veterinary soluble sulfachlorpyrazine sodium powder had been implemented. The content of soluble sulfachlorpyrazine sodium powder was determined by potentiometric titration. The result showed that the titration was aberrant. According to the standard method, one of the two identifications was unqualified. It revealed that some unknown compounds may be doped in the sample. Then the screening of the sample through ultra high performance liquid chromatography coupled with quadrupole time-of-flight tandem mass pectrometry (UHPLC-Q/TOF MS) showed that the suspicious additives were found in the sample. Furthermore, double confirmation and content determination were accomplished by high performance liquid chromatography-diode array detection (HPLC-DAD). Mequindox and sulfadimidine as the illegal additives were detected at 40.3 and 16.4 mg/g respectively. By summarizing the above progress of deduction, validation and content determination, a good pattern was developed for screening illegal additives in veterinary drugs which provided a reference for the inspection of illegal adulterations in veterinary drugs.

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Construction and evaluation of gel filtration/ion exchange comprehensive two-dimensional liquid chromatography system ZHANG Zheng, TANG Tao, YANG Sandong, SUN Yuanshe, LI Tong, ZHANG Weibing 2017, 35 (5):  526-532.  DOI: 10.3724/SP.J.1123.2016.12006 Abstract ( 561 )   [Full Text(HTML)] () PDF (1857KB) ( 97 )   A two-dimensional liquid chromatography (2-D LC) system was developed with gel filtration chromatography (GFC) and ion exchange chromatography (IEC) based on the sizes and electric properties of proteins. A double-trap-column interface was used in the GFC/2×IEC 2-D LC system. To achieve the comprehensive 2-D separation, heart-cutting parallel columns were used in the second dimension considering the isoelectric point range of proteins. A general proteomic platform was established with protein separation, online digestion, peptide separation and mass identification. A TSK-GEL G3000SWXL column (300 mm×7.8 mm, 5 μm), a Hypersil SAX column (100 mm×4.6 mm, 10 μm) and a Hypersil SCX column (100 mm×4.6 mm, 10 μm) were used to separate the yeast protein samples. The GFC/2×IEC 2-D LC system was evaluated with the yeast protein samples (100 μL) of concentration of 13.5 mg/mL. First dimensional GFC fractions were cut for 17 times within 148 min and transferred continuously to the second dimension to continue the separation. Under the optimized conditions, the total peak capacity of 2-D LC system reached 884. The results demonstrated that the 2-D LC system can be used for on-line protein separation. The protein separation module has a great prospect in the field of proteomic research.

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Dispersive liquid-liquid microextraction based on solidification of floating organic drop followed by high performance liquid chromatography for the determination of three alkylphenols in environmental water samples FU Bo, ZHANG Jiping, ZHOU Lu, JIANG Hui 2017, 35 (5):  533-537.  DOI: 10.3724/SP.J.1123.2016.12012 Abstract ( 494 )   [Full Text(HTML)] () PDF (1356KB) ( 108 )   A simple, rapid and eco-friendly method named dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) was developed for the determination of 2-tert-butyl-4-ethylphenol, 4-tert-octylphenol and 2,4-di-tert-butylphenol in wastewater samples coupled with high performance liquid chromatography-ultraviolet detection (HPLC-UV). Octanoic acid was served as extraction solvent, and methanol was selected as dispersive solvent. The parameters affecting the extraction efficiency including the type and volume of the extraction solvents and the dispersive solvents, the pH and the salt addition were optimized. Under optimum conditions, the linear range was 20-1500 μg/L for all the three target alkylphenols. Limits of detection (LODs, S/N=3) were in the range of 0.45-0.61 μg/L. The enrichment factors (EFs) varied from 145 to 169, and the recoveries at three spiked levels were in the range of 80.1%-109.9%. It demonstrated that fatty acids including octanoic acid and nonanoic acid could be used as extraction solvent in DLLME-SFO method. The method is suitable for the determination of alkylphenols in environmental water samples.

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Determination of sulfate ion in four aromatic sulfonates by ion chromatography coupled with on-line solid phase extraction CHEN Ailian, FANG Linmei, LÜ Haixia, SHI Chaoou 2017, 35 (5):  538-543.  DOI: 10.3724/SP.J.1123.2016.11022 Abstract ( 525 )   [Full Text(HTML)] () PDF (970KB) ( 84 )   A new ion chromatography method coupled with on-line solid phase extraction was developed for the determination of sulfate ion in four aromatic sulfonates. A self packed porous graphitized carbon solid phase extraction (PGC-SPE) column was used for on-line sample pre-treatment and a valve switching-large volume injection mode was used for sample injection in the system. After processed by PGC-SPE column, the inorganic ions contained in samples got into a loop and then were flushed into the detection system. The eluent of SPE for on-line matrix enrichment was 1.5 mmol/L sodium carbonate at a flow rate of 0.8 mL/min. The injection volume was 20 μL. The analytical columns were SH-AC-3 (250 mm×4.0 mm)+SH-AG-3 (50 mm×4.0 mm). The column temperature was set at 35℃. The elution was performed by 6 mmol/L sodium carbonate-4 mmol/L sodium bicarbonate at a flow rate of 0.8 mL/min. The results showed that the sulfate ion in the range of 0.50-20.00 mg/L had a good linear relationship and the correlation coefficient was 0.9983. The relative standard deviations (RSDs) of the retention time, peak height and peak area were 0.28%-2.86%. The limit of detection was 0.0106 mg/L. The recoveries were 91.01%-109.3%. The entire online analysis process was completed within 25 min with small injection volume, short analysis time and high efficiency. This method possesses good linearity and repeatability.

