高效液相色谱法测定食用油中特丁基对苯二酚北大核心CSCD

采用高效液相色谱法测定食用油中特丁基对苯二酚的含量。0.500 0g食用油样品用乙腈超声萃取两次(每次2mL),合并萃取液后用流动相稀释至5mL。以C18色谱柱为分离柱,以乙腈(7+3)溶液为流动相,在检测波长290nm处进行测定。特丁基对苯二酚的质量浓度在1～150mg·L^(-1)内与其对应的峰面积呈线性关系,检出限(3S/N)为0.1mg·L^(-1)。方法用于食用油样品的分析,加标回收率为93.5%～98.5%,日内相对标准偏差(n=6)为1.8%,日间相对标准偏差(n=10)为2.9%。     

固相萃取–气相色谱–串联质谱法检测土壤中15种邻苯二甲酸酯

建立了固相萃取结合气相色谱串联质谱联用仪检测土壤中15种邻苯二甲酸酯残留的方法。样品采用丙酮和石油醚超声提取,取上清液浓缩,上弗罗里硅土固相萃取柱净化,收集洗脱液,定容,以气相色谱串联质谱法分析。该方法在20~2 000 ng/g范围内线性关系良好(r~20.999 0),检出限(S/N=3)为0.12~0.61 ng/g。20,50,200 ng/g 3个添加浓度的15种邻苯二甲酸酯的加标回收率在78.9%~101.8%之间,测定结果的相对标准偏差为0.19%~8.34%(n=5)。该方法准确、灵敏,符合痕量分析的要求,适用于土壤中邻苯二甲酸酯类残留的分析。     

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。     

烟草中啶虫脒残留量的测定

建立了烟草中啶虫脒残留量的气相色谱检测方法.样品采用乙腈提取,经弗罗里硅土层析柱净化,用环己烷-异丙醇(体积比为9∶1)溶液淋洗,用电子捕获检测器进行测定.结果表明,该方法的回收率为82.8%～100.3%,相对标准偏差小于5%(n=5),检出限为0.18 μg/g.该法适合于烟草中啶虫脒残留量的检测.     

反相高效液相色谱法测定玉米中玉米赤霉烯酮

建立了反相高效液相色谱法检测玉米中玉米赤霉烯酮的分析方法.该方法的标准曲线回归方程为y=2.97×103 5.23×104ρ(r=0.9998);玉米样品3个水平的加标回收率分别为84.8%,86.7%和89.2%;相对标准偏差分别为4.0%,5.2%和4.4%;加标浓度为50 ng/g的玉米样品日内相对标准偏差为0.69%;玉米样品日间相对标准偏差为2.6%;方法检出限为3.0 ng/g.     

流动注射壳聚糖在线微柱预富集电热原子吸收光谱法测定痕量Cr(VI)

以天然高分子材料壳聚糖作在线预富集柱填料,流动注射与电热原子光谱联用测定痕量Cr(VI)。采样体积5.80mL,采样频率22样/h,富集倍数51倍,线性范围0.02μg/L～0.12μg/L,该方法的检出限(3s,n=11)0.69ng/L,相对标准偏差5.1%(CCr(VI)=0.10μg/L,n=11)。将该方法用于环境水样、茶叶样品和头发样品中Cr(VI)的测定,结果满意。     

磁固相萃取与高效液相色谱-等离子体质谱联用检测癌症病人尿样中的卡铂药物

制备了甲基丙烯酸(MAA)改性Fe3O4纳米颗粒(Fe3O4@SiO2@MAA),建立了磁固相萃取(MSPE)-高效液相色谱(HPLC)-等离子体质谱(ICP-MS)检测癌症病人尿样中药物卡铂(CBP)的新方法。在最优条件下,该方法对CBP的检出限为29.9ng/L,相对标准偏差(RSD,cCBP=0.2μg/L)为9.5%,富集倍数为27.7,线性范围为0.1~100μg/L。不同批次合成的Fe3O4@SiO2@MAA萃取CBP的RSD为11.5%(n=5)。将该方法用于同一癌症病人在化疗过程中和化疗结束后两个尿样中CBP的分析,尿样中完整CBP的浓度分别为51.15μg/L和24.65μg/L,加标回收率为93.2%~103.7%。     

流动注射壳聚糖在线微柱预富集电热原子吸收光谱法测定痕量Cr(Ⅵ)

以天然高分子材料壳聚糖作在线预富集柱填料,流动注射与电热原子光谱联用测定痕量Cr(Ⅵ).采样体积5.80mL,采样频率22样/h,富集倍数51倍,线性范围0.02μg/L～0.12μg/L,该方法的检出限(3s,n=11)0.69ng/L,相对标准偏差5.1%(CCr(Ⅵ)=0.10μg/L,n=11).将该方法用于环境水样、茶叶样品和头发样品中Cr(Ⅵ)的测定,结果满意.     

