三种专用固相萃取柱-高效液相色谱法检测食品中苏丹红含量

建立了专用固相萃取柱-高效液相色谱法检测食品中苏丹红Ⅰ、Ⅱ、Ⅲ、Ⅳ的方法。样品经过正己烷提取,通过苏丹红专用固相萃取柱净化和富集,40℃水浴旋蒸至干后用甲基叔丁基醚-甲醇(体积比4:6)溶解定容,借助Waters Symmetry C₁₈色谱柱(150 mm×4.6 mm,5 μm)分离,以乙腈-水为流动相梯度洗脱,二极管阵列检测器检测,外标法定量。结果表明,四种苏丹红在0.16~2.56 μg/mL内线性相关系数(r)均大于0.9999,不同食品的检出限在2.3~9.7 mg/kg之间。不同品牌的苏丹红专用固相萃取柱去除基质干扰和富集目标物的能力不同,可根据食品种类选择合适的固相萃取柱。ProElut SDH SPE柱普遍适用于不同种类食品的前处理;CNW Poly-sery MIP-SDR SPE柱适用于除辣椒粉以外的大部分食品的前处理;Cleanert Sudan SPE柱适用于浅色、低油脂食品的前处理。对六种食品加标2.0 mg/kg,经过ProElut SDH SPE柱处理后,回收率为83.7%~91.1%,相对标准偏差为2.4%~6.2%(n=6)。该方法净化和富集效果理想,与GB/T 19681-2005相比,具有操作简便、重复性好、准确度高、分析时间短、节省溶剂等特点。     

Sample preparation for photometric determination of histamine in foodstuffs compared with capillary electrophoresis

 To determine levels of histamine, two methods were used, photometry in conjunction with two sample clean-up procedures, and capillary zone electrophoresis (CZE). The two sample clean-up procedures used were liquid liquid extraction (LLE) with n-butanol and solid phase extraction (SPE). Using CZE, the separation of histamine from the matrix was good. The other method, photometry, represents a classic and simple method, that can be employed for in situ measurement of histamine. We found that it was necessary to clean up the samples prior to photometry; if this was not done, the recorded levels of histamine were higher than those determined by CZE. In order to determine levels of histamine, both of these rapid tests were applied to ten different foodstuffs. The levels of histamine measured using photometry following either LLE or SPE were compared. The results indicated that photometry is a suitable method for the measurement of histamine, although the sample solutions have to be purified by either LLE or SPE. Samples do not need to be cleaned up before CZE because there is no interference between histamine and attendant material. Both sample clean-up procedures were applied to the following foodstuffs: tomatoes, sauerkraut, tuna, leaf spinach, cream spinach, white wine and mackerel. The differences of the measured values vary between 3% and 18% for LLE and 6% and 27% for SPE. For the other foodstuffs, such as beef, beer and non-alcoholic beer, only one sample clean-up procedure is suitable. LLE used for beef and beer leads to differences in measured levels of histamine between 18% and 50%, respectively, whereas SPE used for non-alcoholic beer leads to differences of 20%. Received: 3 September 1997 / Revised version: 23 October 1997     

Sample preparation for photometric determination of histamine in foodstuffs compared with capillary electrophoresis

 To determine levels of histamine, two methods were used, photometry in conjunction with two sample clean-up procedures, and capillary zone electrophoresis (CZE). The two sample clean-up procedures used were liquid liquid extraction (LLE) with n-butanol and solid phase extraction (SPE). Using CZE, the separation of histamine from the matrix was good. The other method, photometry, represents a classic and simple method, that can be employed for in situ measurement of histamine. We found that it was necessary to clean up the samples prior to photometry; if this was not done, the recorded levels of histamine were higher than those determined by CZE. In order to determine levels of histamine, both of these rapid tests were applied to ten different foodstuffs. The levels of histamine measured using photometry following either LLE or SPE were compared. The results indicated that photometry is a suitable method for the measurement of histamine, although the sample solutions have to be purified by either LLE or SPE. Samples do not need to be cleaned up before CZE because there is no interference between histamine and attendant material. Both sample clean-up procedures were applied to the following foodstuffs: tomatoes, sauerkraut, tuna, leaf spinach, cream spinach, white wine and mackerel. The differences of the measured values vary between 3% and 18% for LLE and 6% and 27% for SPE. For the other foodstuffs, such as beef, beer and non-alcoholic beer, only one sample clean-up procedure is suitable. LLE used for beef and beer leads to differences in measured levels of histamine between 18% and 50%, respectively, whereas SPE used for non-alcoholic beer leads to differences of 20%. Received: 3 September 1997 / Revised version: 23 October 1997     

