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Chinese Journal of Chromatography
2017, Vol. 35, No. 4
Online: 08 April 2017

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Annual review of capillary electrophoresis technology in 2016 LIU Pinduo, SUN Miao, LIU Xiaohui, NIU Xiameng, ZHAO Xinying, QU Feng 2017, 35 (4):  359-367.  DOI: 10.3724/SP.J.1123.2017.02017 Abstract ( 369 )   [Full Text(HTML)] () PDF (885KB) ( 195 )   This paper reviews the capillary electrophoresis (CE) in 2016. The literature searched from ISI Web of Science published in 2016 (Jan. 1st to Dec.31) is classified and introduced based on drugs and natural products, medical and clinical tests, foods and agriculture, biological molecules, chiral analysis, environmental monitoring, proteomics and metabolomics, CE-mass technology, other compounds and ion analysis. Five international and two national conferences are included and the important reports are introduced briefly. At the end of the paper, the capillary electrophoresis instruments are introduced.

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A real-time wavelet algorithm and its application in chromatographic signal analysis based on finite impulse response filter ZHANG Jing, LI Yu, REN Shunwen 2017, 35 (4):  368-374.  DOI: 10.3724/SP.J.1123.2016.09044 Abstract ( 513 )   [Full Text(HTML)] () PDF (1267KB) ( 77 )   The precise real-time analysis of the chromatographic signal is the key technology in process detection using chromatographic instrument system. Chromatographic signal can be effectively analyzed with the wavelet transform. However, the performance of real-time is not satisfactory and become a bottleneck of its wide applications. As a fast algorithm of wavelet analysis, the multi-resolution analysis (MALLAT) algorithm can still not satisfy the requirements of real-time performance. Considering the MALLAT algorithm and the relationship between filter coefficients of the decomposition and reconstruction, a novel real-time wavelet analysis method based on finite impulse response filter was proposed in this paper. Simulation results showed that the real-time performance of proposed algorithm is greatly improved on the basis of same effects compared with the classical MALLAT wavelet algorithm.

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Preparation and performance evaluation of chromatographic column precoated with graphitized carbon black WANG Zhonglai, SHI Enlin, FU Xiaohai, ZENG Junling, YU Farong 2017, 35 (4):  375-381.  DOI: 10.3724/SP.J.1123.2016.10051 Abstract ( 441 )   [Full Text(HTML)] () PDF (877KB) ( 104 )   A preparation method of special chromatographic column (LZP-930) for liquor analysis was optimized by precoating the graphitized carbon black (GCB) on the inner wall of fused capillary column. Characteristics of the prepared chromatographic column (LZP-930G) were investigated in detail. The retention behavior was evaluated, and the effect of the precoated GCB on the performance of the LZP-930G column was discussed. Results revealed that the plate number, stability and polarity were increased obviously by using the LZP-930G column, so the separation selectivity and chromatographic peak shape of acids and alcohols were improved. All the 53 compounds in the mixed liquor standard sample could be separated simultaneously. The relative standard deviations of retention times and peak areas were less than 0.63% and 4.51% (n=5), respectively. The result showed that the GCB precoated technology can be used for the preparation of high performance chromatographic column for liquor analysis.

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Preparation and evaluation of chromatographic properties of sulfobetaine zwitterionic hydrophilic interaction chromatography stationary phase LI Wenjing, ZHAO Lijuan, WEI Chanling, DAI Xiaojun, GONG Bolin 2017, 35 (4):  382-387.  DOI: 10.3724/SP.J.1123.2016.09035 Abstract ( 497 )   [Full Text(HTML)] () PDF (906KB) ( 115 )   A zwitterionic sulfobetaine functional monomer N,N-dimethyl-N-acryloyloxyethyl-N-ammonium propane sulfonate (DMAEAPS) was synthesized. Dimethyl amino ethyl acrylate (DMAEA) and 1,3-propyl sulfonic acid ester as raw materials were used to synthesize the functional monomer. The DMAEAPS functional monomer was characterized by 1H-NMR and FT-IR. 2-Bromoisobutyryl bromide allyl silicone (Sil-Br) was used as the initiator, CuBr and 2,2-bipyridyl (Bpy) as the catalytic system, and the functional monomer DMAEAPS was grafted on the surface of Sil-Br by atom transfer radical polymerization (ATRP). Then the sulfobetaine zwitterionic stationary phase (Sil-DMAEAPS) was obtained. The Sil-DMAEAPS stationary phase was characterized by element analysis. Chromatographic evaluation in hydrophilic interaction chromatography (HILIC) mode showed that the materials were suitable for use as stationary phase, and the column showed a dual retention mechanism, HILIC mode in acetonitrile-rich mobile phases and RP mode in highly aqueous mobile phases. The separation selectivity and retention of the five polar solutes (benzoin, pyridoxine, rutin hydrate, p-coumaric acid and caffeic acid) on the Sil-DMAEAPS stationary phase were different from the commercially available ZIC®-HILIC. A method for the determination of rutin hydrate in rutin tablets was established. It is simple and accurate for the determination of polar compounds.

