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采用毛细管气相色谱-高分辨率质谱法测定30种腌肉制品中的8种挥发性亚硝胺:检出二乙基亚硝胺,未检出亚硝基吡咯烷。

Determination of eight volatile nitrosamines in thirty cured meat products with capillary gas chromatography-high-resolution mass spectrometry: the presence of nitrosodiethylamine and the absence of nitrosopyrrolidine.

作者信息

Groenen P J, Jonk R J, van Ingen C, ten Noever de Brauw M C

出版信息

IARC Sci Publ (1971). 1976(14):321-31.

PMID:1033915
Abstract

Five samples each of six cured meat products were analysed for the presence of eight volatile nitrosamines. A combined steam distillation-extraction step at pH 8-9 plus a concentration step were used for preparation of extracts. These were analysed, without further clean-up, using a coupled capillary GC-HRMS system at a resolution of 4 000. The MS was used in the fixed mass mode, but after the retention time of each nitrosamine the mass adjustment was tuned to the mass of the next nitrosamine. This combination allowed not only an unambiguous identification of the nitrosamines but also their direct quantitative determination. The products investigated were cooked ham, fermented sausage, raw bacon, mildly fried bacon, fried minced mean and smoked meat. Only one nitrosamine, NDEA, was sometimes found to be present in relatively large amounts. It occurred in two of the bacon samples; the concentration increased during mild frying from 4 and 13 mug/kg to 16 and 43 mug/kg, respectively. It was also present in two of the smoked meat samples in amounts of 7 and 91 mug/kg, respectively. Its identity was further confirmed on a second and third capillary column also coupled to the MS, and by direct introduction of the extracts into the MS at a resolution of 15 000. A silicon compound with practically the same retention time and mass as NDMA, which originates from the antifoam agents used as shown by other investigators, was found in the extracts in amounts corresponding to abuot 2 mug/kg of product. Nevertheless, seven samples were found positively to contain NDMA in amounts of 2-6 mug/kg. NMEA, NMPA, NMBA and NDPA could not be detected in any of the samples, nor could NPip or NPy. That no NPy (i.e., less than 50 mug/kg) was found in the fried bacon samples may be due to the mild frying method used. The use only of capillary GC with a nitrogen-selective detector, without further sample clean up, would have led to many false-positive results due to the presence of other nitrogen-containing compounds.

摘要

对六种腌制肉制品各五个样本进行了八种挥发性亚硝胺的检测分析。采用在pH 8 - 9条件下的联合水蒸气蒸馏 - 萃取步骤以及浓缩步骤来制备提取物。这些提取物无需进一步净化处理,直接使用分辨率为4000的毛细管气相色谱 - 高分辨质谱联用系统进行分析。质谱仪采用固定质量模式,但在每种亚硝胺的保留时间之后,将质量调整到下一种亚硝胺的质量。这种组合不仅能够明确鉴定亚硝胺,还能直接对其进行定量测定。所研究的产品有熟火腿、发酵香肠、生培根、微煎培根、煎肉末和烟熏肉。仅有时发现一种亚硝胺,即N - 二乙基亚硝胺(NDEA)含量相对较高。它存在于两个培根样本中;在微煎过程中,其浓度分别从4μg/kg和13μg/kg增加到16μg/kg和43μg/kg。它也存在于两个烟熏肉样本中,含量分别为7μg/kg和91μg/kg。通过与质谱联用的第二根和第三根毛细管柱,并将提取物以15000的分辨率直接引入质谱仪,进一步确认了其身份。在提取物中发现一种硅化合物,其保留时间和质量与N - 二甲基亚硝胺(NDMA)几乎相同,正如其他研究者所表明的,它源自所用的消泡剂,其含量相当于约2μg/kg的产品。然而,发现有七个样本确实含有含量为2 - 6μg/kg的NDMA。在任何样本中均未检测到N - 甲基乙基亚硝胺(NMEA)、N - 甲基丙基亚硝胺(NMPA)、N - 甲基苄基亚硝胺(NMBA)和N - 亚硝基哌啶(NDPA),也未检测到N - 亚硝基吡咯烷(NPip)或N - 亚硝基吡咯(NPy)。在微煎培根样本中未发现NPy(即含量低于50μg/kg)可能是由于所采用的微煎方法。仅使用带有氮选择性检测器的毛细管气相色谱,而不进行进一步的样品净化处理,由于存在其他含氮化合物,会导致许多假阳性结果。

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