Practical Solid-state NMR

[More than one answer may apply in each case]

1. Adamantane is useful as a setup sample for the following situation(s):
A Checking the shimming
B Referencing 13C shifts
C Adjusting the magic angle
D Calibration of sample temperature
E Setting up cross-polarisation at low spin rates (say < 6 kHz)
F Setting up cross-polarisation at high spin rates (say > 12 kHz)

2. The amount of noise in the spectrum is much higher than normal. The signal
level is more or less unchanged, so what could the problem(s) be?
A Pulse durations are mis-calibrated
B Amplifiers may not be being “blanked” during acquisition
C Amplifiers may be switched off / tripped out
D Filters may be missing
E Probe is incorrectly tuned
F The sample may have leaked out

3. The intensity of the NMR signal is much lower than expected (while noise level is
“normal”). What could the problem(s) be?
A Pulse durations are mis-calibrated
B Amplifiers may not be being “blanked” during acquisition
C Amplifiers may be switched off / tripped out
D Filters may be missing
E Probe is incorrectly tuned
F The sample may have leaked out

4. Close examination of a poor quality spectrum shows that all the lines have a
similar irregular and relatively broad lineshape. What could the problem(s) be?
A The decoupling may have been mis-set
B The magic angle may be mis-adjusted
C The shimming may be poor
D The samples may be amorphous
E The sample may be heterogeneous

5. Close examination of a poor quality spectrum shows that the individual lines are
relatively broad, but with a regular lineshape (~Lorenztian or Gaussian). What
could the problem(s) be?
A The decoupling may have been mis-set
B The magic angle may be mis-adjusted
C The shimming may be poor
D The samples may be amorphous
E The sample may be heterogeneous
6. The spinning appears to be stable (as judged from the spin speed readout), but
the spinning speed is well short of its maximum when the maximum gas
pressures for the probe are being used. What could be the cause(s)?
A The drive tip/cap is worn
B There may be a gas leak
C The spinning module, e.g. the air bearings, may be damaged
D The sample may be badly packed
E The “mark” could be badly drawn / damaged

7. The spectrometer is set up for a single-channel experiment with the correct

experimental parameters, but the user has omitted to check the tuning of the
probe. What may be the result(s)?
A The amplifiers could overload or even be damaged
B The probe may heat up and start to “arc”
C The amount of noise in the spectrum may increase
D The peaks in the spectrum may be broadened
E The sensitivity may be reduced
[What would happen in a double-resonance experiment if the 1H channel was
badly tuned?]

8. You encounter the following experimental “issues”. Using the scale below to
indicate how concerned you would be about each situation: Very (stop and fix
the problem immediately), Moderately (should resolve the problem before
continuing), Slightly (worth noting in a log-book) or Not at all.
i It is impossible to calibrate a reasonable 90/180 pulse duration
ii The 90 pulse durations are ~20% shorter than previously observed
iii Bursts of “noise” are appearing in the NMR signal (FID)
iv The rotor is making an odd grinding noise
v The rotor seems to be spinning stably, but the spin read-out is all over the place
vi The quality of my spectra is much worse than previously observed
vii The tuning is poor, but just on my sample
[There isn’t necessarily a “right” answer in each case, but you should be able to
justify the one you give! ]

9. 3-methoxybenzoic acid (C8H8O3) gives the 13C CPMAS spectrum shown in figure
1, acquired at 75.4 MHz and at a spin-rate of 5.5 kHz. Account for the fact that
there are twelve resolvable signals.
A The spectrum contains spinning sidebands
B The sample is a mixture of two polymorphs
C There are two molecules in the crystallographic asymmetric unit
D The spectrum is exhibiting coupling to H
E The sample is impure
10. In questions 10 - 12 a 13C CPMAS spectrum from the same sample that gave
figure 1 is shown. In each case there is something wrong with the experiment.
What is wrong with the experiment that produced figure 2?
A The recycle delay is too short
B There is a “spike” (one erroneous point) in the FID
C The acquisition time is too short
D The FID has a large DC offset
E The receiver gain is too high
F The first point of the FID is distorted
G The spectral width is too large

