The fragmentation pathway of H2PO2- in MS was obtained by Orbitrap HRMS and the reverse confirmation was carried out by the neutral loss detection experiment. The results showed that H2PO2- with even electron ion would produce the neutral loss of 2H and form a new even electron ion with a pair of lone-pair electrons. Based on this, a LC-MS/MS method was developed for the determination of H2PO2- in flour and flour products. The H2PO2- was separated on an Acclaim Trinity P1 composite ion exchange column, and then detected by MS/MS under MRM mode. Finally, the developed method was validated in terms of the linearity, selectivity, accuracy, precision and matrix effect. The method showed a good linearity (R-2>0.999) in the concentration range of 50 similar to 1500 mu g/L. The LOD and LOQ for H2PO2- were 10.0 mg/kg and 30.0 mg/kg, respectively. The average recoveries and RSDs (n = 6) were 93.0%similar to 102.9% and 2.6 similar to 5.6%, respectively.

Perchlorate (ClO4-), a type of contaminant with high diffusivity and durability, has been widely detected in water and foodstuffs, arousing a global concern. It can interfere with normal function of the human thyroid gland, affecting human health. Therefore, determination of perchlorate in water and foodstuffs, and removal from water are important. This review focuses on the occurrence of perchlorate, mainly in water and foodstuffs, and provides an overview of analytical methods for determination of perchlorate over the last two decades. In addition, merits and drawbacks of the various methods have been considered. This review also highlights the most commonly used approaches for removal of perchlorate from water. Finally, current trends and future perspectives in determination of perchlorate and removal from water are proposed. This review provided a comprehensive understanding of perchlorate occurrence and its removal from water, and had practical significance in reducing the harm of perchlorate to human.

The existing extraction and detection methods of bongkrekic acid (BKA) and isobongkrekic acid (IBKA) are complex, time-consuming and solvent-consuming. In this work, a simple and fast pre-concentration procedure based on Fe3O4/HNTs was developed for the determination of BKA and IBKA in rice noodles using HPLC-Orbitrap HRMS. The structure and morphology of Fe3O4/HNTs was characterized by means of XRD, SEM, FT-IR and VSM. Parameters affecting the extraction efficiency including adsorbent amount, pH, extraction time, type and volume of eluent were investigated by employing the response surface method. Results indicated that the proposed method had favorable linearity in the concentration range of 2-200 μg/L with a correlation coefficient >0.998. Method LOD and LOQ were 0.3 μg/kg and 1.0 μg/kg, respectively. Finally, the method was successfully applied to determine BKA and IBKA in rice noodle samples from southern China with recoveries ranging from 79.8% to 102.6% and relative standard deviation (RSD) of 4.2%-7.1%.

Most of the reported magnetic adsorbents are difficult to absorb multi-class of per- and polyfluoroalkyl substances (PFASs), especially the short-chain PFASs. In this work, a novel fluorine and nitrogen functionalized magnetic graphene (G-NH-FBC/Fe2O3) was first synthesized and characterized by scanning electron microscope (SEM), Fourier Transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and vibrating sample magnetometer (VSM). The as-prepared G-NH-FBC/Fe2O3 was utilized as adsorbents for the magnetic solid-phase extraction (MSPE) of 19 PFASs from water and functional beverages and showed excellent adsorption capacity probably due to the hydrophobic interaction. Under the optimal pretreatment and instrumental conditions, a selective and sensitive high performance liquid chromatography Orbitrap high resolution mass spectrometry (HPLC-Orbitrap HRMS) method was developed for the determination of PFASs. Results indicated that the proposed method had favorable linearity (R2 ≥ 0.994) within a wide range of concentrations. Limit of detection (LOD) and limit of quantification (LOQ) for the developed method ranged from 3 ng/L to 15 ng/L and 10 ng/L to 49 ng/L, respectively. Finally, the method was successfully applied to determine PFASs in drinking water, river water, tap water, factory drainage and functional beverages with recoveries ranging from 71.9% to 117.6% and relative standard deviation of <10%. The prepared G-NH-FBC/Fe2O3 was easy to recycle and could be reused for five times without significant decrease in extraction recoveries of PFASs. These results demonstrated that this novel magnetic G-NH-FBC/Fe2O3 could efficiently enrich PFASs and the proposed method is reliable and robust for the determination of PFASs in water and beverage samples.

