017 of water summary

From: Roger Kautz <rkautz_at_lynx.dac.neu.edu>
Date: Thu, 02 May 2002 15:53:01 -0400

O17 summary


Thanks to the many people who responded with a wealth of hints, tips, and
applications.
I made a concise summary by clipping just the new information as I
encountered it -- so it's "first come, first credit". But my thanks go to
you all.

                                        -- Roger



>I have someone who wants to see O17.
>Does anyone know off the top of their head if it's possible to see
natural abundance O17 in water?
>Dependence on pH and temperature?
>Recommend any references?
>-- Roger


_________________ SUMMARY OF RESPONSES
  (edited for continuity)

Roger

neat D2O should give a nice signal …. You can pulse fairly rapidly.
Any other O17 spectra are much harder to observe. Only highly symmetric
molecules give reasonably sharp lines.
Regards
Clemens Anklin

-------------------
> From: "Rich Shoemaker" <richard.shoemaker_at_colorado.edu>

Hi Roger,
SURE, you should be able to see natural abundance 17-O from tap water
easily. In fact, that was the "official" sensitivity spec. back when we
installed my GE-Omegas in the late 80s, early 90s. I can't remember if
it was one scan, or 4 scans, or what. Either way, it should be easy to
see.

Two good references:

Boykin, David W. (David Withers), CRC Press, 1991
Title: 17O NMR spectroscopy in organic chemistry / editor, David W.
Boykin. Library of Congress Call# QD272.S6 A12 1991

Kintzinger, Jean-Pierre, Marsmann, Heinrich
Title: Oxygen-17 and silicon-29 NMR.../ with contributions by
Jean-Pierre. Library of Congress#: QD603.O1 O9x c.2 .
Publisher: Springer-Verlag, 1981

