NMR Microscopy & High Power Diffusion · 2016. 12. 9. · Couette cell, cone&plate cell,...
Transcript of NMR Microscopy & High Power Diffusion · 2016. 12. 9. · Couette cell, cone&plate cell,...
Innovation with Integrity
Dr. Dieter Gross
User Meeting, 2016
Paris
NMR Microscopy & High Power Diffusion
Innovation with Integrity
2
Pourous Media11%
Flow7%
Downhole well logging7%
Rheology5%
Chemical Engineering & Catalysts
5%
Electrophoresis, Batteries, Fuel Cells, Supercapacotors
5%
Dispersions, Emulsions, Suspensions, Micells
4%
Polymers and Gels3%Plants & Wood
3%Food3%
Tablets 1%
Biofilms & Membranes3%
Filters & Biofouling1%
Mice2%
Tissue & Cartilage6%
Insects1%
Contrast agents & Nanoparticles
1%
Drying1%
Glass1%
NQR1%
MPI1%
HR_MAS1%
Combustion1%
Probes & Transmitters2%
Magnets2%
DNP & Hyperpolarisation & Parahydrogen
3%
2D Correlation Spectroscopy4%
Acquisition & Processing Methods
16%
ICMRM Cambridge 2013
3
Coils
Micro Coils, Solenoid Coils, Saddle Coils, Birdcage and SAW Coils
4 4
Rf-Coils for Microimaging N
Field MHz
200 300 400 500 600 700 750 800 900 950 10
Magnet Types
Standard Bore 52 mm, Wide Bore 89 mm, Super Wide Bore 154 mm 3
Single tuned coils 1X or X
1H, 7Li, 13C, 17O, 19F, 23Na, 31P, 129Xe, … 121
Double tuned coils1 H/X
1H/2H, 1H/13C, 1H/19F, … 120
Special combinations X/X
19F/13C, … n/n
Planar Coils
50 mm
100 mm
500 mm
1 mm
2 mm
5 mm
10 mm
15 mm
20 mm
25 mm 10
Volume coils
1 mm 2 mm 5 mm 10 mm
15 mm
20 mm
25 mm 30 mm 35 mm 40 mm 66 mm 11
RF Coils for Microimaging
5 5
Coil Type Fields Diameters Single Tuned
Double Tuned N
Microcoil 10 4 121 4.840
Surface Coil 10 5 121 6.050
Surface Coil 10 5 120 6.000
Volume Coil 10 10 121 12.100
Volume Coil 10 10 120 12.000
SWB Coil 4 4 121 1.936
SWB Coil 4 4 120 1.920
Total 44.846
Possible Coils for Microimaging
6 6
Coil Type Fields Diameters Single Tuned
Double Tuned N
Microcoil 10 4 121 4.840
Surface Coil 10 5 121 6.050
Surface Coil 10 5 120 6.000
Volume Coil 10 10 121 12.100
Volume Coil 10 10 120 12.000
SWB Coil 4 4 121 1.936
SWB Coil 4 4 120 1.920
Total 44.846
Developed Versions > 600
Only ~ 1.3 %
Realized Coils for Microimaging
7 7
Microimaging
RheoNMR
Laboratory on a Chip
Dieter Gross MRS / User Meetings 2016
RheoNMR
Combination of Rheology
MR Microscopy
N MR Spectroscopy
Dieter Gross
Bruker-Biospin GmbH Germany
Rheology deals with deformation and flow of matter
RheoNMR
Rheology is everywhere in our daily life
10
Parameters s Stress = Force/Area v Velocity . g time dependent strain or strain rate Viscosity = stress / strain
G viscoelastic modulus G = stress / strain rate G(w) = G’(w) + i G’’(w) G’ storage modulus (elastic) G’’ loss modulus (viscous)
RheoNMR
Examples of flow curves
Ares-2 Rheometer from TA Instruments
RheoNMR
Couette cell, cone&plate cell, plate&plate cell , tube
RheoNMR is the combination of
Rheology
MR Microscopy
NMR spectroscopy
Time Domain NMR (Relaxometry)
Rheology provides information about mechanical properties by viscosity, energy
storage and energy loss modulus determination.
