A gadolinium spin label with both a narrow central transition and short tether for use in double electron electron resonance distance measurements

Anokhi Shah; Amandine Roux; Matthieu Starck; Jackie A. Mosely; Michael Stevens; David G. Norman; Robert I. Hunter; Hassane El Mkami; Graham Smith; David Parker; Janet E. Lovett

doi:10.1021/acs.inorgchem.8b02892

A gadolinium spin label with both a narrow central transition and short tether for use in double electron electron resonance distance measurements

Anokhi Shah, Amandine Roux, Matthieu Starck, Jackie A. Mosely, Michael Stevens, David G. Norman, Robert I. Hunter, Hassane El Mkami, Graham Smith, David Parker, Janet E. Lovett

Research output: Contribution to journal › Article › peer-review

Abstract

The design, synthesis, and application of a nine-coordinate gadolinium(III)-containing spin label, [Gd.sTPATCN]-SL, for use in nanometer-distance measurement experiments by EPR spectroscopy is presented. The spin label links to cysteines via a short thioether tether and has a narrow central transition indicative of small zero-field splitting (ZFS). A protein homodimer, TRIM25cc, was selectively labeled with [Gd.sTPATCN]-SL (70%) and a nitroxide (30%) under mild conditions and measured using the double electron electron resonance (DEER) technique with both commercial Q-band and home-built W-band spectrometers. The label shows great promise for increasing the sensitivity of DEER measurements through both its favorable relaxation parameters and the large DEER modulation depth at both Q- and W-band for the inter-Gd(III) DEER measurement which, at 9%, is the largest recorded under these conditions.

Original language	English
Journal	Inorganic Chemistry
Volume	Article ASAP
Early online date	18 Feb 2019
DOIs	https://doi.org/10.1021/acs.inorgchem.8b02892
Publication status	E-pub ahead of print - 18 Feb 2019

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10.1021/acs.inorgchem.8b02892

GdSL-InorgChem
Copyright © 2019 American Chemical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at 10.1021/acs.inorgchem.8b02892
Accepted author manuscript, 4.58 MB

Meeting the Sensitivity Grand Challenges: Meeting the sensitivity Grand Challenges in Pulsed Electron Magnetic Resonance
Smith, G. M. (PI), Bode, B. E. (CoI), Lovett, J. E. (CoI), Pliotas, C. (CoI), Robertson, D. (CoI) & Schwarz-Linek, U. (CoI)
EPSRC
1/12/17 → 30/11/20
Project: Standard
RS Research Fellowship Renewal: Biological Structure Determination by EPR Spectroscopy: The Next Steps
Lovett, J. E. (PI)
The Royal Society
16/02/17 → 15/02/20
Project: Fellowship
State of the art pulse EPR instrumentati: State of the art pulse EPR instrumentation for long range distance measurements in biomacromolecules
Smith, G. M. (PI), Bode, B. E. (CoI), Naismith, J. (CoI), Schiemann, O. (CoI) & White, M. (CoI)
The Wellcome Trust
1/09/12 → 31/08/17
Project: Standard

A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for use in Double Electron Electron Resonance Distance Measurements (dataset)
Shah, A. (Creator), Roux, A. (Creator), Starck, M. (Creator), Mosely, J. (Creator), Stevens, M. (Creator), Norman, D. (Creator), Hunter, R. I. (Creator), El Mkami, H. (Creator), Smith, G. M. (Creator), Parker, D. (Creator) & Lovett, J. E. (Creator), University of St Andrews, 25 Feb 2019
DOI: 10.17630/7c07c45b-af1c-4051-a291-65a243b06efc
Dataset

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Cite this

Shah, A., Roux, A., Starck, M., Mosely, J. A., Stevens, M., Norman, D. G., Hunter, R. I., El Mkami, H., Smith, G., Parker, D., & Lovett, J. E. (2019). A gadolinium spin label with both a narrow central transition and short tether for use in double electron electron resonance distance measurements. Inorganic Chemistry, Article ASAP. Advance online publication. https://doi.org/10.1021/acs.inorgchem.8b02892

