Dear Edward,

Thank you very much for your detailed reply.
I'll try to reply point by point:

Temperature control:
I did have a recent temperature calibration in place, but did not calibrate 
when setting up the experiment.
I probably should have done that.

I did use heat compensation blocks during the experiment, but did not do single 
scan or experiment interleaving.

Is there a way to account for this in relax, or is re-recording of the data the 
only remedy?


Single diffusion tensor estimate:
I looked through the local tm model results and they appear to be all over the 
place, although the relaxation behavior of the protein predicts that they 
should be rather similar.
chi2 values were generally in the double to three (hundreds) digit region. The 
model selection changes from residue to residue.
I don't believe that this sample dimerizes, but have not done a dilution series 
yet.

R1, R2, NOE:
All fittings were done in Relax and heights and noise were measured following 
recommendations in the relax manual. I also compared fits to fitting with other 
methods. The errors and curve fits look ok.

13C Coupling:
I think I did not formulate this question clearly. My concern was with the 
effect of dipolar couplings from 13C carbons on relaxation.
There is no question that the scalar coupling must be taken care of at the 
experimental level and this is of course what I did.
Upon looking into this further, I believe that the effect from the dipolar 
couplings should be negligible.

With best regards,
Andras



On Apr 16, 2019, at 9:32 AM, Edward d'Auvergne 
<[email protected]<mailto:[email protected]>> wrote:

       External Email - Use Caution

On Mon, 15 Apr 2019 at 19:18, Boeszoermenyi, Andras
<[email protected]<mailto:[email protected]>>
 wrote:


Dear Relax Community,

I am trying to do model free analysis with relax 4.0.3 on a linux workstation 
in script mode.

I have a high resolution (1.1 Angstrom) crystal structure of a 30 kDa protein 
and added protons to the pdb.
For the model free I have T1, T2, HetNOE data sets at 600 MHz and 750 MHz (both 
spectrometers were Bruker) and all values make sense. The analysis of the data 
fits well, with small standard deviations for the vast majority of residues.

I am using the "black-bocks" dauvergne-protocol and all calculations run 
perfectly fine.

However, the Chi-squared test produces ridiculously high chi-squares ~17000 and 
then of course the wrong model is selected.

Hi Andras,

This could be due to a number of factors:

   - Missing or poor temperature calibration or control (see the
"Temperature control and calibration" section of the "Relaxation
curve-fitting" chapter of the manual, i.e.
http://www.nmr-relax.com/manual/Temperature_control_and_calibration.html
).

   - Inadequacy of the single diffusion tensor estimate.  Please
compare the local tm model results to the final selected diffusion
model.  What is the total chi2 value for the local tm model?  Could
there be partial dimerisation, even if it is non-specific?

   - Incorrect errors in the R1, R2, and steady-state NOE values.
Did you use relax to obtain this data?  And how did you perform the
error analysis?  If the errors are too small, the final chi-squared
value will be very high and the model-free models chosen will be
wrong.  See the "From spectra to peak intensities for the relaxation
rates" section of the "Relaxation curve-fitting" chapter of the
manual, i.e. 
http://www.nmr-relax.com/manual/From_spectra_to_peak_intensities_for_the_relaxation_rates.html
.  And, for example, the "NOE script mode - setting the errors"
section of the "Calculating the NOE" chapter of the manual, i.e.
http://www.nmr-relax.com/manual/NOE_script_mode_setting_the_errors.html
.

There are other factors as well.  I suggest looking at the relaxation
curves for the R1 and R2 very carefully, including error bars, to see
if there is any issue with the base data.  These curves are produced
automatically by the relax auto-analyses and can be visualised in
XMGrace.  The steady-state NOE data and parameter plots should also be
carefully checked.



Did anyone make this experience, and would any one have a suggestion on how to 
fix it?

See above.  This has been seen many, many times before.  The above 3
reasons are probably the most common ones - with temperature
calibration and control being the number one culprit.  You may be able
to find the old threads on the relax users mailing list archive on
this subject:  https://sourceforge.net/p/nmr-relax/mailman/nmr-relax-users/



One more information. I ran the NMR experiments on a perdeuterated and 13C, 15N 
labeled sample. I did not find a way to correct for 13C couplings in the model 
free script. Might that have a role in this, and is there a way to correct for 
that?

This will be an issue.  I have never encountered literature on the
subject of dealing with this on the data analysis level.  I thought
that this is usually dealt with by minimising the effect during the
experiment.  Do you have any references/papers that state otherwise?
I would be interested in reading about it.

I hope the above info helps.

Regards,

Edward



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