HPLC测定亚麻籽油苦味肽的纯化富集前处理研究

比较了高效液相色谱(HPLC)定量测定亚麻籽油苦味肽(CLE)的溶剂萃取法和固相萃取法(SPE)纯化富集前处理效果,并对不同规格SPE硅胶小柱填料的前处理效果作了对比。结果表明,通过溶剂萃取法和固相萃取法前处理的亚麻籽油样品,进行HPLC定量测定时,CLE均可以在液相色谱中得到良好的分离,前处理方法并不影响CLE的出峰时间及峰形。但与溶剂萃取法相比,SPE所提取的环肽样品中甘油三酯及其他杂质显著减少,这有利于保护液相色谱柱、提高柱效。随着SPE硅胶小柱填料量的增加,CLE测定值减小,使用填料规格为0. 5 g的SPE硅胶小柱可以得到较好的分离及富集效果。SPE硅胶小柱预处理所得物经超高效液相色谱-质谱联用分析证实为CLE。SPE可有效提取富集亚麻籽油所含的CLE,适用于HPLC定量检测CLE的前处理,该方法样品加标回收率为92. 62%,组内精密度相对标准偏差为0. 62%,组间精密度相对标准偏差为1. 79%。     

Determination of radiation-induced hydrocarbons in processed food and complex lipid matrices A new solid phase extraction (SPE) method for detection of irradiated components in food

 Detection of irradiated components in processed food with complex lipid matrices can be affected by two problems. First, the processed food may contain only a small amount of the irradiated component, and the radiation-induced hydrocarbons may be diluted throughout the lipid matrix of the whole food. Second, in complex lipid matrices, the detection of prior irradiation is often disturbed by fat-associated compounds. In these cases, common solid phase extraction (SPE) Florisil clean-up alone is inadequate in the detection of prior irradiation. Subsequent SPE argentation chromatography of the Florisil eluate allows the measurement of small amounts of irradiated lipid-containing ingredients in processed food as well as the detection of prior irradiation in complex lipid matrices such as paprika and chilli. SPE argentation chromatography is the first method available for the selective enrichment of radiation-specific hydrocarbons from even complex lipid matrices, thus enabling the detection of irradiation doses as low as 0.025 kGy. Furthermore, by using radiation-induced hydrocarbons in the detection of prior irradiation of paprika and chilli powder, a second independent method, the first being measurement of thermoluminescence, is available for the analysis of these matrices. Such analysis could be achieved by using this highly sensitive, cheap and easy to perform combined SPE Florisil/argentation chromatography method, without the need for sophisticated techniques like SFE-GC/MS or LC-GC/MS, so that highly sensitive detection of prior irradiation could be performed in almost every laboratory. Received: 19 February 1996/Revised version: 24 May 1996     

固相萃取-液相色谱法测定水果中的氨基甲酸酯与有机磷农药

建立了固相萃取-高效液相色谱同时测定水果中4种氨基甲酸酯与一种有机磷的方法.对提取溶剂、固相萃取柱种类、洗脱剂类型和用量及检测的色谱条件进行筛选和优化.样品经乙腈超声提取,弗罗里硅土固相萃取柱净化,净化后的样品采用液相色谱柱分离,以甲醇:水(体积比70∶ 30)为流动相,紫外检测波长为210nm,流速1.0mL/min...     

Comparison of two different methods for the separation of lipid classes and fatty acid methylation in reindeer and fish muscle

In the present study different methods for the separation of lipid classes and methylation were compared and evaluated for method optimisation in muscle tissue. Fish and reindeer muscle were tested as fish represents a high proportion of polyunsaturated FA (PUFA) and reindeer a moderate amount of PUFA. Lipids were separated either by solid phase extraction (SPE) into neutral (NL) and polar lipids (PL) or by thin layer chromatography into triacylglycerols (TAG) and phospholipids. All fractions were methylated with or without boron trifluoride (BF₃). The two different separation methods showed differences between PL and phospholipids, while TAG and NL were largely similar. Methylation method did not lead to important differences when comparing within the different separation methods, though methylation with BF₃ generally resulted in similar or higher values of methylated FA, indicating a more complete methylation. The content of PUFA in the muscle tissue did not affect these outcomes. Separation of lipids by SPE, followed by methylation with BF₃ was judged to be the best overall method, though not suitable for analysis of samples with labile fatty acids.     

