基于超临界流体色谱-串联质谱法同时测定乳液中α,β-不饱和醛  

Simultaneous Determination ofα,β-Unsaturated Aldehydes in Emulsion Using Supercritical Fluid Chromatography-Tandem Mass Spectrometry

作　　者：王曙 魏世肖 张浩[1] 孙尚德[1] 毕艳兰[1] WANG Shu;WEI Shixiao;ZHANG Hao;SUN Shangde;BI Yanlan(College of Food Science and Engineering,Henan University of Technology,Zhengzhou 450001,China)

机构地区：[1]河南工业大学粮油食品学院,河南郑州450001

出　　处：《食品科学》2025年第9期303-313,共11页Food Science

基　　金：国家自然科学基金青年科学基金项目(32202198);河南省科技研发计划联合基金项目(242103810086);郑州市科技局自然科学项目(22ZZRDZX23)。

摘　　要：为有效提高乳液中α,β-不饱和醛的风险检测水平,本研究采用超临界流体色谱-串联质谱(supercritical fluid chromatography-tandem mass spectrometry,SFC-MS/MS),建立高效、灵敏的同时测定乳液中8种α,β-不饱和醛的检测方法。通过对SFC-MS/MS参数和前处理条件进行优化,结果表明,以超临界CO_(2)流体和乙腈作为流动相,在电喷雾离子源负离子模式下,4 min内便可实现对8种α,β-不饱和醛的同时检测,且α,β-不饱和醛在各自样品浓度范围内均呈现良好的线性关系,定量限均低于1.8μg/kg,加标回收率为85.8%~106.7%,测定准确度相对标准偏差均低于7.86%。优化后的前处理条件为2,4-二硝基苯肼添加量1.25 mg、衍生化时间30 min、乙腈提取4次,二氯甲烷复提3次。此外,利用建立的方法评价了3种多酚型抗氧化剂——水溶性没食子酸、水油两亲型没食子酸丙酯以及水油不溶的槲皮素对亚麻籽油水包油乳液贮藏过程中α,β-不饱和醛的减控作用,发现乳液贮藏过程中α,β-不饱和醛快速积累,主要为丙二醛、4-羟基-2-己烯醛和4-羟基-2-壬烯醛,且3种抗氧化剂对α,β-不饱和醛具有显著减控作用,效果最强的为没食子酸丙酯。本方法操作简单、分析高效、环境友好,可用于对乳液食品体系加工、贮藏及使用过程中产生的α,β-不饱和醛进行灵敏、准确检测。In order to effectively improve the detection ofα,β-unsaturated aldehydes in emulsion,this study established an efficient and sensitive detection method using supercritical fluid chromatography-tandem mass spectrometry(SFC-MS/MS).Sample pretreatment conditions and SFC-MS/MS parameters were optimized.It was found that the simultaneous detection of eightα,β-unsaturated aldehydes was achieved within 4 minutes using a mobile phase composed of supercritical CO_(2) fluid and acetonitrile under the negative ionization mode.Theα,β-unsaturated aldehydes showed good linearity over their respective concentration ranges,limits of quantification(LOQ)lower than 1.8μg/kg and spiked recoveries between 85.8%and 106.7%.The relative standard deviations(RSD)of accuracy were lower than 7.86%.The optimized pretreatment conditions were as follows:1.25 mg of 2,4-dinitrophenylhydrazine,derivatization time of 30 minutes,four cycles of extraction with acetonitrile,and three cycles of re-extraction with dichloromethane.Furthermore,the established method was used to evaluate the effects of three polyphenolic antioxidants:water-soluble gallic acid,water-oil amphipathic propyl gallate and water-and oil-insoluble quercetin on reducing the eightα,β-unsaturated aldehydes in linseed oil-in-water emulsion during storage.The results showed thatα,β-unsaturated aldehydes accumulated rapidly during the storage of the emulsion,mainly malondialdehyde,4-hydroxy-2-hexenal and 4-hydroxy-2-nonenal,while all three antioxidants significantly mitigated the accumulation ofα,β-unsaturated aldehydes,with propyl gallate being the most effective.This method is a simple,efficient,environment-friendly,sensitive,and accurate one for the detection ofα,β-unsaturated aldehydes generated during the processing,storage,and use of emulsion-based foods.

关 键 词：超临界流体色谱-串联质谱 乳液 亚麻籽油 油脂氧化 α β-不饱和醛 

分 类 号：TS227[轻工技术与工程—粮食、油脂及植物蛋白工程]