Ugh. I was worried it was due to efficiency issues with the vendor
API.

Sigh. Regardless of whether the scan numbers are real or made-up, I
think that the non-chronological order of the scans in the file is an
issue. I suspect others will be surprised by this too.

At the time of conversion it is possible to read in one way and write
in another without having to resort globally (read from # experiments
"caches" in turn) but without an experiment annotation in the spectra
metadata, a global retentionTime sort is the only robust alternative I
can think of (though linear time merge sort for # experiments
monotonicly increasing runs is doable, I guess). There are
retentionTime repeats (empty spectra before the real spectrum with the
correct retention time). More about this next.

How can I detect that the retention time is not monotonic without
reading a large chunk of the file? I guess I can look for a magic
string in the first 1K of the file (.wiff, Analyst) to decide whether
to do this expensive check, and fix.

Without explicit information in the .wiff file data structure,
formally determining the precursor scan may not be possible, but the
"cycle,experiment" grouping (as opposed to experiment,cycle) will
capture the right relationships by chronology for the vast majority of
LC-MS/MS datasets.

- n

On Jan 19, 12:49 pm, Matthew Chambers <[email protected]>
wrote:
> I am well aware of this issue, but there's no schematic rule about the file 
> being in retention time
> order. And there is no scan number for a WIFF scan (since it uses the 
> arbitrary index that pwiz
> translates to, that part at least actually does increase monotonically). Use 
> mzML and nativeID! :)
>
> The problem is the WiffFileReader API takes a relative eternity to switch 
> between experiments. It's
> quite slow enough as it is. :) You'll be happy to hear that the new API does 
> not have the same
> problem. With the current API it would be faster (except possibly with huge 
> profile data) to first
> convert to XML and then use a sorting filter to convert the XML to another 
> file sorted by retention
> time. Currently there is a sorting filter, but no built-in predicates that 
> use it are accessible
> from the command-line.
>
> I'm not actually sure HOW to tell which scan is the precursor scan. In 
> Thermo, figuring out the
> precursor scan with certainty without parsing the scan event list (which 
> comes in a fascinating
> variety of formats) can be quite tricky. I don't know if the same problems 
> exist in ABI and there's
> no scan event list to check (AFAIK), so I punted.
>
> -Matt
>
> On 1/19/2011 11:34 AM, Nathan Edwards wrote:
>
> > I've had this problem with a variety of tools and their handling .wiff
> > data file from Analyst, and now having gotten msconvert to work
> > (thanks Matt) I was hoping that msconvert did it "right".
>
> > Unfortunately, it doesn't seem so.
>
> > I believe that the scan number and retention times should increase
> > monotonically in the mzXML file and in a tandem mass-spectrometry
> > experiment, I expect the MS1 scan to be immediately followed by the MS/
> > MS scans whose precursors are derived from the MS1 scan.
>
> > A number (n>= 2) of converters (msconvert&  ABI's) for .wiff files do
> > not respect this file structure and output the spectra by experiment
> > and cycle, with all experiment 1 (MS1 spectra) first, then all
> > experiment 2 (MS/MS from first selected precursor peak from each MS1
> > spectrum), then all experiment 3, etc.
>
> > In the msconvert mzXML output, there isn't even any reference in the
> > MS2 spectra to assist in determining the correct MS1 spectrum to
> > associate with the MS2 spectrum.
>
> > It is possible to use various tricks to try and determine cycle,
> > experiment, and MS1/MS2 relationships but at the least these require
> > sorting (globally) on retentionTime, an expensive proposition for
> > large mzXML files.
>
> > I'd be happy to provide an example mzXML output to demonstrate the
> > issue.
>
> > - n

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