EPR spectrometer & dosimetry

in Hokkaido University

( )
2014.09.16
Kwon Choi
Lets say about EPR
Which exist around nucleus
Unpaired electrons
Electron Paramagnetic Resonance
Lets say about EPR
Paramagnetism is
a form of magnetism whereby certain materials are attracted
by an externally applied magnetic field,
and form internal, induced magnetic fields in the direction of
the applied magnetic field. () Paramagnetic properties are
due to the presence of some unpaired electrons, (.)

(from Wikipedia <Paramagnetism>)
Electron Paramagnetic Resonance
Which you may not be familiar with
Lets say about EPR
In other word, align their direction
into the direction of the extenal
magnetic field.

Electron Paramagnetic Resonance
Which you may not be familiar with
Lets say about EPR
Electron Paramagnetic Resonance
Which you may not be familiar with
Form induced magnetic field

Up spin and down spin electrons have different energy states.
This Energy Splitting is determined by the strength of the
external magnetic field.
=geBB0
ge : g factor, 2.00231930436153 (a.u.)
for electron
B : Bohr magneton, 9.2740096810
24
(a.u.)
Lets say about EPR
Electron Paramagnetic Resonance
Resonance absorption
Absorption of electromagnetic energy
at a certain frequency in a static external magnetic field
by a quantum excitation of the material
Lets say about EPR
Electron Paramagnetic Resonance
Resonance absorption
Energy

Absorption of the
electromagnetic
energy
E =
Release of the
energy (heat, light)
Excitation of electrons Relaxation
The electromagnetic energy with the energy equal to the energy splitting of electrons,
= E = geBB0 makes the resonance
2. Population distribution of electrons between two energy levels :
(Boltzmanns equation)
T : temperature
k : Boltzmann constant
1. Under the resonance :
The population of the lower level is greater than that
of the upper level.
Net energy absorption
http://encyclopedia2.thefreedictionary.com/Electron+Paramagnetic+Resonance+EPR
Energy
emission
Energy
absorption
Both transitions with
same probability
=
#
#
<
How energy absorption occur
E = -
1
2

0
E =
1
2

0
=geBB0
Microwave

Variant frequency of EM wave is
used by the use.
The frequency of EM wave is determined by the utility.
Frequency => Energy splitting (Better signal)
Dielectric loss (Heat loss)
Skin depth (Lower penetration)
= (
2

)
1/2

: Resistivity of material

0
: dielectric constant
: Frequency
Skin depth,

How deep the electromagnetic wave can penetrate
The frequency of EM wave is determined by the use.
Frequency => Energy splitting (Better signal)
Dielectric loss (Heat loss)
Skin depth (Lower penetration)
Dielectric loss
In water
= (
2

)
1/2

: Resistivity of material

0
: dielectric constant
: Frequency
Skin depth,

How deep the electromagnetic wave can penetrate
At 1 GHz
(L-band)
Resistivity
(m)
Skin depth
(cm)
Muscle 0.8 1.5
Liver 1 1.7
Fat 7-12 4-6
Bone 10-25 5-8
Brain 1 1.7
The frequency of EM wave is determined by the use.
Frequency => Energy splitting (Better signal)
Dielectric loss (Heat loss)
Skin depth (Lower penetration)
Dielectric loss
In water
= (
2

)
1/2

: Resistivity of material

0
: dielectric constant
: Frequency
Skin depth,

How deep the electromagnetic wave can penetrate
At 1 GHz
(L-band)
Resistivity
(m)
Skin depth
(cm)
Muscle 0.8 1.5
Liver 1 1.7
Fat 7-12 4-6
Bone 10-25 5-8
Brain 1 1.7
The frequency of EM wave is determined by the use.
Frequency => Energy splitting (Better signal)
Dielectric loss (Heat loss)
Skin depth (Lower penetration)
Dielectric loss
In water
Under L-band (1-2 GHz) is
appropriate for the use in vivo.
=geBB0
External magnetic field / mT
Because of the magnetic
modulation
-> Basic form of an EPR signal
For
Microwave

Variant frequency of EM wave is
used by the use.
External magnetic field / mT
=geBB0
External magnetic field / mT
Because of the magnetic
modulation
-> Basic form of an EPR signal
Microwave

Variant frequency of EM wave is
used by the use.
What can we observe with EPR?
Flaw of the
optic fiber
New material
(Ion liquid)
Process of
chemical
reaction from
UV irradiation
Tooth enamel of
the irradiated
human
In vivo brain
/ tumor
How did radicals form in observed objects?
Elapse of time
Mix the stable
radical into the
new material
Unstable radicals
are formed by
the break of
chemical bonds
Stable radicals are
formed in the
tooth enamel
Quantity of
radicals,
relationship with
the amount of
radiation
Quantity of
radicals,
distribution,
relationship with
tumor
Inject stable radicals
into the vessel or
region of interest
What information do you want?
Quantity,
distribution,
location and
quantity of flaw,
Interaction
between stable
radical and new
material
Dynamics
(Change of
structure,
quantity,
characteristics
with the time
elapse
Enamel
What can we observe with EPR?
Flaw of the
optic fiber
New material
(Ion liquid)
Process of
chemical
reaction from
UV irradiation
Tooth enamel of
the irradiated
human
In vivo brain
/ tumor
How did radicals form in observed objects?
Elapse of time
Mix the stable
radical into the
new material
Unstable radicals
are formed by
the break of
chemical bonds
Stable radicals are
formed in the
tooth enamel
Quantity of
radicals,
relationship with
the amount of
radiation
Quantity of
radicals,
distribution,
relationship with
tumor
Inject stable radicals
into the vessel or
region of interest
Radiation dosimetry using tooth enamel
Requirement
Possibility of radiologic emergency situation
(terrorist attack using a nuclear weapon, accident of nuclear power plants)
Need of patients triage (distinguish who may be irradiated)
- Who exposed to over certain amount of radiation need rapid care.
- Victims with doses starting at about 2 Gy can benefit from urgent
medical treatment.
General publication does not have the proper dosimeter.
EPR tooth dosimetry can be used for triage in situ.
Conventional blood test can be done at remote place that takes time.
Radiation dosimetry using tooth enamel
Hydroxyapatite

