胶束电动毛细管色谱测定塑料食品包装袋中邻苯二甲酸酯类化合物的研究

采用胶束电动毛细管色谱法对5种邻苯二甲酸酯类化合物(邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP))和邻苯二甲酸二正辛酯(DOP))进行了分离研究,考察了溶液的pH值、胶束浓度和有机改性剂等对分离的影响。结果表明:以5 mmol/L硼砂-25 mmol/L十二烷基硫酸钠(SDS)-15%(体积分数)甲醇溶液为电泳缓冲液(pH 9.2),采用压力进样方式,25 kV恒压下进行分离,在波长200 nm处检测,各组分在17 min内可达到基线分离。DMP、DEP、DBP、DEHP和DOP的检出限分别为0.13 mg/L、0.14 mg/L、0.38 mg/L0、.13 mg/L和0.10 mg/L。本法应用于塑料食品袋中邻苯二甲酸酯类化合物的测定,回收率范围为81.80%~118.87%,峰面积的相对标准偏差(RSD)小于4.30%(n=10),测定结果满意。     

塑料中邻苯二甲酸酯类化合物的高效液相色谱分析

采用高效液相色谱法对塑料制品中的邻苯二甲酸酯类化合物进行了测定。塑料样品经粉碎后，用乙醇溶解后超声提取，直接用高效液相色谱分析，外标法定量。该方法精密度1．07％～1．98％，回收率76．0％～96．0％。此方法简便、易行，分离度较好，可作为测定塑料制品中增塑剂邻苯二甲酸酯类的方法。     

气相色谱法测定邻苯二甲酸酯

建立了气相色谱分析邻苯二甲酸酯的方法.选择邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二正丁酯(DBP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二正辛酯(DOP)7种标物,对实验方法的准确程度进行了分析.7种标物的线性相关系数都能达到0.999以上,线性范围在0.01～1g/L之间;保留时间的相对标准偏差都在0.1%以内,峰面积的相对标准偏差在2%以内.     

气相色谱法同时测定塑料食品包装袋中4种有机残留物

食品塑料包装袋中的有机残留物甲苯是一种对人体有害的化合物.包装食品用的塑料制品.其含量为卫生和食品监督部门所严格控制.其中的异丙醇、丁酮和乙酸乙酯虽毒性不大,但它们的大量使用以及在环境中的行为不甚明了,因此建立一种同时测定4种组分的分析方法是十分必要的.有关顶空气相色谱法同时测定食品塑料包装袋中的4种残留组分的研究还未见报道.本文研究了一种简便、快速、准确的静态顶空气相色谱法,可同时测定塑料食品包装袋中的甲苯、异丙醇、丁酮和乙酸乙酯.该法操作简便,灵敏度高,重现性好,结果令人满意.     

高效液相色谱法测定塑料袋装食品中的邻苯二甲酸酯

采用高效液相色谱法测定用塑料袋盛装的食品中的邻苯二甲酸酯(PAEs),供试的食品为馒头、油饼、黄瓜和番茄.用同种塑料食品袋与纸袋分别盛装30 min,进行高速分散后超声波提取15 min,经弗罗里硅土层析柱净化,后用高效液相色谱进行分析,外标法定量.该方法的加标回收率为82.7%～107.6%,RSD为1.4%～6.9%,检出限DMP为0.988 ng,DEP为0.749 ng,DBP为0.702 ng,DEHP为1.920 ng.     

超声微波协同萃取-气相色谱法测定土壤中邻苯二甲酸酯类化合物

研究了超声微波协同萃取-气相色谱测定土壤中的邻苯二甲酸酯类化合物。考察了萃取溶剂、微波功率、萃取时间等因素对回收率的影响,得到了最佳萃取条件为:以正己烷/丙酮(1∶1)为萃取剂,溶剂用量为60 mL,微波辐射功率为100 W(超声功率固定为50 W),萃取12 min。该条件下,模拟土样中酞酸酯的平均回收率可达92.5%。方法的检出限为0.05~0.16 mg/kg,相对标准偏差(RSD)5.8%。与直接超声、开放式微波萃取法相比,此法具有明显的优势。方法用于实际土样的测定,所得结果与索氏抽提的结果相当。     

