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CH968
2-5pm
17th February 2014
NMR Theory
Every nucleus has a magnetic moment given
by:
Ih
Gyromagnetic ratio
Nuclear spin
Plancks constant
NMR Theory
NMR Theory
The two spin states for I = nuclei are m =
and m = -.
When placed in a uniform magnetic field, B0,
the spins align in one of two opposite
directions.
B0
m=
m = -
NMR Theory
The energy of each spin state is proportional
to the magnetic moment and B0:
hmB0
E E B0
2
m = or -
NMR Theory
The transition energy is then:
hB0
E
2
The transition is induced by applying radiation
with this energy, or this frequency:
B0
E h
2
NMR Theory
At the resonant frequency, the pulses energy
is absorbed and nuclei are promoted to a
higher energy level.
We try to measure this absorbance.
m = -
m = -
NB
B0
NA
mm==-
NB
e
NA
kT
Very small!
FT NMR
Because of the small difference between NA and NB every
sample has net magnetisation, which is aligned with the
applied field (B0).
Instead of scanning the frequencies, a single pulse containing
all of them is applied over time t.
The length of the pulse is such that the magnetisation is
tipped 90
z
/2 pulse
y
B0
x
FT NMR
The magnetisation now precesses like a top
the time for one revolution round the z axis is
the same as the resonant frequency.
We measure this frequency by positioning a
detector coil along the y axis, this gives us a
cosine wave:
FT NMR
Since all environments are simultaneously excited,
we actually see a superposition of lots of cosines.
The magnetisation also decays over time (i.e. it
returns to being along the z axis).
Both of these give us the Free Induction Decay (FID)
spectrum:
FT NMR
The FID is then converted to the spectrum
with which we are familiar by a Fourier
transform:
A little demonstration
http://www.youtube.com/watch?v=7aRKAXD4dAg&feat
ure=player_detailpage
Polymers
NMR signals always broad in the 1D NMR of polymers
(each monomer is similar to its neighbours, therefore signals
overlap)
Interactions usually broaden the NMR resonance lines of a
spectrum. In (non-viscous) liquids these interactions are
averaged by rapid isotropic motions of the molecules in
polymers by bond rotations of the backbone and the sidechain or groups. The fast isotropic motions average the
interactions to zero or to a single finite value representing the
average interaction.
Line broadening due to slow relaxation as a result of larger
mass, therefore slower tumbling
Conversion by 1H NMR
ATRP
CH3
O
CH3O
(CH2 )2O
CH2
Br
CH2 O
m
H
CH3
(1)
CH3
O
O
CH3
Cu(I)Br
Toluene
N
C5H13
O
CH3O
(CH2 )2O
CH2
CH3
COOCH3
CH2
CH2 O
CH3
(2)
COOCH3
CH2
CH3
Br
CH3
Alkene signals
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
Compare integration of monomer and polymer signals and work out conversion
Conversion by NMR
Hp = 1.75
Hm = 1
Bromo-styrene
Conversion =
Hp
Hp + Hm
= 1.75/2.75
= 63.5%
Conversion by NMR
Error on this
measurement?
Conversion by NMR
Conversion by NMR
Error in A0
Pach, M.; Zehm, D.; Lange, M.; Dambowsky, I.; Weiss, J.; Laschewsky, A. J. Am. Chem. Soc. 2010, 132, 8757
Godula, K.; Rabuka, D.; Nam, K. T.; Bertozzi, C. R. Angew. Chem., Int. Ed. Engl. 2009, 48, 4973
Pach, M.; Zehm, D.; Lange, M.; Dambowsky, I.; Weiss, J.; Laschewsky, A. J. Am. Chem. Soc. 2010, 132, 8757
Godula, K.; Rabuka, D.; Nam, K. T.; Bertozzi, C. R. Angew. Chem., Int. Ed. Engl. 2009, 48, 4973
S
O
S
O
31
10
C - can be affected
by grease
2.00
2.16
8.0
ppm (t1)
7.0
6.0
5.0
4.0
3.0
2.0
1.0
a
i
b
c
d
m = 25
f, g
ppm
Norbornene signals
Postma, A.; Davis, T. P.; Donovan, A. R.; Li, G.; Moad, G.; Mulder, R.; O'Shea, M. S. Polymer 2006, 47, 1899
Molecular weight - Mn
1H
Set integration of
A=2
Integration of D
= DP
Mn = (DP x Mr of
monomer) + Mr
of CTA
S
O
31
10
C - can be affected
by grease
B
30.85
2.00
8.0
ppm (t1)
7.0
6.0
5.0
4.0
3.0
2.0
1.0
Molecular weight
Poly(ethylene glycol) diacrylate, commercially available from Aldrich
Copolymerisation composition
LCST measurement
A graph to show the ratio of 1H NMR signal intensities for PNIPAM C-H next to
methyl groups (assigned as e in inset, at 3.8 ppm) as a function of temperature in
D2O solution (6 mg/mL) for the PMA27-b-PNIPAM47 diblock copolymer.