ASE-GC-MS法同时测定农用地土壤中的多环芳烃、多氯联苯和有机氯农药

建立同时检测农用地土壤中15种多环芳烃、7种多氯联苯和8种有机氯农药的方法,对样品前处理流程及仪器工作参数进行优化。样品经正己烷–二氯甲烷(1∶1)加速溶剂萃取,以硅酸镁小柱净化,二氯甲烷–正己烷(1∶4)洗脱,用气相色谱–质谱法同时测定。各目标化合物在质量浓度在5.0～500μg/L范围内相对响应因子的相对标准偏差均小于9.3%;平均加标回收率为60.3%～105.6%,相对标准偏差为1.7%～12.8%(n=6),方法检出限为0.12～0.40μg/kg。该方法快速、稳健,净化效果好,能满足农用地土壤中30种持久性有机污染物的检测要求。     

加速溶剂萃取/气相色谱-负化学电离质谱法对土壤中毒杀芬的测定研究

建立了加速溶剂萃取/气相色谱-负化学电离质谱法测定土壤中毒杀芬的方法.在加速溶剂萃取实验条件优化的基础上,确定了最佳实验条件:系统压力12.4 MPa,萃取溶剂为正己烷-丙酮(体积比1 : 1),萃取温度100 ℃,静态萃取时间10 min,循环2次.萃取液经活性炭与弗罗里硅土复合小柱净化后,氮吹至1.0 mL,于GC-MS仪上测定.结果表明,毒杀芬的线性范围为0.3 ～3 000 ng/g(毒杀芬总量),相关系数均不小于0.999 0,方法检出限为0.10 ～1.00 ng/g,平均回收率为86% ～104%,相对标准偏差(n=7)为6.8% ～13.5%.     

Humic acid-bonded silica as a novel sorbent for solid-phase extraction of benzo[a]pyrene in edible oils

A novel solid-phase extraction (SPE) sorbent, humic acid-bonded silica (HAS), was prepared. Humic acids (HAs) were grafted onto silica matrices via an amide linkage between humyl chloride and the amido terminus of 3-aminopropyltrimethoxysilane (APTS)-silica gel. The resulting material was characterized by Fourier transform infrared spectrometer, elemental analysis, and nitrogen adsorption analysis. This sorbent exhibits an excellent adsorption capacity for some electron-abundant analytes owing to its peculiar structure. In this paper, we choose benzo[a]pyrene (BaP) in oil as a probe to validate the adsorption capacity of the material. Thus a fast, cheap and simple SPE method with humic acid-bonded silica cartridge for edible oil clean-up, followed by high-performance liquid chromatography (HPLC) with fluorescence detection was established. The effects of experimental variables, such as washing and elution solvents, and the amount of sorbents have been studied. The recoveries of BaP in edible oils spiked at 0.2-100 μg kg⁻¹ were in the range of 78.8-102.7% with relative standard deviations ranging between 1.3 and 9.3%; the limit of detection was -0.06 μg kg⁻¹.     

Humic acids as both matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and adsorbent for magnetic solid phase extraction

In the present study, humic acids (HAs) were applied as both a matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and an adsorbent of magnetic solid phase extraction (MSPE) for the first time. As natural macromolecule compounds, HAs are inherently highly functionalized and contain laser energy absorbing–transferring aromatic structures. This special molecular structure made HAs a good candidate for use as a MALDI matrix in small molecule analysis. At the same time, due to its good adsorption ability, HAs was prepared as MSPE adsorbent via a simple co-mixing method, in which the commercially available HAs were directly mixed with Fe₃O₄ magnetic nanoparticles (MNPs) in a mortar and grinded evenly and completely. In this process, MNPs were physically wrapped and adhered to tiny HAs leading to the formation of magnetic HAs (MHAs). To verify the bi-function of the MHAs, Rhodamine B (RdB) was chosen as model compound. Our results show that the combination of MHAs-based MSPE and MALDI-TOF-MS can provide a rapid and sensitive method for the determination of RdB in chili oil. The whole analytical procedure could be completed within 30 min for simultaneous determination of more than 20 samples, and the limit of quantitation for RdB was found to be 0.02 μg/g. The recoveries in chili oil were in the range 73.8–81.5% with the RSDs less than 21.3% (intraday) and 20.3% (interday). The proposed strategy has potential applications for high-throughput analysis of small molecules in complex samples.     

