气相色谱-质谱法测定眼用全氟丙烷气体中甲醇、甲醛

建立气相色谱–质谱(GC–MS)联用法与气相色谱(GC)法测定眼用全氟丙烷气体中甲醇、甲醛杂质的方法。甲醇采用GC–MS法定性、GC法定量分析,在51.1～511μL/L浓度范围内线性良好(r~2=0.998 5),检出限为4μL/L,测量结果的相对标准偏差为2.73%(n=6),加标回收率为91%～94%;甲醛采用GC–MS定性、定量分析,质谱选择离子(SIM)模式以m/z 29作为甲醛的定量离子,在21.36～106.8μL/L浓度范围内线性良好(r~2=0.999 1),检出限为5μL/L,测量结果的相对标准偏差为3.19%(n=6),加标回收率为89%～94%。该方法灵敏度高,重复性好,简便可行,可用于眼用全氟丙烷气体的质量控制。     

固相萃取-超高压液相色谱-串联质谱同时分析环境水样中四环素类和喹诺酮类抗生素

应用固相萃取及超高压液相色谱-质谱联用技术,建立了环境水样中4种四环素类和6种喹诺酮类抗生素的同时分析方法。样品经HLB固相萃取柱富集、净化后用甲醇洗脱,以超高压液相色谱-串联质谱仪多反应监测(MRM)离子模式定性、定量分析。以河水和海水为基质,卡巴氧为替代物进行回收率评价,4种四环素类抗生素在加标质量浓度分别为20.0 ng/L和100.0 ng/L时的回收率为94.0%～117.0%,相对标准偏差为2.0%～9.7%(n=4),方法的检出限均为20.0 ng/L;6种喹诺酮类抗生素在加标质量浓度分别为5.0 ng/L和20.0 ng/L时的回收率为63.6%～93.9%,相对标准偏差为1.6%～8.1%(n=4),方法的检出限为0.4 ng/L。结果表明,所建立的方法可成功地应用于近岸海域表层环境水样中目标抗生素残留的分析。     

气相色谱-质谱法测定酒中16种邻苯二甲酸酯

应用气相色谱-质谱法测定酒中16种邻苯二甲酸酯的含量。样品经乙酸乙酯提取,所得提取液用DB-5MS UI色谱柱分离,在全扫描/选择离子监测共用模式下测定。16种邻苯二甲酸酯的质量浓度均在0.5~10.0mg·L-1范围内与其峰面积呈线性关系,方法的检出限(3S/N)在0.01~0.10mg·L-1之间。日间加标回收率在83.7%~114%之间,日间相对标准偏差(n=6)在3.4%~9.8%之间;日内加标回收率在81.9%~113%之间,日内相对标准偏差(n=6)在1.5%~6.7%之间。     

超高效液相色谱-串联质谱法同时测定饮料金属罐内壁涂层中11种双酚类物质迁移量

建立了超高效液相色谱-串联质谱法(UPLC-MS/MS)同时测定饮料金属罐内壁涂层中11种双酚类物质的迁移量。样品经不同条件的迁移试验后,取浸泡液进行过滤,以Agilent Eclipse XDB-C_(18)色谱柱分离,以不同体积比的乙酸铵溶液和甲醇的混合液为流动相进行梯度洗脱,在电喷雾离子源(ESI)和多反应监测(MRM)正负离子模式下进行分析。结果表明,在优化的实验条件下,11种双酚类物质的线性关系良好,相关系数(R~2)均大于0.99,方法检出限为0.04～4.0μg/kg,定量限为0.1～13.3μg/kg,在低、中、高3个加标水平下的回收率为75.1%～107.9%,相对标准偏差(n=6)为1.7%～5.9%。该方法适合于饮料金属罐内壁涂层中11种双酚类物质迁移量的日常检测。     

