Principi di NMR

di macromolecole
(soluzione + stato solido)

anno accademico 2008/2009

 NMR Spectrometer Structure
NMR
Workstation

NETWORK

MAGNET
BSMS
SHIM&LOCK
CONTROL

TRANSMITTER
Acquisition
Processor

COMMUNICATION
CONTROL
UNIT

RECEIVER

ACQUISITION
CONTROL
The NMR Magnet
 Spin ½ Isotopes
Isotopes with EVEN mass numbers have integer spin
Isotopes with ODD mass numbers have half integer spin
 Isotopes with EVEN mass numbers have integer spin
Isotopes with ODD mass numbers have half integer spin

Numbers of protons and neutrons both even: I=0

(12C: 6p + 6n; 16O: 8p + 6n)

Numbers of protons and neutrons both odd: I>1 (I: integer value 1, 2, 3)
2H: 1p + 1n. I=1
10B: 5p + 5n. I=3
Nuclear Isotopes
Nuclear Zeeman Splitting

Zeeman splitting = 2I +1
 2πµ
γ=
Ih

ϖ 0 = −γB0

µB0
hυ 0 =
I
Thermal equilibrium
TRANSVERSE MAGNETIZATION

Rotation of a spin around the x-axis

Polarization distribution after a pulse

TRANSVERSE RELAXATION
The induction of an NMR signal
Basic 1D sequence for NMR

γ 1 H B 1 ≈ 50kHz → B 1 = 10G
H H

Block Decay
Ramificazioni e gruppi terminali
Stereochimica
Geometric Isomerism
HIGH RESOLUTION SOLID STATE NMR

Isotropic Chemical Shift gives information about composition of the

material, constitution and conformation of the molecules.

Multiplicity of Signals gives information about intra and intermolecular

symmetry, crystalline packing.

Relaxation Times give information about molecular mobility in the solid

state.

PHENOMENON TECHNIC
Couplings (especially dipolar:1H-1H; 1H-13C) High Power Decoupling
Chemical Shift Anisotropy (CSA) Magic Angle Spinning
Long Relaxation Time for Rare Nuclei (13C) Cross Polarization (CP)
 SIGNAL BROADENING DUE TO DIPOLAR COUPLING

Especially critical for hydrogen NMR.

13C resonance is influenced by magnetic moments of the surrounding 1H nuclei and

this effect has a strong angular dependence (θC-H). It also depends on the distance
between the two nuclei (rC-H).

An isolated 13C-1H couple in a single crystal generates a so-called Pake spectrum.

 Pake Pattern for an isolated C-H couple
Microcrystalline samples generate broad spectra due to the overlapping
of the specific orientations.

The broadening is cancelled by the application of high power decoupling (HPD)

of 500-1000 Watts.
 CHEMICAL SHIFT ANISTROPY
The chemical shift is anisotropic and depends on the orientation of the molecule
with respect to the principal magnetic field.

The carbon spectrum is extremely wide (10-200 ppm) and may cover the structural
information.
The chemical shift is defined by the sum of the three principal components of the
tensor: σ11, σ22, σ33.

A polycrystalline organic sample explores all the possible orientations and

therefore the resulting spectrum is a convolution of a large number of signals.
Anisotropia del Chemical Shift
For an axial symmetry of the bond σ11 = σ22 ≠ σ33. The lineshape presents
a singularity on one edge that represents σ⊥.

A more general lineshape is generated when the three components are

different σ11 ≠ σ22 ≠ σ33.

σiso σiso

σ11 = σ22 = σ⊥ σ33 = σII σ11 σ22 σ33

MAS Rotor Types
 Standard bore MAS probe

proton trap

stator flip mechanism

bearing gas inlet

BN stator
RF electronics
RF coil
NMR solonoidal coil in MAS
system
Cross-Polarization
 Cross-Polarization
Abundant spins I: 1H, 31P
Diluted spins S: 13C, 29Si, 15N SL

ω1 I = γ I B 1 I
ω 1S = γ S B 1S SL

γ I B 1 I = γ S B 1S
Hartmann-Hahn Match
 Thermodynamic Picture of CP
1
βS =
ΘS 1 1
βI = = (B0 / B1 )
ΘI ΘL
Kinetics of CP: examples

M S0 = 149 ± 8
T1ρI = 5.8 ± 0.6ms
TIS = 1.1 ± 0.1ms

0 −1
M
M s (t) = S
1 − TIS / T1ρI
[exp(− t / T ) − exp(− t / T )]
1ρI IS
 The Nature of Polymers

Polymers are long chain molecules comprising

large numbers of basic repeat units.

amorphous phase

crystalline phase
interphases
 NMR of Polymers
Solution NMR: Monomer Composition, Sequence Distribution and
Tacticity.