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Enantioseparation of 2-(substituted phenyl) propanoic acids with hydroxypropyl-β-cyclodextrin as a chiral additive:investigation of substituent influence on enantiorecognition WANG Xiaoping, LU Mengxia, BU Zhisi, LÜ Liqiong, TONG Shengqiang 2017, 35 (5):  544-550.  DOI: 10.3724/SP.J.1123.2016.12020 Abstract ( 449 )   [Full Text(HTML)] () PDF (1205KB) ( 80 )   2-(Substituted phenyl) propanoic acids were successfully enantioseparated by reversed-phase high-performance liquid chromatography with hydroxypropyl-β-cyclodextrin as a mobile phase additive.The effect of the mobile phase composition,including the aqueous buffer,the organic modifier,and the concentration of the additive,were investigated.The aqueous buffer pH,the type and percentage of the organic modifier,and the additive concentration had a great influence on the retention time and peak resolution.Enantioseparations were achieved on an YMC ODS-C18(150 mm×4.6 mm,5 μm) column.The mobile phase was composed of acetoni-trile and 0.10 mol/L of phosphate buffer at pH 3.3 containing 25 mmol/L of the hydroxypropyl-β-cyclodextrin additive.The binding constants of the inclusion complex between each of the 2-(substituted phenyl) propanoic acids and hydroxypropyl-β-cyclodextrin were determined,and the formation of the inclusion complex was investigated.The results showed that the stoichiometries for all of the inclusion complexes between hydroxypropyl-β-cyclodextrin and enantiomers were 1:1.It was found that the electron-donating group of the enantiomer was advantageous for enantiorecognition by hydroxypropyl-β-cyclodextrin.The results provide a useful reference for the influence of the enantiorecognitionfactors produced by hydroxypropyl-β-cyclodextrin.Key words:enantioseparation;high-performance liquid chromatography (HPLC);2-(substituted phenyl) pro-panoic acids;hydroxypropyl-β-cyclodextrin

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Determination of oxygenates and anilines in motor gasoline by gas chromatography LI Changxiu 2017, 35 (5):  551-557.  DOI: 10.3724/SP.J.1123.2016.11018 Abstract ( 596 )   [Full Text(HTML)] () PDF (1092KB) ( 135 )   A test method for the determination of oxygenates and anilines in motor gasoline was established using a gas chromatograph (GC) with heart-cut accessories and two chromatographic columns. A nonpolar DB-1 column (30 m×0.32 mm×1.0 μm) was used as the pre- column and a polar GS-OxyPLOT or CP-Lowox column (10 m×0.53 mm×10 μm) was used as the analysis column. In a test run, the gasoline sample was first separated according to the boiling points on the nonpolar column. By solenoid valve switching, the compounds of boiling points below 2-hexanone were cut to the GS-OxyPLOT or CP-Lowox column, whereas the other compounds were put through a restrictor to a flame ionization detector (FID). The oxygenates were separated from the hydrocarbons on the GS-OxyPLOT or CP-Lowox column and detected by the FID. When a second run was performed, the solenoid valve switching time was set at the point when m-methyl aniline was all eluted from the nonpolar column into the polar column. Anilines were separated from hydrocarbons and oxygenates on the GS-OxyPLOT or CP-Lowox column. Dimethoxy-ethane was used as the internal standard for quantitation. Methyl tert-butyl ether (MTBE), methanol, methylal, sec-butyl acetate, ethyl acetate, aniline, N-methyl aniline and o/m/p-methyl aniline in motor gasoline were detected and quantitated. The linear ranges were 0.01%-10% (mass fraction) with recoveries of 86.0%-102.6%. The method provides an effective way for quality control of motor gasoline.

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Determination of choline chloride in milk powder and jelly by solid phase extraction-ultra high performance liquid chromatography-tandem mass spectrometry WANG Hui, LIU Jiang, LI Xihui, CAO Yang, HUANG Xiaobei, LI Yongqiang 2017, 35 (5):  558-562.  DOI: 10.3724/SP.J.1123.2016.12024 Abstract ( 712 )   [Full Text(HTML)] () PDF (845KB) ( 146 )   An analytical method was developed for the determination of choline chloride in milk powder and jelly by solid phase extraction-ultra high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The samples were centrifuged after hydrolyzation 3 h in 10 mL 0.02 mol/L ammonium acetate (glacial acetic acid adjust pH to 3.0). The supernatant was cleaned up by a DIKMA ProElut PLS column (60 mg/3 mL). The target compounds were separated by an Agilent ZORBAX 300 SCX column (150 mm×2.1 mm, 5 μm). Qualitative and quantitative analyses were carried out by multiple reaction monitoring (MRM) mode with positive electrospray ionization (ESI+). The limit of detection (LOD, S/N=3) and the limit of quantitation (LOQ, S/N=10) were 0.15 mg/kg and 0.50 mg/kg, respectively. The recoveries of choline chloride spiked in milk powder and jelly were 70.8%-100.2%, with RSDs no more than 6.83% (n=6). The standard curves showed good linearity in the concentration range from 0.05 to 8.0 mg/L with correlation coefficient (r) of 0.996. The method was applied to detection of commercially available choline chloride in milk powder and jelly. The contents of choline chloride in real milk power and jelly samples were 251.0-2448 mg/kg and 0.261-0.314 mg/kg, respectively. The developed method is accurate, reliable, sensitive, and suitable for the determination of choline chloride in milk powder and jelly.