the brocode of nmr: broadband cooperative...

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


Dipolar Couplings:


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


IBG2 / IOC 4 23.01.2015

Couplings in NMR


Dipolar Couplings:


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


IBG2 / IOC 5 23.01.2015

Why decoupling? Sensitivity!


Quinine

1D 13C NMR (1% natural abundance)

IBG2 / IOC 6 23.01.2015

Why decoupling? Interpretability!


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,…)


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


𝜌 𝑡 = 𝐼𝑥 cos 𝜋𝐽𝑡 + 2𝐼𝑦𝑆𝑧sin(𝜋𝐽𝑡)

𝐼𝑥 𝑡 = cos(𝜋𝐽𝑡)

IBG2 / IOC 10 23.01.2015






IBG2 / IOC 11 23.01.2015




1/Tp „Harmonics“

1/2Tp „Subharmonics“



IBG2 / IOC 12 23.01.2015

Bilevel decoupling

Sideband modulation is delayed by multiples of Tp/2 using short strong pulses


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


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%


sim

exp

1 2 4

IBG2 / IOC 15 23.01.2015

WURST @ RFRMS = 4.4 kHz side view


1 2 4

sim

exp

IBG2 / IOC 16 23.01.2015

WURST @ RFRMS = 4.4 kHz side view (RMS)


sim

exp

1 2 4

IBG2 / IOC 17 23.01.2015

BROCODE: the new testament


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


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


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%


sim

exp

1 2 4

IBG2 / IOC 21 23.01.2015

WURST @ RFRMS = 2 kHz side view


sim

exp

1 2 4

IBG2 / IOC 22 23.01.2015

WURST @ RFRMS = 2 kHz side view (RMS)


sim

exp

1 2 4

IBG2 / IOC 23 23.01.2015

BROCODE @ RFRMS = 2 kHz top view


sim

exp

1 2 4

IBG2 / IOC 24 23.01.2015

BROCODE @ RFRMS = 2 kHz side view


sim

exp

1 2 4

IBG2 / IOC 25 23.01.2015

BROCODE @ RFRMS = 2 kHz side view (RMS)


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…)



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


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


Thank you for your attention!

the brocode of nmr: broadband cooperative...

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