11. What is wrong with the experiment that produced figure 3?

A The recycle delay is too short
B There is a “spike” (one erroneous point) in the FID
C The acquisition time is too short
D The FID has a large DC offset
E The receiver gain is too high
F The first point of the FID is distorted
G The spectral width is too large

12. What is wrong with the experiment that produced figure 4?

A The recycle delay is too short
B There is a “spike” (one erroneous point) in the FID
C The acquisition time is too short
D The FID has a large DC offset
E The receiver gain is too high
F The first point of the FID is distorted
G The spectral width is too large

13. Figure 5 shows a 119Sn spectrum. There is a single tin species in the sample.
Which line is the centreband?
A The central line (with equal numbers of sidebands on either side)
B The most intense line
C The line at the centre-of-gravity of the pattern
D The line nearest 0 ppm
E Cannot be certain from this spectrum
14. You have a mixture of materials (X and Y). They each contain a single
phosphorus environment, give similar linewidths, have similar cross-polarisation
behaviour and there is more of X than Y. You know that for X T1(H) = 2 s and
T1(P) = 50 s and for Y T1(H) = 1.5 s and T1(P) = 20 s. Which recycle should you
choose to get the best signal-to-noise ratio from a 31P CPMAS experiment?
A 10 s
B 7.5 s
C 250 s
D 100 s
E 2.4 s

15. You now want to record a direct-polarisation MAS spectrum from the mixture (in
question 14) so that you can integrate the signal intensities and directly
determine the ratio of X to Y. Which recycle should you use to record the
spectrum?
A 10 s
B 7.5 s
C 250 s
D 100 s
E 2.4 s

16. You are carrying out a 15N CPMAS experiment with high power 1H decoupling
on a rigid polymer. The duty cycle for the experiment can be roughly defined
as (contact + acquisition times)/(contact + acquisition times + recycle delay).
Which of the following conditions are safe to use?
A contact 1 ms, acquisition 20 ms, recycle 1 s [duty cycle 0.02]
B contact 1 ms, acquisition 50 ms, recycle 0.2 s [duty cycle 0.20]
C contact 20 ms, acquisition 70 ms, recycle 0.2 s [duty cycle 0.31]
D contact 5 ms, acquisition 10 ms, recycle 0.2 s [duty cycle 0.07]
E contact 1 ms, acquisition 2 s, recycle 30 s [duty cycle 0.06]

17. You want to carry out a 13C DPMAS experiment on a rubbery polymer. Which
of the following conditions are safe to use?
A acquisition 80 ms, recycle 0.5 s, full power CW decoupling [duty cycle 0.14]
B acquisition 200 ms, recycle 0.5 s, full power CW decoupling [duty cycle 0.29]
C acquisition 200 ms, recycle 0.5 s, 30% CW decoupling power [duty cycle 0.29]
D acquisition 200 ms, recycle 0.5 s, full power TPPM decoupling [duty cycle 0.29]
E acquisition 100 ms, recycle 2 s, full power TPPM decoupling [duty cycle 0.05]

18. Figure 6 shows a 23Na MAS spectrum. There is one sodium environment in the
sample. What information does the spectrum give you?
A The sodium is experiencing dipolar coupling to another nucleus
B The sodium environment has cubic symmetry
C The sodium environment is asymmetric
D The magic-angle is mis-set
E The sodium environment is axially symmetric
19. For the spectrum shown in figure 6 which position, marked by the numbers, is
most likely to be closest to the isotropic chemical shift?
A 1
B 2
C 3
D 4
E 5

20. You have the following probes, with the attributes listed, available to you.
Probe Sample Maximum Shortest
volume / μl spin-rate / kHz achievable
90° pulse / μs
A 450 7 4
B 160 12 3
C 52 18 2
D 20 25 1.7
E 150 static 1.5

Choose the appropriate probe(s) for each of these cases

i You are investigating the effect of hydrogen bonding on the 15N chemical shift in
an unlabelled organic material of which you have 1 g.
ii You want to record a 13C CPMAS spectrum to investigate polymorphism in an
unlabelled organic material of which you have 50 mg.
iii You are studying a labelled organic molecule and need a 13C spectrum with the
maximum amount of resolution. You have 0.5 g of sample.
iv You are studying a motional process in a deuterium labelled sample. You have
0.2 g of sample.
v You need a quantitative 29Si spectrum from a derivatised silicate sample of which
you have 0.4 g.
vi You are investigating the number of tin sites in the crystallographic asymmetric
unit of an inorganic compound. Related materials contain tin sites that have
shielding anisotropies of ~ 1000 ppm. You have 1 g of sample.