气相色谱法测定塑料食品包装袋中甲苯残留

提出一种食品塑料包装袋中残留甲苯的气相色谱分析方法。     

气相色谱法测定茶叶中邻苯二甲酸酯

建立了同时检测茶叶中5种邻苯二甲酸酯类(PAEs)的气相色谱(GC)-氢火焰离子(FID)检测方法,并对市售部分茶叶中的PAEs含量进行了测定。茶叶样品采用同时蒸馏萃取,处理后以HP-5石英毛细管柱分离,GC-FID法进行检测,外标法定量。5种PAEs在各自检测浓度范围内线性关系良好,其线性相关系数均达到0.999以上,检出限(LOD)为2.63~8.42μg/L,加标回收率在78.2%~111.3%之间,相对标准偏差(RSD)均小于5%,方法可以满足实际茶叶样品中5种PAEs的分析检测。     

气相色谱-质谱法测定水产品中24种邻苯二甲酸酯类化合物

建立了同时测定水产品中24种邻苯二甲酸酯类化合物(PAEs)的气相色谱-质谱(GC-MS)分析方法。称取1.0 g样品于10 mL玻璃离心管中,加内标D4-DEHP溶液(10 mg/L)100μL,氯化钠0.5 g,以5 mL乙腈-乙酸乙酯(1∶1)超声提取5 min,4 000 r/min离心5 min,移取上层有机相。再加入3 mL乙腈-乙酸乙酯重复提取。合并两次的提取液浓缩至1～2 mL后,经Florisil玻璃固相萃取柱净化,洗脱液在50℃下氮吹至近干,用正己烷超声溶解定容至1 mL,供GC-MS分析。24种PAEs的定量下限(LOQ)为1～500μg/kg,检出限(LOD)为0.1～100μg/kg。选取鱼、虾为研究基质考察方法的准确度及精密度,24种PAEs在3个添加水平时的平均回收率及相对标准偏差(n=6)分别为73%～120%、2.0%～19.7%。结果表明,该方法提取效率高,净化效果好,重复性强,能够满足水产品中邻苯二甲酸酯类化合物的检测需求。     

饮水中痕量邻苯二甲酸酯类化合物的色谱测定

本文提出了包括疏水吸附剂富集及气相色谱或液相色谱分析方法。报道了邻苯二甲酸酯在Amberlite XAD-2和SS401上的富集容量,研究了水样pH和流速对回收率的影响,GC采用填充柱或毛细柱,HPLC采用细径反相柱,适用于分析大分子量邻苯二甲酸酯。当取样量为10升时,本法的检测极限为ppb水平。     

Simple and rapid determination of phthalates using microextraction by packed sorbent and gas chromatography with mass spectrometry quantification in cold drink and cosmetic samples

A simple and rapid method using microextraction by packed sorbent coupled with gas chromatography and mass spectrometry has been developed for the analysis of five phthalates, namely, diethyl phthalate, benzyl‐n‐butyl phthalate, dicyclohexyl phthalate, di‐n‐butyl phthalate, and di‐n‐propyl phthalate, in cold drink and cosmetic samples. The various parameters that influence the microextraction by packed sorbent performance such as extraction cycle (extract–discard), type and amount of solvent, washing solvent, and pH have been studied. The optimal conditions of microextraction using C₁₈ as the packed sorbent were 15 extraction cycles with water as washing solvent and 3 × 10 μL of ethyl acetate as the eluting solvent. Chromatographic separation was also optimized for injection temperature, flow rate, ion source, interface temperature, column temperature gradient and mass spectrometry was evaluated using the scan and selected ion monitoring data acquisition mode. Satisfactory results were obtained in terms of linearity with R² >0.9992 within the established concentration range. The limit of detection was 0.003–0.015 ng/mL, and the limit of quantification was 0.009–0.049 ng/mL. The recoveries were in the range of 92.35–98.90% for cold drink, 88.23–169.20% for perfume, and 88.90–184.40% for cream. Analysis by microextraction by packed sorbent promises to be a rapid method for the determination of these phthalates in cold drink and cosmetic samples, reducing the amount of sample, solvent, time and cost.     

在线富集-微乳液毛细管电动色谱法分析食品塑料袋中邻苯二甲酸酯类化合物

建立了微乳液毛细管电动色谱(MEEKC)模式下,采用常规样品堆积模式(normal stacking mode, NSM)和反向极性堆积模式(reversed electrode polarity stacking mode, REPSM)两种在线富集邻苯二甲酸酯类化合物(phthalate esters, PAEs)的简便、有效方法。与常规MEEKC方法相比,REPSM-MEEKC方法使4种PAEs的检测灵敏度提高了937.5～7143倍。考察了常规MEEKC的分离条件,分别对影响两种富集过程的一些因素进行了研究,同时对两种富集方法的重现性和检出限等进行了考察。NSM-MEEKC和REPSM-MEEKC对邻苯二甲酸酯类化合物的检出限(按信噪比(S/N)=3计)分别为0.021～0.33 mg/L和0.7～4 μg/L。其中,灵敏度更高的REPSM-MEEKC方法已成功应用于食品塑料袋中邻苯二甲酸酯类化合物的测定,加标回收率为89.1%～105.6%,结果令人满意。     

