超高效液相色谱-线性离子阱/静电场轨道阱质谱对化妆品中抗生素类成分的快速筛查和确证

目的建立化妆品中抗生素快速筛查和确证的超高效液相色谱-线性离子阱/静电场轨道阱高分辨质谱法(ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry)。方法采用超声波辅助提取化妆品中的抗生素类化合物,提取液经ACQUITY BEH C18色谱柱分离,以水(含5 mmol/L乙酸铵和0.1%甲酸)-乙腈为流动相,梯度洗脱分离。静电场轨道阱一级全扫描得到的准分子离子的精确质量数用于快速筛选分析,保留时间和离子阱的二级质谱数据用于进一步定性确证。结果 36种抗生素的精确质量相对偏差小于5×10-6(5 ppm),线性相关系数r2大于0.994,方法检出限(limit of detection)均≤10μg/kg,方法的加标回收率为54.15%~117.55%,相对标准偏差(relative standard deviation)为1.19%~13.25%。结论应用该方法对不同剂型的50余种化妆品实际样品筛查的分析结果良好,说明该方法是化妆品中抗生素类成分快速筛选和确证的有效方法。     

高压液相色谱-线性离子阱串联质谱法测定红葡萄酒中多菌灵和甲基硫菌灵

目的 建立红葡萄酒中多菌灵和甲基硫菌灵残留的高压液相色谱-串联线性离子阱质谱(HPLC-LIT-MS/MS)检测方法。方法 样品经过乙腈提取, 在梯度洗脱程序下经CAPCELL PAK CR 1:20色谱柱分离后, 采用HPLC-LIT-MS/MS, 在二级质谱选择反应监测(SRM)模式进行测定。结果 红葡萄酒中多菌灵和甲基硫菌灵添加水平为10、20、50 μg/L时, 平均回收率分别为82.5%~103.1%和93.7%~115.2%。检出限(LODs)分别为0.063 μg/L和0.019 μg/L, 定量限(LOQs)分别为0.125 μg/L和0.075 μg/L。结论 该方法快速简便, 灵敏度高, 准确度和精密度均满足痕量分析要求。     

Determination of bixin and norbixin in meat using liquid chromatography and photodiode array detection

The development of an analytical method that enables routine analysis of annatto dye, specifically bixin and norbixin, in meat tissue is described. Liquid-solid extraction was carried out using acetonitrile. Analysis was by HPLC with photodiode array detection using two fixed wavelengths (458 and 486 nm). The possibilities of ion trap mass spectrometry (MS) were also assessed. Method performance characteristics, according to Commission Decision 2002/657/EC, were determined, with recoveries between 99 and 102% and calibration curves being linear in the 0.5–10 mg kg^?1 range. The limit of quantification was 0.5 mg kg^?1.     

高效液相色谱-高分辨质谱法测定奶粉及保健品食品中的左旋肉碱

目的建立高效液相色谱-高分辨质谱法测定奶粉及保健食品中左旋肉碱的含量。方法奶粉及保健食品样品经适量40℃水溶解后,加乙酸锌沉淀蛋白,待样品冷却至室温后用水定容至50mL,并超声提取30 min。在4℃条件下,待测溶液经8000 r/min的速度离心3 min,取上清液过0.45μm水相滤膜。经质谱正离子模式测定,同位素内标法定量。结果左旋肉碱0.1～4.0μg/mL范围内呈良好线性关系,相关系数为1.0000,方法检出限为0.1μg/kg,定量限为0.2μg/kg。加标回收率为98%～110%,相对标准偏差为0.2%～0.5%。对奶粉质控样品进行测定,结果与证书结果一致。结论该法前处理简单、测定快速、准确度高,灵敏度好,适用于奶粉及保健食品中左旋肉碱的快速分析检测。     

Determination of malachite green residues in rainbow trout muscle with liquid chromatography and liquid chromatography coupled with tandem mass spectrometry