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Synthesis and characterization of 3,4-di(3-phenoxy-4-fluoro phenyl)-2,5-diphenyl phenyl grafted polysiloxane as stationary phase for gas chromatography WANG Huan, HAN Xue, HE Xinxin, WANG Bing, WU Bo 2017, 35 (4):  388-397.  DOI: 10.3724/SP.J.1123.2016.07026 Abstract ( 385 )   [Full Text(HTML)] () PDF (1002KB) ( 86 )   A new high-temperature stationary phase called 3,4-di(3-phenoxy-4-fluoro phenyl)-2,5-diphenyl phenyl grafted polysiloxane (DPFP) was synthesized and statically coated on fused-silica capillary columns. The chromatogram of the polyethylene pyrolysis products showed that the DPFP column still owned good separation ability until 360℃. The column efficiency of the DPFP was 3324 plates/m (retention factor (k)=4.24, naphthalene, 0.25 mm i. d.). McReynolds constants revealed that the polarity of the stationary phase was moderate. Abraham system constants indicated that DPFP possessed strong dipole-induced dipole interactions and H-bond acceptance with analytes. Analysis of Grob test mixtures showed good selectivity of DPFP and inner-surface inertness of the column. Furthermore, the aromatic isomers, substituted benzenes, polycyclic aromatic hydrocarbons, and fatty acid esters could be well separated on the column, thereby indicating that DPFP had great potential for application.

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Determination of dimethyl yellow in foods by liquid chromatography-tandem mass spectrometry coupled with solid phase extraction LI You, XU Dunming, YI Xionghai, SHENG Yonggang, SHI Yiyin, ZHAO Shanzhen, DENG Xiaojun 2017, 35 (4):  398-404.  DOI: 10.3724/SP.J.1123.2016.10042 Abstract ( 557 )   [Full Text(HTML)] () PDF (1428KB) ( 144 )   A liquid chromatography-tandem mass spectrometry (LC-MS/MS) was established for the determination of dimethyl yellow (DMY) in foods. The samples spiked with D5-dimethyl yellow (D5-DMY) as the internal standard were extracted with ethyl acetate, cleaned up by a ProElut DMY SPE column. The separation was performed on an XDB-C18 column (50 mm×4.6 mm, 1.8 μm) with the mobile phases of 5 mmol/L ammonium acetate aqueous solution containing 0.1% (v/v) formic acid and acetonitrile containing 0.1% (v/v) formic acid. The identification and quantitation of DMY was performed by MS/MS in positive electrospray ionization (ESI+) and multiple reaction monitoring (MRM) mode. The quantitative analysis was carried out by internal standard method. A good linear relationship, with the correlation coefficient (r2) greater than 0.999, was found in the mass concentration range of 0-50 μg/L. The limit of detection (LOD, S/N>3) and the limit of quantitation (LOQ, S/N>10) were 2 μg/kg and 10 μg/kg, respectively. The recoveries of DMY in foods spiked with 10, 20 and 100 μg/kg varied from 93.3% to 98.9%, and the relative standard deviations (RSDs) were between 1.6% and 3.9% (n=6). The method can effectively correct the ionization suppression, and it is sensitive, accurate and suitable for the monitoring of DMY in sufu, chili sauce, egg, dried bean curd, candy and ham.

