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Deborah G. Mitchell 2013 University of Denver Rapid-scan Workshop Department of Chemistry and Biochemistry University of Denver
Rapid-scan EPR
Magnetic field is swept through resonance in a time that is short relative to the relaxation time T2. May cause oscillations on the trailing edge of the signal. The decay of the oscillations is dependent on T2 and inhomogeneous broadening. Rapid-scan spectrum can be deconvolved to obtain absorption spectrum.
Comparison of rapid scan (1.8 MG/s) and conventional CW EPR spectra of the low-field nitrogen hyperfine line of 15N-mHCTPO.
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Power Saturation: Because of the rapid passage through resonance, the rapid scan EPR signal is less easily saturated.
BW resonator
Methods
A Bruker E500-T is used to record rapid-scan signals with: a.) Locally designed coil driver: The Resonated Coil Driver (RCD) can operate at 100% duty cycle with 80 G sweep width and 50 kHz sweep frequency b.) Rapid scan coils: Relative to solid wire, Litz wire decreases AC resistance (which allows us to operate at higher currents).
Hypoxanthine/Xanthine Oxidase
O2
Superoxide
Xanthine Oxidase
Hypoxanthine
6 M/min O2- production was produced by a mixture of xypoxanthene/xanthine oxidase. A) CW spectrum with 55 G sweep width, 0.75 G modulation amplitude, single 42 s scan, and 20 mW (B1 = 170 mG) microwave power. B) The first integral of spectrum in part A. C) Deconvolved rapid-scan spectrum obtained with 55 G scan width, 51 kHz scan frequency, 20 mW (B1 = 150 mG) microwave power, ~4 seconds acquisition time.
Mitchell, D. G., et al. (2013). Biophy.J. 105: 338-342.
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Rapid-scan
Rapid-scan of samples with long electron relaxation times (T1 and T2)
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0.2% N@C60
a-Si:H
T1 12 s, T2 3.3 s
Bpp 6G Field-swept echo detected spectrum obtained with constant 500 ns spacing between pulses, SRT = 100 s, 1024 shots/point, 10 scans Conventional field-modulated firstderivative CW EPR spectrum acquired with 2 G modulation amplitude at 30 kHz, and B1 = 35 mG. FT EPR not an option with hydrogenated silicon sample because of short T2*
Mitchell, D. G., et. al. Mol. Phys. 111: 2664 2673 (2013).
Virginia Meyer
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Endohedral N@C60 is an intriguing sample because of its long electron relaxation times due to the shielding of its carbon cage. Quantum Computing: Each N@C60 would function as a qubit T1 160 s, T2 2 s, Bpp ~225 mG
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Virginia Meyer
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CW spectrum acquired with 0.05 G modulation amplitude at 6 kHz and B1 = 0.25 mG, one scan. Field-swept echo detected spectrum with a constant 600 ns spacing between pulses, SRT = 3 ms, 64 shots/pt, 1 scan FT-EPR of data obtained with an SRT of 200 s, 24o tip angle, and 40960 averages
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Summary of Results
Sample T1 (s)a T2 (s)a Bpp (G)a
a-Si:H
40 M OX63 N@C60
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14 120 160 200
3.3
5 2.8
6
0.16 0.25
Rapid scan S/N RS rate (MG/s) relative to CW 3.9 0.6 1.5 4.7 >250 11.5 25 14.4
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~1c
2300
230
0.045
0.03
5.8
0.14
140
Relaxation Times
Mitchell, D. G., et. al. Mol. Phys. 111: 2664 - 2673 (2013).
Summary of Results
Benefits of Rapid-scan EPR :
Larger linear response range Fast Data Acquisition Collect undistorted absorption spectra of samples with long T1 Enhanced S/N Transient Species (Spin Trapping)
Acknowledgements
University of Denver Advisors: Drs. Gareth and Sandra Eaton Dr. Mark Tseitlin Richard Quine Eaton Group: George, Mike, Virginia, Josh, Jason, Priyanka, and Hanan Fellow DU graduate students: Josh, Paul, Jennifer, Brittany, and many more.
Collaborators Spin Trapping: Gerald Rosen, University of Maryland, School of Pharmacy Bacteria: Barbee Lab: Breanna Symmes and Katherine Nesler also Heather Wilkins and Aimee Winter from Dr. Linsemanns lab Diamond: Dr. Mark Newton, University of Warwick Hydrogenated Silicon: Dr. Alexander Schegg, Helmholtz-Zentrum Berlin fr Materialien und Energie GmbH N@C60: Dr. Aharon Blank, School of Chemistry Bruker Biospin: Ralph Weber, Chuck Hanson, Peter Hofer
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Eaton Group
(Clockwise from Left): Hanan, Richard, George, Josh, Mark, Jason, Gareth, Debbie, Virginia, Sandy, Priyanka
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