getting more from nmr - lancaster university · stolen from: “nuclear magnetic resonance” by p....
TRANSCRIPT
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Michael ThrippletonSteve Wimperis
Getting More from NMR
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Purpose:
• To provide a guide to the background knowledgenecessary for recording good quality NMR spectra
• To introduce some of the many modern NMRtechniques available to laboratory chemists for bothassignment and structure determination
• To give a brief introduction to what is possible (andnot possible!) with solid-state NMR
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Overview:
1. NMR basics: recording and processing good spectra (SCW)
2. NMR experiments for assignment (MJT)
3. NMR experiments for structure determination (MJT)
4. Introduction to NMR of solids (SCW)
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NMR basics: recordingand processing good spectra
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Suggested reading:
highlyrecommendedat this levelmore for the real
enthusiast
more for the realenthusiast
good under-graduate text
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Motion is complex ⇒ view problem in “rotating frame”where Larmor precession is removed (or nearly removed)
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rate of precession:ν1 = γB1/2π (cf. ν0 = γB0/2π)
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Spectrometer detects FID in rotatingframe, so it appears to oscillate ataudio- and not radio-frequencies
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maximum signal obtainedwith “90°” or “π/2” pulse
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Fourier transformation
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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Signal is digitized
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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Relaxation
transverse (T2)relaxation
longitudinal (T1)relaxation
Stolen from: “Nuclear Magnetic Resonance” by P. J. Hore
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In ideal world…
W = 1/(πT2)
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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But spatial B0 inhomogeneity broadenslines and hides natural linewidth
therefore, we shim the magnetand spin the sample
Stolen from: “Nuclear Magnetic Resonance” by P. J. Hore
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Quadrature detection
Stolen from: “NMR: The Toolkit” by P. J. Hore et al.
orthogonal detectors(in rotating frame)
FT
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R = 1/(πT2)
Absorption and dispersion Lorentzian lineshapes
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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NMR basics: recordingand processing good spectra
Acquiring spectra
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The “pulse-acquire” experiment
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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Pulse length calibration
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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Signal averaging
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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Signal averaging
if we acquire N transients(or “scans”) then s/nincreases by √N
Stolen from: “Nuclear Magnetic Resonance” by P. J. Hore
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Signal averaging
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
how long should wewait between scans?
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T1 measurement
inversion-recoveryexperiment:180° – τ – 90° acquire
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T1 measurement
estimate T1 from null point
How long between scans?
Allow ~5 T1 for a careful relaxation time (T1) measurement (!);
~1.5 T1 for a typical pulse-acquire experiment
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spectral width (SW)
offset (O1)
Spectrum parameters
realimaginary
sampling period = 2 × “DW” = 1/SW
In time domain
Acquire “TD” points in FID (TD/2 real and TD/2 imaginary),so total duration of FID is TD.DW = TD/(2.SW)
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Importance of acquisition time
truncation artefacts
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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Importance of acquisition time
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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NMR basics: recordingand processing good spectra
Processing
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Weighting functions
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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Zero filling
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
TD “SI”
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Signal phase
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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“Phasing” the spectrum
Stolen from: “NMR: The Toolkit” by P. J. Hore et al.
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“Phasing” the spectrum
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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there is a deadtime (“DE”) betweenpulse and start of acquisition
a
b
during DE, lines acquire phase that islinear function of their frequency
a b
0
⇒ need to do two phase corrections: a frequency-independent(“zeroth-order”) correction and a frequency-dependent (“first-order”) one
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Frequency-dependent phase correction
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
note that this correctionvaries the phase acrossthe linewidth, which iswrong!
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NMR basics: recordingand processing good spectra
Two-dimensional NMR
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Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
1D
2D
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Basic experiment
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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Basic experiment
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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Two-dimensional Fourier transform
Stolen from: “NMR: The Toolkit” by P. J. Hore et al.
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Two-dimensional Fourier transform
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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Double-absorption Lorentzian lineshape
Stolen from: “Understanding NMR Spectroscopy” by J. Keeler
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To end…
• Have discussed some of the basic features ofpractical NMR spectroscopy
• In next two lectures (5 pm tomorrow and Tuesday)MJT will discuss some of the advanced NMRmethods available for spectral assignment andstructure determination
Thank you for your attention!