Post on 26-Dec-2015
Introduction and Scope of this Course
(Mission Impossible[1])
Spectroscopic methods that means:
•·
[1] The topic means material for several year's courses. Consequently, this course (and text) can rather give a coarse overview and a collection of literature to go for the details. No completeness is claimed and no perfection!
• NMR spectroscopy•· Dielectrical spectroscopy•· Infrared spectroscopy •· UV-vis spectroscopy•· X-ray spectroscopy
Mass spectroscopy• dynamic-mechanic spectroscopy
Material properties of polymers:
•Chemical structure•Configuration•Conformation•Physical Structure•Dynamics
in the liquid and in the solid state
Infrared Spectroscopy: 760 nm….1mm
near infrared“quartz-infrared”
~ 10,000…4,000 cm-1
NIR
middle infrared“conventional” infrared~4,000…250 cm-1
far infrared< 250 cm-1
use of quartz cuvettes and light pipeshigher order absorptions (lower intensity)liquids can be measured in thicker layers
4000 cm-1…50 cm-1
fundamental vibrations4000 cm-1…400 cm-1
fundamental vibrations12500 cm-1…4000 cm-1
overtones & combinations
scattering absorption absorption
monochromatic excitation source dispersed polychromatic radiation
information from scattered radiation information from absorbed radiation
homonuclear functionalitieschanges in polarizability
polar functionalitieschanges in dipol moment
CH/OH/NHfunctionalities
high structural selectivity high structural selectivity low structural selectivity
Iraman~ c Lambert-Beer-Law Lambert-Beer-Law
no sample preparation required
no sample preparation required
sample preparation required (except ATIR)
sample volume µLsample thickness µm
sample thickness up to cm-rangesample volume µLsample thickness µm
light-fiber optics>100 m
light-fibre optics>100 mlimited
Raman MIR NIR
1790-1720 very strong
1610-1590,1600-1580 and1510-1490
Modif.EpoxiesPolycarbo=nates
Alkyd-,Polyesters,Cellulose=ether,PVC (plasticized)
Polyvinyl=acetate,PVC-copo=lymers
Cellulose=esterPolyure=thane
Acrylics,Polyester Phenol
derivatives,Epoxies
Polystyrenes,Arylsilicones,Aryl-alkyl=Silicone Co=polymers
Polyamides,amines
Nitrocellulosecellophan
Cellophan, Alkylcellulose,PVA, PEO
PAN, PVC,Polyvinyliden chlorid,POM
Alkylsilicone,aliphatic hy=drocarbons,Polytetra=Fluorethylene,Thiokol
1450 -1410 sharp1680 - 1630 strong
1550 - 1530
1610 –1590,1600 – 1580 and1510 - 1490
3500 - 3200
1100 - 1000
1450 - 1410 sharp840 - 820
3500 - 3200
strong
All numbers have the meaning of wave numbersand are given in cm-1
yes no
Inte
nsi
ty, arb
itra
ry u
nit
s
1/d= 2/n (1/ n = number of minima between two maxima and
wave length
3500-3200 cm-1
1790-1720 cm-1
1610-1590
1600-1580 cm-
1
1510-1490
1680-1630 cm-1 1550-1530 cm-1
Polyamid
epoxies, polycarbonate, alkyd resins, polyesters,cellulose-ether, PVCpoly(vinyl acetate), PVC-copoly., cellulose ester, PUacryl polymers
Phenol resins, epoxies, aryl polymers
1790-1720 cm-1
modified epoxides, polycarbonate, Alkyd resins, polyester, cellulose ester, cellulose ether, PVC (plast), PVAc, PVC-copolym., PU, acrylics
1610-1590 1600-1580 cm-1
1510-1490
modified epoxides, polycarbonate, Alkyd resins, polyester, cellulose ester, cellulose ether, PVC (plast)
820-840 cm-1
modified epoxies, polycarbonate polycarbonate
?
polycarbonate
1610-15901600-1580 cm-1
1510-1490 1450-1410 cm-1
1100-1000 cm-1
typical pattern of normal PC
typical pattern of PU
C-O-C-ether region
Poly (ether urethane)
? cellulose ester or polyurethane ?