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Determination of milk allergen caseins in foods by ultra performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry ZHAN Lina, CHEN Qin, GU Shuqing, DENG Xiaojun 2017, 35 (4):  405-412.  DOI: 10.3724/SP.J.1123.2016.10034 Abstract ( 487 )   [Full Text(HTML)] () PDF (926KB) ( 191 )   Based on ultra performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry (UPLC-Q/Orbitrap MS) system, a rapid screening and quantitative detection method for milk allergen caseins was developed. After the sample was extracted with protein extraction buffer, a 5 kD ultrafiltration membrane was used to remove small molecule impurities. The extracted protein was then digested by trypsin. The full-scan mass spectra obtained by the data-dependent acquisition (DDA) mode were used for protein identification, and parallel reaction monitoring (PRM) technique was used for quantitative analysis of the target signature peptide. The internal standard peptide and the internal standard substances for every signature peptide were designed and synthesized to reduce the matrix effect and eliminate the loss in sample pretreatment. The proposed method showed a good linear relationship in the range of 5-250 μg/L. The limits of quantitation were in the range of 0.2-5.5 μg/kg. The observed recoveries ranged from 68.8% to 104.4%, and the RSDs were lower than 6%. This method can be used for rapid screening and quantitative analysis of milk allergen casein in juice, jam, bread and breakfast cereals.

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Determination of monosaccharide in Spirulina polysaccharide by ultra performance liquid chromatography-tandem mass spectrometry ZHAO Dan, FENG Feng, SU Youzhi, ZHANG Jingnan, YU Lian, SU Jin, ZHANG Feng 2017, 35 (4):  413-420.  DOI: 10.3724/SP.J.1123.2016.09038 Abstract ( 675 )   [Full Text(HTML)] () PDF (899KB) ( 242 )   An ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed for the determination of 12 carbohydrates in hydrolysate of Spirulina including rhamnose, xylose, arabinose, fructose, mannose, glucose, galactose, mannitol, ribose, fucose, glucuronic acid and galacturonic acid. Samples were extracted with deionized water using ultrasonic-assisted extraction (UAE) and hydrolysis by trifluoroacetic acid (TFA). The hydrolysate was separated on a Waters Acquity BEH Aminde column (100 mm×2.1 mm, 1.7 μm) using 10 mmol/L ammonium formate/water -10 mmol/L ammonium formate/acetonitrile solution as the mobile phase. The electrospray ionization tandem quadrupole mass spectrometric analysis was carried out in the negative ion mode using multiple reaction monitoring (MRM). The limits of detection were 0.005-0.15 mg/kg and the linear ranges were 0.05-5 mg/L. The average recoveries were 80.21%-121.6% at the spiked levels of the carbohydrates contents of 50%, 100% and 150% found in samples. The method was applied to analyze the samples of Spirulina. Fucose, galactose, arabinose, rhamnose, glucose, fructose, xylose, and ribose were detected in most of the samples, and their contents were in the range of 0.3-889.4 mg/g. The type and content of carbohydrates that can be detected in the sample were significantly different. Common characteristic peaks were identified as fucose, galactose, arabinose, rhamnose, glucose, fructose, xylose, ribosethe. However, mannitol and mannose were not detected in all samples. This developed method could provide technical support and basic data for the study of structure and activity of polysaccharide from Spirulina.

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Monitoring of dynamic changes of 15 steroids in serum by liquid chromatography-tandem mass spectrometry TONG Hongbin, TONG Haijiang, LU Dezhao 2017, 35 (4):  421-426.  DOI: 10.3724/SP.J.1123.2016.09015 Abstract ( 436 )   [Full Text(HTML)] () PDF (891KB) ( 183 )   A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the determination of 15 steroids. Acetonitrile containing internal standard was added to the serum samples to precipitate the proteins. Then the derivatization of the samples was conducted with 100 mmol/L hydroxylamine hydrochloride. The separation of the samples was performed on an Agilent-C18 column (50 mm×3.0 mm, 2.7 μm), and quantified with internal standard method. The steroids were determined by multiple-reaction monitoring (MRM) with electrospray ionization (positive mode) MS. The 13 steroids showed linear relationships from 0.05 to 20 ng/mL (R2≥0.9956) with limits of detection no more than 1 ng/mL; cortisol and dehydroepiandrosterone sulfate showed linear relationships from 50 to 2000 ng/mL (R2≥0.9979) with limits of detection less than 0.5 ng/mL. The method was used for the monitoring of the dynamic changes of steroids in a menstrual cycle of women. The 15 steroids fluctuated with different properties, in which androgens reached the peak in late follicular phase, progesterone (estrogens) reached the peak in luteal phase, while the changes of cortical steroids were not so evident. The method is sensitive and repeatable. The data in this project can provide some references for clinical practice.

