全二维气相色谱-飞行时间质谱测定PBAT生物降解膜中挥发性有机物  

Determination of Volatile Organic Compounds in PBAT Biodegradable Films by Headspace Solid-phase Microextraction Combined with GC×GC-TOF MS

作　　者：崔欢 高维常 刘艳霞 李洪勋 周淑平 陈文生[1] 蔡凯 CUI Huan;GAO Wei-chang;LIU Yan-xia;LI Hong-xun;ZHOU Shu-ping;CHEN Wen-sheng;CAI Kai(Guizhou Provincial Key Laboratory for Information Systems of Mountainous Areas and Protection of Ecological Environment,Guizhou Normal University,Guiyang 550001,China;Guizhou Academy of Tobacco Science,Guiyang 550081,China)

机构地区：[1]贵州师范大学贵州省山地环境信息系统与生态环境保护重点实验室,贵州贵阳550001 [2]贵州省烟草科学研究院,贵州贵阳550081

出　　处：《分析测试学报》2021年第7期1004-1010,共7页Journal of Instrumental Analysis

基　　金：贵州省科学技术基金资助项目(20191212,20182335);贵州省烟草专卖局项目(201910)。

摘　　要：采用顶空固相微萃取(HS-SPME)结合全二维气相色谱-飞行时间质谱技术(GC×GC-TOF MS)对聚己二酸对苯二甲酸丁二酯(PBAT)生物降解膜中主要挥发性有机物(VOCs)进行分析测定,并考察了萃取纤维头类型、平衡温度、平衡时间、萃取时间对HS-SPME在生物降解膜中VOCs测定的影响。结果显示:以聚二甲基硅氧烷-二乙烯基苯-碳分子筛羧乙基(PDMS-DVB-CAR)为萃取头、80℃下分别平衡与萃取目标物10 min与40 min,在进样口260℃条件下解析3 min后进GC×GC-TOF MS分析,采用基质谱数据库与结构谱图等定性,内标法定量,生物降解膜中共检出55种VOCs,按结构可分为苯系物、萘、醛酮、醇、酯、茚、胺、酚、其它类共9类。相比常规一维气相色谱,全二维气相色谱可有效分离生物降解膜中的同系物、异构体及干扰物质,获得准确的定性结果。方法的日内和日间相对标准偏差(RSD)均不高于19%,表现出较好的稳定性和可重复性。对不同厂家(A、B、C、D)PBAT生物降解膜中的55种VOCs进行检测并多元统计分析,主成分分析结果显示,PBAT A与PBAT B样品重叠,VOCs差异较小,PBAT A+B、PBAT C与PBAT D有明显差异,VOCs差异较大,表明同类型不同来源的生物降解膜中具有不同的物质组成。热图分析显示,PBAT D中的苯系物与PBAT A+B中的萘、胺类、酚类化合物含量较高,而PBAT C中的VOCs普遍偏低。由此表明建立的HS-SPME结合GC×GC-TOF MS检测方法具有准确可靠、简单、快速等优点,对PBAT生物降解膜的安全评价及使用具有一定的参考价值。A method suitable for qualitative and quantitative analysis was established to determine the main volatile organic compounds(VOCs)in poly(butylene adipate terephthalate)(PBAT)biodegradable films by headspace-solid-phase microextraction(HS-SPME)combined with comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry(GC×GC-TOF MS).Effects of type of SPME fiber,equilibrium temperature,equilibrium time and extraction time on extraction efficiencies for VOCs in biodegradable films were investigated.The optimal SPME extraction conditions were as follows:polydimethylsiloxane-divinylbenzene-carboxen(PDMS-DVB-CAR)fiber was at 80℃extraction temperature for equilibrium time of 10 min and extraction time of 40 min.Then the fiber was introduced into the GC×GC-TOF MS injector port and the extract was desorbed at 260℃for 3 min.The VOCs were identified using standard mass spectrum databases and structure spectra and quantified by internal standard method.Results indicated that 55 VOCs in the biodegradable film were identified.Compared with one-dimensional GC-MS,GC×GC-TOF MS can effectively separate homologues,isomers,and interfering compounds,and then obtain more accurate quantitative results.The identified compounds can be divided into 9 types according to the compound structure,including:benzenes,naphthalenes,aldehydes and ketones,alcohols,esters,indenes,amines,phenols,others,etc.The intra-day and inter-day precision are both no more than 19%with good repeatability and reproducibility.The 55 VOCs in 4 kinds(A,B,C,D)of PBAT biodegradable films from different manufacturers were analyzed with multivariate statistical analysis.The principal component analysis(PC A)showed that PBAT A+B,PBAT C and PBAT D are obviously different,while PBAT A and PBAT B samples overlap.The PBAT biodegradable films from different manufacturers can be distinguished with VOCs composition,and each biodegradable film has a characteristic difference,The heatmap analysis shows the higher benzene homologues for PBAT D and naphtha

关 键 词：PBAT生物降解膜 顶空固相微萃取 全二维气相色谱-飞行时间质谱 挥发性有机物 

分 类 号：O657.7[理学—分析化学]