NMR Signals Enhanced by Dynamic Nuclear … workshop...1 NMR Signals Enhanced by Dynamic Nuclear...
Transcript of NMR Signals Enhanced by Dynamic Nuclear … workshop...1 NMR Signals Enhanced by Dynamic Nuclear...
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NMR Signals Enhanced by
Dynamic Nuclear Polarization
Application to Structural Biology
and Material Science
Frank Engelke
Bruker BioSpin GmbH
TeraHertz Workshop Lausanne, 11.-13. Feb. 2013
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1. Nuclear magnetic resonance (NMR)
and electron spin resonance (ESR or EPR)
2. Dynamic nuclear polarisation (DNP)
3. DNP-NMR in liquids
4. Solid-state DNP NMR
5. Applications
NMR signals enhanced by DNP – Application to structural biology and material science
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Nuclear Magnetic Resonance - NMR
Figure courtesy of Sami Jannin, EPFL
Atomic nuclei (1H, 13C, …),
Intrinsic angular momentum (spin),
Magnetic moment,
External const. magnetic field.
Quantization of spins,
splitting of energy levels
(Nuclear Zeeman effect)
defines spin Larmor
frequency
Transition between
Zeeman levels.
If irradiation with an ac field
oscillating at Larmor frequency
(radio frequency range)
then resonance.
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Electron Paramagnetic Resonance - EPR
Figure courtesy of Sami Jannin, EPFL
Analog for the electron spin:
Spin quantization
Energy level splittingirradiation
Transitions between
Zeeman levels.
If irradiation with an ac field oscillating
at electron Larmor frequency
(microwave frequency range)
then resonance.
Magnetic moment of electron
ca. 660 times larger than proton magnetic
moment
Electron spin resonance frequencies
ca. 660 times higher than those of 1H NMR.
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NMR of spin-1/2 nuclei
Nucleus Natural Sensitivity NMR EPR
abundance (abs.) frequency frequency
(%) at 14.1T (MHz) (GHz)
1H 99.98 1 600 395
19F 100 0.83 564.5
31P 100 0.066 242.9
13C 1.1 0.00018 150.9
29Si 4.7 0.00037 119.2
15N 0.37 0.0000039 60.8
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Zeeman coupling and chemical shift
• Zeeman coupling: Splitting of energy levels in external constant
field B0
• Chemical shift: Local variation of B0 caused by magnetic shielding
of nuclei by surrounding electrons, bond specific
and dependent on spatial orientation of molecules
relativ to B0 (anisotropic)
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NMR of liquids
120 µl flow NMR probe
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Overview
Magnets - B0
NMR console - B1 + NMR signal
Probes - B0 + B1 + sample + NMR signal
Accessories - additional functionality
for example, for DNP
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NMR magnets
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© Copyright Bruker Corporation. All rights reserved. Copyright © 2011 Bruker Corporation. All rights reserved. www.bruker.com
Pulses in FID out
NMR Experiment
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© Copyright Bruker Corporation. All rights reserved. Copyright © 2011 Bruker Corporation. All rights reserved. www.bruker.com
Analog FID out / Receiver
Spectrum
Conversion to digital: ADC
Mathematical
representation of FID
Digital FID
Digitization of a properly filtered
(anti-aliasing) FID gives the exact
mathematical representation of
the NMR signal. FFT
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© Copyright Bruker Corporation. All rights reserved. Copyright © 2011 Bruker Corporation. All rights reserved. www.bruker.com
Pulses in / Transmitter
Conversion to analog: DAC
Mathematical
representation of RF Numerically
Controlled
Oscillator A mathematically exact representation of
the excitation signals can be converted
to real distortion-free RF using an D/A
converter
Digital Pulse Sequence
Pulse Sequence (Theory)
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Some basic issues …
Figure courtesy of
S. Jannin, DNP course EPFL 2012
Na spins at lower energy level
Nb spins at upper energy level
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Polarization and magnetic resonance signal
Some basic issues …
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NMR magnets
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Electron polarization vs. nuclear spin polarization
Some basic issues …
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What is DNP?