contained in teeth and bones

-> Suitable probe for dose reconstruction.
- High content of hydroxyapatite
- Completely formed in childhood
- Once formed never remodelled.
1. Carbonate impurities in hydroxyapatite crystals
Radiation
exposure

radicals
(EPR sensitive stable radical as probe)
2. Tooth enamel is preferred for the retrospective dosimetry
-> Co
2
-
-radicals are accumulated over 10
7
years
"Boys, be ambitious!
Be ambitious not for money or for
selfish aggrandizement, not for that
evanescent thing which men call fame. Be
ambitious for that attainment of all that a
man ought to be."
Regrettably, today in Korea this good
maxim is generally used as
Boys, be ambitious for fame and money!
, !
,
.

.
William S. Clark Ph.D.
Farm (Part of the school of agriculture)
Farm (Part of the school of agriculture)
A little history about the discovery of
electron paramagnetic resonance
Phenomenon called Electron
Paramagnetic Resonance (EPR)
Yevgeny Konstantinovich Zavoisky (1907 1976)
Discover of electron paramagnetic resonance (1944)
Stalin Prize (1949)
Lenin Prize (1957)
International EPR Society Prize (1977)
Hero of Socialist Labour (1969)
Phenomenon called Electron
Paramagnetic Resonance (EPR)
Isior Issac Rabi
Nobel Prize in Physics (1944)
Discovery of Nuclear Magnetic Resonance (1938)
Zavoisky was impressed at Rabis discovery, NMR
and tried to detect NMR in liquids and solids.
Tooth dosimetry in Hokkaido University
Frequency : about 1.15 GHz
In-house EPR spectrometer for tooth dosimetry
Surface coil resonator for in vivo use
Surface coil resonator construction
Surface coil resonator construction
Home-made coaxial tube
(Copper / Teflon)
Home made surface coil (Silver)
Sugawara et al, 2014,
IEEE
Data Acquisition Program
In-house program made using Labview
Show the signal of each scan (upper) and
integration of number of those signals (lower)
SNR histogram (right)
Dosimetery
Synthetic Hydroxyapatite as dosimeter
- Used as a dental graft / implant
- Good substitute of human tooth enamel
Used electronic scale for the normalization of hydroxyapatite
samples
- Hydroxyapatite samples are irradiated different doses.
Irradiated dose
(cGy)
Weight
(g)
0 0.2542
10 0.1255
30 0.1231
50 0.1292
100 0.1338
200 0.127
300 0.1253
600 0.0845
-0.008
-0.006
-0.004
-0.002
0
0.002
0.004
0.006
39 39.5 40 40.5 41 41.5 42 42.5 43
(mT)
Example : 600 cGy sample
EPR signal acquired at 1 scan
-0.06
-0.04
-0.02
0
0.02
0.04
0.06
0.08
39 39.5 40 40.5 41 41.5 42 42.5 43
Integrated EPR signal (50 scans)
The quantity of radiation-induced radical can be determined relatively
by the peak-to-peak intensity of the spectrum.
External magnetic field / mT peak-to-peak intensity
-0.06
-0.04
-0.02
0
0.02
0.04
0.06
0.08
39 39.5 40 40.5 41 41.5 42 42.5 43
The quantity of radiation-induced radical can be determined relatively
by the peak-to-peak intensity of the spectrum.
External magnetic field / mT peak-to-peak intensity
Too noisy to determine the exact
peak-to-peak intensity
(mT)
-0.06
-0.04
-0.02
0
0.02
0.04
0.06
0.08
39 39.5 40 40.5 41 41.5 42 42.5 43
The quantity of radiation-induced radical can be determined relatively
by the peak-to-peak intensity of the spectrum.
External magnetic field / mT peak-to-peak intensity
Too noisy to determine the exact
peak-to-peak intensity
Need of curve fitting
Curve fitting
Robinson et al., 1998, Journal of Magnetic Resonance
-0.08
-0.06
-0.04
-0.02
0
0.02
0.04
0.06
39 39.5 40 40.5 41 41.5 42 42.5 43
Including center frequency, linewidth, modulation frequency, Zeeman modulation
Also resulted signal intensity determined with the correction using
number of scans, weight of the sample
To determine the signal intensity
Results
Irradiated dose
(cGy)
signal intensity
0 0.01981
10 0.04742
30 0.05276
50 0.05455
100 0.06130
200 0.06347
300 0.08646
600 0.11268 0
0.02
0.04
0.06
0.08
0.1
0.12
0 100 200 300 400 500 600 700
(cGy)
(a.u.)
200 cGy sample didnt show good signal intensity.
As expected, doses under 100 cGy did not show
Discussion
1. Noise make the spectroscopy difficult.
Contamination of the surface coil is one reason.
Sugawara et al.
Improvement of the baseline stability by HCl cleaning of the resonator
Discussion
2. Too small and various size of hydroxyapatite samples
-> Different amount of effect from the magnetic field of the surface coil
3. Only one sample per each radiation dose
Thank you for listening!