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题名	新型质谱电离技术及其在四溴双酚 A衍生物分析中的应用研究
作者	田永
学位类别	博士后
答辩日期	2015-05
授予单位	中国科学院研究生院
授予地点	北京
导师	江桂斌 ; 史建波
关键词	电喷雾萃取电离 质谱 四溴双酚A 衍生物 质谱校正，Extractive electrospray ionization Mass spectrometry Tetrabromobisphenol A derivatives Mass spectrometry calibration
其他题名	A study on novel ionization methods of mass spectrometry and its application in analysis of Tetrabromobisphenol A derivatives
学位专业	环境科学与工程
中文摘要	质谱（MS）是通过制备、分离和检测气相离子实现待测组分鉴定和分析的常用分析技术。利用质谱进行分析和检测已经成为环境日常分析和研究的必要手段。近年来，新型常压电离方法的建立和发展，为质谱在环境分析中的应用提供了新的研究方向。开发和利用新型的电离技术，解决质谱在环境分析中存在的问题，提高环境分析的效率、灵敏度、准确度，已经成为质谱和环境科学研究的重要内容。本研究报告通过发展和利用电喷雾萃取电离技术、高效液相色谱（HPLC）柱后衍生技术建立了适于环境水样中四溴双酚A（TBBPA）衍生物的质谱分析方法，拓展了质谱在环境分析中的应用范围；通过利用电喷雾萃取电离技术进行质谱分析校正，进一步改善了质谱分析的准确度和可靠性。     本文首先介绍了质谱及新型电离技术的发展，阐述了电喷雾解析电离（DESI）、实时直接分析电离（DART）和电喷雾萃取电离（EESI）技术的原理，综述了新型常压电离技术在环境分析中的应用实例，分析了TBBPA 及其衍生物的研究现状。     利用电喷雾反应萃取电离技术发展了适用于难电离组分——TBBPA 衍生物的质谱分析方法，实现了工业废水中四溴双酚A 双烯丙醚（TBBPA-BAE）、四溴双酚A 双（2-羟乙基）醚（TBBPA-BHEE）、四溴双酚A 双缩水甘油醚（TBBPA-BGE）和四溴双酚S 双烯丙醚（TBBPS-BAE）的质谱分析。该电离过程通过利用电喷雾硝酸银溶液产生活性Ag+，Ag+与中性的TBBPA 衍生物雾滴在EESI 过程中发生碰撞、萃取、反应，最终形成TBBPA 衍生物与Ag+的加合离子（[M + Ag]+）。质谱碰撞诱导解离实验结果证实了TBBPA 衍生物[M + Ag]+的形成，证实了TBBPA 衍生物可通过EESI-MS 实现直接分析。本方法在最优条件下，对于TBBPA-BHEE、TBBPA-BGE、TBBPA-BAE 和TBBPS-BAE 的检出限为0.37、0.050、0.76 和4.6 μgL-1，线性范围上限达到1000 μg L-1（R2 ≥ 0.9919），对于四种衍生物测定的相对标 准偏差均小于7.8%（n = 9）。利用本方法可实现工业废水、河水和自来水中TBBPA 衍生物的快速分析检测。      利用Ag+柱后衍生电喷雾质谱（ESI-MS）技术建立了一种适于分析水样中的痕量TBBPA 衍生物的主产物，TBBPA-BHEE、 TBBPA-BGE、 TBBPA-BAE；和三种副产物，四溴双酚A 单（2-羟乙基）醚（TBBPA-MHEE）、四溴双酚A 单缩水甘油醚（TBBPA-MGE）和四溴双酚A 单烯丙醚（TBBPA-MAE）的分析方法。利用硝酸银作为柱后衍生试剂，Ag+可以在色谱分离后与TBBPA 衍生物形成[M +Ag]NO3 络合物，通过电喷雾可以得到[M + Ag]+离子，最后进入质谱实现TBBPA衍生物的检测。在最优条件下，6 种TBBPA 衍生物通过HPLC-ESI-MS 可在10 分钟内实现分离和分析。方法检出限在0.16 ~ 1.96 μg L-1 之间，线性范围上限达到200μg L-1 (R2 ≥ 0.9957)，7 次测定10 μg L-1 TBBPA 衍生物的相对标准偏差均小于7.7%。对于实际样品分析的加标回收率在81.3~114.9%之间，能够实现环境水样中痕量 TBBPA 衍生物的分析。     利用EESI 技术建立了实时质谱分析校正方法，实现了质谱分析质量分辨和信号强度的校正。研究通过电喷雾引入三种标准试剂（赖氨酸，Lys；脯氨酸，Pro；组氨酸，His），样品喷雾引入待测组分（甲硫氨酸，Met）进行质谱分析校正。实验结果证实，校正试剂与待测组分的信号强度（Pro-Met，Lys-Met 和His-Met）存在线性相关，皮尔逊相关系数分别为0.9231，0.9080 和 0.8804（P < 0.01）。可以通过最小二乘原理建立校准试剂和待测组分信号之间的线性关系，并且可以利用该线性关系校准待测组分信号。经过校正，10 μg L-1 Met 检测的信噪比由2.3 增加至4.3，标准曲线的线性决定系数（R2）由0.9758 增加至0.9980。低分辨质谱检测50分钟待测组分的质荷比与标准值比较的差异分布由0.037 ± 0.02 减小至-0.001 ± 0.02Da。高分辨质谱Orbitrap 检测28 分钟待测组分的质量误差由0.87ppm 减小至0.37ppm。应用于标准品(GBW(E)100062)和实际样品（鸡饲料）质谱分析结果表明， 本方法能够有效提高质谱检测准确度。
英文摘要	Mass spectrometry (MS) is a technique widely used for the identification of compounds, by producing, separating and detecting ions in the gas phase. It has been a necessary technique for the environmental researches and routing analyses. Because of the developments of ambient ionization methods, the mass spectrometry is enabled for new applications. The MS equipped with the novel ambient ionization method for better efficiency, sensitivity and accuracy has become an important research area of environmental analysis in recent years. In the present report, the developments and the applications of the ambient ionization methods for environmental analyses were reviewed in detail. Reactive extractive electrospray ionization (EESI) and post-column derivatization coupled with electrospray ionization (ESI) were developed for tetrabromobisphenol A derivatives identification in water samples, respectively. Moreover, the EESI was used for calibrating the accuracy and reliability of mass spectrometry in this report.     We introduced the developments of mass spectrometry and the novel ambient ionization techniques, elaborated the mechanisms of desorption electrospray ionization (DESI), direct analysis in real time (DART) and extractive electrospray ionization (EESI), reviewed the applications of novel ambient ionization methods for environmental analysis, and summarized the research background of TBBPA and its derivatives.     