Infrared Spectroscopy: 760 nm….1mm
near infrared“quartz-infrared”
~ 10,000…4,000 cm-1
NIR
middle infrared“conventional” infrared~4,000…250 cm-1
far infrared< 250 cm-1
use of quartz cuvettes and light pipeshigher order absorptions (lower intensity)liquids can be measured in thicker layers
NIR
•Hydrogen-containing groups are dominant•Information is often implicid, coupled vibrations•Not suited for trace analysis
•Easy analysis of aqueous solutions•Process-analysis•Use of light-pipes even without cuvette (reflection)•Easy analysis of powders using diffuse reflection•Characterisation of fillers•Determination of water contents in liquids and solids
general pertubationmechanical, electric, electro-magnetic, chemical,…
Electro-magnetic probeIR
X-ray, UV-vis, NMR,…
Samples are exposed to external pertubations such as:
temperaturepressurestress
Resolution (the large number) of overlapping NIR bands can be enhancedand MIR and NIR correlation spectra are very useful for peak assignement
NMR can provide information about:•Polymers in Solution
•The microstucture of polymer chains•Resonance assignement•regioisomerism•Stereochemical configuration•Geometric isomerism•Isomerism in diene polymers•Asymmetric centres in the main chain•Branching and cross-linking•End groups•Configurational statistics•Copolymerization sequences•Chain conformation in solution•Intermolecular association
1H: natural abundance 99.9844relative sensitivity 1chemical shift range 10 ppm1H-1H-spin-spin coupling chemical environmentchemical structure, regiochemistry, stereochemistry,conformation
13C: natural abundance 1.108%relative sensitivity 1.5910-2
Chemical shift range 250 ppmlong relaxation times sensitive to subtle changes in the near electronicenvironment but insensitive for long-range inter-actions (solvent effects, diamagnetic anisotropy of neighbouring groups)no homonuclear couplingSeparate resonance for every C in a molecule
But also other e. g.: Si, O, N, P, Al, Xe (!)…can be important
Characterization in the Solid StateChain conformation in the solid stateSolid-solid transitionsOrganization in the solid stateIn multi-phase polymersOrientationImaging
Dynamics of Polymers in the Solid StateSemicristalline polymersAmorphous polymers
Polymer SystemsPolymer blends and miscibilityMultiphase systems
• spin-echo pulses• selective scalar-spin decoupling• off-resonance decoupling• selective 13C-excitation• selective multiplet acquisitation (DANTE)• signal enhancement by polarisation tranfer• proton multiplicity on carbons (INEPT, DEPT)• C-C connectivity (INADEQUATE)• 2-Dimensional (and higher) NMR (COSY, NOESY)
“Many of the substantial improvements in NMR are the result of the spin gymnastics that can be orchestrated by the spectroscopist”*) onthe Hamiltonean with a mystic zoo of weird pulse sequences**)
*) T. C. Farrar **)M. Hess
“Advances in liquid and solid state NMR techniques have so changed the picture that it is now possible to obtain detailed information about
• the mobilities of specific chain units• domain structures• end groups• run numbers• number-average molecular weights• minor structure aberations
in many synthetic and natural products at a level of 1 unit per 10,000 carbon atoms and below”
J. C. Randall (eds.) NMR and Macromolecules, ACS-Symp. Ser. 247, American Chemical Society, Washington DC (1984), p. 245
10-12 10-10 10-8 10-6 104 102 100
T1, T2, NOE 2D exchange
correlation times [s]
2H lineshape
CSA lineshape
dipolar lineshape
T1
2H echo
dynamic rangemeasured bydifferent NMR-techniques
nuclei with a spin quantum number I *)
angular momentum J = ħ {I (I+1)}1/2
magnetic moment mI = I, I-1, I-2…0…-I (2I+1) states
nuclear magnetic moment (z-component) µz = **) ħ mI
energy of the state: E = µz B0 = - ħ mI
B0
Larmor-frequency: 0 = 20 = B0 mI
an ensemble of isolated spins I = 1/2in an external field B0 split up into two states (lower) and
(higher)energy difference: E = E-E=h0= ħ 0= ħ B0
in an external field B0:
*) integers are Bosons others are Fermions **) (experimental) magnetogyric ratio
E = h =ħ = ħB 0
N = N exp(- kbT)
N
N
E(B0=14.1T) 0.5 J
B0
B1
E=ħ (spin =1/2 nuclei)
B = H
B = magnetic flux density (induction) [T]*)
H = magnetic field strength [A m-1] = permeability