固相萃取- 高效液相色谱检测法测定食用菌中三聚氰胺残留量

建立食用菌中三聚氰胺的固相萃取- 高效液相色谱检测法。样品经三氯乙酸、乙腈提取,离心,混合型固相萃取小柱净化后,过0.45μm 滤膜,用配有二极管阵列检测器(PAD)的液相色谱仪检测,外标法定量。同时,以三聚氰胺标准品进行添加回收率测定,结果显示,本方法对三聚氰胺的测定低限为2.0mg/kg,回收率为81.3%～91.7%,测定的相对标准偏差均不大于5.6%。本方法能满足食用菌中三聚氰胺残留量常规检测的需要。     

浓缩石榴汁中熊果苷的超高效液相-串联质谱检测方法研究

建立了浓缩石榴汁样品中熊果苷含量测定的固相萃取-超高效液相-串联质谱测定方法。样品用水稀释,HLB和氨基固相萃取柱净化,采用BEHAmide色谱柱(100mm×2.1mm,1.7μm)分离,以乙腈和水梯度洗脱,多反应监测模式测定,定量离子对为m/z271.2>108.0,定性离子对为m/z271.2>160.9,外标法定量。熊果苷的检测限为0.006mg/kg,在0.004～0.2mg/L浓度范围内,熊果苷的线性相关系数为0.9994,熊果苷的加标回收率均在80.6%～108.1%范围内,相对标准偏差均低于8.3%。该方法样品净化效果良好,检测简便、快速、准确,能够满足浓缩石榴汁中熊果苷含量测定和定性确证的要求。     

Analysis of patulin in apple products by liquid–liquid extraction,solid phase extraction and matrix solid-phase dispersion methods: a comparative study

Patulin is a marker of quality in the apple and apple juice industry and due to the potential risk for human health, reliable and potential methods for extracting patulin from a sample are therefore needed. In this study, the three methods with liquid–liquid extraction, matrix solid-phase dispersion (MSPD) and with solid-phase extraction (SPE) were studied for extracting patulin from different apple products. Result showed that for AJC and apple sample, MSPD method is most suitable for extracting patulin among the three methods. The recovery rates of AJC and apple sample were 80.35–114.46 and 79.68–94.32%, respectively, the coefficient variations were 3.18–4.90%; For dilute juice, SPE procedure is suitable for analysis of patulin and the recovery rates were and 85.35–90.14%.     

Use of automated solid-phase extraction equipment for the determination of isoniazid in milk

The possibility of using automated equipment for solid phase extraction of isoniazid from milk has been investigated. This equipment provides two noteworthy advantages: it shortens the time of analysis and avoids SPE column plugging, stabilizing flow rates. After setting the correct programme on software controlling the equipment, some validation parameters have been determined to obtain recovery and repeatability data. The mean recovery for spiked samples resulted in the range 75-95%, the standard error ranged from -5 to -20% while the RSD varied from 2 to 22%. Therefore the method can be considered reliable and fast.     

Determination of ergosterol in paddy rice using solid phase extraction

Ergosterol, the predominant sterol found in most fungi, is considered as an indicator of fungal invasion in grain. An extraction method based on solid phase extraction (SPE) has been developed for determination of ergosterol in unmilled rice, generally called paddy. The samples obtained by extraction through SPE have been analysed by HPLC. The method has been validated in experiments with paddy subjected to different drying treatments and recoveries above 85% have been obtained. SPE appeared to be simple, quick, reliable and consistent for ergosterol analysis. The ergosterol levels obtained in the paddy samples were found to be within the expected range and were comparable with those found using conventional methods. Copyright © 2004 Society of Chemical Industry     

