对邻苯二甲酸酯使用的限制导致广泛使用替代增塑剂(AP),如有机磷酸酯,己二酸,柠檬酸盐还有癸二酸.然而,因为增塑剂通过不稳定的非共价键与塑料制品中的聚合物结合,他们可以很容易地从这些产品中迁移出来,造成环境污染。特别是,他们从食品包装中迁移出来,容器,和其他食品接触材料和进入食品引起了极大的关注。毒理学研究表明,AP含有可能影响内分泌功能并引起神经毒性的潜在有毒物质,遗传毒性,和其他不良影响。因此,他们对食物的潜在风险不可低估。芝麻油是日常烹饪的必需品。近年来的风险监测结果表明,芝麻油中的邻苯二甲酸酯含量通常超过标准限值。然而,芝麻油中AP的潜在风险尚未报告.一些常见的AP检测方法包括气相色谱-质谱法,气相色谱-三重四极杆质谱,和液相色谱-三重四极杆质谱。不幸的是,这些方法使用低分辨率质谱,并且受到分辨率的限制,扫描速率,和分析模式。气相色谱-四极杆飞行时间质谱(GC-Q-TOF/MS)具有分辨率高,灵敏度,分析速度。在全扫描模式下,GC-Q-TOF/MS能够准确采集复杂底物中低含量目标化合物的全谱质量数,从而实现高效的筛选和定量分析。在农药残留和污染物的痕量分析中表现出突出的优势。此外,它具有很强的定性和高筛选能力。个人化合物数据库和文库(PCDL)的建立解决了可以测量的化合物数量的限制,并且能够在不使用标准产品的情况下快速鉴定靶标。此外,增加同步筛选的目标数量可以对新目标进行回顾性分析。在这项研究中,建立了一种基于GC-Q-TOF/MS的芝麻油中54种AP的测定方法。将样品用乙腈萃取并使用PSA/二氧化硅固相萃取柱纯化。然后通过GC-Q-TOF/MS以全扫描模式收集样品的质谱信息,使用已建立的高分辨率质谱数据库搜索54个AP,以同时实现广谱筛选,定性鉴定,和多个目标的定量分析。比较了不同提取溶剂和纯化方法对样品提取和纯化的影响。通过优化GC分离条件,提高了筛选结果的准确性,质量提取窗口,保留时间偏差,和其他筛选参数。54种AP的筛选检测限(SDLs)范围为0.01至0.02mg/kg;具体而言,41个化合物的SDL为0.01mg/kg,13个化合物的SDL为0.02mg/kg。定量限范围为0.02-0.04mg/kg。在最佳条件下,使用该方法快速筛选了80个芝麻油样品。从80个芝麻油样品中鉴定出5个AP,并使用基质匹配的外标法进行定量分析。该定量方法的结果表明,五种AP在0.01-0.2mg/L范围内具有良好的线性关系,所有相关系数均大于0.99。用空白芝麻油样品进行标准回收率试验,验证了方法的准确性和精密度。在0.04,0.08,0.2mg/kg的三个标准水平下,五个AP的回收率从71.3%到97.8%不等,相对标准偏差(RSD)范围为0.4%至6.1%(n=6)。所开发的方法是快速的,准确,敏感,并具有高吞吐量。因此,它可以实现高效的筛选,定性鉴定,以及对芝麻油中54种AP的定量分析,为监测食品中的其他污染物提供了潜在的解决方案。
Restrictions on the use of phthalates have led to the wide use of alternative plasticizers (APs) such as organophosphate, adipate, citrate, and sebacate. However, because plasticizers combine with polymers in plastic products via unstable noncovalent bonds, they can easily migrate out of these products, causing environmental pollution. In particular, their migration out of food packaging, containers, and other food-contact materials and into food has raised great concerns. Toxicological studies have shown that APs contain potentially toxic substances that can affect endocrine functions and cause neurotoxicity, genotoxicity, and other adverse effects. Thus, their potential risks to food should not be underestimated. Sesame oil is a necessity in daily cooking. The results of risk monitoring in recent years have indicated that sesame oil often contains phthalates in excess of the standard limits. However, the potential risks of APs in sesame oil have not yet been reported. Some common detection methods for APs include gas chromatography-mass spectrometry, gas chromatography-triple quadrupole mass spectrometry, and liquid chromatography-triple quadrupole mass spectrometry. Unfortunately, these methods use low-resolution mass spectrometry and are limited by the resolution, scan rate, and analysis mode. Gas chromatography-quadrupole time-of-flight mass spectrometry (GC-Q-TOF/MS) has the advantages of high resolution, sensitivity, and analysis speed. In full-scan mode, GC-Q-TOF/MS can accurately collect the full-spectrum mass number of target compounds with low content levels in complex substrates, thereby realizing efficient screening and quantitative analysis. It shows outstanding advantages in the trace analysis of pesticide residues and pollutants. Furthermore, it features strong qualitative and high screening abilities. Establishment of a personal compound database and library (PCDL) addresses limitations in the number of compounds that can be measured and enables the rapid identification of targets without the use of standard products. In addition, increasing the number of targets for synchronous screening enables the retrospective analysis of new targets. In this study, a method based on GC-Q-TOF/MS was developed for the determination of 54 APs in sesame oil. The samples were extracted with acetonitrile and purified using a PSA/silica solid-phase extraction column. The mass-spectral information of the samples was then collected by GC-Q-TOF/MS in full-scan mode, and the 54 APs were searched using an established high-resolution mass-spectrum database to simultaneously achieve the broad-spectrum screening, qualitative identification, and quantitative analysis of multiple targets. The effects of different extraction solvents and purification methods on sample extraction and purification were compared. The accuracy of the screening results was improved by optimizing the GC-separation conditions, quality-extraction window, retention-time deviation, and other screening parameters. The screening detection limits (SDLs) of the 54 APs ranged from 0.01 to 0.02 mg/kg; specifically, the SDL of 41 compounds was 0.01 mg/kg and that of 13 compounds were 0.02 mg/kg. The limits of quantification were in the range of 0.02-0.04 mg/kg. A total of 80 sesame-oil samples were rapidly screened using this method under optimal conditions. Five APs were identified from the 80 sesame-oil samples and quantitatively analyzed using the matrix-matched external-standard method. The results of this quantitative methodology showed that the five APs had good linear relationships in the range of 0.01-0.2 mg/L, with all correlation coefficients greater than 0.99. The accuracy and precision of the method were verified using a standard recovery test with blank sesame-oil samples. Under the three standard levels of 0.04, 0.08, and 0.2 mg/kg, the recoveries of the five APs ranged from 71.3% to 97.8%, and the relative standard deviations (RSDs) ranged from 0.4% to 6.1%(n=6). The developed method is fast, accurate, sensitive, and has high throughput. Thus, it can realize the efficient screening, qualitative identification, and quantitative analysis of the 54 APs in sesame oil and provides a potential solution for the monitoring of other contaminants in food.