The first one (Boykin) has been very useful to me in the past.
Cheers,
-Rich S.
---
Richard K. Shoemaker, Ph.D.
NMR Facility Director
University of Colorado at Boulder
_________________
Easy. Since the relaxation of O-17 is very fast
you can scan very fast and get a good S/N in a very short time.
(T1 of water is 10-20 ms, of organic oxygens under 1 ms)
You could increase the temperature to get sharper signals.
O-17 of water is strongly pH and Temperature dependent.
Reference is water, but 1,4-dioxane is much more convenient
and it has the same shift as water at 40 degrees Celsius (0 ppm).
If you want to study molecules in water you might want to get rid of the 
water signal.
I've done several studies on O-17, nat. abundance and enriched.
You might want to check them out:
1. J. Lauterwein, J. Schulte, M. Schumacher and M. Cerny, Magn. Reson. 
Chem. 30, 312, (1992), “17O NMR Spectra of the 1,6-Anhydro--D-Hexopyranoses 
and Related Compounds. Determination of Configurational Effects on the 
Chemical Shifts.”
2. J. Schulte and J. Lauterwein, Magn. Reson. Chem., 30, 334, (1992), 
“Lanthanide-Induced Shifts in the 17O NMR Spectra of 
1,6-Anhydro--D-hexopyranoses. Evidence for Tridentate Complexing.”
3. J. Schulte and J. Lauterwein, J. Magn Reson. Ser. A 101, 95, (1993), 
“Water Suppression in 17O NMR Spectroscopy.”
4. J. Schulte and J. Lauterwein, Magn. Reson. Chem., 34, 527, (1996), 
“Application of 17O Chemical Shift Substitution Parameters to 
D-Hexopyranoses.”
5. J. Schulte and J. Lauterwein, Magn. Reson. Chem., 34, 703, (1996), “2D 
17O,1H Chemical Shift Correlation Spectroscopy.”
6. J. Schulte, J. Magn. Reson., 134, 168, (1998), “Sequential Inversion 
Recovery with RIDE Simultaneous Suppression of Two Solvent Signals in 17O 
NMR Spectroscopy.”
Jürgen Schulte, Ph.D.
______________
Dear Roger,
Water is (or at least was until IUPAC adopted a new system last year) the
standard for 17O chemical shifts. Therefore, I doubt if anyone has measured
its dependence on pH and temperature. …
Roy Hoffman,
Hebrew University
________________
Take D2O, it contains more O17 than normal H2O.
Dr. Matthias Findeisen
_______________
… The trick is to open up the sweep width, use a small
data table size, and use a 90 degree pulse. You can collect thousands of
transients in minutes.
Have fun,
Kenner Christensen
Chemistry Department NMR Facility
University of Arizona
____________
One problem that you could find is the probe signal ( oxygen signal from 
the borosilicate)
JOE 8-)
--
Jose R. Martinez-Ortiz joenmr_at_caribe.net
San Juan, PR 00931-1352
----------------
…the lines are so broad, it usually doesn't matter if there is a
slight variance due to temp and pH. Of course, I run solid-state NMR.
Gary Turner
Spectral Data Services, Inc. Contract NMR Data Acquisition
818 Pioneer St. Used NMR equipment newsletter
Champaign, IL 61820
phone : (217)352-7084
fax : (217)352-9748
e-mail :sdsnmr_at_sdsnmr.com
__________
…Most of the stuff I've seen done with O-17 in water has to do with 
T2/linewidth
changes rather than any chemical shift measurements (bound vs free water,
exchange, etc.). Brevard and Granger show a spectrum with good S/N (50:1?)
using 1000 transients, 90 degree pulse, and 0.1 second rep rate. They show
a 80 Hz linewidth on a 90MHz instrument.
Good Luck.
Steven K. Silber
___________
. … pH will effect linewidth of the proton coupled resonance. The argument 
is that at a pH either higher than or lower than 7 the base or acid 
catalyzed exchange of protons allows for a narrowing of the line. My 
experience is that the linewidths vary from 80 to 60 hertz at 11.74T(500MHz).
Paul Molitor
U Illinois, Urbana-Champaign
---------------
…  if using dilute H20, can see the triplet from H coupling (too much 
exchange in bulk water to see it).  … if you search with my name, might 
find some stuff from then.
Dr. Herbert Schwartz
---------------
…. I don't think temp or pH matter too much to just seeing a signal. You 
may need to use an anti-ringing sequence depending on your probe.
I still use my trusty copy of "Handbook of High Resolution Multinuclear 
NMR" by Brevard and Granger (1981) when hunting a new nucleus.
Regards,
John Harwood
_____________
…Set up the instrument to
observe O17, tune probe (with water sample in the magnet), pulse a few
hundred times (no recycle delay and a short aquisition time) with a
resonable flip angle. Once you see the signal, measure the w1/2 of the
peak and reset the acquisition time to 1/(w1/2). Then calibrate the
pulse width (PW90). You generally run O17 spectra with no recycle delay
since relaxation is dominated by quadrupole relaxation. The exercise
is to pulse as fast as you can. If you want to quantitate a spectrum
you may need to varify that your acquisition parameters will allow
quantitation just as you would for any other NMR experiment. Incidently,
water is the "TMS" for O17.
Hope this helps.
Regards,
Dave Lankin
-------------------
Hello,
It is very easy to see in water. …. On the other hand, seeing O17 in "real" 
samples requires a lot of
scans. Fortunately, because of the quadrupole, the relaxation is fast. We
typically set the d1 times (Bruker or Varian) to 0s because T1 relaxation
takes place during the FID. For one sample lately I wrote a Hahn echo
sequence, because quite a bit of signal was lost in the dead time of the
probe. I do not know anything about the temperature and pH dependence.
For any nucleus, my first book to look at is "Handbook of High Resolutions
Multinuclear NMR", C. Brevard, P. Granger, Wiley, 1981.
Good luck
Ulli
Ulrike Werner-Zwanziger
------------------------
Yes, we used to run O17 all the time at 54.2 MHz. It is a fairly easy 
experiment and won't take much machine time.  We used O17 linewidths to 
measure "water mobility" in starch -water mixtures. The line width for pure 
water was about 48 Hz.
Also, Berger, Braun, Kalinowski has a chapter on O17.
Gary Juneau.
________________
 >Recommend any references?
…. A lot of work with 17O was done in Physical
Chemistry (e.g. Lennart Piculell - spelling? -) at the University of
Lund, at least in the 1980s.
_______________
Roger,
Look for papers by John Hunt and Harold Dodgen. Then did lots of O17 -
metal complex stuff in the 80's. Back then, O17 was the most expensive
commodity on the planet, so the concentrations were as low as the fields.
Dr. Doug Wheeler
University of Wyoming
______________
A good reference book for many 'different' nuclei used to be 'NMR and the
Periodic Table' by Harris & Mann. If you can't track a copy down try
contacting Brian Mann directly who will I'm sure be happy to help out
Ian Marshall
Analytics Group , SCYNEXIS Europe Ltd.
--------------------
I've used PW90 and AT = 0.1 s (or in some cases shorter), thus obtaining 
good S/N with D2O in just a few minutes.  Probe ringing can be a problem at 
frequencies lower than ca. 40 MHz.
Joan Mason has a good chapter in her book "Multinuclear NMR".
David French
------------------------
The reviews by Kintziger (1983) in 'NMR of Newly Accessible Nuclei', P.
Laszlo, ed., and Gerothanassis (1994) in Progr. NMR Spectroscopy' are the
ones I know, likely to be more out there.
Good Luck!
Lazaros Kakalis
Rutgers University at Newark
Received on Thu May 02 2002 - 18:37:34 MST

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