第八章 质谱法.pptVIP

第八章 质谱法 质谱仪的一般结构 通常的离子化方法 电子轰击离子化 EI 化学电离离子化 CI 正化学电离离子化 PCI 负化学电离离子化 NCI 大气压力离子化 API 电喷雾离子化 ESI 大气压化学电离离子化 APCI 离子化方式 离子化和碎片 质量分析器 四极杆 ~80% 的台式质谱仪 (~3000/年) HP, PE, TMQ, Shimadzu 离子阱 ~20%的台式质谱仪 (~700/年) Varian, TMQ 飞行时间 (ToF) 目前用户较少 (50-60/年) Leco, Micromass, TMQ 扇形磁场 通常不是台式仪器 四极质量分析器 离子阱 原理与四极杆的非常相似，离子被存储在RF和DC场中，扫描场逐出精确m/z的离子。 飞行时间质量分析器 扇形磁场质量分析器 Electron Impact Ionization (EI) Electron Impact Ionization (EI) Thermal electrons (ca. 70 eV) hit molecules and ionize them. Ample fragment ions = ample structural information Finger print Positive Chemical Ionization (PCI) Positive Chemical Ionization (PCI) Reagent gas molecules are ionized first. Sample molecules are ionized mainly by 損roton transfer? Quasi molecular ions easily produced useful for molecular weight verification. Comparison of EI and PCI Negative Chemical Ionization (NCI) Negative ion formation by electron capture associative resonance capture dissociative resonance capture ion-pair production Negative ion formation by ion-molecule reactions proton transfer charge exchange nucleophilic addition nucleophilic displacement Negative ion formation by electron capture (associative resonance capture) MX + e- (~0 eV) MX-. 质谱图的样子? 质谱图... 断裂机理 2. α断裂 3. i 断裂 4. 逆 Diels-Alder 反应 5. Mclafferty 重排 Configuration of GCMS Ion Source Design- Increased ionization efficacy - Ion Lens- High ion introduction to mass analyzer - Quadrupole Rod - Minimize losses in transit to the Quadrupole - rotary pump turbo molecular pump (151 L/sec) Turbo Molecular Pump Air cooled and oil free Turbomolecular Pump (TMP) with lubricant impregnated ceramic bearings is maintenance free for up to 25,000 hours. Provides high quality vacuum in less than 5 mins. Ion detection GCMS-QP5050A NCI sensitivity 200fg Hexachlorbenzene OFN (octafluoronaphthalene) NCI scan mode GCMS-QP5050A NCI pesticides date 3 Comparison between EI and NCI extract from cabbage (pest