高温燃烧水解-离子色谱法测定煤中的氟和氯

建立高温燃烧水解-离子色谱法测定煤中氟和氯含量的方法。间隔测量煤标准物质和待测煤样,以煤标准物质特性量值的变化扣除系统漂移的影响,提高了测定结果的准确度和重复性。氟含量在0.042~2.018μg/mL范围内与其色谱峰面积呈良好的线性关系,线性相关系数r=0.995 8,检出限为0.011μg/g,测量结果相对标准偏差为6.32%(n=6);氯含量在0.046~2.292μg/mL范围内与其色谱峰面积呈良好的线性关系,线性相关系数r=0.999 8,检出限为0.010μg/g,测量结果的相对标准偏差为0.7%(n=6)。用该方法对煤标准物质进行测定,氟、氯测定结果与标准值一致。该方法简便快速,灵敏度高,结果准确,可用于煤中氟和氯含量的测定。     

液相色谱法测定水产品中亚甲基蓝残留量

建立了水产品中亚甲基蓝残留的样品处理方法和分析测定方法。样品经乙腈提取,正己烷去脂、二氯甲烷萃取后浓缩,用液相色谱仪-紫外检测器进行分析测定。亚甲基蓝的定量限为5.0μg/kg,检出限为2.5μg/kg,在5～1000 ng/mL范围内标准曲线线性良好,3种水产品添加5个浓度水平的平均回收率为71.4%～92.8%,相对标准偏差均小于6%(n=6)。方法适用于水产品中亚甲基蓝残留的定性定量分析。     

液相色谱法测定化妆品中4种禁用酚类物质

建立了水基类、乳液类、膏霜类、粉类和蜡基类化妆品中4种禁用酚类物质(间苯三酚、4-硝基愈创木酚、酚酞和地乐酚)含量测定的液相色谱方法。样品经溶剂萃取,氮吹浓缩后采用优化的定容液定容,以液相色谱保留时间和紫外吸光度定性,外标法定量。结果表明,4种禁用酚类物质在一定浓度范围内线性关系良好,r~20.99,方法的检出限(LOD)为1.5～6.0 mg/kg,定量下限(LOQ)为5.0～20.0 mg/kg。4种禁用酚类物质的平均回收率为81.3%～100%,相对标准偏差(RSD)为1.0%～8.2%。方法前处理简单、操作性强,适用于化妆品中4种禁用酚类物质的检测。     

电感耦合等离子体质谱法测定矿物渣中微量铀和钍

采用改进的微波消解程序处理矿物渣样品,用185Re作为内标同位素,以在线内标加入法补偿样品的基体干扰,提出了测定矿物渣中微量铀和钍的电感耦合等离子体质谱法.铀和钍的方法检出限分别为0.017,0.021 ng·g-1;铀和钍的平均加标回收率(n=6)分别为99.0%,101.3%;相对标准偏差(n=6)分别为4.02%和3.54%.两种标准物质中铀和钍的测定结果与标准值相符合.     

气相色谱-质谱法同时检测水体中的微量对硫磷和甲基对硫磷

采用固相萃取气相色谱–质谱法同时检测水体中的微量对硫磷和甲基对硫磷。水样用固相萃取柱进行富集,以丙酮洗脱,经气相色谱–质谱仪进行定性定量分析。对硫磷、甲基对硫磷的质量浓度在0.01~1.0μg/mL范围内与其色谱峰面积均呈良好的线性关系,线性相关系数不小于0.995,检出限分别为0.004,0.002μg/mL。对硫磷、甲基对硫磷测定结果的相对标准偏差均小于5%(n=6),重复性小于10%(n=6),加标回收率在82.2%~90.5%之间。该方法检测速度快,灵敏度度高,可用于水体中微量对硫磷和甲基对硫磷的检测。     