Transfer of magnetization (polarization) of a (macroscopic)
system of electron spins to a (macroscopic) system of nuclear
spins.
Which tools do we need in oder to fully understand DNP?
- Equilibrium and non-equilibrium thermodynamics
- Electron and nuclear spin relaxation
- Quantum mechanics and quantum statistics
- Radical chemistry, chemistry of the sample
- Theory and practice of microwave/sub-THz interaction with matter
Some basic issues …
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A very concise history of DNP
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Hyperpolarization techniques
Hyperpolarization
DNP (µ waves)
CIDNP ODNP
CP PHIP
Hyperpolarization:
increase of spin polarization MI above the Boltzmann polarization
by establishing a coupling between a low-polarized spin system I
with a spin system S of high polarization or coherence order.
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How to transfer the polarization of the electron spin
system to the nuclear spin system?
DNP mechanisms
Overhauser
effect Thermal mixing Cross effect Solid effect
Chemically
induced DNP
Optically
induced DNP
DNP and fractional
Quantum Hall effect
in semiconductors
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From where do we get the electron spins?
What is a radical?
The electrons in atomic or molecular orbitals are often
spin paired (spin-up and spin down) yielding a net e spin of zero. In
radicals this “rule“ is violated and at least a single electron spin is
not paired resulting in a paramagnetic center.
Some basic issues
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NMR of solids Magic angle spinning - MAS
13C CSA 1H-1H
DD
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• Enhance nuclear polarization by
transfer from electron spins
• Principles known for 50 years
• Potential gains: γe/ γN
– For protons: ~660
– For carbons: ~2600
• Ingredients:
– Unpaired electron spin
– µ wave excitation
4% e- polarization
@ 700 MHz / 90 K
0.006% 1H polarization
@ 700 MHz / 90 K
(µw) DNP
Dynamic Nuclear Polarization
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Solid-state DNP NMR
µ DNP
Liquids Solids
Low field High field
sample shuttling
Low field High field
DNP melting experiments
Polarize at low temperature in low
field and transport/melt the sample
or perform polarizing and melting
in high field
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Solid-state DNP NMR
Principle components of an DNP-NMR spectrometer for low-temperature MAS
solid-state NMR
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Gyrotrons for DNP applications: Basic specifications of 263 GHz gyrotron
Microwave frequency 263 GHz
Microwave output power
1-50 W
Power stability ± 1%
Frequency stability ± 10 ppm
Frequency tuning ± 50 MHz
Output microwave beam
Gaussian beam
Operation modes Continuous on operation 10 days or longer
Easy and safe operation
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Microwave transmission to the NMR sample
• Internal mode converter:
• Transform gyrotron cavity TE03 cavity mode to a Gaussian beam
• Step-cut launcher (axial cut in wall)
• Five-mirror transmission system to steer and shape RF beam
• Corrugated waveguide:
• Very small ohmic loss for Gaussian beam
• Loss possible due to mode conversion in case of tilt or offset
• Some broadband capability
p d
w
2a OD
p = λ/3 d = λ/4 w < 0.5p Gaussian beam waist = 0.64a
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Transmission line components
Inside NMR probe:
8 mm waveguide
Main (19 mm) transmission line
• Microwave transmission line from gyrotron window to NMR sample
• Corrugated waveguide:
• 0.28 x 0.28 mm groove
every 0.38 mm (1/3
wavelength at 263 GHz)
in 19 mm ID waveguide
• Waveguide sections
joined end to end and
held on support structure
• Helical tap for 8 mm probe waveguide
• Directional coupler for power and frequency measurements