A novel analytical strategy based on reactive extractive electrospray ionizaion (EESI) tandem mass spectrometry for detection of tetrabromobisphenol A bis(2-hydroxyethyl ether) (TBBPA-BHEE), tetrabromobisphenol A bis(glycidyl ether) (TBBPA-BGE), tetrabromobisphenol A bis(allylether) (TBBPA-BAE), and tetrabromobisphenol S bis(allylether) (TBBPS-BAE) in industrial waste water samples was developed. Active silver cations (Ag+), generated by electrospraying a silver nitrate methanol solution (10 mg L-1), collides the neutral TBBPA derivatives molecules in the EESI source to form [M+Ag]+ complexes of the analytes under the ambient conditions. Upon collision-induced dissociation (CID), characteristic fragments of the [M+Ag]+ complexes were identified for confident and sensitive detection of the four TBBPA deriv detection (LODs) of TBBPA-BHEE, TBBPA-BGE, TBBPA-BAE and TBBPS-BAE were 0.37, 0.050, 0.76, and 4.6 μg L-1, respectively. The linear ranges extended to 1000 μg L-1 (R2 ≥ 0.9919), and the relative standard deviations (RSDs) were less than 7.8 % (n=9. TBBPA derivative manufacturing industrial waste water, river water and tap water samples were fast analyzed with the proposed method.     A sensitive silver ion post-column derivatization electrospray ionization mass spectrometry method was developed for the identification and quantitation of TBBPA derivatives in water samples. Six major TBBPA derivatives, including TBBPA-BHEE, TBBPA-BGE, TBBPA-BAE, tetrabromobisphenol A mono(2-hydroxyethyl) ether (TBBPA-MHEE), tetrabromobisphenol A mono(glycidyl) ether (TBBPA-MGE) and tetrabromobisphenol A mono(allyl) ether (TBBPA-MAE), were selected as the target compounds. By applying the silver cations (Ag+) as the post-column derivatization reagent, the TBBPA derivatives formed complexes ([M + Ag]NO3) online, which could be effectively electrosprayed to generate ionic clusters ([M + Ag]+) for sensitive mass analysis. Under the optimized conditions, the 6 TBBPA derivatives were separated and detected within 10 min. The limits of detection (LODs) were between 0.16 and 1.96 μg L-1, and the linear ranges extended to 200 μg L-1 (R2 ≥ 0.9957). The relative standard deviations (RSDs) were less than 7.7% for 10 μg L-1 of TBBPA derivatives (n=7). The proposed method was successfully applied in environmental water samples analysis. The spiked recoveries ranged from 81.3% to 114.9%, suggesting the accuracy and feasibility of the method.     A real time online calibration of mass shift and intensity alteration to improve the accuracy of measurements for identification and quantitation in trace mass spectrometric analysis was demonstrated using extractive electrospray ionization (EESI) mass spectrometry (MS). The signals of authentic compounds (e.g., Lysine (Lys), Proline (Pro) and Histidine (His)) spiked into the extractive solution for the EESI process were used as the references to calibrate the signal of analytes (e.g., Methionine (Met)) in the untreated sample solution. The analyte signal was synchronously recorded with the reference signals, showing the Pearson correlation coefficients between the Pro-Met, Lys-Met and His-Met of 0.9231, 0.9080 and 0.8804 (p < 0.01), respectively. Thus the analyte signals at a given recording time point was calibrated based on these correlations and the instant signal responding. The calibrated signal of Met at 10 μg L-1 was improved with a better signal-to-noise ratio (S/N from 2.3 to 4.3), a better linearity (R2 from 0.9758 to 0.9980) and a reduced relative standard deviation (RSD from 9.8% to 6.0%). The shift of mass-to-charge ratio of Met signal between the detected and theoretical values was decreased from 0.037 ± 0.02 to -0.001 ± 0.02 for 50 min detection using a linear ion trap mass analyzer. The maximum mass error was deducted from -0.87 to -0.34 ppm for 28 min detection using an orbitrap mass analyzer. This method has been validated using a certified standard amino acids solution (GBW(E)100062) and applied for quantitative detection of Met in chicken feed samples, showing that the method is useful to improve the accuracy of mass spectrometric analysis.
内容类型	学位论文
源URL	[http://ir.rcees.ac.cn/handle/311016/34376]
专题	生态环境研究中心_环境化学与生态毒理学国家重点实验室
推荐引用方式 GB/T 7714	田永. 新型质谱电离技术及其在四溴双酚 A衍生物分析中的应用研究[D]. 北京. 中国科学院研究生院. 2015.

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