烟熏食品中苯并(a)芘的产生机理及防止方法

本文主要从当前备受关注的烟熏食品的安全问题出发,简述了烟熏食品中的有害物质--苯并(a)芘(benzo(a)pyrene)的产生机理、毒害、检测及防止方法,为今后更好的研究苯并(a)芘,控制其在烟熏食品中的含量提供一定的理论基础.     

电化学分析法快速测定烧烤类食品中的苯并(a)芘

基于苯并(a)芘(benzo(a)pyrene,BaP)的电化学氧化还原特征,建立一种快速测定烧烤类食品中BaP含量的电化学分析方法,优化测定条件为乙腈-水(1∶3,V/V)作为溶剂、电解质LiClO_4浓度0.15 mol/L、硫酸浓度0.1 mol/L、富集时间10 min,在此条件下,BaP的氧化峰电流随其浓度的增大而增大,而且浓度在0~100 nmol/L范围内呈线性关系,检测限为0.187 nmol/L(R_(SN)=3)。该方法的稳定性和重复性较好,检测时间短,利用该法对烤羊肉串样品中的BaP进行检测,回收率为96.67%~101.56%,检测结果与高效液相色谱法基本一致,可用于烧烤类食品中BaP的快速检测。     

Determination of PAHs in various smoked meat products and different samples by enzyme immunoassay

An enzyme immunoassay was used to determine benzo[a ]pyrene (BaP) in smoked meat products and other samples of food and environmental origin. The method used has a detection limit (3 σ) of 0.1 μg kg⁻¹ and a coefficient of variation less than 10%. The main aim of the study was to compare the possible influence of different smoking processes and packaging material on the amount of BaP deposited on smoked meat product, mainly different sausages. The lowest amount of BaP was found when smoke produced by steam in the indirect method smoking‐chamber was used. A slightly protective effect of polyamide casing was noted. © 1999 Society of Chemical Industry     

二维液相色谱法测定烧烤肉制品中苯并（a）芘

烧烤肉制品由于富含动物油脂,在炭火高温烧烤熟制品过程中,容易出现苯并（a）芘超标问题,具有较高安全隐患。建立二维液相色谱仪检测烧烤肉制品中苯并（a）芘的方法。第1维为分离、富集柱,采用Inertsil ODS柱（4.6 mm×150 mm,5 μm）,流动相为乙腈-水（85∶15,V/V）,流速1.0 mL/min,可以实现500 μL样品中目标物苯并（a）芘的富集与分离;第2维采用ChromSpher Pi柱（3.0 mm×80 mm,5 μm）,流动相为异丙醇-乙腈（60∶40,V/V）,流速1.2 mL/min,可以有效分离、测定样品中的苯并（a）芘。结果表明：烧烤肉制品中苯并（a）芘在1.0～20.0 ng/mL范围内呈线性关系,其线性回归方程为y=1.847 1x－0.103 3（r=0.999）,检出限为0.08 μg/kg,在1.00、3.00、5.00、10.00 μg/kg加标水平下,加标回收率为97.1%～105.2%,相对标准偏差为1.55%～2.77%。     

Benzo[a]pyrene and total polycyclic aromatic hydrocarbons (PAHs) levels in vegetable oils and fats do not reflect the occurrence of the eight genotoxic PAHs

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were determined in 115 samples of olive oil (extra virgin olive oil, virgin olive oil, olive oil, pomace olive oil and blended olive oil), cooking oil (corn oil, sunflower oil, sesame oil, palm olein oil, soya oil, canola oil, mustard oil, peanut oil and mixed vegetable oil) and fat (butter and table margarine) collected from retail stores in Kuwait. Carcinogenic benzo[a]pyrene (BaP) was detected in 43% of the samples analyzed. Benz[a]anthracene and chrysene were detected in 37 and 45% of the samples, respectively, that did not contain BaP. Of the individual non-carcinogenic PAHs, naphthalene showed the highest mean concentration (14 µg kg^?1), while for the carcinogenic PAHs, BaP (0.92 µg kg^?1) and chrysene (0.87 µg kg^?1) showed the highest mean values. Approximately 20% of the samples within the olive oil and cooking oil sub-categories exceeded the EU maximum tolerable limit for BaP, with the highest level of 6.77 and 11.1 µg kg^?1, respectively. For the fat sub-category, 9% of the samples exceeded the tolerance limit, with the highest level of 3.67 µg kg^?1. The Kuwaiti general population's dietary exposure to the genotoxic PAHs (PAH8: benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene and benzo[ghi]perylene) was estimated to be 196 ng day^?1 (3.3 ng kg^?1 bw day^?1, assuming an average adult body weight of 60 kg). Results indicated that PAH8 and BaP_eq (total sum benzo[a]pyrene equivalents) are more reliable measures of the concentrations of other carcinogenic PAHs in oil and fat samples, while BaP and PAHs alone are not good indicators of the occurrence or degree of contamination by carcinogenic PAHs in these food products.     