Solid state NMR: Structure of Polymers in the Condensed State, Phase

Distribution, Interfaces and Mobility.

Totally amorphous polymers

Semicrystalline Polymers
Polymer Blends
Oriented Polymers
Liquid Crystalline Polymers

Advantages:
- an increase in sensitivity, because the sample is not diluted.
- the possibility to study insoluble polymers.
- no-destructive technique: the polymer can be re-analyzed.
-powder, pellets, beads, film, fibers.
 Solid State NMR of Polymers

Conformation Mechanical
Properties

Chemical Shift
Dynamic
Multiplicity Packing Morphology
Properties
Relaxation

Mobility Modeling
 Carbon-13 Nuclear Magnetic Resonance of Polymers
Spinning at the Magic Angle

…further improvements were reached via cross polarization (CP), magic angle
spinning (MAS) and the combination of MAS and dipolar decoupling techniques.

Schaefer, J.; Stejskal, E. O. J. Am. Chem. Soc. 1976, 98 (4), 1031-1032.

Schaefer, J.; Stejskal, E. O.; Buchdahl R. Macromolecules 1977, 10 (2), 384-405.
 Conformational Structure
φ
i γ
C C C C C C

φ= 180° (trans) φ= 60° (gauche)

di-γγ = 4Å di-γγ = 3Å

∆δ = 5 ppm
Tonelli, A. E.. NMR Spectroscopy and Polymer Microstructure: The Conformational Connection, 1989
 Crystalline Modifications of Linear Polyethylene (PE)

13C CP-MAS DD
orthorhombic

monoclinic
crystalline
(~33 ppm)

amorphous

13C
Amorphous
MAS DD (~31 ppm)

13C CP-MAS spectra of linear PE samples

McBrierty, V. J.; Packer, K. J. Nuclear Magnetic Resonance in Solid Polymers, 1993, Cambridge University Press.
Russell, K. E.; Hunter, B. K.; Heyding, R. D. Polymer, 1997, 38 (6), 1409-1414.
 Crystalline-Amorphous Structure of Polyethylene

13C MAS DD Fully Relaxed

Spectrum without CP

Kuwabara, K.; Kaji, H.; Horii, F.; Bassett, D. C.; Olley, R. H. Macromolecules 1997, 30 (24), 7516-7521.
 Distribution of branches in the crystalline
and noncrystalline regions
molecular-level structure model

amorphous

crystalline

13C CP-MAS DD Spectra

schematic morphological model for bulk PE

 Chain Diffusion between Crystalline and Amorphous regions

2D Exchange Pulse Sequence

T = 363 K

T = 373 K

the PE chains can diffuse from the crystalline

lamellae to the interfacial regions.

Schmidt-Rohr, K.; Spiess, H. W.

Macromolecules 1991, 24(19), 5288-93.
 Isotactic Polypropylene

Bruckner, S.; Meille, S. V.; Sozzani, P.; Torri, G. Makromol. Chem., Rapid Commun. 1990, 11 (2), 55-60.
Syndiotactic Polypropylene
 Syndiotactic Polypropylene

helix s(2/1)2
(ttgg)n

Sozzani, P.; Simonutti, R.; Galimberti, M. Macromolecules 1993, 26 (21), 5782-9.

 Syndiotactic Polypropylene

extended chain

Chatani form

Sozzani, P.; Galimberti, M.; Balbontin, G. Makromol. Chem., Rapid Commun. 1992, 13 (6), 305-10.
Sozzani, P.; Simonutti, R.; Comotti, A. Magnetic Resonance in Chemistry 1994, 32 (Spec. Issue), S45-S52.
Metastable crystalline form

Variable temperature
13C CP-MAS spectra

T = 353 K

T = 333 K

T = 323 K

T = 298 K
 Simultaneous Crystallization of Isotactic and
Syndiotactic Sequences of Polypropylene
isotactic sequences

α2 form
disordered
form

b)

extended
s(2/1)2 helix form
chain

syndiotactic sequences

50.2 46.8 43.4 40.0 36.6

(ppm)

Comotti, A.; Simonutti, R.; Bracco, S.; Castellani, L.; Sozzani, P. Macromolecules 2001, 34 (14), 4879-4885.