@article{dcb7689956c342a6a2e706fe98a046b8,

title = "A gadolinium spin label with both a narrow central transition and short tether for use in double electron electron resonance distance measurements",

abstract = "The design, synthesis, and application of a nine-coordinate gadolinium(III)-containing spin label, [Gd.sTPATCN]-SL, for use in nanometer-distance measurement experiments by EPR spectroscopy is presented. The spin label links to cysteines via a short thioether tether and has a narrow central transition indicative of small zero-field splitting (ZFS). A protein homodimer, TRIM25cc, was selectively labeled with [Gd.sTPATCN]-SL (70%) and a nitroxide (30%) under mild conditions and measured using the double electron electron resonance (DEER) technique with both commercial Q-band and home-built W-band spectrometers. The label shows great promise for increasing the sensitivity of DEER measurements through both its favorable relaxation parameters and the large DEER modulation depth at both Q- and W-band for the inter-Gd(III) DEER measurement which, at 9%, is the largest recorded under these conditions.",

author = "Anokhi Shah and Amandine Roux and Matthieu Starck and Mosely, {Jackie A.} and Michael Stevens and Norman, {David G.} and Hunter, {Robert I.} and {El Mkami}, Hassane and Graham Smith and David Parker and Lovett, {Janet E.}",

note = "Funding from ERC (266804), EPSRC (EP/R013705/1, EP/M508214/1), Carnegie Trust (RIG007510), Wellcome Trust for a Multi-User Equipment Grant (099149/Z/12/Z), and the Royal Society for a University Research Fellowship to JEL.",

year = "2019",

month = feb,

day = "18",

doi = "10.1021/acs.inorgchem.8b02892",

language = "English",

volume = "Article ASAP",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society (ACS)",

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TY - JOUR

T1 - A gadolinium spin label with both a narrow central transition and short tether for use in double electron electron resonance distance measurements

AU - Shah, Anokhi

AU - Roux, Amandine

AU - Starck, Matthieu

AU - Mosely, Jackie A.

AU - Stevens, Michael

AU - Norman, David G.

AU - Hunter, Robert I.

AU - El Mkami, Hassane

AU - Smith, Graham

AU - Parker, David

AU - Lovett, Janet E.

N1 - Funding from ERC (266804), EPSRC (EP/R013705/1, EP/M508214/1), Carnegie Trust (RIG007510), Wellcome Trust for a Multi-User Equipment Grant (099149/Z/12/Z), and the Royal Society for a University Research Fellowship to JEL.

PY - 2019/2/18

Y1 - 2019/2/18

N2 - The design, synthesis, and application of a nine-coordinate gadolinium(III)-containing spin label, [Gd.sTPATCN]-SL, for use in nanometer-distance measurement experiments by EPR spectroscopy is presented. The spin label links to cysteines via a short thioether tether and has a narrow central transition indicative of small zero-field splitting (ZFS). A protein homodimer, TRIM25cc, was selectively labeled with [Gd.sTPATCN]-SL (70%) and a nitroxide (30%) under mild conditions and measured using the double electron electron resonance (DEER) technique with both commercial Q-band and home-built W-band spectrometers. The label shows great promise for increasing the sensitivity of DEER measurements through both its favorable relaxation parameters and the large DEER modulation depth at both Q- and W-band for the inter-Gd(III) DEER measurement which, at 9%, is the largest recorded under these conditions.

AB - The design, synthesis, and application of a nine-coordinate gadolinium(III)-containing spin label, [Gd.sTPATCN]-SL, for use in nanometer-distance measurement experiments by EPR spectroscopy is presented. The spin label links to cysteines via a short thioether tether and has a narrow central transition indicative of small zero-field splitting (ZFS). A protein homodimer, TRIM25cc, was selectively labeled with [Gd.sTPATCN]-SL (70%) and a nitroxide (30%) under mild conditions and measured using the double electron electron resonance (DEER) technique with both commercial Q-band and home-built W-band spectrometers. The label shows great promise for increasing the sensitivity of DEER measurements through both its favorable relaxation parameters and the large DEER modulation depth at both Q- and W-band for the inter-Gd(III) DEER measurement which, at 9%, is the largest recorded under these conditions.

U2 - 10.1021/acs.inorgchem.8b02892

DO - 10.1021/acs.inorgchem.8b02892

M3 - Article

SN - 0020-1669

VL - Article ASAP

JO - Inorganic Chemistry

JF - Inorganic Chemistry

ER -

A gadolinium spin label with both a narrow central transition and short tether for use in double electron electron resonance distance measurements

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Projects

Meeting the Sensitivity Grand Challenges: Meeting the sensitivity Grand Challenges in Pulsed Electron Magnetic Resonance

RS Research Fellowship Renewal: Biological Structure Determination by EPR Spectroscopy: The Next Steps

State of the art pulse EPR instrumentati: State of the art pulse EPR instrumentation for long range distance measurements in biomacromolecules

Datasets

A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for use in Double Electron Electron Resonance Distance Measurements (dataset)

Cite this