固相萃取-高效液相色谱法测定食品基质中5种不同合成红色着色剂

目的建立一种固相萃取-高效液相色谱法(solidphaseextraction-highperformanceliquid chromatography,SPE-HPLC)测定食品中5种人工合成红色着色剂(新红、苋菜红、胭脂红、诱惑红、赤藓红)的方法。方法比较ProElut PWA-2, Cleanert PWAX和Sep-Pak Plus QMA 3种不同SPE小柱的净化效果,比较Eclipse XDB C_(18)、Venusil XBP C_(18)及Agilent TC-C_(18) 3种色谱柱对5种着色剂的分离情况,按照GB 5009.35-2016《食品中合成着色剂的测定》对食品中5种着色剂进行测定。结果 Pro Elut PWA-2 SPE固相萃取小柱进行样品净化效果最优, Agilent TC-C_(18)色谱柱在10 min内有较好的分离度。加标浓度为0.5～50 mg/kg时,该方法回收率为90.3%～103.9%,相对标准偏差(relative standard deviation, RSD)值为1.18%～7.11%。结论该方法快速、准确,适合用于不同食品基质中5种合成着色剂定性、定量测定。     

二醇基硅胶固相萃取-多维质谱对乌鳢组织脂质组学分析

建立以二醇基键合硅胶(Si O2/diol)为填料的固相萃取(solid-phase extraction,SPE)和基于多维度串联质谱的鸟枪法分离纯化并测定乌鳢肌肉组织中的磷脂。利用Folch法和SPE法提取并纯化磷脂,比较3种不同填料SPE柱的萃取效果,优化SPE参数,最佳条件:上样量100?μL,淋洗液p H值为2,洗脱液为体积分数50%乙腈溶液1 m L。所得提取物以直接进样的方法流动注射入电喷雾离子源,经三重四极杆质谱的母离子扫描和中性丢失扫描模式,实现对磷脂分子种类的鉴定和定量。同时,通过多维度串联质谱分析,得到各个磷脂分子中2条脂肪酸链长度和不饱和度信息。实验结果显示,乌鳢样品中成功检出磷脂酰胆碱、磷脂酰乙醇胺、磷脂酰肌醇和磷脂酰丝氨酸4类磷脂,共计67种磷脂分子,且大部分磷脂均含有不饱和脂肪酸链。本方法简单高效,分析准确快捷,结果稳定。     

基于固相萃取-液相色谱-串联质谱法的纺织品中三氯生和三氯卡班的测定

采用固相萃取-液相色谱-串联质谱技术(SPE-LC-MS/MS)建立了同时测定纺织品中三氯生和三氯卡班的分析方法。样品用二氯甲烷超声提取,C18固相萃取净化后分析。串联质谱在多反应监测(MRM)模式下检测目标分析物,以保留时间和特征离子对(母离子和碎片离子)信息比较进行定性和定量分析。三氯生和三氯卡班的线性范围分别为1.0~50.0 ng/mL、0.25~50.0 ng/mL。方法的定量限为1.0和0.25 μg/kg,平均回收率为84.5% ~ 108.2 %,相对标准偏差小于8.1 %。实验结果表明该方法准确、灵敏,可用于纺织品中三氯生和三氯卡班的分析测定。     

气相色谱-质谱检测葡萄酒中氨基甲酸乙酯预处理方法的比较研究

目的比较液液萃取法、固相萃取法和分散式固相萃取法作为预处理方法对葡萄酒中的氨基甲酸乙酯的处理效率。方法葡萄酒样品中的氨基甲酸乙酯分别用二氯甲烷进行液液萃取,用氨基甲酸乙酯专用柱进行固相萃取,用乙腈、石墨化炭黑和N-丙基乙二胺进行分散式固相萃取,再以气相色谱-质谱联用仪测定其含量。结果 3种预处理方法的平均回收率均在70%~110%之间,相对标准偏差(n=5)均小于6%。液液萃取法处理单个样品成本小于5元,富集倍数可达5倍,可用于低含量样品的预处理和进出口企业的产品合规性检测;固相萃取法操作简便,每人每工作日可处理40个样品,可用于企业的高通量检测;分散式固相萃取法成本适中、回收率最佳、综合预处理效率高,一次预处理可同时检测葡萄酒中农药残留和氨基甲酸乙酯含量,适用于葡萄酒中多种危害物质的筛查。结论三种方法各具优势,综合考虑处理效率和实验成本,分散式固相萃取法更适合葡萄酒生产企业的日常应用。该方法已用于葡萄酒中氨基甲酸乙酯的含量测定。     

