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X-Band Rapid-scan EPR:A Comparison of CW, Pulse, and Rapid-scan EPR

Deborah G. Mitchell 2013 University of Denver Rapid-scan Workshop Department of Chemistry and Biochemistry University of Denver

Applications of X-band Rapid-scan EPR


Define rapid-scan EPR Rapid-scan EPR of transient species (spin trapped radicals) Applications of rapid-scan EPR to samples with long relaxation times

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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Mitchell, D. G., et. al. J. Magn. Reson. 214, 221226 (2012).

CW vs. Rapid-scan EPR


Detection: In rapid-scan EPR, the signal is detected directly. In CW, phase sensitive detection is used. Scan Rate: In rapid-scan EPR, the field is scanned more rapidly than in normal CW. Resonator Q: If Q is high, linewidths may be broadened at high scan rates. In CW EPR, high Q is routinely used. res
Q

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).

Rapid-scan of Spin Trapped Adducts

Hypoxanthine/Xanthine Oxidase
O2
Superoxide

Xanthine Oxidase

Hypoxanthine

Spin Trapping Scheme

Spin trapping of BMPO-OOH

Dr. Jerry Rosen

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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BMPO-OOH: CW/RS comparison


CW
BMPO-OOH with a O2production rate of 0.1 M/min. The concentration of BMPOOOH is about 0.3 M. Both collected in 30 seconds. A) CW spectrum obtained with standard spin trapping conditions 20 mW (B1 = 170 mG) microwave power. B) Deconvolved rapid-scan spectrum obtained with 51 kHz scan frequency, 53 mW (B1 = 250 mG) microwave power.
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Rapid-scan

Mitchell, D. G., et al. (2013). Biophy.J. 105: 338-342.

Detection of BMPO-OOH with E. Faecalis CW/RS comparison


BMPO-OOH in a suspension of E. faecalis with 2x106 CFU/mL and a O2- production rate of 0.2 M/min. The concentration of BMPO-OOH is about 0.5 M. Both were collected in 30 seconds A) CW spectrum obtained with standard spin trapping parameters. B) Deconvolved rapid-scan spectrum obtained with 51 kHz scan frequency, 53 mW (B1 = 250 mG) microwave power.
Mitchell, D. G., et al. (2013). Biophys. J. 105: 338 342

Rapid-scan of samples with long electron relaxation times (T1 and T2)

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Rapid-scan EPR: why is it useful when T1 andT2 are very long?


Examples of easily saturated samples (long T1): Diamond N@C60 OX63 a-Si:H E defects in quartz Collecting undistorted conventional CW spectra of these samples is difficult.
Larger Linear Power Region: Magnetic field is on resonance for a short time relative to CW. The power absorbed by the spins, for the same microwave B1 and time, is less than in conventional CW spectra.
Faster Scan Rate Less Saturation for Same B1.
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Power dependence of Rapid-scan and CW

Rapid-scan is collected at 1.5 MG/s

0.2% N@C60

a-Si:H

S/N is enhanced with rapid scan EPR


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Mitchell, D. G., et. al. Mol. Phys. 111:2664 2673 (2013).

X-band EPR of Hydrogenated Silicon


Plasma Enhanced Chemical Vapor Deposition of Silicon. EPR is used to quantify defects in sample.
Sample provided by Alexander Schnegg

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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RS/CW comparison of solid 0.2% N@C60


Sample provided by Aharon Blank

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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Mitchell, D. G., et. al. Mol. Phys. 111:2664 - 2673 (2013).

E' defects in Irradiated Quartz


240 kGy (24 MRad) with 60Co rays T1= 100 s, T2= 20 s Because relaxation times are so long, an unsaturated CW spectrum that is free from passage effects is difficult to obtain. CW EPR obtained in 1 minute using 0.02 mW power, 10 kHz modulation frequency and 0.05 G modulation amplitude.

Virginia Meyer

Mitchell, D. G., et al. (2011). Rad. Meas. 46:993-996.

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Rapid scan to understand defects in Diamond


Diamond sample with 20 ppb nitrogen defects. T1 2.3 ms, T2 0.2 ms, Bpp 45 mG For CW, must operate at 70 dB (20 nW) to be within the linear region. Data took 14 minutes to collect.

Sample provided by Mark Newton

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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Mitchell, D. G., et. al. Mol. Phys. 111:2664 - 2673 (2013).

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

B1 for CWb (mG) 35 ~12 6 17

B1 for rapid scanb (mG) 200 96 53 220

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

E' in irradiated fused quartz NS0 in diamondd

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~1c

2300

230

0.045

0.03

5.8

0.14

140

Relaxation Times

Improvement of Rapidscan EPR over CW

S/N enhancement of Rapid-scan over CW increases with increasing relaxation time


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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)

Other Applications of Rapid-scan EPR


Absorption spectrum is good for imaging Frequency scans can be performed similarly, especially at high EPR frequency, where the resonator bandwidth is 19 large.

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

$$$- NSF Graduate Research Fellowship $$$- NSF IDBR 0753018

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Eaton Group

(Clockwise from Left): Hanan, Richard, George, Josh, Mark, Jason, Gareth, Debbie, Virginia, Sandy, Priyanka

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