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)

Research output: Contribution to journalArticle

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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 languageEnglish
Pages (from-to)3015-3025
Number of pages11
JournalInorganic Chemistry
Volume58
Issue number5
Early online date18 Feb 2019
DOIs
Publication statusPublished - 4 Mar 2019

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Electron resonance
Spin Labels
Distance measurement
Gadolinium
gadolinium
Electron transitions
Electrons
electrons
Sulfides
Cysteine
Paramagnetic resonance
Spectrometers
Labels
Modulation
Spectroscopy
cysteine
Proteins
Experiments
spectrometers
proteins

Cite this

Shah, Anokhi ; Roux, Amandine ; Starck, Matthieu ; Mosely, Jackie A. ; Stevens, Michael ; Norman, David G. ; Hunter, Robert I. ; El Mkami, Hassane ; Smith, Graham M. ; Parker, David ; Lovett, Janet E. / A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for Use in Double Electron Electron Resonance Distance Measurements. In: Inorganic Chemistry. 2019 ; Vol. 58, No. 5. pp. 3015-3025.
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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

A Gadolinium Spin Label with Both a Narrow Central Transition and Short Tether for Use in Double Electron Electron Resonance Distance Measurements. / Shah, Anokhi; Roux, Amandine; Starck, Matthieu; Mosely, Jackie A.; Stevens, Michael; Norman, David G.; Hunter, Robert I.; El Mkami, Hassane; Smith, Graham M.; Parker, David (Lead / Corresponding author); Lovett, Janet E. (Lead / Corresponding author).

In: Inorganic Chemistry, Vol. 58, No. 5, 04.03.2019, p. 3015-3025.

Research output: Contribution to journalArticle

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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 - 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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DO - 10.1021/acs.inorgchem.8b02892

M3 - Article

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SP - 3015

EP - 3025

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

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