Hi Kristina, I’m not certain I fully understand your issue, but maybe I can
answer some questions:



Partial old:

Name: DIETIIQK/2 *(old entry, original library)*

308.1581  226.5     ?

309.0826  359.4     ?

325.6734  1596.8    b6-35^2/0.000,b6-36^2/0.492

329.1945  141.2     a6^2/0.000

343.1920  668.4
b6^2/0.000,y3-45/-0.042,y6-45^2/-0.516,y6-46^2/-0.024



Partial new:

Name: DIETIIQK/2 *(new entry, combined library)*

308.1581  226.5     ?

309.0826  359.4     ?

326.1680  1596.8    ?

328.2231  141.2     m4:6/0.000

344.1816  668.4     m3:5/0.000



The first two peaks are fine. For the third entry, I am guessing that in
the original library this peak got shifted to exact m/z of the presumed
interpretation b6-35^2. But this is a highly unlikely interpretation. So in
the new entry, that peak retains its original m/z (i.e. not snapped to a
presumed interpretation) and a “?”. SpectraST seems to be smarter about not
assigning a silly interpretation.



For the next peak with intensity 141.2, the old library had an
interpretation of a6^2 and the m/z is snapped to that interpretation. But
a6^2 is a super unlikely interpretation, or maybe let’s call it impossible
and wrong. In the new library, this same peak has been interpreted as an
internal fragmentation ion and the m/z has been snapped to that. The m4:6
means that the peptide was fragmented in two places such that you get a
little ion that is TII and has a charge so you see it. Internal
fragmentation turns out to be fairly common and so m4:6 is far more
plausible an interpretation than a6^2. Same for m3:5 (ETI). Not necessarily
correct, but far more plausible than an a6^2 and a b6^2.



So I’m guessing that the first spectrum comes from a version where internal
fragmentation was not yet supported, and the second spectrum comes from a
newer version of SpectraST that knows about internal fragmentation and
interprets peaks better.



Does that seem like a reasonable explanation of what’s going on? Henry
might know more.



Regards,

Eric













*From:* [email protected] <[email protected]>
*On Behalf Of *Kristina Plate
*Sent:* Friday, September 20, 2019 6:22 AM
*To:* spctools-discuss <[email protected]>
*Subject:* [spctools-discuss] Combination of consensus libraries and import
in MRM format via spectraST



Hello again,



as I described before (topic: *What happens during consensus building?*) I
have a problem with some messed up spectra in my spectral libraries.

I combined four spectral libraries and built consensus spectra. Afterwards
I reimported the combined consensus spectral library in MRM format and
converted it in an assay library. When I checked the SPTXT file I found
some *slightly changed spectra* and new *"ion types" m*. Please see my
example of an old, normal spectrum and the corresponding new one below:



Name: DIETIIQK/2 *(old entry, original library)*

LibID: 4160

MW: 960.5481

PrecursorMZ: 480.2740

Status: Normal

FullName: X.DIETIIQK.X/2 (CID-QTOF)

Comment: AvePrecursorMz=480.5611 BinaryFileOffset=23385298
FracUnassigned=0.09,1/5;0.23,11/20;0.06,7/31 MassDiff=-0.0014 Mods=0 NAA=8
NISTProtein=Id_02 NMC=0 NTT=1 Nreps=1/1 OrigMaxIntensity=11 Parent=480.274
Pep=Tryptic PrecursorIntensity=0 Prob=1.0000 Protein=1/Id_02
RawSpectrum=file_02_04.69683.69683 RetentionTime=2745.2,2745.2,2745.2
Sample=1/sample_02,1,1 Se=1^C1:pb=1.0000/0,fv=2.7040/0 Spec=CREATE
TotalIonCurrent=8.9e+003 iRT=33.4,33.4,33.4

NumPeaks: 31

308.1581  226.5     ?

309.0826  359.4     ?

325.6734  1596.8    b6-35^2/0.000,b6-36^2/0.492

329.1945  141.2     a6^2/0.000

343.1920  668.4
b6^2/0.000,y3-45/-0.042,y6-45^2/-0.516,y6-46^2/-0.024

353.2183  967.7     y3-35/0.000

354.2183  480.9     y3-35i/0.000

355.2183  481.6     y3-35i/0.000

358.1609  442.5     b3/0.000,y6-17^2/0.456,y6-18^2/0.948

358.1970  96.7 ?

365.2030  293.0     ?

373.2367  296.2     ?