21. Which of the following should you not do in an NMR laboratory?

A Use a mobile phone
B Eat or drink
C Try and repair an electrical fault in the spectrometer
D Allow anyone unfamiliar with magnets into the room
E Use the CD drive to listen to music with headphones
Practical Solid-
state NMR

Figure 1

180 160 140 120 100 80 60 40

δC/ppm

Figure 2

180 160 140 120 100 80 60 40

δC/ppm
Figure 3

180 160 140 120 100 80 60 40

δC/ppm

Figure 4

180 160 140 120 100 80 60 40

δ C /ppm
Figure 5

600 400 200 0 -200 -400 -600

δSn / ppm

Figure 6
2
4

5
1

0 -5 -10 -15 -20 -25 -30

δNa / ppm
Practical solid-state NMR (answers)
1. Use of adamantane as a set-up sample: ABE
A Yes. The intrinsic 13C linewidths in adamantane are very narrow (<1 Hz?), making it very
sensitive to variations in shimming. On a practical note: ensure that the decoupling power is
not excessive (<30% of full power) if acquiring very long FIDs!
B Yes. Again, the sharp lines are useful here.
C No. As a plastic crystal, the adamantane spectrum is barely affected by the magic angle
setting.
D No. The adamantane spectrum is not significantly temperature dependent
E Yes. The high S/N of the spectrum and short relaxation times makes setting up CP with
adamantane quite straightforward. Bear in mind that adamantane is an atypical sample;
other experimental aspects e.g. decoupling are best evaluated on rigid solid samples
F No. The weak dipolar interactions (intermolecular) mean that the Hartmann-Hahn matching
condition breaks up into “sidebands” at even quite modest spinning speeds. Any match
found might not be appropriate for a “normal” solid. It may be impossible to find a match at
all at higher spinning speeds.

2. Unusually noisy spectra: BD

A No
B Yes. Noise from the amplifier can leak through and contaminate the signal. The NMR signal is
so weak that the amplifier corresponding to the detected signal in particular must be actively
“blanked” during acquisition.
C No
D Yes. In particular, if another nucleus (typically 1H) is being decoupling during acquisition then
filters must be used to prevent noise around the NMR frequency of the detected nucleus
leaking through and swamping the signal.
E No
F No
Note how most other problems (including A, C, E and F) affect the amount of signal.

3. Low signal: ACEF

A Yes.
B No (see question 2).
C Yes (no pulse, no signal!)
D No (see question 2)
E Yes
F Yes (obviously!)
How would you go about distinguishing these different possibilities?

4. Nasty lineshapes: C, possibly E.

If the lineshapes are practically identical, shimming is the likely culprit (although shimming has
 to be fairly bad before it has a noticeable effect on solid-state spectra). Most other
experimental problems (and amorphous samples) tend to result in smooth, if broad,
lineshapes.

5. Broad but smooth lineshapes: ABD

A Yes (e.g. proton transmitter is significantly off resonance).
B Yes. A scaled powder pattern will be observed if the “anisotropy to mis-set ratio” is sufficiently
high, but the mis-set would normally have to be very large for this to be obvious.
C Unlikely (see question 4).
D Yes.
E Unlikely.

6. Spinning speed has “plateau-ed”: AB

A Yes.
B Yes (a leak will normally be obvious from the noise!)
C Unlikely: damage to the air bearings (or rotor module) is most likely to cause “bad” or
temperamental spinning behaviour.
D Unlikely: again the rotor will tend to be “hard to spin”.
E No. A bad mark could only lead to an erratic spin read-out

7. Effect of poor tuning: AE

A Yes. Bad tuning means that power will be reflected back from the coil and into the amplifiers
which may overheat (if not protected).
B No. Mis-tuning does not, necessarily, affect the RF power in the probe so will not lead to
increased heating. Never simply turn up the power level to get the 90 length you want!
C No. Probe tuning is unrelated to the amount of noise in the spectrum
D No. Probe mis-tuning cannot affect the appearance of the spectrum (in a single-channel
experiment), only its intensity. If the 1H channel was mis-tuned in a double resonance
experiment then the lines might be broadened.
E Yes. Assuming that the tip angles had been correctly optimised in the past, they will no
longer be correct, and so the amount of signal will be reduced.

