Deconvolution Reporting Software 051409 - Agilent .MSD Deconvolution Reporting Software (MSD-DRS

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Transcript of Deconvolution Reporting Software 051409 - Agilent .MSD Deconvolution Reporting Software (MSD-DRS

  • MSD DeconvolutionReporting Software

    (MSD-DRS or DRS)(MSD-DRS or DRS)A tool to Aid in the Identification and Quantitationof Target Compoundsof Target Compounds

    Mike SzelewskiAgilent TechnologiesM 14 2009May 14, 2009

    20090514 e-Seminar

    Page 1

  • TICs of surface water extracts

    How many ypesticides are in these samples ?

    5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00

    5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00

    20090514 e-Seminar

    Page 2

    5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00

  • Seventeen (17) surface water samples

    CDFA* Agilent DRSAgilent DRS

    (N

    567 927

    CDFA* Agilent DRS (Original) (New Database)Targets Found (not counting 37 Same 37 Same 37(not counting

    ISTD)37 + 34 more +99 more

    False Positives 1 0 0

    Processing Time

    ~8 hrs (ChemStation

    Only)20 minutes 34 min

    *CDFA is the California Department of Food and Agriculture

    y)

    20090514 e-Seminar

    Page 3

    Data files courtesy of Dr. Mark Lee and Steve Siegel

  • DRS Report from 3 Integrated Processes

    Total ion chromatogram

    Targets are identified by comparison to locked R T s and 3 qualifier ion

    Deconvoluted Target spectra confirmed by AMDIS searched

    AMDIS deconvolutescomponent spectra and

    searches target MS database using locked RT as a qualifier

    Quant Results

    R.T.s and 3 qualifier ion ratios, then quantified using target ion area vsISTD cal table

    AMDIS, searched against NIST08 MS database

    Confirmed NIST08 hits

    g q

    Confirmed AMDIS hits

    AMDIS Quant Result

    Combined quantitative and qualitative HTML S t

    Quant Results Confirmed NIST08 hits

    20090514 e-Seminar

    Page 4

    Summary report

  • Report-Spinach Example 1CSpinach Report, results from 3 DRS processesNIST 08 Match and Hit number of the top 100 hits from 191,000+ compounds

    20090514 e-Seminar

    Page 5

    ISTD, used for targets amount Match against

    AMDIS library

    RT diff in secs vs expected locked RT

  • A t ti M t l D l ti dDRS is Based on Industry Standard AMDIS

    Automatic Mass spectral Deconvolution and Identification Software

    Developed to automatically detect chemicals in Developed to automatically detect chemicals in violation of Chemical Weapons Convention

    Identify compounds at low concentration levels in complex matrices

    Developed by National Institute of Standards and TechnologyTechnology

    Retention Time can be used as a qualifier, so RTL is a big advantage

    20090514 e-Seminar

    Page 6

  • A t ti M t l D l ti dTrue Deconvolution using AMDIS

    Automatic Mass spectral Deconvolution and Identification Software

    All spectra are deconvoluted not just those selected All spectra are deconvoluted, not just those selected by the user

    Identification is based on full spectral matching

    User does not have to pick ions

    More confidence in result using all ions

    Published algorithims, not proprietary

    Accepted for world-wide use

    20090514 e-Seminar

    Page 7

  • AMDIS Deconvolution Pulls Out Individual Components and their Spectra p p

    Deconvoluted components and spectra

    t iTIC

    Components and Mixed Spectra

    matrixTIC

    Component 1C t 2

    interference

    Component 2

    Component 3

    Deconvolution

    target

    20090514 e-Seminar

    Page 8

  • 17 280

    How Does Deconvolution Work?

    50

    170 0

    310

    75

    18516

    0 00

    Extracted Ion Ch t

    160 shapeChromatograms

    (EIC)

    Aft d

    50170

    p

    same shape and same retention time

    After de-skewing

    0280

    75 late retention time 185 shape & early retention time

    20090514 e-Seminar

    Page 9

    310 early retention time

  • Eliminate Ions that Do Not Fit the Criteria 17 280

    50

    170 0

    310

    75

    18516

    0 00

    Extracted IonOnly the ions in black have the

    5017

    Extracted Ion Chromatograms

    (EIC)

    black have the same shape

    and retention time as shown028

    0

    time as shown by 50, 170, 280 -

    plus others

    20090514 e-Seminar

    Page 10

  • Combine Ions That Do Fit the Criteria 17 280

    50

    170 0

    These bi dExtracted Ion

    Chromatograms (EIC)

    combined deconvoluted

    ions are a 50

    ( C)component

    170

    20090514 e-Seminar

    Page 11

    280

  • What can you do with a full spectrum component ?

