质谱离子化技术和谱图解析方法研究

发布时间：2017-12-26 23:10

本文关键词：质谱离子化技术和谱图解析方法研究　出处：《南京大学》2017年硕士论文　论文类型：学位论文

【摘要】：质谱(Mass Spectrometry,MS)是一种将离子化后的物质按质荷比(m/z)不同来进行分离并检测的分析方法。由于质谱技术进行检测分析具有高灵敏度、高特异性、快捷高效、可以实现多种物质的同时检测等优点,已经广泛应用于食品、药品、爆炸物、生物样品以及各种其他材料的检测分析。在质谱技术的发展过程中,离子源的开发和海量质谱数据的合理利用一直是至关重要的问题。为了实现使用质谱技术进行更高灵敏度、更高抗干扰性能的检测以及复杂谱图数据的快速解析和利用,我们发展了一套新型的离子源技术和高效的谱图解析方法,具体如下:(1)在第一个工作中,我们在纳喷雾电离离子化(Nano-Electrospray Ionization,Nano-ESI)和解析电喷雾离子化(Desorption Electrospray Ionization,DESI)的基础上发展了名为纸锥解析电喷雾离子化(Paper Cone Desorption Electrospray Ionization,PC-DESI)的新型离子化方法。该方法使用纳喷雾电离作为解析电喷雾初始离子源,产生的溶剂带电液滴解析出环形包饶在喷雾针前端周围的纸锥上的样品,解析的样品离子经纸锥前端开口飞出,然后抵达质谱被检测。相比传统的DESI,该方法具有以下优点:①具有更高的灵敏度和信号强度。采用喷雾针-纸锥中轴-质谱入口共线的设计,提高样品的离子化效率,并且因纸锥的存在,使得离子化的样品不会四处飞散,提高了离子的传输效率。②样品离子化效率的提高,有效降低了溶剂中成分对质谱信号的干扰。③集合了纳喷雾电离的优点,使得PC-DESI无需雾化气的辅助即可完成检测,大大简化了装置,并且仅有若干微升的溶剂需求。(2)在第二个工作中,我们发展了一种名为定量主成分分析(Quantitative Principal Component Analysis,qPCA)的方法,来实现繁冗化学信号的自动解析并将其归属到各个成分,然后运用数学模型进行成分的定量计算。我们在论文中详细阐述了 qPCA的原理及其计算方法,并分别使用计算机产生的模拟谱图信号和实际实验获得的拉曼光谱(RS)、傅里叶变换红外光谱(FT-IR)、紫外可见光谱(UV-vis)、核磁共振(NMR)、质谱(MS)谱图数据对该方法进行了可靠性验证。验证结果表明,qPCA都达到了相当高的计算准确度,并且明显优于手动计算以及多元曲线分辨-交替最小二乘迭代法(Multivariate Curve Resolution-Alternate Least Square,MCR-ALS)。
[Abstract]:Mass spectrometry (Mass Spectrometry MS) is a kind of material after ionization mass to charge ratio (m/z) analysis method for separation and detection of different. The mass spectrometry technology has been widely applied in food, medicine, explosives, biological samples and other materials detection and analysis because of its high sensitivity, high specificity, fast and efficient, and the simultaneous detection of various substances. In the development of mass spectrometry, the development of ion sources and the rational utilization of mass mass spectrometry data have been a crucial issue. In order to achieve higher sensitivity, using mass spectrometry detection of higher anti-jamming performance and complex spectrum and rapid analytical map data and use, we developed a new ion source technology and efficient spectrum analysis methods, the details are as follows: (1) in the first work, we in the nano electrospray ionization (Nano-Electrospray Ionization Nano-ESI) analysis and electrospray ionization (Desorption Electrospray, Ionization, DESI) on the basis of the development of a cone of electrospray ionization (Paper Cone Desorption Electrospray Ionization, PC-DESI) new ionization method. The method uses nanofiltration ionization as the analytical electrospray initial ion source, and produces the solvent charged droplet to analyze the samples on the paper cone around the front end of the spray needle, and the analytical sample ions fly out through the front end of the cone cone, and then arrive at the mass spectrum to be detected. Compared with the traditional DESI, this method has the following advantages: (1) it has higher sensitivity and signal intensity. The design of the spray needle cone axis - MS entrance collinear, improve the ionization efficiency of the sample, and due to the paper cone, the ionized sample not scattered, improve the transmission efficiency of ions. The improvement of the efficiency of sample ionization effectively reduces the interference of the components in the solvent to the mass spectrum signal. Thirdly, the advantages of nano spray ionization are assembled, so that PC-DESI can complete the detection without atomization gas assistance, which greatly simplifies the device and only needs a few micro rise solvents. (2) in the second work, we developed a quantitative analysis of principal components (Quantitative Principal Component Analysis, qPCA) method to realize automatic analysis and its complicated chemical signals belonging to each component, and then use the mathematical model into the quantitative calculation. We elaborate the principle of qPCA and its calculation method in the paper, simulation and using computer generated spectra Raman spectra obtained signal and actual experiment (RS) and Fu Liye transform infrared spectroscopy (FT-IR), ultraviolet visible spectroscopy (UV-vis), nuclear magnetic resonance (NMR), mass spectrometry (MS) spectral data the method of reliability verification. The verification results show that qPCA achieves fairly high computation accuracy and is superior to manual computing and Multivariate Curve Resolution-Alternate Least Square (MCR-ALS).
【学位授予单位】：南京大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.63

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