气相色谱-质谱法测定饮用水源中的痕量酚类物质

采用PSD小柱固相萃取-气相色谱-质谱法同时测定饮用水源中的8种痕量酚类污染物。水样中加入替代物溶液后,采用PSD固相萃取小柱富集待测物,以乙酸乙酯进行洗脱。洗脱液经氮气吹至近干后,用丙酮-正己烷(4+96)溶液定容。待测物在DM-35MS毛细管色谱柱上分离,质谱分析中选择电子轰击离子源和选择离子监测模式。8种酚类物质的质量浓度在2.0~1 000μg·L~(-1)范围内与其峰面积呈线性关系,检出限(3S/N)在0.43~1.03μg·L~(-1)之间。加标回收率在85.8%~96.7%之间,测定值的相对标准偏差(n=6)小于5.0%。实际水样分析发现,饮用水源中的苯酚残留量最大,为酚类污染物的代表物质。     

Quantification of polyphenols with potential antioxidant properties in wines using reverse phase HPLC

A RP-HPLC method with photodiode array detection (DAD) was developed to separate, identify and quantify simultaneously the most representative phenolic compounds present in Madeira and Canary Islands wines. The optimized chromatographic method was carefully validated in terms of linearity, precision, accuracy and sensitivity. A high repeatability and a good stability of phenolics retention times (< 3%) were obtained, as well as relative peak area. Also high recoveries were achieved, over 80.3%. Polyphenols calibration curves showed a good linearity (r(2) >0.994) within test ranges. Detection limits ranged between 0.03 and 11.5 microg/mL for the different polyphenols. A good repeatability was obtained, with intra-day variations less than 7.9%. The described method was successfully applied to quantify several polyphenols in 26 samples of different kinds of wine (red, rosé and white wines) from Madeira and Canary Islands. Gallic acid was by far the most predominant acid. It represents more than 65% of all phenolics, followed by p-coumaric and caffeic acids. The major flavonoid found in Madeira wines was trans-resveratrol. In some wines, (-)-epicatechin was also found in highest amount. Canary wines were shown to be rich in gallic, caffeic and p-coumaric acids and quercetin.     

Simultaneous qualitative and quantitative analyses of the major constituents in the rhizome of Ligusticum Chuanxiong using HPLC-DAD-MS

An HPLC-DAD-MS method was developed for the qualitative and quantitative analysis of the major constituents in Chuanxiong (the dried rhizome of Ligusticum chuanxiong Hort). Twenty compounds including phenolic constituents, alkylphthalides and phthalide dimers were identified using online ESI-MS and comparisons with literature data and standard compounds, and six of them were quantified by HPLC-DAD simultaneously. A comprehensive validation of the method including sensitivity, linearity, repeatability and recovery was conducted. The linear regressions were acquired with R(2) > 0.99 and limit of detection (LOD, S/N = 3) values were between 1.5 and 2.5 ng. The repeatability was evaluated by intra- and inter-day assays, and relative standard deviation (RSD) values were reported within 1.87%. The recovery studies for the quantified compounds were observed in the range of 96.36-102.37% with RSD values less than 2.63%. These phenolic constituents and alkylphthalides, the major constituents in Chuanxiong, are generally regarded as the index for the quality assessment of this herb. The overall procedure is accurate and reproducible, which is considered suitable for the qualitative and quantitative analyses of a large number of Chuanxiong samples.     

HPLC‐DAD methodology for the quantification of organic acids,furans and polyphenols by direct injection of wine samples

This article proposes a simple and sensitive HPLC method with photo‐diode array detection for the analysis of organic acids, monomeric polyphenols and furanic compounds in wine samples by direct injection. The chromatographic separation of 8 organic acids, 2 furans and 22 phenolic compounds was carried out with a buffered solution (pH 2.70) and acetonitrile as mobile phases and a difunctionally bonded C18 stationary phase, Atlantis dC18 (250×4.6 mm, 5 μm) column. The elution was performed in 12 min for the organic acids and in 60 min for the phenolic compounds, including phenolic acids, stilbenes and flavonoids. Target compounds were detected at 210 nm (organic acids, flavan‐3‐ols and benzoic acids), 254 nm (ellagic acid), 280 nm (furans and cinnamic acid), 315 nm (hydroxycinnamic acids and trans‐resveratrol) and 360 nm (flavonoids). The RSD for the repeatability test (n=5) of peak area and retention times were below 3.1 and 0.3%, respectively, for phenolics and below 1.0 and 0.2% for organic acids. The RSDs expressing the reproducibility of the method were higher than for the repeatability results but all below 9.0%. Method accuracy was evaluated by the recovery results, with averaged values between 80 and 104% for polyphenols and 97–105% for organic acids. The calibration curves, obtained by triplicate injection of standard solutions, showed good linearity with regression coefficients higher than 0.9982 for polyphenols and 0.9997 for organic acids. The LOD was in the range of 0.07–0.49 mg/L for polyphenols (cinnamic and gallic acids, respectively) and 0.001–0.046 g/L for organic acids (oxalic and lactic acids, respectively). The method was successfully used to measure and assess the polyphenolic fingerprint and organic acids profile of red, white, rosé and fortified wines.     