    Identification by matching against an AMDIS user library- Locked RT or RI can also be part of the library entryp y y

    Send to NIST Search for additional confirmation All components can be NIST searched, not just target compounds

    Add to an existing library

    Build a user library of deconvoluted components, in NIST, AMDIS or Agilent formatsg

    Component spectra are flat files that can easily be shared or edited

    Full spectrum graphics output confirms compound for reports Often required by government agencies and courts (drugs)

    20090514 e-Seminar

    Page 12

  • A portion of RTLdemo.D, clean standards

    3000000

    3500000

    4000000

    4500000

    5000000

    5500000

    6000000

    6500000

    7000000

    Abundance

    TIC: RTLdemo.d

    16.604

    Quant results show NOidentified compounds at 16.604

    16.10 16.20 16.30 16.40 16.50 16.60 16.70 16.80 16.90 17.00 17.10 17.20 17.300

    500000

    1000000

    1500000

    2000000

    2500000

    3000000

    Time-->

    min, using a target and 3 qualifier ions

    Abundance

    1000

    2000

    3000

    4000

    5000

    6000

    7000

    8000

    9000

    Scan 2530 (16.604 min): RTLdemo.d286

    125

    263

    79

    47 197168 233 323100 146

    50 100 150 200 250 300 350 400 450 5000

    m/z-->

    3000

    4000

    5000

    6000

    7000

    8000

    9000

    Abundance

    #218: Chlorpyrifos Methyl286

    125

    A single hit is hard to believe, especially with a 99 match quality the danger

    50 100 150 200 250 300 350 400 450 5000

    1000

    2000

    3000

    m/z-->

    7947

    170 197 321228100 146 260 405343 430375 476498 of reverse search

    20090514 e-Seminar

    Page 13

  • Deconvoluted Peaks from AMDIS

    There are 2 small T symbols indicating Targets found by AMDIS

    20090514 e-Seminar

    Page 14

  • Match First of 2 Peaks from AMDIS

    Black is uncleanedBlack is uncleaned spectrum at 16.599 min White is deconvoluted spectrum at 16.6000 min

    Chlorpyrifos methyl AMDIS match = 94 r.t. = 0.4 sec NIST05 r-match = 89NIST05 r-match = 89 NIST05 f-match = 87 Probability = 97.5

    20090514 e-Seminar

    Page 15

  • Match Second of 2 Peaks from AMDIS

    Black is uncleanedBlack is uncleaned spectrum at 16.599 min White is deconvoluted spectrum at 16.6000 min

    Methyl parathion AMDIS match = 94 r.t. = 0.4 sec NIST05 r-match = 91NIST05 r match 91 NIST05 f-match = 90 Probability = 97.9

    20090514 e-Seminar

    Page 16

  • Can I ?

    Add Compounds to Existing AMDIS databases ? Yes, detailed instructions are in the Help files, you start with a

    d t fil th t t i th d( ) t dd A t ldatafile that contains the compound(s) to add. App notes also available. remember to add these to your Chemstation method also

    B ild AMDIS D t b ?Build my own AMDIS Databases ? Yes, detailed instructions are in the Help files, you start with a

    user Library, in Agilent format, of your compounds. App notes also available. If you havent already created a Library in Agilent format, try

    this. Collect all your data in one or more files using RTL conditions Use Excel and the rtl import command toconditions. Use Excel and the rtl_import command to simultaneously create a Library in Agilent format and a quant database.

    20090514 e-Seminar

    Page 17

  • Agilent Databases - # Compounds Part #

    Hazardous Industrial Chemicals 731 G1671AA

    Pesticides 927 G1672AAPesticides - 927 G1672AA

    Indoor Air Toxics 171 G1673AA

    Forensic Toxicology 723 G1674AAForensic Toxicology 723 G1674AA

    Japanese Positive List 430 G1675AA

    Fiehn Metabolomics - > 1000 G1676AA

    Environmental Semivolatiles 343 G1677AA

    DRS Base Product, rev A.04 G1716AA

    20090514 e-Seminar

    Page 18

  • Report-Spinach Example 1CToxicology Sample using G1674AA

    20090514 e-Seminar

    Page 19

  • DRS Results from Environmental Soil and Water Samples using G1677AASamples using G1677AA

    Total for8 samples

    Total Real Positives based on manual review 183

    Chemstation False Positives at 20% Absolute 35Qualifier Ion Criteria

    Chemstation False Negatives at 20% Absolute 56Qualifier Ion CriteriaQualifier Ion Criteria

    AMDIS False Positives 11

    AMDIS False Negatives 11g

    Both AMDIS and Chemstation Same False Negatives 0

    Both AMDIS and Chemstation Same False Positives 2

    20090514 e-Seminar

    Page 20

  • DRS A.04 Quantitation on the Deconvoluted Ion

    AMDIS Information fully integrated into QEdit

    No need to switch between programs

    R l d lib t di l d f i lRaw, clean and library spectra displayed for visual confirmation

    Deconvoluted target ion for easier integration

    5000

    6000

    Raw MSD 70 Prochloraz 70

    g g

    2000

    3000

    4000

    Raw MSD 70 Prochloraz 70

    Interfering 70

    0

    1000

    2000

    1645 1646 1647 1648 1649 1650 1