An effective method was developed for the simultaneous determination of 4 kinds of antioxidants and 8 kinds of the ultraviolet absorbers in plastic packaging baked foods by QuEChERS enhanced matix removal-lipid (EMR-Lipid) combined with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) . The samples were extracted by acetonitrile-acetone (1 : 1 , V/V) . The 12 targets were separated on a Waters BEH C-18 column by gradient elution with methanol-10mmol/L ammonium acetate as mobile phase , ionized with positive and negative electrospray ionization (ESI+/-), detected under multiple reaction monitoring mode (MRM), and quantified with external standard method. The result showed that the 12 kinds of analytes presented favorable linearity in the respective linear range , with correlation coefficients (R-2) of more than 0.9978. The method detection limits (S/N = 3) were in the range of 5. 0 - 10. 0 mu g/kg, except for the Antioxidant 2246 was 150.0 mu g/kg. The average recoveries (n=6) ranged from 80.3% to 118.5%, with intra-day relative standard deviations (RSD, n=6) of 1.7%-9.8% and inter-day RSD (n=5) of 4.5%-9.9%. The developed method had simple pre-treatment procedure, satisfactory purification and sensitivity, and was suitable for the simultaneous determination of antioxidants and ultraviolet absorbers in plastic packaging baked foods.

The present work reported a high-throughput strategy for the analysis of 21 perfluorinated compounds (PFCs) in drinking water, tap water, river water and plant effluent from southern China by supramolecular solvent (SUPARS) vortex-mixed microextraction combined with high performance liquid chromatography-Orbitrap high resolution mass spectrometry (HPLC-Orbitrap HRMS). The SUPRAS without heating assistance is less solvent-consumption, meeting the requirements for green environmental protection and sustainable development. Parameters in the microextraction such as volume of dodecanol and tetrahydrofuran (THF), vortexing extraction and centrifugation time, salt concentration were investigated. The optimal extraction conditions were 250 μL of undecanol, 1.0 mL of THF and 20.0% (w/v, 4 g) NaCl. Under the optimum conditions, method limit of detection and method limit of quantitation in the ranges of 0.01-0.08 μg/L and 0.03-0.25 μg/L, good recoveries (72.5-117.8%) and intra-day precision (1.1-11.2%, n = 6), high enrichment factors (48-78) were obtained. The developed method was successfully applied for analysis of PFCs in 13 drinking water, tap water, river water and plant effluent samples collected from southern China. Perfluorobutane sulfonic acid was detected in one river water with concentration of 0.48 μg/L and 1H,1H,2H,2H-Perfluorooctane sulfonic acid was detected in one river water and two plant effluent samples with concentrations in the range of 0.14-0.67 μg/L.

Ethyl carbamate (EC) and N-nitrosoamines (NAs) are toxic contaminants which can be typically formed in fermented alcoholic beverages. In the present work, a novel approach for simultaneous analysis of EC and NAs in beer and yellow rice wine based on ice-bath assisted sodium hydroxide purification and GC-MS/MS was firstly established. Samples were extracted with acetonitrile-ethyl acetate after addition of internal standards. The extraction solution system was purified by sodium hydroxide solid under ice-bath. After concentration, target analyzes were separated on a HP-INNOWAX quartz capillary column and determined under dynamic multiple reactions monitoring mode of MS/MS. The limits of detection and quantification (LOD and LOQ), matrix effect, recovery and precision of the method were evaluated. Results were linear in the concentration range 2-200 mu g/L for all analyzes of interest, with regression coefficients higher than 0.999. LODs and LOQs were in the ranges of 0.1-0.5 mu g/kg and 0.5-1.5 mu g/kg, respectively. The mean recoveries M three spiked levels were between 81.5% and 121.0%. The intra- and inter-day precisions were in the ranges of 2.2-9.4% and 1.6-7.9%, respectively. The validated method was successfully applied to determine thirteen targets in commercial beer and yellow rice wine. EC was detected in all beers and yellow rice wines with the concentrations ranging from 1.18 to 22.90 mu g/ L. Results indicated wide EC contamination and confirmed its urgency for monitoring EC in fermented alcoholic beverages.