Determination of volatile oak compounds in aged wines by multiple headspace solid-phase microextraction and gas chromatography–mass spectrometry (MHS-SPME–GC–MS)

Multiple headspace solid-phase microextraction (MHS-SPME) with gas chromatography–mass spectrometry is proposed for quantification of nine volatile oak compounds in aged wines. These compounds are formed and extracted by wine when it is matured in oak barrels and are responsible for particular organoleptic properties and the high quality of these wines. Some important variables of the extraction process, for example volume of sample and extraction time, were studied. Extraction of 50 μL wine was performed with a divinylbenzene–Carboxen–polydimethylsiloxane fibre at 55 °C for 60 min. For calibration the same conditions were used, except that the wine was substituted by 50 μL of a standard solution in synthetic wine. The linearity, detection limits, and repeatability of the method were determined by use of standard solutions in synthetic wine. Detection limits were between 0.01 and 10 μg L⁻¹ (for eugenol and furfural, respectively) and repeatability, expressed as relative standard deviation, was from 2 to 6%. The method was used to analyse six red wines and the concentrations obtained were statistically compared with those obtained by the standard addition method for the same wines.     

Simultaneous determination of saponins and isoflavones in soybean (Glycine max L.) by reversed-phase liquid chromatography with evaporative light-scattering and ultraviolet detection

The first validated analytical method permitting the simultaneous qualitative and quantitative determination of isoflavones and saponins in soy has been developed. It combines liquid chromatography with an ultraviolet and evaporative light-scattering detector (ELSD). Within less than 30 min, 6 isoflavones (detected at 254 nm) and 4 triterpene saponins (monitored with the ELSD) were baseline separated, using a reversed-phase C18 column and a mobile phase consisting of water and acetonitrile, both containing 0.025% triflouroacetic acid. The method was validated for limit of detection (LOD), linearity, repeatability, precision, and accuracy. LOD was 3.2-6.0 ng/mL for isoflavones and 10.4-14.2 microg/mL for saponins, and linearity was indicated by R2-values of 0.997 and higher. Intra- and interday precisions of the assay were below 7.0% for all of the compounds except for one, which was only present in trace amounts in the samples. Repeatability was indicated by very stable retention times and relative standard deviations well below 4.0% for multiple injections (n = 3). Accuracy was confirmed by recovery rates between 96.8 and 101.0%, respectively. Different sample matrixes were successfully analyzed, proving the wide range of applicability of this method, including soybeans, capsules, liquids, and instant soy drinks.     

Determination of some phenolic compounds in red wine by RP-HPLC: method development and validation

A methodology employing reversed-phase high-performance liquid chromatography (RP-HPLC) was developed and validated for simultaneous determination of five phenolic compounds in red wine. The chromatographic separation was carried out in a C(18) column with water acidify with acetic acid (pH 2.6) (solvent A) and 20% solvent A and 80% acetonitrile (solvent B) as the mobile phase. The validation parameters included: selectivity, linearity, range, limits of detection and quantitation, precision and accuracy, using an internal standard. All calibration curves were linear (R(2) > 0.999) within the range, and good precision (RSD < 2.6%) and recovery (80-120%) was obtained for all compounds. This method was applied to quantify phenolics in red wine samples from Santa Catarina State, Brazil, and good separation peaks for phenolic compounds in these wines were observed.     

