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 M. 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 M. Smith, David Parker, Janet E. Lovett

Centre for Biodiscovery

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9 Citations (Scopus)

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
Pages (from-to)	3015-3025
Number of pages	11
Journal	Inorganic Chemistry
Volume	58
Issue number	5
DOIs	https://doi.org/10.1021/acs.inorgchem.8b02892
Publication status	Published - 4 Mar 2019

Bibliographical note

Funding Information:
The authors thank the ERC (266804), EPSRC (EP/R013705/ 1, EP/M508214/1), and the Carnegie Trust (RIG007510) for financial support, the Wellcome Trust for a Multi-User Equipment Grant (099149/Z/12/Z), and the Royal Society for a University Research Fellowship to JEL. We also thank Professor Catherine Botting and Dr. Sally Shirran for assistance with MALDI TOF at St Andrews.

Publisher Copyright:
© 2019 American Chemical Society.

Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.

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10.1021/acs.inorgchem.8b02892

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Shah, A., Roux, A., Starck, M., Mosely, J. A., Stevens, M., Norman, D. G., Hunter, R. I., El Mkami, H., Smith, G. M., 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, 58(5), 3015-3025. https://doi.org/10.1021/acs.inorgchem.8b02892

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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 Smith, {Graham M.} and David Parker and Lovett, {Janet E.}",

note = "Funding Information: The authors thank the ERC (266804), EPSRC (EP/R013705/ 1, EP/M508214/1), and the Carnegie Trust (RIG007510) for financial support, the Wellcome Trust for a Multi-User Equipment Grant (099149/Z/12/Z), and the Royal Society for a University Research Fellowship to JEL. We also thank Professor Catherine Botting and Dr. Sally Shirran for assistance with MALDI TOF at St Andrews. Publisher Copyright: {\textcopyright} 2019 American Chemical Society. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.",

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Shah, A, Roux, A, Starck, M, Mosely, JA, Stevens, M, Norman, DG, Hunter, RI, El Mkami, H, Smith, GM, Parker, D & Lovett, JE 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, vol. 58, no. 5, pp. 3015-3025. https://doi.org/10.1021/acs.inorgchem.8b02892

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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 M.

AU - Parker, David

AU - Lovett, Janet E.

N1 - Funding Information: The authors thank the ERC (266804), EPSRC (EP/R013705/ 1, EP/M508214/1), and the Carnegie Trust (RIG007510) for financial support, the Wellcome Trust for a Multi-User Equipment Grant (099149/Z/12/Z), and the Royal Society for a University Research Fellowship to JEL. We also thank Professor Catherine Botting and Dr. Sally Shirran for assistance with MALDI TOF at St Andrews. Publisher Copyright: © 2019 American Chemical Society. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.

PY - 2019/3/4

Y1 - 2019/3/4

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.

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DO - 10.1021/acs.inorgchem.8b02892

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AN - SCOPUS:85062371195

SN - 0020-1669

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SP - 3015

EP - 3025

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 5

ER -

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

Abstract

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