A new magnetic sorbent named as ferromagnetic fluorinated graphene (FG@Fe3O4) was prepared for extraction and enrichment of 10 kinds of fluorine-containing pesticides in tea soups , which were then detected by gas chromatography tandem triple quadrupole mass spectrometer (GC-MS/MS). The transfer rate of fluorine-containing was also investigated. Due to the pi electrons and F atoms , FG@Fe3O4 could form pi-pi conjugation and fluorous-fluorous interaction with fluorine-containing pesticides, and the magnetic sorbent displayed excellent adsorption performance for 10 kinds of fluorine-containing pesticides. Scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectrometry and vibrating sample magnetometer were used to characterize the sorbents. The main parameters, such as sorbent amount, desorption solvent, extraction time were investigated. The adsorption properties of different sorbents and the recycle times of FG@Fe3O4 were also investigated. Under the optimum conditions , the linear relations were good in the corresponding concentration range with the correlation coefficients of more than 0. 998. The method limits of detection (S/N= 3) and method limits of quantitation (S/N=10) ranged from 0. 3 mu g/kg to 6. 0 mu g/kg and 1.0 mu g/kg to 20. 0 mu g/kg, respectively. The average recoveries ranged from 71. 2% to 108. 4% and the intra-day precisions were 2. 6% - 8. 7% at three standard spiked levels. This developed method was successfully applied for the detection of 10 tea soup samples , among which flubendiamide was detected in 2 samples, flufenoxuron was detected in 2 samples , and triflumizole was detected in one sample. The transfer rate of different fluorine-containing pesticide from teas to infusion was different.

A novel mixed hemimicelles and magnetic dispersive solid-phase extraction method based on long-chain ionic liquids for the extraction of five fluorescent whitening agents was established. The factors influenced on extraction efficiency were investigated. Under the optimal conditions, namely, the pH of sample solution at 8.0, the concentration of long chain ionic liquid at 0.5 mmol/L, the amount of Fe3 O4 nanoparticle at 12 mg, extraction time at 10 min, pH 6.0 of methanol as eluent, and the desorption time at 1 min, satisfactory results were obtained. Wide linear ranges (0.02-10 ng/mL) and good linearity were attained (0.9997-0.9999). The intraday and interday RSDs were 2.1-8.3%. Limits of detection were 0.004-0.01 ng/mL, which were decreased by almost an order of magnitude compared to direct detection without extraction. The present method was applied to extract the fluorescent whitening agents in two kinds of paper samples, obtaining satisfactory results. All showed results illustrated that the detection sensitivity was improved and the proposed method was a good choice for the enriching and monitoring of trace fluorescent whitening agents.

The present work presents a novel and rapid analytical method for the simultaneous analysis of bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF) and bisphenol S (BPS) in edible oil based on dispersive micro solid phase extraction (DMSPE) for the first time followed by isotope dilution-ultra high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). The edible oil sample was dispersed by n-hexane and extracted with ammoniated methanol-water solution. Then the target analytes were dispersedly absorbed using the polymer anion exchange (PAX) as the sorbent and eluted by acidic methanol. After that, four bisphenols were separated on a C18 column by gradient elution with methanol and 0.05% ammonium hydroxide in water as mobile phase, detected by MS/MS under multiple reactions monitoring (MRM) mode and quantified by internal standard method. The PAX amounts, adsorption time, concentrations of formic acid in the elution solvent and volume of elution solvent for the DMSPE technique were optimized. The limit of detection and quantitation (LOD and LOQ), matrix effect, recovery and precision of the developed method were investigated. Results indicated that BPS and the rest three bisphenols displayed excellent linearity in the concentration ranges of 0.1-50μg/L and 0.5-250μg/L, respectively, with correlation coefficients (R2) all larger than 0.998. Achieved MLODs (S/N=3) varied between 0.1-0.4μg/kg for all bisphenols. The mean recoveries at three spiked levels in edible oil were in the range of 87.3-108%. Intra-day precision (n=6) and inter-day precision (n=5) were <9% and <11%, respectively. This method is of rapid-and-simple pretreatment, accurate and sensitive, and suitable for the simultaneous determination of bisphenols in edible oil.