B or H ?? A question of “taste”B ~ origin of the fieldH ~ field properties
T = kg s-2 A-1 = V s m-2 =104 G
H0
rf-transmission andDetection coil (antenna)
laboratory (static) frame:coordinates x, y, z
rotating frame:coordinates x’, y’, z’
• branching in PE• thermal oxidation in PE• stereoregularity e.g. PMMA, PP• directional isomerism (regio-isomerism: head-tail,…)• copolymer structure
• comparison of the chemical shift with known model-compounds• calculation of 13C-shifts by the (additive) increment method• synthesis of polymers with known structure or compositional features• selective 13C-enrichment• comparison of experimental results with calculated intensities (simulation of the polymerisation kinetics)• determination of C-H bonds (INEPT)*, C-C bonds (INADEQUATE)*• 2-dimensional techniques
* These are specific pulse sequences for particular spectral editing
“The concept of the rotating frame is of paramount importance in NMR-spectroscopy. For almost all classical descriptions of NMR-experiments are described using this frame of reference”
D. E. Traficante
rotating frame y’
X’
B0
B1
static laboratory frame
y
x
z=z’the frame is rotating withthe frequency of the appliedrf-field
a nucleus with the Larmor frequencyequal to the rotation of the frame isstatic with respect to the frame
the original focussed and in-phase in the x-y plane rotating magnetisationdecreases by two effects:
•interaction with the environment (“the lattice”) •Relaxation time T1 (spin-lattice relaxation, longitudinal relaxation)
•interaction with neighbouring spins (dephasing) •Relaxation time T2 (spin-spin relaxation, transversal relaxation)Mz(t)-Mz(t=0) ~ exp
[-t/T1]My(t)-My(t=0) ~ exp [-t/T2]
the “effective” T2 (T2*) is responsible for
the line broadening (transversal relaxation + inhomogeneous field
broadening):1/2= 1/(T2
*)1/2= line-width at ½ of the peak-height [Hz]T1 is the longitudinal relaxation time in the rotating frame.
T1 >T1
in solids and in solutions of high polymers: T1>>T2
T2 is affected by molecular motion at the Larmor frequency and low-frequency motions around 102-103 Hz
non-viscous liquids T1 = T2
T1 sensitive to motions 5-500 MHz*)
T1 is sensitive to motions in the tens kHz-range
13C-Relaxations
*) short range, high frequency segmental motions, local environment is reflected
90°-pulse dephasing
slow
fast
180°-pulse
Re-focussing re-focussed and echoslow
fast
only the “inhomogeneous”contribution of the T2is refocus= sed
the resultof the “true” T2-process is not re-focussed
the echo decays according to the true T2
Direct chemical exchange (e. g.: the hydroxyl proton of an alcohol with water protons)
Magnetization exchange (e. g.: cross-polarization, NOE)
Decoupling of heteronuclear spin coupling causes the NUCLEAR OVERHAUSER EFFECT (NOE)
Decoupling 1H-13C saturates 1H and changes the 13C-spin population
excess 13C in the lower level compared with the equilibrium distribution
more energy is absorbed
E = 1 + (C)
NOE depends on the specific resonance makes quantification difficult
better S/N
The NOE is sensitive to the distance NOESY experiment
The total Hamilton operator is given by the sum of the individual interactions:
= z + q + dd + + k + J
z = zeeman interaction with the external magnetic field (constant term)q = quadrupol interactiondd = direct dipolar interaction = magnetic shielding (chemical shift) reflects the chemical environmentk = knight shiftJ = indirect coupling
z q dd k J
A-B A-B
2 single crystals AB with different orientationwith respect to B0
B0
powder pattern of a polycrystalline AB“iso” corresponds to an (isotropic) solution
powder pattern of a polycrystalline ABbut fully anisotropic, tensor componentsas indicated
The relaxation times are correlated with molecular motions
Cross-Polarization and Magic Angle Spinning
lattice
TCH
T1H T1
H
1H spins TH
T1CT1
C
13C spins TC
HBrf1H = CBrf
1C
Hartmann-Hahn condition
spin temperaturespin temperature
Broad lines
narrow is beautiful
…but line shape can also tell us a lot
2D-Experiments can be useful:
•for the separation of shifts and scalar couplings in isotropic phase in particular in weakly coupled homo-and heteronuclear systems
•in oriented phase, especially in static powders or magic-angle spinning samples information can be extracted by separation of dipolar couplings and anisotropic chemical shifts that cannot be obtained (easily) from 1D-spectra