人工抗原苯并芘的化学合成与分析

以苯并芘（benzo(a)pyrene,BaP）为起始反应物,通过碘代、Heck偶联两步化学反应合成苯并芘的羰基衍生物,再经肟化反应将羰基羧基化,采用活化酯法将羧基化半抗原与载体蛋白（牛血清蛋白）进行偶联,制备苯并芘的人工抗原。采用红外光谱（infrared spectroscopy,IR）、核磁共振波谱（nuclear magnetic resonancespectrum,NMR）和质谱（mass spectrometer,MS）对苯并芘中间产物进行表征,并用紫外扫描的方法对人工抗原进行鉴定。本实验成功羧化了苯并芘,并成功构建人工抗原,苯并芘与载体蛋白的偶联比为28∶1。     

Carcinogenic polycyclic aromatic hydrocarbons (PAH) determined in Nigerian kundi (smoke-dried meat)

Chemical analyses of kundi show that, apart from a high level of carcinogenic benzo (a)pyrene (10·5–66·9 ng g^?1), eight other polycyclic aromatic hydrocarbons (PAH) are present at various concentrations. The high levels of PAH in kundi are due to the high glow and smoking temperatures averaging 926°C and 191·5°C, respectively. Column chromatography was used for PAH extraction with propylene carbonate as the eluting chemical; thin layer chromatography (TLC) on acetylated cellulose layer plates was used for separation, and the determination was performed using spectrophotofluorimetry. The public health implications of PAH as one of the possible carcinogenic factors in the high incidence of primary liver and stomach cancer reported in Nigeria are highlighted.     

全自动固相萃取-高效液相色谱法测定熏烤肉制品中苯并(a)芘含量

建立全自动固相萃取-高效液相色谱法检测熏烤肉制品中苯并(a)芘的方法。样品经正己烷提取、分子印迹小柱净化,高效液相色谱-荧光检测器检测,流动相为乙腈-水（90∶10,V/V）,流速1.0 mL/min。结果表明：苯并(a)芘在0.0～45.2 ng/mL质量浓度范围内线性关系良好,相关系数（R2）为0.999 7,检出限为0.12 μg/kg,回收率为97.2%～100.2%,相对标准偏差为1.4%～2.6%。该方法灵敏度高,稳定性好,批处理速度快,接触有机试剂较少,适用于熏烤肉制品中苯并(a)芘残留量测定。     

在线净化-液相色谱法快速测定熏烤水产品中的苯并（a）芘

建立在线净化-液相色法测定熏烤水产品中的苯并(a)芘的条件及方法。使用乙酸乙酯提取后即可直接上样分析,经C8在线净化柱净化后,C18色谱柱分离,荧光检测器检测。苯并(a)芘[benzo(a)pyrene,BaP]的方法检出限为0.035 ng/mL。利用该方法对熏烤水产品中BaP进行测定,线性相关系数为0.9999,平均回收率为89.6%~99.0%,相对标准偏差为1.3%~3.1%。     

熏烤肉制品风味和有害物质的形成及其防止方法

熏烤是一种传统的肉品加工方法,在熏烤时形成特有的风味,但安全隐患也随之产生。文章简单阐述了熏烤肉制品的风味形成及熏烤过程中苯并芘和丙烯酰胺的形成机理,针对熏烤肉制品的高温性探讨了降低熏烤肉品中苯并(a)芘和丙烯酰胺含量的方法。     

Optimisation of microwave assisted extraction (MAE) for polycyclic aromatic hydrocarbon (PAH) determination in smoked meat