采用新型固相萃取柱快速测定食用植物油中苯并［a］芘

研究了Bond Elut ENV新型固相萃取柱在食用植物油中苯并[a]芘快速检测中的应用,建立了快速测定食用植物油样品中苯并[a]芘残留量的固相萃取/液相色谱/荧光检测法。样品用正己烷溶解,固相萃取净化,SUPELCOSILTMLC-PAH(25 cm×4.6 mm,5μm)色谱柱分离,以乙腈-水(95∶5)为流动相,荧光检测(λex=297 nm,λem=408 nm),外标法定量。苯并[a]芘的检出限为0.3μg/kg,在1.0～50.0μg/L范围内线性关系良好,相关系数为0.999 6,方法的回收率为79%～102%,相对标准偏差不高于9.4%。该方法准确、实用、简便、快速,在食用植物油的苯并[a]芘残留量检测方面有广泛的应用前景。     

Polycyclic aromatic hydrocarbons (PAHs) in edible oils by gas chromatography coupled with mass spectroscopy

The occurrence of polycyclic aromatic hydrocarbons (PAHs) in nine edible oils of three categories of oil samples, such as soy bean oil, mustard oil and coconut oil, has been studied to determine the contamination degree of this type of oil samples. Eight major carcinogenic polycyclic aromatic hydrocarbons (PAHs), such as naphthalene, anthracene, phenanthrene, fluorene, pyrene, crysene, benzo(a)pyrene and benzo(a)anthracene, were identified and quantified in the extract of edible oils collected from Bangladeshi Markets by gas chromatography and mass spectroscopy. All of the carcinogenic PAHs are not present in the edible oils. A few of the carcinogenic PAHs are present in the oils but it is within the permissible limit. The results for the recoveries of naphthalene, fluorene, phenanthrene, anthracene, pyrene, crysene, benzo(a)anthracene and benzo(a)pyrene were in the range of 56–84%. The limit of detection (LOD) of the GC–MS method, established at signals three times that of the noise for naphthalene, fluorene, phenanthrene, anthracene, pyrene, crysene, benzo(a)anthracene and benzo(a)pyrene, was 2.0–2.5 ng, respectively.     

固相萃取-高效液相色谱-荧光法测定方便面和烤肠中的苯并[a]芘

建立了固相萃取-高效液相色谱-荧光法检测方便面和烤肠中苯并[a]芘的方法。采用正己烷作为提取溶剂,经苯并[a]芘专用固相萃取柱HiCapt Benzo富集净化,高效液相色谱-荧光法对样品中苯并[a]芘进行分离分析。苯并[a]芘的质量浓度在0.5~20.0μg/kg范围内与色谱峰面积呈良好的线性关系,相关系数R2为0.9997。方便面和烤肠中苯并[a]芘的加标回收率分别为92.2%~98.3%和95.9%~97.9%,日内和日间相对标准偏差分别为3.34%~5.01%和2.11%~4.07%。与传统方法相比,该方法快速简单、有机溶剂消耗少,在油炸烟熏食品的苯并[a]芘分析中具有较大应用前景。     

A magnetite/oxidized carbon nanotube composite used as an adsorbent and a matrix of MALDI-TOF-MS for the determination of benzo[a]pyrene

A magnetite/oxidized carbon nanotube composite, Fe(3)O(4)@SiO(2)/OCNT, was fabricated in a simple way, and it was successfully used as a magnetic solid-phase extraction sorbent and a significant matrix of the matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) for the detection of benzo[a]pyrene (BaP).     

ASE-SPE/GC-MS测定土壤中16种PAHs质量控制研究

优化了土壤中16种优控多环芳烃( PAHs)的分析方法,建立了一套完备的质量控制体系,解决了PAHs分析中常见的技术难点,如苯并(a)芘(BaP)回收率低,基质复杂的样品净化效果不理想,萘(Nap)和菲(Phe)挥发损失和环境本底影响等.样品经加速溶剂提取(ASE),固相萃取(SPE)净化,逐级减压浓缩,气相色谱质谱( GC - MS)测定,并以氘代苯并a芘(BaP - d12)作回收率指示物.实验比较了3种正相SPE吸附剂的效果,发现弗罗里硅土对BaP存在明显的降解现象,BaP的定量应使用同位素稀释法,以降低其分析不确定度;氧化铝对PAHs的吸附性过强,不利于样品净化;硅胶最为理想.PAHs的仪器检出限为0.26～5.7 pg,方法检出限为0.067 ～0.97 ng/g(干重),土壤基质加标回收率为71％～ 122％,相对标准偏差为1.6％～8.3％.将该法用于7个电子废物焚烧区域农田土壤样品的测定,PAHs含量在28～ 283 ng/g(干重)之间,样品中BaP-d12的回收率为90％～124％,各项质控指标符合检测要求.     