A method for the determination of malachite green and its major metabolite leucomalachite green in rainbow trout muscle is reported with limits of detection of 0.8 and 0.6 μg kg^-1, respectively. Residues were extracted with an acetonitrile-acetate buffer mixture and partitioned into methylene chloride. Clean-up of the extracts was performed on alumina and propylsulfonic acid solid-phase extraction columns using the automated solid-phase extraction system. The chromatographic separation of malachite green and leucomalachite green was achieved on a Chromspher 5B column using an acetonitrile-acetate buffer mobile phase. Leucomalachite green was converted to malachite green by post-column oxidation before spectrophotometric detection at 600 nm. The mean recoveries of malachite green and leucomalachite green from control rainbow trout muscle spiked at 2-50 μg kg^-1 were 65% (range 63.4-65.9%, relative standard deviation 3.9-16.1%) and 74% (range 58.3-82.6%, relative standard deviation 3.3-11.4%), respectively. Qualitative confirmation of the determined residues was performed with liquid chromatography coupled with tandem mass spectrometry detection with limits of detection of 2.5 and 1 μg kg^-1 for malachite green and leucomalachite green, respectively.     

分散固相萃取-高效液相色谱串联质谱测定甘蓝及土壤中的啶虫脒

建立了甘蓝和土壤中啶虫脒的分散固相萃取-高效液相色谱串联质谱检测方法,该方法以1%乙酸乙腈为提取溶剂（1∶99,v/v）,以无水硫酸镁（Mg SO4）、十八烷基键合硅胶（C18）和N-丙基乙二胺（PSA）富集净化,0.1%甲酸-水和甲醇梯度洗脱,C18柱分离,HPLC-MS/MS测定。方法线性范围0.01²mg/L,相关系数为0.9994,定量限（LOQ）为0.01mg/kg。在0.05、0.5、1.0mg/kg加标浓度下,啶虫脒在甘蓝中的回收率为84.8%¹07%,在土壤中的回收率为96.5%¹15%,相对标准偏差小于10.92%。该方法能够满足甘蓝及土壤中啶虫脒残留限量检测要求。      

亲水作用色谱-质谱法同时检测鱼肉中 链霉素和双氢链霉素残留

目的 建立一种亲水作用色谱串联质谱技术同时检测鱼肉中链霉素和双氢链霉素残留的分析方法。方法 以鱼肉为原料, 样品经磷酸盐缓冲溶液提取, 固相萃取柱净化后, 采用亲水作用色谱柱分离, 在正离子模式下以电喷雾电离串联质谱进行测定, 外标法定量。结果 链霉素和双氢链霉素在2.0?50 μg/L质量浓度范围内线性关系良好, 在10、20、50 μg/kg三个加标水平下, 方法的回收率为80.2%?97.1%, 相对标准偏差为3.3%?7.2%。结论 该方法简便、快速、实用、准确, 各项技术指标满足国内外法规的要求, 可用于鱼肉中链霉素和双氢链霉素残留的确证检测。     

Measurement of theanine using reverse-phase ion-pair liquid chromatography with photodiode array detection

There is increasing demand for theanine as a taste-enhancing additive and as a supplement for improving and maintaining human health. We describe the development of an ion-pair reversed-phase liquid chromatographic method for the analysis of theanine in tea. Samples may be directly analysed after sonication for 10 min. The mobile phase consists of an aqueous 2 mM solution of pentadecafluorooctanoic acid (ion pair reagent) and acetonitrile (82:18, v/v). The theanine peak is detected using a UV detector at 200 nm. The limit of detection is 5.1 ng and the limit of quantitation is 15.6 ng. The method is accurate with recoveries higher than 97%.     

The determination of phenolic profiles of Serbian unifloral honeys using ultra-high-performance liquid chromatography/high resolution accurate mass spectrometry

Polyphenolic profiles of 44 unifloral Serbian honeys were analyzed using ultra-high-performance liquid chromatography (UHPLC) coupled with hybrid mass spectrometer which combines the Linear Trap Quadrupole (LTQ) and OrbiTrap mass analyzer. Rapid UHPLC method was developed in combination with a high sensitivity accurate mass scan and a simultaneous data dependent scan. The honey samples were of different botanical origin: acacia (Robinia pseudoacacia), sunflower (Helianthus annuus), linden (Tilia cordata), basil (Ocimum basilicum), buckwheat (Fagopyrum esculentum), oilseed rape (Brassica napus), and goldenrod (Solidago virgaurea). The presence of 43 compounds, mainly flavonoids, was proven in all honey samples by their characteristic mass spectra and fragmentation pattern. Relatively high amounts of chrysin, pinocembrin and galangin were identified in all honey extracts. p-Coumaric acid was not detected in basil, buckwheat and goldenrod honey extracts. A larger amount of gallic acid (max value 1.45 mg/kg) was found in the sunflower honey, while a larger amount of apigenin (0.97 mg/kg) was determined in the buckwheat honey in comparison with other honeys. The samples were classified according to the botanical origin using pattern recognition technique, Principal Component Analysis (PCA). The LTQ OrbiTrap technique was proven to be reliable for the unambiguous detection of phenolic acids, their derivatives, and flavonoid aglycones based on their molecular masses and fragmentation pattern.     

