the brocode of nmr: broadband cooperative...
TRANSCRIPT
KIT – Universität des Landes Baden-Württemberg und
nationales Forschungszentrum in der Helmholtz-Gemeinschaft
Institute for Biological Interfaces II and Institute for Organic Chemistry (KIT)
www.kit.edu
The BROCODE of NMR: BROadband COoperative DEcoupling of Nuclear Spins
Tony Reinsperger, Franz Schilling, Steffen J. Glaser, Burkhard Luy
QCC Workshop, Nottingham 23.01.2015
IBG2 / IOC 2 23.01.2015
Couplings in NMR
Tony Reinsperger: BROadband COoperative DEcoupling
Dipolar Couplings:
Distances and Orientation
D ~ 0-47 kHz
N
S
N
S
HX
H
HO
3J
R
H
R H
R H
R
J ~ 125 Hz
J ~ 160 Hz
J ~ 250 Hz
three-bond
couplings:
torsion angles
one-bond couplings:
bond strength
J ~ 0-20 Hz
Scalar / J couplings
IBG2 / IOC 3 23.01.2015
Couplings in NMR
Tony Reinsperger: BROadband COoperative DEcoupling
Dipolar Couplings:
Distances and Orientation
D ~ 0-47 kHz
N
S
N
S
HX
H
HO
3J
R
H
R H
R H
R
J ~ 125 Hz
J ~ 160 Hz
J ~ 250 Hz
three-bond
couplings:
torsion angles
one-bond couplings:
bond strength
J ~ 0-20 Hz
absent in
liquids
Scalar / J couplings
IBG2 / IOC 4 23.01.2015
Couplings in NMR
Tony Reinsperger: BROadband COoperative DEcoupling
Dipolar Couplings:
Distances and Orientation
D ~ 0-47 kHz
N
S
N
S
HX
H
HO
3J
R
H
R H
R H
R
J ~ 125 Hz
J ~ 160 Hz
J ~ 250 Hz
three-bond
couplings:
torsion angles
one-bond couplings:
bond strength
J ~ 0-20 Hz
absent in
liquids
BROCODE
Scalar / J couplings
IBG2 / IOC 5 23.01.2015
Why decoupling? Sensitivity!
Tony Reinsperger: BROadband COoperative DEcoupling
Quinine
1D 13C NMR (1% natural abundance)
IBG2 / IOC 6 23.01.2015
Why decoupling? Interpretability!
Tony Reinsperger: BROadband COoperative DEcoupling
2D 1H,1H NOESY spectrum Lysozyme
0.4% 15N natural abundance
IBG2 / IOC 7 23.01.2015 Tony Reinsperger: BROadband COoperative DEcoupling
Principle of Heteronuclear Decoupling
Observation of protons (spin I) and irradiation of carbons (spin S)
J12
Spin I Spin S
Spin I coupled
RF
Spin I decoupled
IBG2 / IOC 8 23.01.2015
BROCODE: the old testament
1) robust spin inversion: adiabatic sweeps
(CHIRP, WURST, sech/tanh,…)
2) robust phase cycles:
(P5M4, STUD+,…)
3) artifact cancellation:
(bilevel, ECHO-WURST,…)
Tony Reinsperger: BROadband COoperative DEcoupling
Ray Freeman Malcolm Levitt Eriks Kupce Tom Skinner
JMR 43 (1981) 502-507
JCP 83 (1985) 2775-2802
JMR A 115 (1995) 273-276
JMR A 122 (1996) 81-84
JMR 124 (1997) 474-478
IBG2 / IOC 9 23.01.2015
Origin of Sideband artifacts
Spurious modulation according to
Tony Reinsperger: BROadband COoperative DEcoupling
𝜌 𝑡 = 𝐼𝑥 cos 𝜋𝐽𝑡 + 2𝐼𝑦𝑆𝑧sin(𝜋𝐽𝑡)
𝐼𝑥 𝑡 = cos(𝜋𝐽𝑡)
IBG2 / IOC 10 23.01.2015
Origin of Sideband artifacts
Spurious modulation according to
Tony Reinsperger: BROadband COoperative DEcoupling
𝜌 𝑡 = 𝐼𝑥 cos 𝜋𝐽𝑡 + 2𝐼𝑦𝑆𝑧sin(𝜋𝐽𝑡)
𝐼𝑥 𝑡 = cos(𝜋𝐽𝑡)
IBG2 / IOC 11 23.01.2015
Origin of Sideband artifacts
Spurious modulation according to
Tony Reinsperger: BROadband COoperative DEcoupling
1/Tp „Harmonics“
1/2Tp „Subharmonics“
𝜌 𝑡 = 𝐼𝑥 cos 𝜋𝐽𝑡 + 2𝐼𝑦𝑆𝑧sin(𝜋𝐽𝑡)
𝐼𝑥 𝑡 = cos(𝜋𝐽𝑡)
IBG2 / IOC 12 23.01.2015
Bilevel decoupling
Sideband modulation is delayed by multiples of Tp/2 using short strong pulses
Tony Reinsperger: BROadband COoperative DEcoupling
N = 2 Harmonics collapse
IBG2 / IOC 13 23.01.2015
Bilevel decoupling
Sideband modulation is delayed by multiples of Tp/2 using short strong pulses
Tony Reinsperger: BROadband COoperative DEcoupling
