質(zhì)譜的講義1ppt課件

1、第四節(jié)、串聯(lián)質(zhì)譜運用一、碰撞誘導(dǎo)裂解CAD二、源內(nèi)CAD三、IRMPD和ECD一、碰撞誘導(dǎo)裂解CADAPI 4000 LC/MS/MSLinearVarian 1200 GC/MS/MS180o二、源內(nèi)CAD三、IRMPD和ECDInfrared Multiphoton Dissociation: IRMPD Electron Capture Dissociation: ECD MagnetESI sourcecapillaryionguidecellDifferential pumping stagesCO2 - LaserHPLCfast MS/MS coupled to HPLCInfr

2、ared Multiphoton Dissociation (IRMPD)Hot topic at this years ASMS !NNON HSOHSOONHNSOOrN H2ONOsHONNFNNNFFOOOOOOHHOOOOOOO m = 1.1 ppm m = 0 ppm m = 0 ppm m = 0.9 ppm m = 1.4 ppm m = 0.6 ppm236s145613465SORI-CADMS/MS TICIRMPD MS/MS TIC2Infrared Multiphoton Dissociation (IRMPD)Applications for IRMPDMS/M

3、S with HPLCNo need for pulsed gas, faster MS/MS experimentHigh throughput proteomicsRapid acquisition of MS/MS fragment information from peptides with accurate massSingly charged peptides from MALDI are often difficult to fragment by CID in FTMSGeneral Structural Characterization of Natural Products

4、, Drug Candidates, Oligonucleotides, Other UnknownsIRMPD gives more extensive fragmentation with many compound classes150200250300350400450500550600650m/zSORI-CADIRMPDConversion efficiency: 98%time to acquire single scan: 3sConversion efficiency: 67%time to acquire single scan: 1sMH+MH+Sample: reser

5、pineMass spec.: 3.0 T FTMSCompare IRMPD with “normal SORI CID - Ions Present2.02.53.03.5min1234562.02.53.03.5min123456IRMPD TICAcquisition rate = 1 HzCAD TICAcquisition rate = 0.3 HzCompare IRMPD with “normal SORI CID - Duty Cycle200300400500600700800900100011001200m/zMALDI FTMS of LHRHIRMPD MS/MS o

6、f the MH+IR laser: 200ms 50% powerb2y6y5y4y3b6b7b8b4b3b5H2Ob4H2OMH+MH+-H2OIRMPD Data Examples (2)ECD 9 eV M+nHn+ + e- M+nH(n+1)+ + 2e- M-nHn- + e- M-nH(n-1)- + 2e- M-nHn- + e- (M-nH(n-1)-)*transient + 2e- fragments + e- More energetic electrons may cause double ionization and Coulombic explosion.400600800100012001400m/zRemaining +2 Parent Ion After ECDc10c6c7c8c9c5C Sequence Ions in the ECD Spectrum of Substance P69830040050060070080090010001100120013001400m/z2435170019002100230025002700m/zc25C21c22c23