Determination of volatile oak compounds in wine by headspace solid-phase microextraction and gas chromatography-mass spectrometry

A headspace solid-phase microextraction (HS-SPME) and gas chromatography (GC) coupled to mass spectrometry (MS) method was developed to identify and quantify 14 volatile oak compounds in aged red wines. The most important HS-SPME variables were optimised by experimental design technique in order to improved the extraction process. The selected conditions were: 10 mL of sample in 20 mL sealed vials with addition of 30% of sodium chloride (saturated solution), divinylbenzene-carboxen-polydimethylsiloxane (DVB-CAR-PDMS) fibre, 10 min of pre-incubation time, 70 degrees C of temperature and 60 min of extraction time without agitation. The features of the method were established for the studied compounds in terms of linear range, slope and intercept of the calibration graphs, detection and quantification limits and repeatability. For all compounds detection limits were below their threshold levels and repeatability, in terms of relative standard deviation, was good, with values between 3 and 11%. Finally, the method was applied to the analysis of six aged red wines by both internal standard and standard addition calibration methods. The concentrations obtained with both methods were statistically compared.     

Liquid chromatographic-mass spectrometric determination of phenolic compounds using a capillary-scale particle beam interface.

A capillary-scale particle beam interface was used to detect 18 phenolic compounds in red wine samples. This technique allows reproducible, library searchable electron ionization spectra at only 1 microliter/min mobile phase flow-rate for a sensitive detection of the analytes in complex matrices. The method makes use of a narrow bore, reversed-phase packed capillary column for sample separation. Detection limits were in the low picogram range for most compounds. Sensitivity and response linearity were evaluated for eight phenolic acids, which are often encountered in red wines. The phenolic compound composition was outlined in two red wines obtained using different aging processes.     

Analysis of phenolic glycosides and saponins in Primula elatior and Primula veris (primula root) by liquid chromatography, evaporative light scattering detection and mass spectrometry

This paper describes the first liquid chromatographic method suitable for the simultaneous determination of bioactive compounds, saponins and phenolic glycosides, present in Primula elatior and Primula veris, including the NMR data of primulaverin and primeverin. Optimum separations were obtained with a Synergi 4mum Fusion RP 80A column, using 0.025% TFA in water and 5% acetonitrile in methanol as mobile phase. Saponins were detected by evaporative light scattering detection (ELSD), whereas the phenolic glycosides were monitored by UV at 210 nm. The method was validated for repeatability (sigma(rel) or=97.1%) and sensitivity (LOD 相似文献   

Stir bar sorptive extraction for the analysis of wine cork taint

A magnetic stir bar with a polydimethylsiloxane coating was used to absorb 2,4,6-trichloroanisole, 2,3,4,5-tetrachloroanisole, pentachloroanisole and their respective phenols from synthetic and real wine samples. The stir bar sorptive extraction method was optimised to obtain the best extraction conditions in terms of temperature, time, pH and NaCl addition. The stir bar was desorbed in a thermal desorption system coupled to a gas chromatograph-mass spectrometer. The method proposed showed good linearity over the concentration range tested and correlation coefficients ranged from 0.96 to 0.99 for all the analytes. The reproducibility and repeatability of the method was estimated between 1.29 and 4.02%. With no a pre-concentration step and with a much reduced analysis time, all the analyzed compounds showed detection and quantification limits that were lower than those observed with other methods found in the bibliography. Except for pentachlorophenol due to its poor absorptivity in polydimethysiloxane, in red wines, LOD ranged between 7.56 and 61.56 pg/l, and LOQ ranged between 17.21 and 205.11 pg/l; while in white wines, the LOD ranged between 5.82 and 30.50 pg/l and LOQ ranged between 19.41 and 101.61 pg/l. These concentrations were always lower than their respective olfactory thresholds values.