•isotropic and anisotropic chemical shift components can be separated in two frequency domains in the solid state
2D-Experiments can be designed to
•separate different interactions (shifts, couplings)
•Correlate transitions of coupled spins
•Study dynamic processes (chemical exchange, cross-relaxation, transient Overhauser effects, spin diffusion…)
2-dimensional*) NMR
*) and higher
• correlated 2D-NMR• exchange 2D-NMR• resolved 2D- NMR
molecular connectivities, distances
interactions
In fact projections (contour plots) of 3D-spectra
The many possible experiments can be categorised as:
molecular motion, environment
Advantage over e. g. decoupling: no loss of information, just unravellingof overlapping signals
•The properties and motions of a spin system are represented by the Hamilton Operator H*)
*) in fact in NMR a reduced Hamiton spin operator Hs is sufficient
•When H contains contributions of different physical origin (e. g.: chemical shift, dipolar or scalar couplings…)
it is sometimes possible to separate these effects in a multi-dimensional plot
preparation evolution mixing detection
•system is prepared in a coherent non-equilibrium state•System evolves under the influence of what ever modification (pulse sequence)
•Transformation into transversal magnetization•Measurement of the transversal magnetization
collect incremented FIDs
type of experiment
X-axis Y-axis information
heteronuclear J-resolved C JCH
heteronuclear coupling constants
homonuclear J-resolved H JHH
homonuclear J and
heteronuclear chemical
shift
C correlation of H andC
COSY C correlation of all scalar coupling interactions
NOESY H, JHH , JHHspatial proximity of non-bonded protons
INADEQUATE X A +X
heteronuclear connecti-vities
2D-spectra, if the spins are modulatedBy spin-spin, chemical shift or dipole-dipoleInteractions during the evolution time
Coupling resolved spectra:y- axis coupling informationx- axis chem shift information
Coupling correlated spectra:y- axis chem shift informationx- axis chem shift information
correlated through homo-or heteronuclearor dipolar coupling
Exchange spectra: y- axis chem shift information x- axis chem shift information
correlated through chemical exchange, conformational or motional effects, orOverhauser effects from non-bonded H
J-coupling
COSY-experiment
Evolution: -t1- -t2
protons arrange according to their phasescontrolled by their individual chemical shift
sampling of the magnetization components
diagonal: all auto-correlated Hoff-diagonal: cross-correlated H with another H, shows connectivities
C CH2
CH3
CH3n
PIB
CH2
CH3
ppm (1H)
ppm 13C
CH3
CH2
C
Hetero-nuclear-2D-spectrum, no diagonalpeaks
The off-diagonal (cross-peaks) indicatethat the nuclei A and B are geometricallycloser than about 0.5 nm.
The density of cross-peaks can be fairlyhigh in real spectra (e.g.: proteins). In this case further dimensions can helpto resolve the interactions
Combined with molecular modelling andConformation-energy studies the distanceInformation can lead to 3-dimensionalMolecule structures in solution
Parella T, Sánchez-Fernando F, Virgili A (1997) J Magn Reson 125, 145
when there is a cross-peak it showsthat the spins A and B are geometrically
closer than ~0.5 nm
a real 2D proton NOE spectrumof a protein*)
For further peak assignment higher dimensions of spectroscopy are required
*)After G. W. Vuister, R. Boelens, R. Kaptein (1988) J. Magn. Res. 80, 176
Example of a 2D-NOE Spectrum
PS/PVME blend cast from CHCl3
PS/PVME blend cast from toluene
after: P. Carvatti, P. Neuenschwander, R. R. Ernst (1985) Macromolecules 18, 119
Diagonal: spin exchange, same types of spins
Off-diagonal peaks: spin diffusion among chemically different spins
no cross-peaks between PS and PVME
cross-peaks between PS and PVMEindicating (molecular) mixed domains
Self-diffusion
Spin-echo experiment
aquisitionHahn-echo pulse sequence
= diffusion time = gradient pulse length = magnetogyric ratiog = gradient strengthE = signal amplitude
unrestricted diffusion
D = diffusion coefficientRh = apparent hydrodynamic radius = viscosity of the pure solventr2 = mean-square diffusion length
Stokes-Einstein
Einstein-Smoluchowsky
6rh3