UHPLC-MS/MS methods to determine fourteen antibacterial agents in infant disposable hygiene products were developed.

A selective, sensitive and useful method, based on modified QuEChERS cleanup combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) in the negative-ion electrospray ionization (ESI-) mode, was developed and validated for the simultaneous determination of three inorganic anions including perchlorate (ClO4-), bromate (BrO3-) and hypophosphite (H2PO2-) in flour. The extraction parameters and LC-MS/MS conditions were optimized by single-factor experiment and sorbent combination in modified QuEChERS clean-up was optimized through response surface analysis. Three target analytes were separated on a normal-phase Phenomenex Luna Silica (2) column (150mm×2.0mm, 5μm, 100Å) with the mobile phase of a mixture of 5mmol/L ammonium acetate water solution and acetonitrile, detected by MS/MS under multiple reaction monitoring and quantified by external standard method. The developed method was validated in terms of the sensitivity, linearity, accuracy and precision, and matrix effect. The method showed a good linearity (R2>0.999) for all analytes in their respective concentration ranges. The ILOQs and MLOQs for perchlorate, bromate and hypophosphite were 0.1, 0.5, 5.0μg/L and 2.0, 6.0, 60.0μg/L, respectively. The average recoveries of three target analytes from the negative samples spiked at three different concentrations were in a range from 84.6% to 104.9%. The intra-day precision (n=6) and inter-day precision (n=5) of the target analytes were in the ranges of 2.9%-6.9% and 6.4%-8.2%. The matrix effect of this method was observed between 0.83 and 1.17 and was acceptable. The validated method was successfully applied to determine the concentrations of these inorganic anions in flour. Results found that perchlorate and hypophosphite were detected in 33 out of 50 and 7 out of 50 flour samples.

A sensitive UPLC-MS/MS method was established for the simultaneous determination of seven fluorescent whitening agents in flour matrix. Samples were ultrasonically extracted by trichloromethane-acetone. Then analytes were separated on a C18 column and detected by MS/MS. The developed method was validated in terms of the linearity, matrix effect, accuracy and precision. The method showed a good linearity (r>0.997) for all analytes in their respective concentration ranges. The LOQ for seven analytes were in the range of 2.5-25.0μg/kg. The matrix effect was not significant and almost negligible. The average recoveries of seven analytes from the negative samples spiked at three different concentrations were in a range from 81.5% to 105%. The intra-day precision and inter-day precision were in the ranges of 2.9-9.0% and 6.7-11.2%. The developed method was successfully applied to analyze forty commercial flours and FWA184 was detected in three samples with the concentrations of 31-60µg/kg.

In the present study, 11 4,4'-diaminostilbene-2,2'-disulfonic acid based fluorescent whitening agents with different numbers of sulfonic acid groups were separated by using an ionic liquid as a mobile phase additive in high-performance liquid chromatography with fluorescence detection. The effects of ionic liquid concentration, pH of mobile phase B, and composition of mobile phase A on the separation of fluorescent whitening agents were systematically investigated. The ionic liquid tetrabutylammonium tetrafluoroborate is superior to tetrabutylammomnium bromide for the separation of the fluorescent whitening agents. The optimal separation conditions were an ionic liquid concentration at 8 mM and the pH of mobile phase B at 8.5 with methanol as mobile phase A. The established method exhibited low limits of detection (0.04-0.07 ng/mL) and wide linearity ranges (0.30-20 ng/mL) with high linear correlation coefficients from 0.9994 to 0.9998. The optimized procedure was applied to analyze target analytes in paper samples with satisfactory results. Eleven target analytes were quantified, and the recoveries of spiked paper samples were in the range of 85-105% with the relative standard deviations from 2.1 to 5.1%. The obtained results indicated that the method was efficient for detection of 11 fluorescent whitening agents.