MR Microscopy provides information at the mechanical length scale by
spatially and temporally resolved velocity maps and shear rate maps.
NMR spectroscopy provides information at the molecular length scale by spatially and
temporally resolved NMR spectra, relaxation times and diffusion constants.
RheoNMR
Components of the
RheoNMR Accessory
Developed by Tim Brox
and Petrik Galvosas,
Victoria University of
Wellington, NZ
RheoNMR Accessory for MicWB40 Microimaging Probes
14 14
Application Examples
Food
Micells
Polymers
Granular Flow
2H spectroscopy under shear
RheoNMR
0 1000 2000 3000 4000
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Experimantal Data
FIT
Monom
er
convers
ion X
/ -
Reaction time t / -
15
Cylindrical Couette Cell
sauce slips at the inner surface,
variable shear across the annulus,
low slip at the outer surface,
transition in shear rate,
shear thinning towards the outer
surface
RheoNMR
Courtesy of Paul T. Callaghan
16
Test the macroscopic
properties:
“FLOW and PLOP”
The velocity is first decreasing,
then increasing with radius,
similar to plug flow.
Indication for yield stress
properties.
RheoNMR
Courtesy of Paul T. Callaghan
17
NMR Flow Visualisation
of heterogeneous shear
and extension:
The fundamental
assumption of shear rate
constancy is not valid for
certain classes of fluid!
„Shear Banding“
RheoNMR
Courtesy of Paul T. Callaghan
18
„Shear Banding“
Fluid separates into
coexisting phases of
widely differing viscosity.
Flow instability.
Molecular ordering
effects.
RheoNMR
Courtesy of Paul T. Callaghan
KIT – The Research University in the Helmholtz Association
Institute of Thermal Process Engineering
www.kit.edu
Influence of Fluid Dynamics on Polymerization
Kinetics Measured by Rheo-NMR
Construction of an appropriate Rheo-NMR equipment
E. Laryea, G. Guthausen, T. Oerther, M. Kind
Reaction Monitoring under Shear
The influence of fluid-dynamics on the kinetics of polymerisation observed by RheoNMR
RheoNMR
Chemical reaction & NMR
spectrum under shear
Reaction Monitoring under
Shear
Courtesy of Nils Schuhardt and Esther Laryea, KIT Karlsruhe Germany
Institute of Thermal Process Engineering 21
Solvent: Xylene
Free Radical Polymerization (FRP)
09.12.2016
R = Radical, I =Initiator, M = Monomer, P = Polymer, k Coefficients , f = Radical efficiency
Initiation
Propagation
Termination
Decomposition f
f∙
)1
2(exp
][2exp][][
01
0
tk
k
IkMM d
d
d
t
pkf
k
kk 21with
Theoretical decay of monomer; batch polymerization
Institute of Thermal Process Engineering 22 09.12.2016
a b
8.0 6.4 4.8 3.2 1.6 0.0
chemical shift d / ppm
a b
a
b Methyl methacrylate
MMA Poly (methyl
methacrylate)
PMMA
Determination of monomer conversion by 1H NMR spectroscopy
1H NMR spectra of 50 wt% MMA,
49.5 wt% Xylene and 0.5 wt%
AIBN initial composition,
400MHz 5mm Tubes
Polymerization – Model System
Institute of Thermal Process Engineering 23
Construction – Rheo-NMR Cell
Inner and outer cylinder made
out of PEEK
Gap width 1 mm
Radius ratio η =𝑅𝑖
𝑅𝑜= 0.895
Concentric arrangement
realized by bearings
Temperature control via a hot
nitrogen stream
Inner cylinder coupled with
speed controlled drive
09.12.2016
coupling
bearing
heating
adapter
inner
cylinder
outer
cylinder seal
bearing
Institute of Thermal Process Engineering 24
7.5 7.0 6.5 6.0 5.5
Experimental data
Chemical shift \ ppm
Spectra under shear