388.2554  1744.6    y3/0.000,b7-36^2/-0.955

424.1714  315.8     b4-35/0.000,b4-36/0.984

442.1820  644.1     b4-17/0.000,b4-18/0.984

457.7633  546.4     p-45^2/0.000,p-46^2/0.492,y4-44/0.414

458.2791  109.5     p-44^2/0.000,b4/-0.929

471.7608  110.9     p-17^2/0.000,p-18^2/0.492

472.2608  111.1     p-17^2i/0.000

477.1321  111.6     ?

480.2740  336.0     p^2/0.000

484.3130  224.9     y4-17/0.000,y4-18/0.984

501.3395  523.5     y4/0.000

553.1674  240.4     ?

567.3501  487.3     y5-35/0.000

584.3766  247.1     y5-18/0.000

602.3872  2935.1    y5/0.000

696.3927  205.5     y6-35/0.000,y6-36/0.984

714.4032  2211.4    y6-17/0.000,y6-18/0.984

731.4298  10000.0   y6/0.000

732.4298  414.9     y6i/0.000



Name: DIETIIQK/2 *(new entry, combined library)*

LibID: 4673

MW: 960.5481

PrecursorMZ: 480.2740

Status: Normal

FullName: X.DIETIIQK.X/2 (CID-QTOF)

Comment: AvePrecursorMz=480.5611 BinaryFileOffset=20613807
FracUnassigned=0.09,1/5;0.25,13/20;0.17,13/31 MassDiff=-0.0014 Mods=0 NAA=8
NISTProtein=Id_02 NMC=0 NTT=1 Nreps=1/1 OrigMaxIntensity=11 Parent=480.274
Pep=Tryptic PepContext=1/NTPR_DIHE PrecursorIntensity=0 Prob=1.0000
Protein=1/Id_02 RawSpectrum=file_02_04.69683.69683
RetentionTime=2745.2,2745.2,2745.2 Sample=1/sample_02,1,1
Se=1^C1:pb=1.0000/0,fv=2.7040/0 Spec=CREATE TotalIonCurrent=8.9e+003
iRT=33.4,33.4,33.4

NumPeaks: 31

308.1581  226.5     ?

309.0826  359.4     ?

326.1680  1596.8    ?

328.2231  141.2     m4:6/0.000

344.1816  668.4     m3:5/0.000

353.2183  967.7     y3-35/0.000

354.2183  480.9     y3-35i/0.000

355.2183  481.6     y3-35i/0.000,m5:7/-0.016

358.1609  442.5     b3/0.000

358.1970  96.7 ?

365.2030  293.0     ?

373.2367  296.2     ?

388.2554  1744.6    y3/0.000

424.1714  315.8     b4-35/0.000

441.1980  644.1     b4-18/0.000

457.2713  546.4     p-46^2/0.000,m3:6/0.006

459.2086  109.5     b4/0.000

471.2688  110.9     p-18^2/0.000

472.2512  111.1     ?

477.1321  111.6     ?

480.2410  336.0     ?

484.3130  224.9     y4-17/0.000

501.3395  523.5     y4/0.000

553.1674  240.4     ?

568.3124  487.3     ?

584.2763  247.1     ?

602.3872  2935.1    y5/0.000

695.4087  205.5     y6-36/0.000

713.4192  2211.4    y6-18/0.000

731.4298  10000.0   y6/0.000

732.4675  414.9     ?



I assumed before, that it was an issue with the consensus building, but I
figured out that it took action during the *import via spectraST into MRM
format*.



Now, I just saw that I don't have this problem when I use the single
libraries. Even with consensus libraries built with with an older spectraST
version the MRM import works just fine.

Maybe there is the *problem in the combination of the spectral libraries?*
I already got them as single consensus libraries and combined them with the
following command



spectrast -cNcombined_lib -cd -cu -cr1 -cy1 -cAC -cJU
Lib_01.splib Lib_01.splib Lib_01.splib Lib_01.splib



Could this be an issue here. Do I have to rebuild all libraries before
combining them?



I would be really happy about any suggestions. Thank you in advance!



Kind regards,

Kristina

____________________

Kristina Plate, MSc. Biomathematics



University of Greifswald

Center for Functional Genomics of Microbes

Institute for Microbiology

Department of Microbial Proteomics

Felix-Hausdorff-Str. 8

17489 Greifswald



phone:   +49 3834 420-5925

fax: +49 3834 420-5902

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