8. How are worried are you?

i Moderately: An impossibly long 90 means there is a fundamental problem which needs to be
resolved. It is not, necessarily, dangerous.
ii Slightly: “Drift” in the calibration is not necessarily a problem, but should be logged to allow
any long term changes to be spotted. The previous calibration may have been poor. If the
90 duration is close to the probe specification, check that the powers are not excessive.
iii Very: Noise bursts in the FID are caused by “arcing” - electrical breakdown in the probe. Stop
immediately and try to resolve the problem as you risk permanent damage to the probe.
iv Very: A smoothly spinning rotor produces a clean single-frequency tone (if audible). A
grinding noise indicates that the rotor is scraping against the air bearings. Stop spinning
 immediately as this will be damaging the spinning module.
v Moderately/slightly: Looks like a problem with spin read-out e.g. spin mark is poor,
tachometer needs adjustment. This is not critical (spin rate can be determined from spinning
sidebands), unless a reliable read out is required e.g. for stabilised spin speed control.
vi Moderately: Something is wrong. Diagnose and fix the problem
vii Not at all: Some samples are “lossy” e.g. ionic solutions, meaning that the tuning will
necessarily be poor. You’ll need to settle for longer 90s etc. for a given RF power. Don’t be
tempted to increase the RF amplitude to compensate!

9. More signals than carbons in the molecule: C(B)

A This spectrum was obtained with a sideband suppression experiment so only low-intensity
residual sidebands are visible, however, the spin-rate is such that the spinning sidebands are
in the wrong positions to account for the “extra” signals (a spin-rate of 5.5 kHz at 75.4 MHz is
~73 ppm)
B Possibly, but the polymorph ratio would need to be close to 50:50 to give ~1:1 pairs
C Most likely. A number of the lines occur in 1:1 pairs. This often indicates that there are two
molecules in the asymmetric unit. Resolving pairs for all the signals in a spectrum is relatively
rare. It is possible to have more than two molecules in the asymmetric unit, so spectra can be
even more complicated.
D No. This must be a 1H decoupled spectrum to give such narrow lines. If it wasn’t the lines
would be severely broadened through dipolar coupling.
E Not in the sense that an impurity is a small amount of an unrelated substance.

10. Truncation of the FID: C

C Yes. The “wiggles” at the base of the peaks are an indication that the signal has not fully
decayed by the end of acquisition time. Increasing the acquisition time will solve the
problem (but be careful with decoupling powers for long acquisition times)
G Not directly, although, depending on the spectrometer software, changing the spectral
width may automatically change the acquisition time (e.g. halving the spectral width would
double the acquisition time).

11. Receiver overload: E

The irregular nature of the baseline is indicative of a receiver overload. Here there is too
much signal from the sample and the full intensity of the signal cannot be digitally
represented. Bad cases of arcing can result in a spectrum with a similar appearance. Dips in
the baseline at the base of a peak in a spectrum contain a smaller number of lines are also
symptomatic of a receiver overload. To solve, reduce the receiver gain or add an
attenuator to the signal path before the preamp. or take some sample out.

12. “Spike” in the FID: B

B Yes. One erroneous data point produces a single frequency oscillation in the baseline. The
nearer this is to the start of the FID, the slower the oscillation.
D This would produce a central (“transmitter”) spike in the spectrum.
F This produces a vertical offset in the spectrum.

13. Determination of centreband: CE

A Not necessarily
B Sometimes but not always
C Yes, the centreband is at the centre-of-gravity of the pattern. But can you tell which line it is
from this spectrum? See E.
D Not necessarily
E Yes. Ideally you need a second spin-rate to be certain. The centreband is at the centre-of-
gravity of the pattern. The sum of all n × I where n is the sideband number (going outwards
from 0 – the centreband) and I its intensity should be equal for sidebands on either side of the
centreband. The centreband is at 100 ppm in this spectrum.

