基質輔助鐳射解吸電離飛行時間質譜儀是一種重要的儀器被用來對生物樣品做結構分析，通過諸如源後裂解和碰撞誘導裂解兩種方式實現。然而同碰撞誘導裂解比較，源後裂解具有較低的裂解效率。 / 本課題的目的就是提升我們原有的基質輔助鐳射解吸電離飛行時間質譜儀在結構分析方面的能力。對儀器的改造包括(a)將原有的兩級反射器替換為曲線場反射器(b)安裝一個高壓浮地的碰撞室(c)安裝一個同軸的粒子探測器。曲線場反射器和同軸粒子探測器可以實現母離子跟碎片離子的同時監測，碰撞室可以實現母離子的碰撞裂解。在儀器的性能評估實驗中，母離子和所有的源後裂解的碎片離子同時被探測器記錄。在碰撞誘導裂解實驗中，母離子與碰撞氣體分子發生高能碰撞後大多生成了小質量數的碎片離子，實驗中還發現將碰撞室浮地後，碎片離子的質量解析度和信號強度都有了顯著改進。 / 通過比較曲線場反射器和兩級反射器的性能，我們提出了一種雜化反射器設計，這種反射器在第二片和最後一片電極片上都有可調電壓。第二片和最後一片電極片之間的電場遵循曲線場分佈。這種反射器有兩種操作模式：MS 和MS/MS 模式。類比實驗和分析計算的結果顯示在MS 模式裡，通過調整兩個可調電壓u1 和u2，不同質量離子在反射器裡的反轉點可以被設置在一個最優的位置從而得到最優的質量解析度。在MS/MS 模式裡，一個全質量範圍的譜圖和若干個較窄質量範圍的譜圖可以通過改變兩個可調電壓獲得，其中較窄質量範圍的譜圖具有更高的質量解析度用來分析某個質量範圍內的碎片離子的細節資訊。這些結果表明這種雜化反射器兼具曲線場反射器和兩級反射器的優點。 / Matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (MALDI-TOFMS) is an important instrument for structural analysis of biological samples through such as post-source-decay (PSD) or collision-induced dissociation (CID) analysis. However, PSD analysis is a relatively low-efficiency method compared with CID analysis. / This project aims to upgrade the TOF instrument to a high performance TOF/TOF instrument. The modification involves (a) the replacement of the two-stage reflectron with a home-built curved-field reflectron (CFR); (b) the fabrication of a high voltage floated collision cell; and (c) the installation of a coaxial microchannel plate (MCP) detector. The CFR and coaxial detector allow simultaneous reflection of precursor ions and all fragment ions. The collision cell provides an effective means of ion activation (CID). In the performance test, precursor ions with almost all the fragment ions were recorded simultaneously in PSD analysis. In CID experiments, the precursor ions were found to undergo fragmentation due to high energy collision with the target gas and by floating the collision cell to high potential (several kV), the mass resolution and signal intensities of low mass fragment ions were improved substantially. / By comparing the performance of curved-field and two-stage reflectron, a hybrid reflectron was proposed, which has adjustable high voltages U1 and U2 on the second and last electrode element, respectively. The electrostatic potential between the second and last electrode element follows curved-field distribution. There are two operation modes for this reflectron: MS and MS/MS mode. Results from theoretical investigation and experiments showed that in MS mode, optimal energy compensation could be achieved through tuning the values of U1 and U2; in MS/MS mode, a full mass scale spectrum as well as spectra segments with high mass resolution within a narrower mass range could be obtained by setting U1 and U2 with appropriate values. These results indicated that the hybrid reflectron had the advantages both of curved-field reflectron and two-stage reflectron. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Li, Gang. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 131-137). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / TABLE OF CONTENTS / LIST OF FIGURES / LIST OF TABLES / ABBREVIATIONS / Chapter Chapter One --- Background Introduction / Chapter 1.1 --- Matrix-assisted laser desorption/ionization (MALDI) --- p.2 / Chapter 1.1.1 --- Laser desorption --- p.2 / Chapter 1.1.2 --- Matrix-assisted laser desorption/Ionization --- p.3 / Chapter 1.2 --- Time-of-flight mass spectrometry --- p.8 / Chapter 1.2.1 --- Linear time-of-flight mass spectrometer --- p.8 / Chapter 1.2.2 --- Reflectron time-of-flight mass spectrometer --- p.9 / Chapter 1.2.2.1 --- Linear-field reflectron --- p.11 / Chapter 1.2.2.2 --- Nonlinear-field reflectron --- p.14 / Chapter 1.3 --- Structural analysis using time-of-flight mass spectrometer --- p.17 / Chapter 1.3.1 --- Post-source decay (PSD) analysis --- p.17 / Chapter 1.3.2 --- Collision-induced dissociation (CID) analysis --- p.20 / Chapter 1.4 --- Project introduction --- p.26 / Chapter Chapter Two --- Instrumentation / Chapter 2.1 --- Instrumentation --- p.28 / Chapter 2.1.1 --- Laser system --- p.28 / Chapter 2.1.2 --- Flight tube and vacuum system --- p.28 / Chapter 2.1.3 --- Ion source --- p.32 / Chapter 2.1.4 --- Deflector and time ion selector --- p.36 / Chapter 2.1.5 --- Two-stage gridless reflectron --- p.39 / Chapter 2.1.6 --- Detectors, digitizer and computer system --- p.42 / Chapter Chapter Three --- Fabrication of the Modified Tandem Time-of-flight Mass Spectrometer / Chapter 3.1 --- Introduction --- p.48 / Chapter 3.2 --- Implementation of a coaxial MCP detector --- p.51 / Chapter 3.3 --- Design, fabrication and implementation of a curved-field reflectron --- p.57 / Chapter 3.4 --- Design, fabrication and implementation of a floated collision cell --- p.61 / Chapter 3.5 --- Summary --- p.66 / Chapter Chapter Four --- Performance Evaluation of the Modified Instrument / Chapter 4.1 --- MS analysis by using the modified instrument --- p.68 / Chapter 4.2 --- MS/MS analysis by using the modified instrument --- p.73 / Chapter 4.2.1 --- Post-source-decay (PSD) analysis --- p.73 / Chapter 4.2.2 --- Collision-induced-dissociation analysis --- p.75 / Chapter 4.3 --- Mass calibration for the modified instrument --- p.84 / Chapter Chapter Five --- A Design of Hybrid Reflectron / Chapter 5.1 --- Introduction of the hybrid reflectron --- p.90 / Chapter 5.2 --- Characterization of the hybrid reflectron --- p.93 / Chapter 5.2.1 --- Calculations using analytical equations --- p.93 / Chapter 5.2.1.1 --- Analytical calculations for MS operation mode --- p.93 / Chapter 5.2.1.2 --- Analytical calculations for MS/MS operation mode --- p.99 / Chapter 5.2.2 --- Simulation experiments by SIMION --- p.106 / Chapter 5.3 --- Calibration of the instrument using the hybrid reflectron --- p.112 / Chapter 5.4 --- Summary --- p.115 / Chapter Chapter Six --- Fabrication and Performance Evaluation of the Hybrid Reflectron / Chapter 6.1 --- Hardware fabrication of the hybrid reflectron --- p.117 / Chapter 6.2 --- Performance evaluation of the hybrid reflectron --- p.121 / Chapter Chapter Seven --- Concluding Remarks --- p.128 / References --- p.131 / Appendix --- p.138 / Chapter Appendix 1 --- Mathematica program for analytical calculations / Chapter Appendix 2 --- Geometry file used in SIMION simulation experiment / Chapter Appendix 3 --- User program for controlling reflectron high voltage
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_328027 |
| Date | January 2012 |
| Contributors | Li, Gang, Chinese University of Hong Kong Graduate School. Division of Chemistry. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, bibliography |
| Format | electronic resource, electronic resource, remote, 1 online resource ([10], 152 leaves) : ill. (chiefly col.) |
| Rights | Use of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
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