Broad peaks induced by
the measuring cell
Workaround fit by
pseudo-Voigt functions
Nonlinear least-squares
solver
09.12.2016
a
b
Methyl methacrylate
MMA
c c
p- Xylene
a b
c
Fit is in good agreement with the experimental data
7.5 7.0 6.5 6.0 5.5
Experimatal data
Fit (overall)
Chemical shift \ ppm
-0.10
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
Div
erg
ence / -
𝛾 = 𝜔𝑅𝑖
𝑠 = 124 1/s Apparent shear rate:
7.5 7.0 6.5 6.0 5.5
Experimental data
Fit 1 (Xylene,c)
Fit 2 (MMA,a)
Fit 3 (MMA,b)
Chemical shift \ ppm
Institute of Thermal Process Engineering 25
Results – Monomer Conversion
09.12.2016
0 1000 2000 3000 4000
0.0
0.1
0.2
0.3
0.4
0.5
Are
a r
atio
A / -
Reaction time t / -
0 1000 2000 3000 4000
0.0
0.1
0.2
0.3
0.4
0.5
Are
a r
atio
A / -
Reaction time t / -
)1
2(exp
][2exp][][
01
0
tk
k
IkMM d
d
𝐴 𝑡 =𝐴𝑀𝑀𝐴 𝑡
𝐴𝑋𝑦𝑙𝑒𝑛𝑒 𝑡= 0.53 ∙ 𝑒−4.17∙10
−4∙𝑡
𝑋 𝑡 =𝐴 𝑡 = 0 − 𝐴(𝑡)
𝐴 𝑡 = 0
Determination of reaction rate constant 𝒌𝟏 by 1H NMR spectroscopy
0 1000 2000 3000 4000
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Experimantal Data
FIT
Mon
om
er
con
vers
ion X
/ -
Reaction time t / -
Area Ratio
Monomer conversion
Monomer concentration
𝑘1 = 2.7 ∙ 10−3𝑙0.5 ∙ 𝑚𝑜𝑙0.5
𝑠
with 𝑘𝑑 = 1.53 ∙ 10−4𝑠−1
𝛾 = 𝜔𝑅𝑖
𝑠 = 124 1/s Apparent shear rate:
s
The influence of fluid-dynamics on the kinetics of polymerisation observed by RheoNMR
Flowprofile in TCR
RheoNMR
Courtesy of Nils Schuhardt and Esther Laryea, KIT Karlsruhe Germany
Flow Observations of Granular Material
Granular material is defined as a collection of discrete macroscopic particles.
Natural examples include sand, soil and snow.
Numerous industrial processes involve granular material with examples from
agriculture (e.g. rice, sugar and seeds) to pharmaceutical production.
Depending on the properties of the individual particles, overall volume
concentration and applied external stimuli, granular materials can
behave as either a solid, liquid or gas.
NMR is a non-invasive technique for studying materials under shear.
The RheoNMR hardware is well suited for these studies.
The shear devices rheo cells can be tailored to the diameters of particles and
the desired number of grains spanning the fluid domain in SB / WB and SWB
magnets.
RheoNMR
Courtesy of Tim Brox, Petrik Galvosas, Jenifer Brown, Joe Seymour, Sarah Codd, Hilary Fabich, Daniel Holland
RheoNMR
Sample Mean Diameter
/mm ri /mm ro-ri /mm
Lobelia Seeds 0.3 16.0 7.65
Petunia Seeds 0.5 16.0 7.65
Vitamin E
Capsules 1 15.1 8.55
Mustard Seeds 2 11.1 12.55
Samples studies in a dedicated RheoNMR system for a super wide bore magnet.
Courtesy of Tim Brox, Petrik Galvosas, Jenifer Brown, Joe Seymour, Sarah Codd, Hilary Fabich, Daniel Holland
Pulse program for granular flow experiments: Double slice selection 1D imaging
sequence with velocity encoding.
The broadband (hard) p pulse in the PGSE portion allowed short observation times D
over which fewer particle interactions would occur. The encoding time was fixed at
1 ms. For each system multiple experiments were conducted as a function of the
observation time D varied between 1.8 ms to 7 ms.
RheoNMR
Courtesy of Tim Brox, Petrik Galvosas, Jenifer Brown, Joe Seymour, Sarah Codd, Hilary Fabich, Daniel Holland
Top: Axial MRI data for the four granular material systems;
(left to right) lobelia seeds, petunia seeds, vitamin E capsules and mustard seeds.