A rapid extraction method involving microwave assisted extraction (MAE), followed by sample clean-up on a silica cartridge, reversed-phase high performance liquid chromatography (RP-HPLC) and spectrofluorimetric detection, was optimised for polycyclic aromatic hydrocarbon (PAH) determination in smoked meat. Compared to solvent extraction assisted by sonication, MAE, carried out with n-hexane on 2g of lyophilised sample at 115°C for 15min, allowed to obtain better extraction efficiencies. Limits of quantification (LOQ, s/n=10) lower than 0.2μg/kg wet weight were found for all PAHs, except for Fl (0.3μg/kg), P (0.6μg/kg) and IP (0.4μg/kg). The optimised procedure, that presented good analytical performances (with recoveries ranging from 77% to 103%, and precision within 10% for most of the PAHs), was applied to determine PAH content in different smoked meat products from the Italian market.     

Determination of polycyclic aromatic hydrocarbons (PAHs) in commonly consumed Nigerian smoked/grilled fish and meat

Smoking and/or grilling, when carried out with traditional methods involving direct contact with wood combustion fumes, is responsible for high contamination levels with carcinogenic polycyclic aromatic hydrocarbons (PAHs). The aim of this work was to investigate the PAH content of different smoked or grilled meat and fish products commonly consumed in Nigeria. A rapid method involving microwave-assisted saponification and simultaneous extraction followed by solid-phase extraction (SPE), high-performance liquid chromatography (HPLC) separation and spectrofluorometric detection was employed. Samples that were smoked or grilled using traditional systems, which use a wood fire, were heavily contaminated with benzo[a]pyrene (BaP) at levels ranging from 2.4 to 31.2 µg kg^?1 wet weight. Considerably lower contamination levels were found in samples smoked or grilled in the laboratory using a charcoal fire (BaP from 0.7 to 2.8 µg kg^?1 wet weight). The health risk associated with a daily consumption of 100 g of these products was also evaluated using the margin of exposure (MOE) approach. MOE values lower than 10,000 were obtained for all smoked/grilled commercial samples, indicating a potential concern for consumer health.     

液熏技术在水产品加工中的应用

烟熏食品深受人们的欢迎,但因其存在不利健康的因素而受到影响。液熏技术以其产品质量稳定,不含苯并芘,并易于实现工业化连续生产正得到广泛应用。本文综述了液熏技术在水产品中的应用并对未来发展前景作了展望。     

Determination of polycyclic aromatic hydrocarbons in smoked fishery products from different smoking kilns

The levels of 13 polycyclic aromatic hydrocarbons (PAH) were determined by an HPLC method with fluorescence and UV detection and by a GC/MS technique in smoked fishery products from modern smoking kilns with external smoke generation and from traditional smoking kilns. The average benzo(a)pyrene (BaP) concentration of all 35 samples from commercial smoking kilns with external smoke generation was 0.1 g/kg (wet weight) and the sum of the carcinogenic compounds determined in the study, i.e. benz(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenz(a,h)anthracene and indeno(1,2,3-c,d)pyrene did not exceed 4.5 g/kg (wet weight). The BaP levels of the 27 smoked fish samples from traditional kilns ranged from 0.2 g/kg to 4.1 g/kg, with a mean value of 1.2 g BaP/kg. The average concentration of the sum of the carcinogenic compounds was 9.0 g/kg. Large variations were found in the content of the non-carcinogenic PAHs phenanthrene, anthracene, fluoranthene and pyrene in all samples from both types of smoking kilns.     

RP-HPLC法测定食用油中苯并(a)芘的含量

改进了食用油中苯并(a)芘含量的HPLC检测方法.方法采用Elipse PAH色谱柱,以乙腈-水(88/12,体积比)为流动相,流速1.0 mL/min,柱温25℃,进样量10 μL,以384 nm为激发波长,412 nm为发射波长测定荧光强度.方法的检出限为0.4μg/kg,在0.000 8～0.4 μg/mL浓度范围内线性良好,回收率在85％以上.该方法快速、准确、灵敏,且前处理简单,可直接用于食用油中苯并(a)芘含量的检测.     