N = 4 Subharmonics collapse
IBG2 / IOC 14 23.01.2015
WURST @ RFRMS = 4.4 kHz top view
Offset range = 40 kHz, J = 141 Hz (Methanol), sidebands +/- 0.2-2%
Tony Reinsperger: BROadband COoperative DEcoupling
sim
exp
1 2 4
IBG2 / IOC 15 23.01.2015
WURST @ RFRMS = 4.4 kHz side view
Tony Reinsperger: BROadband COoperative DEcoupling
1 2 4
sim
exp
IBG2 / IOC 16 23.01.2015
WURST @ RFRMS = 4.4 kHz side view (RMS)
Tony Reinsperger: BROadband COoperative DEcoupling
sim
exp
1 2 4
IBG2 / IOC 17 23.01.2015
BROCODE: the new testament
Tony Reinsperger: BROadband COoperative DEcoupling
Optimal Tracking
Steffen Glaser Navin Khaneja Burkhard Luy Tom Skinner
Multi-Scan Cooperativity
JMR 172 (2005) 296-305
JMR 201 (2009) 7-17
JMR 207 (2010) 114-123
𝜌 =1
𝑁 𝜌𝑗
𝑁
𝑗=1
IBG2 / IOC 18 23.01.2015
Sideband suppression by Optimal Control
Single scan: Angew. Chem. Int. Ed. 53 (2014) 4475-4479
Multiple scans (this work): beyond composite pulses and adiabaticity
Tony Reinsperger: BROadband COoperative DEcoupling
max 𝐼𝑥 (𝑡)
min𝜎 𝐼𝑥 𝑗,𝑡
IBG2 / IOC 19 23.01.2015
Sideband suppression by Optimal Control
Single scan: Angew. Chem. Int. Ed. 53 (2014) 4475-4479
Multiple scans (this work): beyond composite pulses and adiabaticity
Tony Reinsperger: BROadband COoperative DEcoupling
max 𝐼𝑥 (𝑡)
min𝜎 𝐼𝑥 𝑗,𝑡
IBG2 / IOC 20 23.01.2015
WURST @ RFRMS = 2 kHz top view
Offset range = 40 kHz, J = 141 Hz (Methanol), sidebands +/- 0.5-5%
Tony Reinsperger: BROadband COoperative DEcoupling
sim
exp
1 2 4
IBG2 / IOC 21 23.01.2015
WURST @ RFRMS = 2 kHz side view
Tony Reinsperger: BROadband COoperative DEcoupling
sim
exp
1 2 4
IBG2 / IOC 22 23.01.2015
WURST @ RFRMS = 2 kHz side view (RMS)
Tony Reinsperger: BROadband COoperative DEcoupling
sim
exp
1 2 4
IBG2 / IOC 23 23.01.2015
BROCODE @ RFRMS = 2 kHz top view
Tony Reinsperger: BROadband COoperative DEcoupling
sim
exp
1 2 4
IBG2 / IOC 24 23.01.2015
BROCODE @ RFRMS = 2 kHz side view
Tony Reinsperger: BROadband COoperative DEcoupling
sim
exp
1 2 4
IBG2 / IOC 25 23.01.2015
BROCODE @ RFRMS = 2 kHz side view (RMS)
Tony Reinsperger: BROadband COoperative DEcoupling
sim
exp
1 2 4
IBG2 / IOC 26 23.01.2015
Almost done…
Conclusion
Cooperativity provides additional degrees of freedom
Optimal Tracking does not induce systematic artifacts
Optimal Control yields solutions beyond established limits
Outlook
Some troubleshooting
Applications
High duty cycle experiments (ASAP…)
Perfect lineshape
„exotic nuclei“ (extreme bandwidth / couplings: 19F, 31P, metals…)
Tony Reinsperger: BROadband COoperative DEcoupling
IBG2 / IOC 27 23.01.2015 Tony Reinsperger: BROadband COoperative DEcoupling
Acknowledgements
Prof. Dr. Ilya Kuprov
(Southampton, UK)
BioInterfaces in
Technology &
Medicine – Grad
School
Prof. Dr. Steffen Glaser
Dr. Franz Schilling
Prof. Dr. J.Paradies
2 x 8-core CPU
Number cruncher
IBG2 / IOC 28 23.01.2015 Tony Reinsperger: BROadband COoperative DEcoupling
Picture L to R: Emine Sager, Johanna Becker, David Schulze Sünninghausen, Thomas Gloge
Julyana Machado*, Martin Koos, Hannes Feyrer, Dr. Manuela Rist ∞ Prof. Dr. Burkhard Luy ∞,
Malin Reller, Dr. Sebastian Ehni, Dr. Pavleta Tzvetkova, Dr. Benjamin Görling
Dr. Armando Navarro Vazquez*
Further: PD Dr. Claudia Muhle-Goll, Marika Kromke, Mojtaba Ebrahimi*,
Rebecca Rothenberger, Patrick Schuster, Andreas Kalkbrenner
*visiting scientists
Acknowledgements
Me