All images were 60mm by 60mm (256 points by 256 points).
Bottom: Velocity profiles for the respective granular system. In each experiment the motor
was rotated such that the tangential wall speed was 17.1 mm/s;
All velocity data were acquired with an encoding time D = 5 ms.
The vertical dashed lines indicate the boundaries of the shear cell while the horizontal
dashed line indicates the velocity of the moving wall.
RheoNMR
Courtesy of Tim Brox, Petrik Galvosas, Jenifer Brown, Joe Seymour, Sarah Codd, Hilary Fabich, Daniel Holland
Spatially resolved velocity measurements could be used to describe the
variance in particle velocities.
By observing the variance of velocity as a function of observation time D it would be
possible to estimate the mean collision time;
At observation times less than the mean collision time the variance of velocity is
constant.
These mean collision times relate to the rheology and viscosity of the granular
material and would be of great use for refining theoretical descriptions of granular flow.
NOTE: This type experiment and interpretation of granular flow behavior at different D
is somehow similar to restricted diffusion experiments using short and long diffusion
times D.
RheoNMR
Courtesy of Tim Brox, Petrik Galvosas, Jenifer Brown, Joe Seymour, Sarah Codd, Hilary Fabich, Daniel Holland
2H as a “tracer” for local order in systems under shear
RheoNMR
Courtesy of Tim Brox and Petrik Galvosas, Victoria University of Wellington NZ
2H as a “tracer” for local order in flowing systems
The spin 1 deuteron quadrupole moment interacts (of D2O or other deuterated solvents)
with the electric field gradients caused by the surrounding molecules (micelles, wormlike
surfactants) causing 2H spectral splitting depending on the local order in systems.
This can be used to probe the type and degree of ordered systems under shear by 2H
spectroscopy.
]3[2
)1cos3(
)12(4
3 22
2 IIII
QeVH z
ijzzQ
RheoNMR
Quadrupolar interaction spectroscopy
shear induced order in the wormlike
micelle solution of 18% CTAB / D2O
in 17 mm / 19 mm Couette cell
Cetyltrimethylammonium bromide
2H spectra of D2O as function of
radial position across the gap of
the Coutte cell
Courtesy of Paul T. Callaghan
RheoNMR
Courtesy of Paul T. Callaghan
Outer wall: low stress, single line
Inner wall: high stress,line splitting
finite quadrupol interaction
Formation of a nematic phase at high stress,
transition through a mixed phase region,
isotropic phase at low stress
RheoNMR
Courtesy of Tim Brox and Petrik Galvosas, Victoria University of Wellington NZ
2H spectra collected as a function of
accumulated strain
1. Mix triethylene glycol mono-n-decyl ether C10E3 in
9:1 D2O:H2O.
2. Load sample in Couette cell and shear it at 42o C
and a shear rate of 10 s-1 for approximately one
hour to establish the planar lamella phase (as
identified by 2H spectrum).
3. Once the La structure is established stop the motor
and set the temperature to 25o C where the sample
equilibrates for one and a half hours.
4. Acquiring data at a constant shear rate of 10 s-1
5. NMR data was acquired. a total of 400 NMR
experiments were run with a complete experiment
taking approximately 14 s (total experiment time
approximately 95 min)
Observation of Shear Induced Structural Transitions in a Lyotropic
Nonionic Surfactant System via deuterium spectroscopy
36 36
Conclusions
Spatially resolved velocity maps provide straight forward
identification of wall slip and information about granular flow
Spatially resolved velocity maps visualize changes in the shear
behavior and identifies shear bands
Spectroscopy under shear provides reaction monitoring in situ
under shear conditions
Deuterium spectroscopy under shear provides information about
local ordered or disordered structures on the molecular level
The combination of the NMR parameters with the traditional
rheology parameters enables a better characterization and control of
matter under flow and deformation
RheoNMR
0 1000 2000 3000 4000
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Experimantal Data
FIT
Monom
er
convers
ion X
/ -
Reaction time t / -
Acknowledgements !!!