Microstructure of polyisoprene
4 DIFFERENT MICROSTRUCTURES
1,4
1,2
3,4
Copolymerisation
13C
NMR
5
RAFT-Ethyl
Ethyl-Ethyl
RAFT-RAFT
ppm
5+6
Tacticity
NMR can be used to assess the
stereoregularity of a polymer.
For a given chiral sequence along the polymer
backbone, there is a characteristic peak
pattern.
If you can identify the patterns you can work
out the tacticity of your polymer (this is not
always easy!)
Stereochemistry
Stereochemistry
NMR
PMMA
1H
ATACTIC
NMR
SYNDIOTACTIC RICH
Stereochemistry of Polypropylene
13C
On a high field NMR instrument, the chemical shift of the methyl groups on the polymer
backbone is sensitive to the relative stereochemistry of its four nearest neighbors (two on
each side).
m = meso (syn)
r = racemo (anti)
13C
Stereochemistry of poly(lactide)
Irradiate at the frequency of the signal that you want to remove coupling to with a 2nd pulse
Like an NOE experiment
Tetrad level
Stereochemistry
Homonuclear decoupling is when the nuclei being irradiated are the same isotope as the
nuclei being observed (analyzed) in the spectrum. ie H-H
iii
TETRAD LEVEL
In DMSO so
signals have
shifted
2D NMR
2D NMR takes longer because you have to record
a number of FIDs (usually about 50-500).
Preparation
evolution
t1
Mixing
detection
t2
2D NMR
f2
F2
2D NMR
EXSY = EXchange SpectroscopY (are nuclei
chemically exchanging?)
COSY = COrrelation SpectroscopY (are nuclei
linked by 3J coupling?)
HMQC = Heteronuclear multiple-quantum
correlation (is nucleus B directly attached to
nucleus A?)
HMBC = Heteronuclear multiple-bond correlation
(what other A nuclei are in the vicinity of nucleus
B?)
2D NMR
2D NMR
DOSY = Diffusion Ordered SpectroscopY (is
nucleus A in the same molecule as nucleus B?)
Care needs to be taken when recording DOSY spectra as
small effects can wreck your results e.g. convection
within the tube, correct pulse sequence.
The method you use for extracting diffusion coefficients
is important.
Bear in mind that the breadth of the signals in DOSY
has nothing to do with polymer dispersity!
Stokes Einstein equation
D = diffusion time
2D NMR
2D NMR
Polymer-polymer coupling
A mixture or coupling together???
Diffusion
coefficient
CMC determination
Bakkour, Y.; Darcos, V.; Li, S.; Coudane, J. Polym. Chem. 2012, 3, 2006
CMC determination
DOSY
Bakkour, Y.; Darcos, V.; Li, S.; Coudane, J. Polym. Chem. 2012, 3, 2006
CMC determination
DOSY can be used1:
DOSY
SLS
Bakkour, Y.; Darcos, V.; Li, S.; Coudane, J. Polym. Chem. 2012, 3, 2006
Calibration
curves
Determine
Mw
Calibration
curves
References
NMR Theory:
Spectroscopic Methods in Organic Chemistry
Williams & Fleming
http://www-keeler.ch.cam.ac.uk/lectures/
Whole set of lectures goes into a lot of mathematical detail but well explained
Experimental details
http://chem.ch.huji.ac.il/nmr/techniques/expts.html
Quite technical but very full explanations of how all of the NMR experiments actually
work.