14. Choice of recycle: E

A recycle of 1.2 times T1 will give the best S/N in any given time. In a CP experiment the
recycle is determined by T1(H). As X is the dominant component 2.4 s is the best recycle to
use.

15. Choice of recycle: C

If you want a direct-polarisation experiment to be quantitative (without having to calculate
compensation factors for differing T1s) you need a recycle of 5 times the longest T1(P) (in this
case) in the sample. Here it is 250 s.

16. Duty cycle: AD

For safety, the duty cycle should not exceed 0.2. Duty cycle is a measure of the rf on-time.
Too high and you risk damaging the probe (and heating the sample). So A and D are safe, B
is borderline and C is not acceptable. For B and C, increasing the recycle will make the
experiment safe. For E the duty cycle is low, but 2 s of acquisition time with full power
decoupling is dangerous. You will rarely (if ever) need such a long time for a rigid solid, so
either reduce the acquisition time or, if you really do need it, reduce the decoupling power.

17. Duty cycle: ACE

Again the duty cycle should not exceed 0.2, so A and E are safe. For B and D, the acquisition
conditions are not acceptable, but for C the decoupling power is turned down so these
conditions would be acceptable. Note that it does not matter that one decoupling scheme
is TPPM and the other is CW – the power used is the same. There might be a case for using
TPPM if you have turned down the power as it may be more efficient than CW decoupling.

18. Quadrupolar bandshape: E

A No. This bandshape is characteristic of a second order quadrupolar interaction.
B No. Such an environment would result in a narrow, symmetric line.
C No. This would give a different bandshape.
D Not necessarily.
E Yes. This quadrupolar bandshape is indicative of an axially symmetric environment. Fitting
the bandshape gives a quadrupolar coupling constant of 1.09 MHz and an asymmetry of 0.0.

19. Isotropic shift of a quadrupolar bandshape: A

For a quadrupolar bandshape the isotropic chemical shift is not necessarily at a peak
maximum or, indeed, within the bandshape. For this type of bandshape it is roughly at
position 1. You need to simulate the spectrum to determine the isotropic shift accurately.
Doing that gives a shift of -8.1 ppm in this case.

20. Choice of probe

i. A. Nitrogen-15 has a low natural abundance (0.37%) so you need as much sample in the
spectrometer as possible. Sample volume is the key attribute here, all other factors are
secondary. You have enough sample to fill the rotor for probe A.
ii. C. Per mg of sample, a probe with a small rotor is more sensitive than a larger one. In this
case, probe C will give a better result than using probe A or B even if you reduce this
sample volume or use an inert filler – which is best avoided anyway. The smaller probe will
have other advantages – higher spin-rate and higher decoupling field which may
compensate to some extent for the lack of sample.
iii. D. For maximum resolution you want the highest possible decoupling field so the probe that
can give you the shortest 90° pulse is the one of choice here. High speed spinning might
also help. The lack of sample volume will be offset by the fact that the sample is labelled.
Small volume probes tend to be better shimmed than large volume ones as well.
iv. E. The static 2H bandshape is useful for studying motion.
v. A. Spin-rate and rf field are not key features for 29Si experiments. As a quantitative
spectrum (direct-polarisation) is required a long recycle may be needed and as 29Si has a
low natural abundance (4.70%) we want as much sample as possible in the spectrometer.
vi. C. Spin-rate is the issue here. The probable high shielding anisotropy means the signal will
be split into a large manifold of spinning sidebands. Spinning fast will reduce the number of
sidebands and should make the signal more detectable. The abundance of 119Sn is 8.58%
so fast spinning has to be offset against the reduction in sample volume. Probe C would be
a good choice, especially at higher magnetic fields. Probe B might suffice but if the lines
are broad 12 kHz might not be fast enough to properly separate the sidebands. The low
sample volume for probe D might be a problem.

21. Things not to do in a lab.: ABCDE

A Best avoided (especially if it breaks any local prohibitions).
B Eating or drinking should never be done in any laboratory.
C Electrical work should only be carried out be qualified people. There are lethal voltages
inside a spectrometer.
D Any visitor (whatever the purpose of their visit) should be made aware of the hazards -
particularly of the magnetic field - before they are allowed in.
E This is often banned in departmental safety policies. It is useful to be able to hear a rotor
spinning - in case it suddenly crashes - and for the fire alarm of course!