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DNP NMR MAS probes
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Solid-State NMR/DNP system: 400 MHz / 263 GHz
FMP Berlin, February 2009
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Solid-state NMR/DNP system: 600 MHz / 395 GHz
BBIO, Billerica, July 2012
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Solid-state NMR/DNP system: 800 MHz / 527 GHz
University of Utrecht, November 2012
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Requirements for Solid State DNP-NMR
ne TTB
B11
0
2
1~
Thermal mixing/cross effect (TM/CE) mechanism demonstrated
at high field
• Follows general trend:
DNP signal enhancement
• B1 = microwave field amplitude
• B0 = static magnetic field
• T1e = electron spin lattice relaxation time
• T1n = nuclear spin lattice relaxation time
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Biradicals: two unpaired electron spins in one molecule
• Intermolecular e-e dipolar coupling small (at 10…20mM conc.) • Intramolecular e-e dipole coupling: 22 MHz Song, et al. JACS 128, 2006
Maly, et al. JCP 128, 2008
Data courtesy of M. Rosay, et al., 2009
T1e (100K): on the order of 100 µs
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Solid-state DNP NMR: applications
Examples
• Membrane proteins (proteo and bacteriorhodopsin)
retinal conformations, role of 1H spin diffusion
• TIM: binding ligands to enzymes
• Molecules adsorbed on surfaces
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Rhodopsin
Transducin
membrane Rhodopsin in retina cells
Proteorhodopsin for photosynthesis: 27 kDa membrane protein
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Proteorhodopsin – LT.MAS
Data courtesy of C. Glaubitz, Univ. Frankfurt.
400 MHz 13C CP
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B0
mwaves 100 K
Solid-State Dynamic Nuclear Polarization (DNP)
• Transfer polarization from unpaired
electron spins to nuclear spins
ge >> gn
• Driven by microwave irradiation at
or near EPR frequency
-50300 250 200 150 100 50 0 ppm
15N Chemical Shift
SB
X 16
V. Ladizhansky, University of Guelph
DNP/NMR
H2O/ glycerol
H2O/ glycerol
H2O/ glycerol
H2O/ glycerol
H2O/ glycerol
H2O/ glycerol
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Triose phosphate isomerase dimer. Each subunit 250 aa with 8 a-helices outside and 8 parallel b-strands inside. a/b protein folds including alternating pattern of a-helices and b-strands form a solenoid that closes on itself in a toroidal shape (TIM barrel)
DNP experiments on TIM (TPI)
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Cutting into two triose phosphates
TPI • to be found in
almost every organism
• important enzyme in
glycolysis
(energy production)
• catalyzes the reversible
interconversion
of dihydroxy acetone
phosphate and
D-glyceraldehyde 3-
phosphate
(both are isomers
of triose phosphate)
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13C Chemical Shift (ppm)
DNP experiments on TIM (TPI)
• Frozen solution of microcrystalline yeast triose phophate isomerase (TIM) with 20 mM TOTAPOL in glycerol/water
• 32 scans, 2 second recycle delay
• 9 kHz MAS
• 105 K sample temperature
Acknowledgment:
Ann McDermott, Yimin Xu, Ansgar Siemer, NYSBC
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• DNP-enhanced 13C -13C -
correlation experiment
• Protron-driven spin diffusion with
22 ms mixing time
• 9 kHz MAS, 105 K sample
temperature
• 100 kHz decoupling
• 4 scans, 2.5s recycle delay, 768
t1 points. Total experiment time:
2h 10min
Sample courtesy of Ann McDermott, Yimin Xu,
Ansgar Siemer, NYSBC
DNP experiments on TIM (TPI)
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DNP on molecules adsorbed on surfaces
A. Lesage, M. Lelli, D. Gajan, M.A.Caporini, V. Vitzthum, P. Mieville, J. Alauzun, A. Roussey,
C. Thieuleux, A. Medhi, G. Bodenhausen, C. Coperet, L. Emsley in: Euromar, Florence, 2010.