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Dynamic Nuclear Polarization Enhanced NMR in the Solid-State

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Hyperpolarization Methods in NMR Spectroscopy

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 338))

Abstract

Nuclear magnetic resonance (NMR) spectroscopy is one of the most commonly used spectroscopic techniques to obtain information on the structure and dynamics of biological and chemical materials. A variety of samples can be studied including solutions, crystalline solids, powders and hydrated protein extracts. However, biological NMR spectroscopy is limited to concentrated samples, typically in the millimolar range, due to its intrinsic low sensitivity compared to other techniques such as fluorescence or electron paramagnetic resonance (EPR) spectroscopy.

Dynamic nuclear polarization (DNP) is a method that increases the sensitivity of NMR by several orders of magnitude. It exploits a polarization transfer from unpaired electrons to neighboring nuclei which leads to an absolute increase of the signal-to-noise ratio (S/N). Consequently, biological samples with much lower concentrations can now be studied in hours or days compared to several weeks.

This chapter will explain the different types of DNP enhanced NMR experiments, focusing primarily on solid-state magic angle spinning (MAS) DNP, its applications, and possible means of improvement.

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Abbreviations

APG:

Alanyl-prolyl-glycine

B 0 :

External magnetic field

B 1 :

RF field strength

B 1e :

MW field strength

bCTbK:

bis-cyclohexyl-TEMPO-bisketal

BDPA:

1,3-Bisdiphenylene-2-phenyl allyl

BT2E:

bis-TEMPO-2-ethylene oxide

bTbk:

bis-TEMPO-bisketal

bTbtk-py:

bis-TEMPO-bis-thioketal-tetra-tetrahydropyran

BTOX:

bis-TEMPO tethered by oxalate

BTOXA:

bis-TEMPO tethered by oxalyl amide

BTUrea:

bis-TEMPO tethered by urea

BWOs:

Backward wave oscillators

c :

Concentration

CE:

Cross effect

CIDNP:

Chemically induced dynamic nuclear polarization

CP:

Cross polarization

DMSO:

Dimethyl sulfoxide

DNP:

Dynamic Nuclear Polarization

DOTAPO-TEMPO:

4-[N,N-Di-(2-hydroxy-3-(TEMPO-40-oxy)-propyl)]-amino-TEMPO

DQ:

Double quantum

EIKs:

Extended interaction klystrons

EIOs:

Extended interaction oscillators

EPR:

Electron paramagnetic resonance

FT:

Fourier transform

IMPATT:

Impact ionization avalanche transit-time

INEPT:

Insensitive nuclei enhanced by polarization transfer

K:

Kelvin

MAS:

Magic angle spinning

MRI:

Magnetic resonance imaging

MW:

Microwave

nAChR:

Nicotinic acetylcholine receptor

N e :

Number of electrons

N-f-MLF-OH:

N-Formyl-Met-Leu-Phe-OH

NMR:

Nuclear magnetic resonance

NT-II:

Neurotoxin II

OX063 (Trityl):

Tris{8-carboxyl-2,2,6,6-benzo(1,2-d:4,5-d)-bis(1,3)dithiole- 4-yl}methyl sodium salt

PE:

Paramagnetic effects

PHIP:

Para-hydrogen induced polarization

PRE:

Paramagnetic relaxation enhancement

Q-factor:

Quality factor

S/N:

Signal-to-noise ratio

SD:

Spin diffusion

SE:

Solid effect

SQ:

Single quantum

T:

Tesla

T 1DQ :

Double quantum relaxation time

T 1e :

Electron spin-lattice relaxation time

T 1n :

Nuclear spin-lattice relaxation time

T 1p :

Nuclear relaxation time in the rotating frame

T 1ZQ :

Zero quantum relaxation time

T 2e :

Electron spin–spin relaxation time

T 2n :

Nuclear spin–spin relaxation time

TEMPO:

2,2,6,6-Tetramethylpiperidinoxyl

TJ-DNP:

Temperature-jump dynamic nuclear polarization

TM:

Thermal mixing

TOTAPOL:

1-(TEMPO-4-oxyl)-3-(TEMPO-4-amino)-propan-2-ol

W:

Watt

ZQ:

Zero quantum

Δ :

Inhomogeneous breadth of the EPR spectrum

δ :

Homogeneous EPR linewidth

ε :

Enhancement

γ e :

Gyromagnetic ratio of electron

γ n :

Gyromagnetic ratio of nucleus

κ :

Sensitivity

τ B :

Polarization buildup time constant

τ R :

Rotor period

ω 0e :

Electron Larmor frequency

ω 0I :

Nuclear Larmor frequency

ω R :

Spinning frequency

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Acknowledgements

We gratefully acknowledge very helpful discussions and proof reading of Shimon Vega, Akiva Feintuch, Yonatan Hevov, and Thorsten Maly. UA and HO acknowledge funding from the European Union Seventh Framework programs (FP7/2007–2013 under the grant agreements 261863 (Bio-NMR) and Deutsche Forschungsgemeinschaft (grant 05106/12-1 of the DIP program).

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  1. NMR Supported Structural Biology, Leibniz Institute für Molekulare Pharmakologie, Robert Roessle Str. 10, 13125, Berlin, Germany

    Ümit Akbey, W. Trent Franks, Arne Linden, Marcella Orwick-Rydmark, Sascha Lange & Hartmut Oschkinat

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  1. Ümit Akbey
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  2. W. Trent Franks
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  1. Europ. Neuroscience Institute Göttingen, Göttingen, Germany

    Lars T. Kuhn

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Akbey, Ü., Franks, W.T., Linden, A., Orwick-Rydmark, M., Lange, S., Oschkinat, H. (2013). Dynamic Nuclear Polarization Enhanced NMR in the Solid-State. In: Kuhn, L. (eds) Hyperpolarization Methods in NMR Spectroscopy. Topics in Current Chemistry, vol 338. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2013_436

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