基于PC-12细胞电化学传感器检测苯并(a)芘的研究

本文采用海藻酸钠(SA)与聚电解质膜(PEM)包埋大鼠肾上腺嗜铬细胞瘤(PC-12)细胞的方式构建电化学传感器,用于苯并(a)芘(Benzo(a)pyrene,BaP)对细胞电化学特性影响的研究,并建立了一种BaP分析测定的新方法。PC-12细胞作为识别元件,被包裹在海藻酸钠和聚电解质膜中并固定在电极上。最终使用电化学阻抗谱(EIS),差分脉冲伏安法(DPV)和循环伏安法(CV)进行结果分析。结果表明,BaP在1~5 μmol/L的浓度范围内,以剂量依赖性方式引起电化学阻抗的显著降低,线性方程为y=-418.660x+4234.706,r=0.994,其检测限为0.21 μmol/L。平均回收率高于97％,检测结果的RSD低于5％,表明该传感器具有良好的重现性和稳定性。总体而言,本研究建立的传感器BaP检测方法是一种廉价和简单的方法,稳定性和重现性较高,为BaP的研究提供了新的思路。     

高效液相色谱法测定粮食中苯并芘残留的研究

建立了粮食中苯并芘残留的高效液相色谱测定法.方法采用C18(5μm,4.6mm×250mm i.d)反相色谱柱,流动相为甲醇 水(95∶5),流速1.0mL/min,激发波长365nm,发射波长410nm,柱温35℃,进样量5μL.方法的检出限0.5μg/kg,线性范围0～1000 ng/mL,加标回收率83.3%～88.3%,相对标准偏差为1.86%(n=5).该法具有样品预处理简单,毒性小,灵敏度高,分析时间短等优点,可用于粮食样品的直接测定.     

基于癸硫醇修饰的银纳米点阵列的苯并(a)芘检测

利用阳极氧化铝模板法制备大面积高度有序的可调控的银纳米点阵列,并在其表面组装一层癸硫醇单分子层用于水中苯并(a)芘(benzo(a)pyrene,Ba P)的快速检测。首先,通过扫描电镜、紫外-可见透过光谱、罗丹明6G探针分子对不同扩孔时间制备的银纳米点阵列进行表征,结果表明扩孔时间为80 min制备的基底拉曼增强效果最好,增强因子可达1.6×10~6。然后,在此基底表面修饰一层癸硫醇分子,利用癸硫醇与BaP之间的疏水相互作用可以实现BaP的预富集,进而实现BaP的高灵敏度、稳定的检测。研究表明:利用此基底检测Ba P的检测限可达1.0 ng/mL,特征峰处的相对标准偏差为9.7%,满足高稳定性表面增强拉曼光谱基底的标准。该方法在BaP快速检测方面具有极大的潜力。     

黑加仑、猕猴桃、小白菜提取物抗苯并[a]芘致突变作用的实验研究

研究猕猴桃、小白菜、黑加仑提取物提取物抗苯并[a]芘的致突变作用。结果表明3种果蔬提取物的抗诱变能力不同,由强到弱依次为:黑加仑、猕猴桃、小白菜。其中高剂量的3种果蔬提取物取物对苯并[a]芘诱导的鼠伤寒沙门氏菌TA98致突变作用的抗诱变等级达到高强度等级(+++)。SPSS17.0统计学软件分析表明:与阳性对照组比较存,中、高剂量的果蔬提取物的抗诱变效果极显著(P<0.01)。     

Polycyclic aromatic hydrocarbons (PAHs) in meat products and estimated PAH intake by children and the general population in Estonia

The concentrations of benzo[a]pyrene and 11 other polycyclic aromatic hydrocarbons (PAHs) were analysed from 322 commercial, cured meat products and 14 home-grilled meat samples as part of the Estonian food safety monitoring programme during 2001-2005. The maximum acceptable concentration of 5 µg kg^-1 for benzo[a]pyrene was exceeded in 3.4% of samples. The highest PAH concentrations were detected in home-grilled pork samples. Using of disposable grilling unit resulted in 1.6 times higher PAH concentrations compared to the traditional wood-burning grill. The average intake of benzo[a]pyrene and sum of 12 PAHs from meat products was estimated for children (age 1-16 years) on the basis of an individual food consumption questionnaire and, for the general population, based on national food consumption data. The highest total PAH concentrations detected were 16 µg kg^-1 in smoked meat and ham, 19 µg kg^-1 in smoked sausage and 6.5 µg kg^-1 in smoked chicken samples. Since smoking and grilling are prevalent meat-cooking methods in Estonia, the impact of meat products is assessed to be significant in overall PAH intake.