37 37
Montana State Folks, Sarah Codd, Jenifer Brown, Hilary Fabich, Joe Seymour, Tim Brox
KIT, Esther Laryea
Gisela Guthausen
Cambridge & Wellington Folks, Daniel Holland, Hilary Fabich, Petrik Galvosas,Tim Brox
Wageningen, John van Duinhoven
Lab on Chip
for
NMR Microscopy and Localized Spectroscopy
D. Gross, Bruker-Biospin GmbH Germany
39
Standard equipment:
• Bruker Spectrometer
• Microimaging Accessory with 60 A gradient amplifiers
• Micro5 imaging probe and gradient (max strength:4.8 G/cm/A = 2.8 T/m @ 60 A)
• ParaVision software
• Micro-coil rf-inserts
Lab on a Chip
40
• Multi-turn spiral surface coils
• Geometry suitable for flat samples (tissue slices, cell layers)
• Easy access
• Compatible with optical microscopy
• ID = 1000 – 20 μm, OD = 1300 – 158 μm
P.M. Glover, R.W. Bowtell, G.D. Brown, P. Mansfield, Magn. Reson. Med. 31 (1994) 423-428 C. Massin, F. Vincent et al., J. Magn. Reson. 164 (2003) 242-25
NMR Microscopy with Isotropic Resolution below 10 μm Using Dedicated Hardware and Optimised Methods
Lab on a Chip
41
Micro Chamber Micro Chamber asembled with
the encapsulating connector
Encapsulating connector pieces
Samples in a Micro Chamber mounted on a
Micro Coil
Courtesy of Vicent Estede, University of Valencia, Spain
Lab on a Chip
42
Micro Chamber kit mounted
on top of the Micro Coil Insert
Samples in a Micro Chamber mounted on a
Micro Coil
Courtesy of Vicent Estede, University of Valencia, Spain
Lab on a Chip
43
Micro Chamber kit mounted
on top of the Micro Coil Insert
pure water was pumped through the support tubing
Micro Chamber mounted on a Micro Coil
Lab on a Chip
44
Sample in a Micro
Chamber
mounted on a
Micro Coil
overlay of the vector field and the FLASH image of water in the chamber
(in black & white without flow) with the light microscope image of the chamber
mounted on top of the microcoil
Lab on a Chip
45
MicroChamber
fresh MicroChamber
Polluted !!!
Lab on a Chip
Samples in a
Micro Chamber
mounted on a
Micro Coil
Blocked
flow
regions !!!
Construction of a new surface coil design
Simple Design, Surface coil shape adapted to a meander sample cell or a Y-mixer
Surface
Coil
Meadowcroft et al., 2007:
Housing Meander sample container
Courtesy of Dominik Meyer, Giesela Guthausen, Karlsruher Institut für Technologie (KIT), Germany
Lab on a Chip
Flow in a Y Mixer
4 0 -4
Ethanol
[ppm]
8 6 4 2 0
[ppm]
Wasser
Resonator
Saddle coil
Courtesy of Dominik Meyer, Giesela Guthausen, Karlsruher Institut für Technologie (KIT), Germany
Water
Ethanol
Lab on a Chip
T1 weighted image and Velocity Map H2O-Ethanol
Left: high signal intensity of water (shorter T1), low signal intensity of ethanol (saturation effect caused by longer T1)
Right: higher velocity of ethanol,
Water is flowing partly into the ethanol input channel !
No strong mixing !