高压液相色谱-等离子体质谱联用技术 测定水产品中的硼酸

目的 建立高效液相色谱-电感耦合等离子体质谱法(HPLC-ICP-MS)分析水产品中的硼酸含量。方法 采用超声提取法对水产品进行前处理,优化蛋白沉淀剂、提取时间和流动相等条件。结果 该方法对硼酸的检出限为0.015 mg/L,加标回收率为85.1%～112.1%,相对标准偏差(RSD)在6.0%～8.2%之间。结论 该方法测定水产品中的硼酸含量准确、可靠,满足外源性硼酸的检测。     

Determination of tetracyclines in pig and other meat samples using liquid chromatography coupled with diode array and tandem mass spectrometric detectors

Two high performance liquid chromatographic methods (HPLC–DAD and LC–MS/MS) were developed to analyze tetracycline (TC) residues in pig meat (pork) samples. The method involved a sample preparation using a solid–liquid extraction (SLE) by McIlvaine buffer, followed by a solid-phase extraction (SPE) clean-up using Strata-XL cartridges. The developed sample clean-up resulted in a selective chromatogram in the HPLC–DAD separation and a reduced matrix effect (ME) in LC–MS/MS analysis. Moreover, HPLC columns packed with core–shell particles were tested for separation, which further enhanced the sensitivity and the selectivity of determinations. The validation of the methods for pig samples was carried out according to European Union 2002/657/EC decision. In addition, validation was also performed for bovine, chicken, and turkey meat samples using HPLC–DAD method. The performance characteristics of determinations were evaluated with both spiked and incurred samples, and were systematically compared. LC–MS/MS technique was found to be more accurate for spiked samples; however, HPLC–DAD method resulted in more reliable concentrations for incurred samples.     

Quantitative analysis of acrylamide in tea by liquid chromatography coupled with electrospray ionization tandem mass spectrometry

An effective sample preparation procedure was optimized and a liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed for the quantitative analysis of acrylamide in tea. [¹³C₃]-acrylamide was used as internal standard. Acrylamide was extracted at 25 °C for 20 min by 10 ml water followed by 10 ml acetonitrile, and then 4 g of magnesium sulfate and 0.5 g of sodium chloride were added to the above mixture under stirring thoroughly. In order to increase the response of acrylamide, 9 ml acetonitrile layer was taken and concentrated to 0.5 ml. Solid-phase extraction with an Oasis MCX cartridge was carried out for clean-up. The limit of detection (LOD) and limit of quantification (LOQ) were 1 and 5 ng/ml, respectively. The recovery efficiency of the extraction procedure ranged between 74% and 79%. The levels of acrylamide in 30 tea samples were less than 100 ng/g. Black, oolong, white and yellow tea samples had quite low acrylamide contents (<20 ng/g). Higher acrylamide levels occurred in baked, roasted, and one sun-dried green tea samples (46–94 ng/g).     

Optimization of microwave-assisted extraction of anthocyanins in red raspberries and identification of anthocyanin of extracts using high-performance liquid chromatography – mass spectrometry