Zeolite/Fe3O4 as a new sorbent in magnetic solid‐phase extraction followed by gas chromatography for determining phthalates in aqueous samples

In the present study, for the first time, we successfully employed zeolite/Fe₃O₄ as a new magnetic nanoparticle sorbent in magnetic solid‐phase extraction for determining phthalates in aqueous samples. Gas chromatography with flame ionization detection was used to detect the target analytes as a powerful instrumental analysis. Affecting parameters in the extraction process, including the amount of adsorbent, adsorption and desorption time, and volume of desorption solvent, were optimized using a response surface methodology based on central composite design. Under the optimum conditions, the linear range for dibutyl phthalate and bis(2‐ethylhexyl phthalate) was varied in the interval of 10–1700 and 10–1200 μg/L, respectively. Limits of detection were 2.80 μg/L for dibutyl phthalate and 3.20 μg/L for bis(2‐ethylhexyl phthalate). The recovery value for the extraction of target analytes was between 97 and 111%. The repeatability and reproducibility of the new proposed method were obtained: 10–13% and 13–13.5%, respectively. The increased sensitivity in using the proposed method has been demonstrated. Compared with previous methods, the new proposed method is an accurate, rapid, and reliable sample‐pretreatment method.     

A novel quantitation method for phthalates in air using a combined thermal desorption/gas chromatography/mass spectrometry application

In this study, a novel quantitation method was developed to facilitate the simple and effective sampling and analysis of phthalates in air based on a sorbent tube-thermal desorption-gas chromatography-mass spectrometry system combination. The performance of the thermal desorption-based analysis was assessed using three different sorbent combinations [1]: quartz wool (QW) [2], glass wool (GW), and [3] quartz wool plus Tenax TA (QWTN) in terms of relative recovery in reference to a direct injection method. There was no significant difference in the average recovery rate for seven target phthalates based on sorbent tube type (QW, 70.2 ± 4.28; GW, 73.2 ± 8.8; and QWTN, 72.5 ± 5.02%). However, the recovery rate of phthalates in each sorbent tube type was distingusihed by physicochemical properties of the target compound (e.g., molecular weight and boiling point). The recovery rate of the QW tube was high for dimethyl phthalate and diethyl phthalate compared to other sorbent tubes, while that of the GW tube exhibited greater values for dibutyl phthalate, benzyl butyl phthalate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) phthalate, and di-n-octyl phthalate. The simple sorbent tube-thermal desorption approach is feasible for the quantitation of seven phthalates present at 0.45–24.5 ng m⁻³ levels in actual air samples (20 L).     

高效液相色谱法测定硝基涂料中的增塑剂邻苯二甲酸酯类

建立了用高效液相色谱法测定硝基涂料中的邻苯二甲酸酯类化合物的方法。样品待挥发性有机物挥发后,用乙醇提取其中的邻苯二甲酸酯类,直接用HPLC分析,外标法定量。该方法的精密度为2 05%～4 93%,回收率为79 5%～106 0%,检出限为DMP0 14ng,DEP0 22ng,DBP0.61ng。     

Enzyme activity determination by radio gas chromatography on capillary columns

Androgen 5α-reductase from the foreskin of 48 boys in prepubertal age was analyzed by evaluation of the apparent K_m-and V_max- values after tissue incubation. Reaction rates were calculated after determination of specific radioactivity of distinct metabolites, by comparison to the radioactivity of the precursor. Reaction products were separated by radio gas chromatography on capillary columns. The chromatography system was based on multicolumn equipment with column switching facilities and a variable splitter at the outlet of the separation column. A radioactivity monitor (gas proportional counter) was used for measurement of radioactivity in the column effluents. An electron capture detector was used for mass detection of steroid acyl derivatives.     

近两年国内气相色谱的应用进展(Ⅰ)

傅若农男，1930年出生，1953年毕业与北京大学化学系，到1998年退休前一直在北京理工大学(前身为北京工业学院)工作，1986年晋升为教授，并被国务院学位委员会评定为第三批博士生导师。多年来从事色谱分析方面的教学和研究工作，研究方向为：气相色谱和毛细管气相色谱新固定相，