液相色谱_质谱联用的原理和应用.pptVIP

(4)中性丢失扫描 中性丢失扫描分析可用来鉴定和确认类型已知的化合物，例如新生儿遗传疾病筛查中某些检测项目。也可以帮助进行未知物结构判断，例如有中性丢失18Da的意味着-H2O，28-CO，30-HCOH，32-CH3OH，44-CO2等等。 各种扫描方式的原理解释： Q1 Full Scan (Start – Stop)(Q1全扫描) Q1 always used as single MS analyzer Used primarily for ident. of precursor ion SIM - Selected Ion Monitoring(选择离子监测) Used to optimize analyzer for specific ions SIM used for quantitative analyses Q1 SIM used to “optimize” precursor ion Maximize signal in preparation for MS/MS Product Ion Scan(子离子扫描) After identification, the precursor ion is sent into the collision cell and fragmented by CID Q1 is fixed, Q3 sweeps a given mass range Used for structural elucidation First step to developing quantitative method m3+ scanned m1+ fixed Example of Product Ion Spectrum Ephedrine, MW = 165 Precursor Ion Scan(母离子扫描) Q1 sweeps a given mass range, Q3 is fixed Used to determine the “origin” of particular product ion(s) created in the collision cell Frequently used for drug metabolite identification (common product ion observed in the metabolites) m3+ fixed m1+ scanned Example of Precursor Ion Spectrum 600 900 1200 1500 1800 m/z, amu 5 8 7 . 5 7 4 5 . 6 8 9 5 . 6 8 0 2 . 4 6 3 3 . 4 520.3 1105.0 1704.4 600 900 1200 1500 1800 m/z, amu 3.0e6 6.0e6 9.0e6 1.2e7 Intensity, cps 6 0 8 . 3 520.3 802.4 600 900 1200 1500 1800 m/z, amu 3.0e4 6.0e4 9.0e4 Intensity, cps Precursors of 86 (Ile/Leu) Q1 Scan 745.6 Fragmentation When an Ion fragments the following formulas apply: Positive mode (Parent)+ ? A+ + B Neutral Negative mode (Parent)- ? A- + B Neutral Neutral Loss Scan(中性丢失扫描) Q1 Q3 both scan a given mass range but with a constant difference between ranges scanned Spectrum indicates which ions lose a neutral species equal to Q1 - Q3 difference Complement to Precursor Ion Scan Neutral “gain” indicates a multiply charged precursor ion was fragmented Δm m1+ scanned m3+ scanned Multiple Reaction Monitoring (MRM) Precursor ion fixed Product ion fixed Fragmentation (CAD) Many precursor to product ion pairs can be