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 (Lead / Corresponding author), Janet E. Lovett (Lead / Corresponding author)

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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
Early online date	18 Feb 2019
DOIs	https://doi.org/10.1021/acs.inorgchem.8b02892
Publication status	Published - 4 Mar 2019

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.8b02892

Author Accepted ManuscriptAccepted author manuscript, 4.61 MB

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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 = "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.",

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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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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 - 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.

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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SN - 0020-1669

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SP - 3015

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 5

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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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Meeting the Sensitivity Grand Challenge in Pulsed Electron Paramagnetic Resonance (Joint with University of St Andrews)

State of the Art Pulse EPR Instrumentation for Long Range Distance Measurements in Biomacromolecules (Multi-User Equipment Grant) (Joint with University of St Andrews)

Cite this

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

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

Meeting the Sensitivity Grand Challenge in Pulsed Electron Paramagnetic Resonance (Joint with University of St Andrews)

State of the Art Pulse EPR Instrumentation for Long Range Distance Measurements in Biomacromolecules (Multi-User Equipment Grant) (Joint with University of St Andrews)

Cite this