Anthocyanins (Acys) are naturally occurring compounds that impart color to fruit, vegetables, and plants. The extraction of Acys from red raspberry (Rubus idaeus L. var. Heritage) by microwave-assisted process (MAP) was studied. A central composite rotate design (CCRD) was used to obtain the optimal conditions of microwave-assisted extraction (MAE), and the effects of operating conditions such as the ratio of solvents to materials, microwave power and extraction time on the extraction yield of Acys were studied through response surface methodology (RSM). The optimized conditions of MAE were ratio of solvents to materials 4:1 (ml/g), extraction time 12 min, and microwave power 366 W. Under these conditions 43.42 mg of Acys from 100 g of fresh fruits (T _Acy, expressed as cyanidin-3-glucoside), approximately 98.33% of the total red pigments, could be obtained by MAE. The Acys compositions of extracts were identified by high-performance liquid chromatography – mass spectrometry (HPLC-MS), 12 kinds of Acys had been detected and 8 kinds of Acys were characterized. Result indicated that cyanidin-3-sophoroside, cyanidin-3-(2 ^G -glucosylrutinoside), cyanidin-3-sambubioside, cyanidin-3-rutinoside, cyanidin-3-xylosylrutinoside, cyanidin-3-(2 ^G -glucosylrutinoside), and cyanidin-3-rutinoside were main components in extracts. In addition, in comparison with the conventional solvent extraction, MAE is more efficient and rapid to extract Acys from red raspberry, due to the strong disruption of fruit tissue structure under microwave irradiation, which had been observed with the scanning electron microscopepy (SEM). However, the Acys compositions in extracts by both the methods were similar, which were investigated using HPLC profile.     

Detection of pyrrolizidine alkaloids in commercial honey using liquid chromatography–ion trap mass spectrometry

Pyrrolizidine alkaloids (PAs) are known secondary plant metabolites which can cause hepatotoxicity in both humans and livestock. PAs can be consumed through the use of plants for food, medicinal purposes and as contaminants of agricultural crops and food. PA contaminated grain has posed the largest health risk, although any PA contamination in our food chain should be recognised as a potential health threat. For this purpose, retail honeys were tested by LC–MS/MS. The method allows for specific identification of toxic retronecine and otonecine-type PAs by comparison to reference compounds via a spectral library. In total, 50 honey samples were matched to the reference spectra within a set of tolerance parameters. Accurate data analysis and quick detection of positive samples was possible. Positive samples contained an average PA concentration of 1260 μg kg^?1 of honey. Good linear calibrations were obtained (R² > 0.991). LOD and LOQ ranged from 0.0134 to 0.0305 and 0.0446 to 0.1018 μg mL^?1, respectively.     

高效液相色谱-串联质谱法和高效液相色谱法测定蜂蜜中氯虫苯甲酰胺残留量

目的 建立通过一次样品前处理,可供高效液相色谱-串联质谱法(high performance liquid chromatography-tandem mass spectrometry,HPLC-MS/MS)和高效液相色谱法(high performance liquid chromatography,HPLC)2种...     

QuEChERS结合高效液相色谱-串联质谱法测定大白菜中10种喹诺酮类药物残留

摘 要: 目的 建立QuEChERS结合高效液相色谱-串联质谱法测定大白菜中10种喹诺酮类药物残留的检测方法。方法 大白菜样品经提取,采用QuEChERS净化方法,以诺氟沙星-D5为内标,用高效液相色谱-串联质谱法测定,采用正离子电喷雾,多反应监测模式（multiple reactions monitoring, MRM),内标法定量分析10种喹诺酮类药物残留的含量。结果 10种喹诺酮类在5~100 ng/mL的浓度范围内线性良好,检出限为0.1~0.3 μg/kg,定量限为0.3~1.0 μg/kg,平均回收率为76.0%~107%,相对标准偏差为1.5%~8.1%。 结论 本研究建立的QuEChERS结合高效液相色谱-串联质谱法测定大白菜中10种喹诺酮类药物残留的检测方法准确、可靠, 适用于大白菜中喹诺酮类药物残留的检测。     

Determination of tertiary butylhydroquinone in edible vegetable oil by liquid chromatography/ion trap mass spectrometry

A simple, sensitive and accurate analytical method for quantification of tertiary butylhydroquinone (TBHQ) in edible vegetable oil was established by liquid chromatography/ion trap mass spectrometry (LC/ITMS). After extraction, 5 μl of the extracts was directly injected into LC/ITMS for TBHQ determination. Ethanol was selected as the extraction solvent. The optimized fragmentation amplitude was 1.70 V and electrospray ionization (ESI) was more suitable than atmospheric pressure chemical ionization (APCI) for TBHQ detection. The calibration curve showed good linearity (R² = 0.9990) and recoveries from spiked samples ranged from 81.9% to 110.5%. Relative standard deviations of intra-day and inter-day were in the ranges 2.5–5.7% and 3.9–13.8%, respectively. The procedure allows the detection of 0.3 mg/kg TBHQ in edible vegetable oil. Typical edible vegetable oils in the market were detected for TBHQ by the proposed method. As results, TBHQ was detected in blend oil, soybean salad oil and camellia oil samples.     