建立了同时测定动物肌肉组织中27种β-激动剂、3种β-阻滞剂和2种糖肽类抗生素的超高效液相色谱-串联质谱(UPLC-MS/MS)方法.样品经酶解、蛋白沉淀后,以乙酸乙酯-异丙醇(6∶4,V/V)提取,Starata-X-C固相萃取净化,BEH C18色谱柱分离,乙腈-0.1％甲酸梯度洗脱,串联质谱ESI+电离,多反应监测模式检测,外标法定量.结果表明,32种目标物在线性范围内相关性良好(R2 ＞0.995),多巴胺、瑞普特罗、万古霉素和去甲万古霉素的方法检出限为5 μg/kg,其它目标物的检出限为3μg/ks;平均加标回收率为83.6％ ～103％,相对标准偏差(n=6)为3.9％ ～ 10.4％,日间精密度为4.5％ ～9.8％.结果表明,本方法准确、灵敏,适用于动物肌肉组织中β-激动剂、β-阻滞剂,以及糖肽类抗生素的高通量测定.

QuEChERS-based purification coupled with UPLC-MS/MS method, was developed for six quaternary ammonium compounds (QACs) determination in dairy products. Powder samples were firstly dispersed by water. Protein in liquid milk was precipitated and sample solution was extracted by acetonitrile. QuEChERS-based purification was used to purify the solution. QACs were finally separated by HILIC column and detected in MRM mode of MS/MS under ESI(+). The stable isotope benzyl-2,3,4,5,6-d5-dimethyltetradecylammonium bromide (C14-BAC-d5) was used as an internal standard. This method was validated in terms of linearity, sensitivity, precision, accuracy. Linear relations were favorable for QACs over the selected concentration ranges of 0.2-50μg/L, with correlation coefficients greater than 0.999. The limits of detection (LODs) were in the range of 0.4-14.5μg/kg. Recoveries were between 91.2% and 115% with RSDs of 2.8-7.5% for intra-day precision and 3.7-6.7% for inter-day precision. This validated method was successfully applied to determine the QACs concentrations in dairy products.

Traditional identification of fur species is a problem; without unified standards it depends significantly on the experience of the tester. In this study, we developed a method of identification of fur species by DNA barcoding based on 16S rRNA gene. 18 usual fur species sequences of 16S rRNA gene were obtained from Genebank and primers for PCR were designed in the conserved regions. By the optimization of experimental procedure, polymerase chain reaction (PCR) can be successfully performed with DNA isolated from fur. Sequence analyses of the -240bp production of PCR could help us to authenticate the fur species accurately.

An effective method was developed for the simultaneous determination of 15 kinds of plants originated stimulants and exogenous medicines in herbal tea using solid phase extraction (SPE) combined with ultrahigh performance liquid chromatography. tandem mass spectrometry (UPLC-MS/MS). After centrifugation in high speed, the samples were purified using HLB SPE column at pH 4.0 (adjusted by formic acid). A total of 15 targets were separated on a BEH C-18 column by gradient elution with acetonitrile-0.1% formic acid as mobile phase, ionized with positive and negative electrospray ionization (ESI+/-), detected under multiple reaction monitoring (MRM) mode, and quantified with external standard method. The method was validated by evaluating the linearity, recoveries, and precision. Favorable linearity was acquired in the concentration range of 1.0-200 mu g/L, and the limits of detection (LODs) were ranged from 0.1 to 2.0 mu g/L. At the spiked levels of 2.0-100 mu g/L, the average recoveries presented 76.4%-107.0%, with the relative standard deviation (RSD, n = 6) of 2.8% to 9.7% and intra. day precision of 2.7%-12.0%. The procedure was successfully applied to the determination of plants originated stimulants and external medicines in commercial herbal tea.