DNP RMN des Solides Instrumentation - Bruker · Innovation with Integrity DNP RMN des Solides...
Transcript of DNP RMN des Solides Instrumentation - Bruker · Innovation with Integrity DNP RMN des Solides...
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Innovation with Integrity
DNP RMN des Solides Instrumentation
30ème Réunion Utilisateurs RMN, 29 et 30 novembre 2016, Paris
Fabien AUSSENAC, Applications RMN
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
• Low nuclear polarization (P) at thermal equilibrium
B0
12
12
E DE
9.4 T (400 MHz) T=300 K
Spins difference between the 2 energy levels
is only 32 over 1 million!
Spin 1/2 nucleus in B0 magnetic field
● ● ● ●
● ● ● ● ●
Increasing the Sensitivity of NMR
• Pulses sequences
Transferts CP, INEPT
• High magnetic field
S/N B03/2 23.5 T, 1 GHz
• Reduction of electronic noise
Cryoprobe S/N ≈ factor 4
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
Increasing the Sensitivity of NMR Hyperpolarization
● Ultra Low Temperature (few mK) ● Optical pumping (3He, 129Xe, MRI applications) ● Para Hydrogen Induced Polarization (PHIP)
● Dynamic Nuclear Polarisation (DNP)
Figure: Münnemann, Nature Physics, 2011, 7, 522
Hyperpolarization
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
DNP: Dynamic Nuclear Polarization
• Transfer high electron polarization to nuclei:
• Irradiate at EPR frequency (GHz)
• Detect at NMR frequency (MHz)
• High potential gain in sensitivity: 10-100’s+
• Solid State DNP spectrometers: E B0
EPR
NMR
NMR
Magnetic Field
Microwave
Frequency
1H NMR
Frequency
9.4 T 263 GHz 400 MHz
14.1 T 395 GHz 600 MHz
18.8 T 527 GHz 800 MHz
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
Solid-State DNP Spectrometer
Gyrotron
LT-MAS DNP probe
Transmission line
MAS cooling system
Rosay et al., Phys. Chem. Chem. Phys., 2010, 12, 5850 Rosay et al., J. Magn. Reson., 2016, 264, 88
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
Solid-State DNP Spectrometer
Microwave source Gyrotron
DNP Probe
NMR Magnet
Low-temperature Magic Angle Spinning (LTMAS) Cabinet
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
Gyrotrons for DNP-NMR Applications
Gyrotron Schematic
ELECTRON GUN
ANODE
CAVITY
LAUNCHER
MIRRORS
MILLIMETER WAVES
WINDOW
COLLECTOR
ELECTRON BEAM
SUPERCONDUCTING MAGNET
• DNP gyrotrons introduced by Robert Griffin and Richard Temkin at MIT
mc
eB
c
cRF harmonicnn
0
,~
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
395 GHz DNP signal enhancement as a function of microwave power Sample: 1 M of 13C Urea in glycerol-d8/D2O/H2O
(60/30/10) with 10 mM AMUPol 108 K, 12 kHz, 3.2mm sapphire rotor
Gyrotron Microwaves Power Curve
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
Gyrotron Magnet
9.7 T magnet
(527 GHz second harmonic)
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
• Push button user interface: ON/OFF/Standby
• Controls and regulation:
• Temperatures, voltages, water cooling, gyrotron magnet
• Output power stabilization
Gyrotron Control System
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
263, 395, 527 GHz Solids DNP
1H NMR WB NMR Magnet
Gyrotron Frequency
Harmonic Gyrotron magnet
400 MHz 400/89 Ascend DNP
263 GHz 2nd 4.8 T cryogen-free
600 MHz 600/89 Ascend DNP
395 GHz 2nd 7.2 T cryogen-free
800 MHz 800/89 USP RS 527 GHz 2nd 9.7 T cryogen-free
• Second-harmonic with cryogen-free gyrotron magnets for all frequencies:
– Combined site planning guide 263, 395 and 527 GHz
– Yearly control system/high voltage safety service visit. Gyrotron magnet
service required every 2 years
• Sweep coils on all new DNP NMR magnets
• Plus LTMAS cooling system and DNP probe
• Applications areas: biological solids and material science with enhanced sensitivity
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
Sweep coils on all New DNP NMR Magnets
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
398.7 398.9 399.1 399.3 399.5 399.7 399.9 400.1 400.3 400.5
1H Frequency (MHz)
Field dependence curve on 13C Proline in glycerol-d8/D2O/H2O with 15 mM TOTAPOL
400 MHz/263 GHz
DN
P g
ain
(a.
u.)
Power supply
• Different radicals • Samples with endogenous radicals
• Direct DNP on X nuclei
400 DNP Ascend ± 750 Gauss
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
• Available for different rotor sizes: 3.2 mm (28 μL, 15 kHz) 1.9 mm (10 μL, 25 kHz) 1.3 mm (2 μL, 40 kHz)
• H/X/Y and H/X WB probes
• Low sample temperature and R.F. circuit ~100 K
• Cold insert/eject capability
• Individual heaters for VT, bearing
and drive gases for optimal temp. control
• Waveguide for microwave irradiation
• Long term operation (days, weeks)
Low temperature (LT) MAS DNP Probe
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
Axial cross section of a 3.2mm MAS system
Upper part of a 3.2mm LT-MAS DNP probe
LT-MAS DNP Probe
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
LT-MAS DNP Probe
Probe Base
Microwave Waveguide from Gyrotron
Cold Gas and Vacuum Lines From LTMAS Cabinet
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
DNP MAS Rotors
• 3.2 mm: sapphire rotors, zirconium oxide drive caps
• Silicon plugs inserts
• Teflon inserts
• 1.9 & 1.3 mm: zirconia rotors, Vespel drive & bottom caps
1.3 mm
2 mL
40 kHz
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
LT-MAS Heat Exchanger
he
Heat
Chamber heater
Pt100 detects
LN2 filling level
Warm gas in at
2 bar
Cold gas outlet
Exchanger Coil
Chamber P=2.5 bar Boiling @ T= 90 K
60L LN2 Dewar @ 77K
Pressure sense
condensation
P. Allen, F. Creuzet, H.J.M. deGroot, R.G. Griffin, J. Magn. Reson., 1991, 92, 614
• Pressurized heat exchanger chambers
• Automatic refill of liquid nitrogen supply
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris
● Twelve 263 GHz/ 400 MHz ● Ten 395 GHz/ 600 MHz ● Five 527 GHz/ 800 MHz
527 GHz/ 800 MHz
Solid-State DNP Spectrometers 27 Installed Spectrometers WW (Oct. 2016)
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30ème Réunion Utilisateurs RMN – 29-30 novembre 2016 – Maison de la Chimie, Paris 9. Dezember 2016 19 © Copyright Bruker Corporation. All rights reserved