多种食品基体中茚虫威残留气相色谱检测

建立了采用气相色谱检测包括毛豆、青梗菜、柚子、姜、木耳、笋、茶叶、猪肉、鱼肉及鸡肉等多种食品基体中茚虫威残留的方法。采用丙酮 正已烷混合溶剂提取试样中茚虫威残留,ENVI-CARB固相萃取小柱净化植物源性产品、Florisil PR固相萃取小柱净化动物源性产品。对于气相色谱分析,定量限(LOQ)为0.005mg/kg,在添加浓度0.005～0.04mg/kg时,回收率及相对标准偏差分别为74.9%～106.4%及1.9%～11.5%。     

UPLC-MS/MS检测肉制品中16 种杂环胺前处理方法筛选

采用串联固相萃取法（Extrelut-PRS-C18固相萃取柱萃取法、PRS-C18固相萃取柱萃取法）、MCX固相萃取柱萃取法和分散固相萃取法（QuEChERS（quick, easy, cheap, effective, rugged, and safe）法）4 种前处理方法对肉制品中16 种杂环胺（heterocyclic amines，HAs）进行提取，并从方法学和提取成本角度综合比较4 种方法。结果表明：4 种提取方法得到的16 种HAs的回收率和精密度及检出限（limit of detection，LOD）和定量限（limit of quantification，LOQ）存在显著差异，其中QuEChERS法回收率和精密度均优于其他3 种方法。MCX固相萃取柱萃取法和QuEChERS法的LOD和LOQ优于其他2 种方法；MCX固相萃取柱萃取法和QuEChERS法所需经济和时间成本较低。综合分析，QuEChERS法具有快速、简便、便宜、有效、稳固和安全的特点，有利于肉制品中HAs的准确检测，并值得推广应用。     

Application of High-Performance Liquid Chromatography with Diode Array Detector for Simultaneous Determination of 11 Synthetic Dyes in Selected Beverages and Foodstuffs

A simple, inexpensive and robust high-performance liquid chromatography diode array detector (HPC-DAD) procedures are proposed to analyse food dyes in beverages, hard candy and fish roe samples. An ether-linked phenyl stationary phase provides sufficient selectivity and chromatographic performance for separation of 11 sulfonated azo dyes. Beverage samples were only diluted (and degassed when needed) before analysis. Solid-phase extraction (SPE) or matrix solid-phase dispersion (MSPD) procedures are proposed for efficient extraction of the analytes from candies or fish roe samples, respectively. Limits of detection (LODs) were from 0.005 to 0.013 μg mL^?1 and limits of quantification (LOQs) between 0.014 and 0.038 μg mL^?1. HPLC-DAD method was validated in terms of intra- and inter-day accuracy and precision at three concentration levels 2, 1, and 0.1 μg mL^?1. Validation was also performed for SPE and MSPD extraction procedures including intra- and inter-day accuracy (Recovery %) and precision (RSD%), as well as intra-laboratory reproducibility. Application to analysis of beverages and food samples available to consumers proved that described methods are suitable for the routine analysis of dyes in food products.     

柚皮提取物的抑菌作用

用乙醇作提取剂提取柚皮 ,将提取物经过初步分离纯化得到黄酮含量为 1 0 9%的柚皮提取物 (SPE) ,并对其抑制细菌和霉菌的作用进行了研究。用滤纸片扩散法测定了相对抑菌活性 ,采用固体稀释法确定柚皮提取物的最小抑菌浓度 (MIC) ,并进一步研究了 pH值、温度对柚皮提取物抑菌作用的影响 ,采用 3点接种法初步研究了样品对米曲霉、黑曲霉、青霉的抑制作用。结果表明 ,柚皮提取物对大肠杆菌和金黄色葡萄球菌的抑制作用较强 ,其MIC均为 2 5 %;对沙门氏菌的抑制作用较弱 ,其MIC >2 5 %;pH值和温度对柚皮提取物的抑菌活性均有影响 ,SPE在偏酸性条件下抑菌效果较好 ;样品经 5 0℃处理对其抑菌活性影响不大 ;但处理温度提高到 80℃和 1 0 0℃时 ,其抑菌活力明显降低。在供试的 3种霉菌中 ,柚皮提取物对黑曲霉的抑制作用最强 ,抑制率为60 5 %;对米曲霉的作用较差 ,抑制率为 34 3%。