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Determination of vitamin D in infant formula using liquid chromatography-atmospheric pressure chemical ionization tandem mass spectrometry YAN Lijuan, LI Wenbin, HONG Yuchen, WU Min, XU Dunming, LIN Liyi, GU Chunyan 2017, 35 (4):  427-431.  DOI: 10.3724/SP.J.1123.2016.10036 Abstract ( 442 )   [Full Text(HTML)] () PDF (847KB) ( 106 )   A method using liquid chromatography-atmospheric pressure chemical ionization tandem mass spectrometry (LC-APCI-MS/MS) was developed for the determination of vitamin D in infant formula. The milk powder sample was extracted with hexane and tert-butyl methyl ether followed by clean-up with ProElut VDC cartridge. The LC separation was performed on Kinetex C18 column (100 mm×4.6 mm, 2.6 μm) by a gradient elution using water and acetonitrile as the mobile phases with a flow rate of 1.0 mL/min. Identification of vitamin D2 and vitamin D3 was achieved by APCI-MS/MS using multiple reaction monitoring (MRM). The quantification analysis was performed by internal standard method. The calibration curves showed a good linearity in the range of 5-5000 μg/L. The limits of detection (LODs) for vitamin D2 and vitamin D3 in the formula were 2 μg/kg. The limits of quantification (LOQs) for vitamin D2 and vitamin D3 in the formula were 5 μg/kg. The average recoveries of vitamin D from milk powder spiked at 5, 10 and 100 μg/kg levels were between 85.2% and 105.3%, and the relative standard deviations were between 4.7% and 8.1%. The simple, accurate and sensitive method is suitable for the determination of vitamin D in infant formula.

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Prediction of n-octanol-water partition coefficients of hepatotoxicity/nephrotoxicity components in traditional herbs using quantitative structure-retention relationship models by high performance liquid chromatography XIANG Yangyang, YU Huimin, DENG Haishan, CHEN Jingya, ZHANG Aihua, CHI Yumei, HAN Shuying 2017, 35 (4):  432-438.  DOI: 10.3724/SP.J.1123.2016.10044 Abstract ( 442 )   [Full Text(HTML)] () PDF (906KB) ( 107 )   A quantitative structure-retention relationship (QSRR) was proposed to determine n-octanol-water partition coefficients (Kow) of aristolochic acid A, aristolochic acid B, aristololactam and resveratrol in this paper. Sixteen acidic and neutral benzene analogues with reliable experimental Kow data were chosen as model compounds for establishing linear relationship between the apparent n-octanol-water partition coefficient (Kow″) and retention factor of 100% aqueous phase (kw), which corresponds to retention factors of solutes using neat aqueous fraction as mobile phase. Methanol-water mixture was used as mobile phase at various mobile phase pH, and retention time (tR) was rectified by a dual-point retention time correction (DP-RTC). The established models were evaluated by internal and external validations, respectively. QSRR models had good correlation coefficients at different mobile phase pH with correlation coefficients (R2) ranged from 0.980 to 0.987. Both internal (the cross-validated correlation coefficients (Rcv2) of 0.982-0.988) and external (0.6% ≤ relative errors (RE)≤10.9% for all the six verification compounds) validations showed satisfactory results. Kow values of four hepatotoxic/nephrotoxic ingredients in traditional herbs were predicted by QSRR, and compared with the ones obtained by shake-flask method (SFM) and calculated by software as well. The method provided a convenient and rapid way to obtain reliable Kow data. In addition, the proposed protocol realized simultaneous prediction for Kow values of structure-similar components in traditional herbs merely through retention times, thereupon solved the dilemma of Kow measurement by SFM resulting from inaccessibility of separating single component from complex herbs. These Kow data can be applied in toxicity prediction of components in traditional herbs through quantitative structure-activity relationships (QSARs) in a follow-up study.

