Frequency swept pulses for the enhanced resolution of ENDOR spectra detecting on higher spin transitions of Gd(III)

Rogers, Ciarán J.; Bogdanov, Alexey; Seal, Manas; Thornton, Matthew E.; Su, Xun‐Cheng; Natrajan, Louise S.; Goldfarb, Daniella; Bowen, Alice M.

doi:10.1016/j.jmr.2023.107447

Cited by 2 publications

(3 citation statements)

References 41 publications

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“…To achieve the same thermal occupancy of the low-lying levels at the Q-band, an ∼3 times lower temperature has to be employed compared to the W-band. Since we showed above for GB1-Q32C-DO3A that measurements at 6 K are possible, we envisage that collecting spectra at ∼2 K at the Q-band or by enhancing the population of low-lying spin levels by polarization transfer is potentially feasible.…”

Section: Resultsmentioning

confidence: 99%

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Extending the Range of Distances Accessible by ¹⁹F Electron–Nuclear Double Resonance in Proteins Using High-Spin Gd(III) Labels

Bogdanov,

Frydman,

Seal

et al. 2024

J. Am. Chem. Soc.

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Fluorine electron-nuclear double resonance ( 19 F ENDOR) has recently emerged as a valuable tool in structural biology for distance determination between F atoms and a paramagnetic center, either intrinsic or conjugated to a biomolecule via spin labeling. Such measurements allow access to distances too short to be measured by double electron−electron resonance (DEER). To further extend the accessible distance range, we exploit the high-spin properties of Gd(III) and focus on transitions other than the central transition (|−1/2⟩ ↔ |+1/2⟩), that become more populated at high magnetic fields and low temperatures. This increases the spectral resolution up to ca. 7 times, thus raising the long-distance limit of 19 F ENDOR almost 2fold. We first demonstrate this on a model fluorine-containing Gd(III) complex with a well-resolved 19 F spectrum in conventional central transition measurements and show quantitative agreement between the experimental spectra and theoretical predictions. We then validate our approach on two proteins labeled with 19 F and Gd(III), in which the Gd−F distance is too long to produce a well-resolved 19 F ENDOR doublet when measured at the central transition. By focusing on the |−5/2⟩ ↔ |−3/2⟩ and |−7/2⟩ ↔ |−5/2⟩ EPR transitions, a resolution enhancement of 4.5-and 7-fold was obtained, respectively. We also present data analysis strategies to handle contributions of different electron spin manifolds to the ENDOR spectrum. Our new extended 19 F ENDOR approach may be applicable to Gd−F distances as large as 20 Å, widening the current ENDOR distance window.

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Section: Resultsmentioning

confidence: 99%

“…As shown earlier, the use of an adiabatic chirp pulse prior to the Mims sequence allows for the transfer of spin polarization to the observed electron spin transition. For the systems studied here, at low temperatures, this results in a signal enhancement of ca.…”

Section: Methodsmentioning

confidence: 99%

Extending the Range of Distances Accessible by ¹⁹F Electron–Nuclear Double Resonance in Proteins Using High-Spin Gd(III) Labels

Bogdanov,

Frydman,

Seal

et al. 2024

J. Am. Chem. Soc.

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“…[29][30][31] Narrowband-selective amplitude-modulated pulses and broadband frequency-swept pulses originally designed for NMR spectroscopy have been successfully incorporated into EPR experiments, leading to increased sensitivity and enabling increased information content in FT-EPR correlated pulse experiments. 29,[32][33][34][35][36][37][38][39] Pulse shaping capabilities provide an opportunity to revisit excitation selectivity for pulse EPR experiments on spin-correlated radical pairs, in particular for the out-of-phase ESEEM experiment, where broadband excitation can facilitate extension of this experiment to higher frequencies and to a wider range of systems.…”

Section: Introductionmentioning

confidence: 99%

Control of excitation selectivity in pulse EPR on spin-correlated radical pairs with shaped pulses

Panariti,

Conron,

Zhang

et al. 2024

Phys. Chem. Chem. Phys.

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Frequency swept pulses for the enhanced resolution of ENDOR spectra detecting on higher spin transitions of Gd(III)

Cited by 2 publications

References 41 publications

Extending the Range of Distances Accessible by ¹⁹F Electron–Nuclear Double Resonance in Proteins Using High-Spin Gd(III) Labels

Extending the Range of Distances Accessible by ¹⁹F Electron–Nuclear Double Resonance in Proteins Using High-Spin Gd(III) Labels

Control of excitation selectivity in pulse EPR on spin-correlated radical pairs with shaped pulses

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Frequency swept pulses for the enhanced resolution of ENDOR spectra detecting on higher spin transitions of Gd(III)

Cited by 2 publications

References 41 publications

Extending the Range of Distances Accessible by 19F Electron–Nuclear Double Resonance in Proteins Using High-Spin Gd(III) Labels

Extending the Range of Distances Accessible by 19F Electron–Nuclear Double Resonance in Proteins Using High-Spin Gd(III) Labels

Control of excitation selectivity in pulse EPR on spin-correlated radical pairs with shaped pulses

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Extending the Range of Distances Accessible by ¹⁹F Electron–Nuclear Double Resonance in Proteins Using High-Spin Gd(III) Labels

Extending the Range of Distances Accessible by ¹⁹F Electron–Nuclear Double Resonance in Proteins Using High-Spin Gd(III) Labels