Determination of tetracyclines in multi-specie animal tissues by pressurized liquid extraction and liquid chromatography–tandem mass spectrometry

A specific, sensitive and robust pressurized liquid extraction (PLE) and liquid chromatography tandem mass spectrometry (LC–MS/MS) method for determining tetracycline, chlortetracycline, oxytetracycline and doxycycline in bovine, swine, poultry and lamb muscle tissues is presented. PLE was performed using an ASE^® 200 from Dionex and water as extractant, followed by solid-phase extraction (SPE) using an Oasis HLB cartridge. The method was validated for beef, chicken, pork and lamb meat in compliance with the requirements set by Commission Decision, 2002/657/EC [Commission Decision 2002/657/EC (2002). Implementing Council Directive 96/23/EC concerning the performance of analytical methods and interpretation of results. Official Journal of European Communities, L239, 66–98. (Available at: <http://europe.eu.int>)]. The average recoveries of the different meat samples, spiked with the four tetracyclines at three levels (1, 100 and 200 μg kg⁻¹ of each tetracycline), were always higher than 89% with intraday and interday precision lower than 15% and 17%, respectively. A good linearity was established for the four tetracyclines in the range from 5 to 10,000 μg kg⁻¹ with r > 0.995. The limits of quantification (LOQs) were between 0.5 and 1 μg kg⁻¹, which are well below the tolerance levels set by the European Union. The decision limit (CCα) and the decision capability (CCβ) were in the range 101–116 and 112–130 μg kg⁻¹, respectively. Compared with previous methods, sample preparation time required for the analysis and LOQs, are reduced. The method demonstrated its successful application for the analysis of 100 meat samples. Two samples of beef and one sample of chicken out of 25 of each type tested positive while none of 25 samples of either, lamb or pork, tested positive.     

高效液相色谱-高分辨质谱法定性筛查牛奶中49种β-内酰胺类抗生素残留

目的 开发和验证定性筛查牛奶中49种β-内酰胺类抗生素残留的高效液相色谱-高分辨质谱法(high performance liquid chromatography coupled with high resolution mass spectrometry,HPLC-HRMS)。方法牛奶经磷酸盐缓冲液及乙腈提取后,加入硫酸钠(Na2SO4)和氯化钠(NaCl)进行盐析,离心后取部分上清液经Na2SO4和C18混合的分散式固相萃取填料(dispersive solid phase extraction,d-SPE)净化,净化液浓缩定容后,使用HPLC-HRMS分别以全扫描-数据依赖型二级扫描(full scan-data dependent secondary acquisition,Full MS/dd-MS2)和全扫描-平行反应监测二级扫描(full scan-selected ion monitoring/parallel reaction monitoring,Full MS/PRM)两种模式进行数据采集。结果在Full MS/PRM模式下,45种抗生素通过方法验证,假阳性率和...     

光电二极管阵列离子对高效液相色谱法测定米豆腐中溴酸盐的含量

目的建立光电二极管阵列离子对高效液相色谱法测定米豆腐中溴酸盐的方法。方法用水作溶剂超声提取米豆腐中溴酸盐,提取液浓缩后用流动相溶解。经Waters C_(18)色谱柱(250 mm×4.6 mm,5μm),以0.5 mmol/L十二烷基三甲基氯化铵溶液-甲醇(80:20,V:V)洗脱,流速为1.0mL/min,柱温30℃,以保留时间和光谱图定性,以210 nm处的吸光度定量。结果溴酸盐在1.00～100μg/m L范围内线性关系良好,相关系数r~2=0.9997(n=6),平均加标回收率为91.3%～96.1%,相对标准偏差(relative standard deviation,RSD)为0.8%～0.9%。检出限(limit of detection,LOD)与定量限(limit of quantification,LOQ)分别为0.7、2.0 mg/kg。结论该法操作简单,定量准确,专属性强,可用于米豆腐中溴酸盐的检测。