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Simultaneous separation of seven water-soluble vitamins with microemulsion liquid chromatography WU Hongxing, ZHENG Aini, SU Caoyin, YU Nuojun, LI Ning 2017, 35 (4):  439-444.  DOI: 10.3724/SP.J.1123.2016.09037 Abstract ( 396 )   [Full Text(HTML)] () PDF (1386KB) ( 105 )   A novel method was developed for the separation of seven water-soluble vitamins (VB1, VB2, VB6, VB12, VC, folic acid and nicotinamide) with microemulsion liquid chromatography. The impacts of following factors on the separation selectivity were investigated:the type of surfactant, the type of oil phase, the type of co-surfactant, the pH of mobile phase and the column temperature. The optimal conditions for the separation of the seven water-soluble vitamins were as follows:Agilent TC C18 (250 mm×4.6 mm, 5 μm) was used at 30℃; the microemulsion mobile phase was sodium dodecyl sulfate (SDS)/polyoxyethylene lauryl ether (Brij35)/n-butanol/ethyl acetate/water (2:60:66:80:864, mass ratio). Baseline separation of the seven water-soluble vitamins was achieved within 20 min with a flow rate of 0.5 mL/min and the detection wavelength of 254 nm. The calibration curve showed a good linearity with the correlation coefficients above 0.9991 in the linear range from 4 to 36 mg/L. The mean recoveries of VB1, VB2, VB6, VC and nicotinamide were 93.9%-102.9% at different spiked levels. The optimized and validated method can be used for simultaneous determination of water-soluble vitamins in food and pharmaceuticals.

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Simultaneous determination of 73 flavor components in cut tobacco by gas chromatography-triple quadrupole mass spectrometry XU Yong, JIANG Ciqing, LI Chao, WU Yiqin, ZHANG Dan, ZOU Nan, ZHANG Chengming, QIN Yunhua, MIAO Mingming, JIANG Wei 2017, 35 (4):  445-452.  DOI: 10.3724/SP.J.1123.2016.10047 Abstract ( 448 )   [Full Text(HTML)] () PDF (1237KB) ( 98 )   A method for simultaneous determination of 73 flavor components in cut tobacco by gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed. The samples were extracted with anhydrous ether, and the ether extracts were separated on a DB-5MS column (30 m×0.25 mm, 0.25 μm). The interference of complex matrix and peak overlapping of various flavor components were reduced by means of optimizing tandem mass spectrometry parameters. The extracts were analyzed by GC-MS/MS under multiple reaction monitoring (MRM) mode, and internal standard method was applied to quantify the 73 flavor components. The results showed that all the flavor components had good linearity in certain ranges with the correlation coefficients (r2) greater than 0.99. The recoveries of the 73 flavor components at low, middle and high levels ranged from 70.0% to 122.3% with the relative standard deviations (RSDs) of 1.6%-20.4%. The developed method is easy, accurate and sensitive, and it can be applied to the determination of the 73 flavor components in cut tobacco.