Ethanol
Wasser
T1-weighted 1H image Velocity map
Courtesy of Dominik Meyer, Giesela Guthausen, Karlsruher Institut für Technologie (KIT), Germany
Lab on a Chip
49 49
Lab on a Chip
50 50
Broadband Diffusion Probe DiffBB
1H&19F
Broadband 31P to 15N
2H Lock
ATMA Automatic Tuning / Matching
Variable Temperature
New broadband gradient probe with ATMA for diffusion applications optimized for very strong gradient pulses up to 17 T/m fast switching times of less than 300 ms
variable temperature application -40°C to +150°C available as BBO and BBI versions available for Great60 and Great10 amplifiers
51 51
Broadband Diffusion Probe DiffBB
Material science labs in research and industry
Batteries and electrolytes in situ (e.g. 1H, 7 Li, 19F, 23Na, 31P)
Polymers (e.g. 1H, 2H, 13C, 19F)
Porous systems (e.g. 1H)
Food / Pharma (e.g. 1H, 13C, 23Na)
Strong gradient pulses at fast switching times for samples with slow diffusion and short T2 or T2* relaxation times Generation of a collection of experiments for different nuclei and at variable temperatures in one session support by ATMA without the need for changing the probe
52
Ion Mobility in Ionic Liquids by Multi
Nuclear PGSE NMR (MN-PGSE)
• Ionic liquids (IL) also called RTIL room temperature ionic
liquids are molten Salts, liquid at room temperature
• Advantages of Ils:
• Thermally stable
• Hardly inflammable
• Low vapor pressure
• Many technical applications:
• Chemical engineering, …
• Fuel cells
• Super capacitors
• Li-ion batteries
53
Application Note
Ion Mobility in Ionic Liquids by Multi Nuclear PGSE NMR
State of the Art Lithium-Ion Batteries
• Electrolytes consisting of LiPF6 in volatile alkyl carbonates.
• High ionic conductivity around 10 mS/cm at room temperature
• Lithium transference number around 0.35
Test Sample:
0.5 molar LiTNF2 (Lithium bis-Trifluoromethanesulfonimide) (LiTFSI) in
1-Butyl-1-methylpyrrolidinium bis(trifluormethylsulfonyl)imid,
in 1 mm capillary tube
Ion Mobility in Ionic Liquids by Multi Nuclear PGSE NMR
Test Sample:
0.5 molar LiTNf2, often called LiTFSI, dissolved in bmpy NTf2.
Li+ +
• Different Ions in the solution can be detected by looking at different nuclei
• Ion clusters
• Ion clustering can be controlled by additives
• Zwitterions
• Series of PGSTE diffusion experiments at variable temperature
(0oC to 100oC) • 1H, 19F, and 7Li
were measured during one automatic run
• Convection not visible
D independent of D
Sample in Capillary
MN-PGSE:1H, 19F, and 7Li Diffusion Ionic Liquid as used in Lithium-Ion Batteries
D D
• Different ions have different diffusivities
Differences will depend on additives
• All follow the
same thermal activation behavior
• Deviation from Arrhenius law is probably due to the temperature dependence of the viscosity
MN-PGSE:1H, 19F, and 7Li Diffusion Ionic Liquid as used in Lithium-Ion Batteries
D D
• Even at low temperature single exponential behavior
Fast exchange
MN-PGSE:1H, 19F, and 7Li Diffusion Ionic Liquid as used in Lithium-Ion Batteries
• ATMA improves
temperature series,
tuning changes due
to temperature
changes can be
compensated
• ATMA enables
different nuclei
• 1H and 19F are on
the same rf
channel, which
must be tuned at
each change of the
nucleus
DiffBB:1H, 19F, and 7Li Diffusion Ionic Liquid as used in Lithium-Ion Batteries
60
60
High Power Diffusion Probe, DiffBB
High power package
= diffBB + GREAT60 + BCU20
= broadband diffusion probe + 60 A gradient amplifier + gradient cooling
> 17 T/m (1700 G/cm) @ 60 A
> 2% duty cycle @ 60 A
D < 10-14 m2/s*
*If relaxation rates permit
61
61
High Power Diffusion Probe, DiffBB
Low power package
= diffBB + GREAT3/10 + air cooling
= broadband diffusion probe + 10 A gradient amplifier + air cooling
> 2.8 T/m (280 G/cm) @ 10 A
> 2% duty cycle @ 10 A
D < 10-12 m2/s*
Special package price!
*If relaxation rates permit
62
62
High Power Diffusion Probes
Diff50
Diff50 Diff30 DiffBB
RF-coils exchangeable exchangeable fixed
Rf-channels 2 2 BB plus 2H lock
Frequencies 2 nuclei
2 nuclei
broadband
Max Gradient ~ 28.5 T/m ~ 17.5 T/m ~ 17 T/m
Variable Temperature
-40°C to 80°C
-40°C to 80°C
-40°C to 150°C
Tune/Match manually manually ATMA
Imaging Option
with Micro5 gradients system
with Micro5 gradient system
No
Diff30 DiffBB
63 63
www.bruker-biospin.com