Highly sensitive routine method for urinary 3-hydroxybenzo[a]pyrene quantitation using liquid chromatography-fluorescence detection and automated off-line solid phase extraction

Many workers and also the general population are exposed to polycyclic aromatic hydrocarbons (PAHs), and benzo[a]pyrene (BaP) was recently classified as carcinogenic for humans (group 1) by the International Agency for Research on Cancer. Biomonitoring of PAHs exposure is usually performed by urinary 1-hydroxypyrene (1-OHP) analysis. 1-OHP is a metabolite of pyrene, a non-carcinogenic PAH. In this work, we developed a very simple but highly sensitive analytical method of quantifying one urinary metabolite of BaP, 3-hydroxybenzo[a]pyrene (3-OHBaP), to evaluate carcinogenic PAHs exposure. After hydrolysis of 10 mL urine for two hours and concentration by automated off-line solid phase extraction, the sample was injected in a column-switching high-performance liquid chromatography fluorescence detection system. The limit of quantification was 0.2 pmol L(-1) (0.05 ng L(-1)) and the limit of detection was estimated at 0.07 pmol L(-1) (0.02 ng L(-1)). Linearity was established for 3-OHBaP concentrations ranging from 0.4 to 74.5 pmol L(-1) (0.1 to 20 ng L(-1)). Relative within-day standard deviation was less than 3% and relative between-day standard deviation was less than 4%. In non-occupationally exposed subjects, median concentrations for smokers compared with non-smokers were 3.5 times higher for 1-OHP (p<0.001) and 2 times higher for 3-OHBaP (p<0.05). The two urinary biomarkers were correlated in smokers (ρ=0.636; p<0.05; n=10) but not in non-smokers (ρ=0.09; p>0.05; n=21).     

Determination of benzo[a]pyrene in edible oils using phase‐transfer‐catalyst‐assisted saponification and supramolecular solvent microextraction coupled to HPLC with fluorescence detection

For the analysis of edible oils, saponification is well known as a useful method for eliminating oil matrices. The conventional approach is conducted with alcoholic alkali; it consumes a large volume of organic solvents and impedes the retrieval of analytes by microextraction. In this study, a low‐organic‐solvent‐consuming method has been developed for the analysis of benzo[a]pyrene in edible oils by high‐performance liquid chromatography with fluorescence detection. Sample treatment involves aqueous alkaline saponification, assisted by a phase‐transfer catalyst, and selective in situ extraction of the analyte with a supramolecular solvent. Comparison of the chromatograms of the oil extracts obtained by different microextraction methods showed that the supramolecular solvent has a better clean‐up effect for the unsaponifiable matter from oil matrices. The method offered excellent linearity over a range of 0.03– 5.0 ng mL⁻¹ (r > 0.999). Recovery rates varied from 94 to 102% (RSDs <5.0%). The detection limit and quantification limit were 0.06 and 0.19 μg kg⁻¹, respectively. The proposed method was applied for the analysis of 52 edible oils collected online in China; the analyte contents of 23 tested oil samples exceeded the maximum limit of 2 μg kg⁻¹ for benzo[a]pyrene set by the Commission Regulation of the European Union.     

Determination of some polycyclic aromatic hydrocarbons in filter tar of Turkish cigarettes

A simultaneous determination method for the analysis of benzo[a]pyrene (BaP) and dibenzo[a,h]anthracene (DahA) in the filter tar of Turkish cigarettes has been developed. The method involved (a) the extraction of BaP and DahA with n-hexane from ACN solution in which the cigarette filters were extracted, and then (b) purification of the n-hexane extracts by elution on an XAD-2 column using n-hexane/dichloromethane (9:1, v/v) mixture. Separation and quantitative determination of BaP and DahA in the extracts were carried out by HPLC and fluorescence detection on a C18 RP column. The calculated recoveries for BaP and DahA were found in the range of 90-100% for each extraction and clean-up steps. Analysis of various filter tar of Turkish cigarettes showed that an average of 74.28 ng/filter of BaP and 5.24 ng/filter of DahA were present in Turkish cigarettes.