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Simultaneous determination of eight allergenous disperse dyes in blended carpet by supercritical fluid chromatography-ultraviolet detection LOU Chaoyan, JIANG Lei, DUAN Fen, WANG Guoqin, ZHANG Peimin, ZHI Mingyu, ZHU Yan 2017, 35 (4):  453-457.  DOI: 10.3724/SP.J.1123.2016.11017 Abstract ( 428 )   [Full Text(HTML)] () PDF (868KB) ( 79 )   An effective analytical method based on supercritical fluid chromatography (SFC) was developed for the simultaneous determination of eight allergenous disperse dyes (disperse yellow 1, disperse yellow 49, disperse yellow 9, disperse orange 37/76, disperse red 1, disperse orange 1, disperse orange 3 and disperse brown 1). Blended carpet samples with various colours were ultrasonically extracted for 30 min with methanol at 70℃. Then the extracts were filtrated by 0.45 μm filters. Under the optimum conditions of supercritical CO2-methanol modifier (90:10, v/v) as mobile phase, 440 nm as UV detection wavelength, the eight allergenous disperse dyes were separated completely within 12 min. The eight allergenous disperse dyes exhibited satisfactory linearity with correlation coefficients (r2) of 0.9992-0.9998. The limits of detection (LOD, S/N=3) were 0.05-0.10 mg/L. The developed method was validated for the determination of the eight allergenous disperse dyes in blended carpets with good spiked recoveries ranged from 95.6% to 104.2%. The relative standard deviations (RSDs) of the peak areas of the eight allergenous disperse dyes were all less than 1.2% (n=5). The method is convenient, rapid, sensitive, accurate, selective, and adaptable to the application for detecting the eight allergenous disperse dyes in blended carpets.

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Effects of combined the fluid shear stress and tumor necrosis factor-α on cartilage phenotype in a dynamic microfluidic chip SHI Yang, SHENG Kun, ZHANG Min, LI Hongjing, QIN Jianhua 2017, 35 (4):  458-465.  DOI: 10.3724/SP.J.1123.2016.11004 Abstract ( 432 )   [Full Text(HTML)] () PDF (5349KB) ( 158 )   Fluid shear stress as a common form of biomechanics plays an important role in maintaining cell morphology, cell secretion and function in microenvironment. Herein, we proposed a microfluidic platform which could generate four different intensities of fluid shear to study the cellular effects of fluid shear stress on chondrocyte phenotype under low flow condition. Under low flow condition, the primary chondrocytes could keep good activity and morphology. With the increase of shear force, the expressions of collagen type Ⅱ and aggrecan in primary chondrocyte were up-regulated. At the same time, the expressions of collagen type Ⅰ increased. These results indicated that fluid shear stress could improve chondrocyte phenotype maintaining. Moreover, increase of the shear force also accelerated the dedifferentiation of chondrocytes. Tumor necrosis factor-α (TNF-α) plays a negative role in maintaining chondrocyte phenotype. The interaction effect of fluid shear stress and TNF-α on chondrocyte phenotype was investigated on this platform. The results showed that under the combined effects of the shear force and TNF-α, the expressions of collagen type Ⅱ and aggrecan of chondrocytes were significantly down-regulated. This method provided a powerful platform for cartilage tissue engineering and osteoarthritis disease research, and gave a theoretical basis for the joint disease treatment and prevention.

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Determination of polycyclic aromatic hydrocarbons in surface water using large volume stir bar sorptive extraction coupled with thermal desorption-gas chromatography-mass spectrometry FENG Li, ZHANG Shengjun, ZHU Guohua, LI Mufei, LIU Jinsong 2017, 35 (4):  466-471.  DOI: 10.3724/SP.J.1123.2016.11013 Abstract ( 536 )   [Full Text(HTML)] () PDF (888KB) ( 96 )   A fast and sensitive analytical method for the ultra trace determination of 16 kinds of polycyclic aromatic hydrocarbons (PAHs) in surface water based on stir bar sorptive extraction (SBSE) coupled with gas chromatography-mass spectrometry was established. Multiple stir bars simultaneous enrichment with sequential cryofocusing and merged injection technique was used to effectively solve the problem of long adsorption time and small sample volume with SBSE. The conditions of thermal desorption time, cryofocusing temperature of cooled injection system (CIS), CIS desorption time and extraction time were investigated. Under the optimized conditions, the results showed that the linear range was between 0.2 ng/L and 10 ng/L (naphthalene, 0.5-10 ng/L), and the method detection limits (MDLs) of the 16 PAHs ranged from 0.03 ng/L to 0.20 ng/L (naphthalene, 0.50 ng/L). The 11 PAHs were determined in the Qiantang River surface water samples, and the contents were between 0.13 ng/L and 1.57 ng/L. The recoveries of the 16 PAHs spiked in surface water samples at different levels were between 75.6% and 108.9%. The method can be efficiently applied to the determination of PAHs.