13 Radiochemical Methods...

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Radiochemical methods
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Introduction
• Radioactive isotopes
▫ have unstable nuclei that spontaneously change to form
more stable nuclei.
▫ Can emit radiation & / or particles
 alpha, beta, and gamma rays
▫ Radiation is a general property of all radiopharmaceuticals,

when administered gives the patient an inevitable radiation
dose.
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 Element when the N/P ratio becomes higher, the nucleus become unstable;
 Results in the disintegration of the nucleus so as to achieve a stable N/P
ratio and therefore a stable nucleus.
 This process is called radioactive decay.
 Natural radioactive - radioactive process can be spontaneous in some naturally

occurring nuclides;
 Artificial radioactive - instability is brought about by bombarding stable
nuclides with high-energy particles.
 The unstable nuclides disintegrate to form stable nuclides with release of energy and
nuclear particles:
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Type of radiation
 Radiation/particles resulting from any decay process can be
classified as:
 alpha (α),
 beta (β),
 gamma rays (γ), and/or other emissions.
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1. Alpha (α) particle

 are doubly charged, highly energetic helium nucleus
 It consists of 2 proton & 2 neutron ( a stream of positively
charged helium ions , He 2+)
 Has low penetration power but has high ionization power, they
lose energy very rapidly
 can cause extensive damage to organs and tissues
 Not used for treatment & sterilization.
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2. Beta (β) particle:

 is a stream of electrons formed as neutrons changed to protons or
vice-versa
 β - Particle emission has two forms:
65 65
Positron (β+) – if it is positive charge 30 Zn  29 Cu     v
▫ A proton is converted to a neutron
14 14
Negatron (β-) –if it is negative charge 6 C  7 N- v
▫ A neutron is converted to a proton
 Have high penetration power

 Used extensively in nuclear medicine for diagnostic and
therapeutic applications.
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3. Gamma -Rays (γ)

 Gamma rays are produced by nuclear relaxations.
 The release of energy while the excited nucleus returns to the
ground state appears as electromagnetic radiation called γ ray.
 Because γ -Emission is EMR, there is no change in the neutron
number or mass number or atomic number.
 Has high penetration power & high energy EMR

 Used for sterilization
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4. X-ray
 X-Rays originate from orbital electron,
 Where as γ -Rays originate from the decay of a nuclide.
 X-Ray emission is formed from electronic transitions in which

outer electrons fill the vacancies created by the nuclear
process.
 Outer-shell electrons jump to fill the inner-shell vacancy resulting in
an electron orbit reshuffling. This process result in the release of X-
Rays
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Radioactive decay
Rate of radioactive Decay
 It is the rate of disintegration of radioactive particles
 Governed by first order reaction
A = dN/dt = λN
N = No e- λt log N = log No – λt/2.303
A = λ No e- λt = Ao e- λt
 Where: A = activity (dps)
N = No of radioactive atom present in the

sample at time, t
λ = radioactive decay constant
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Radioactive decay …
 unaffected by pressure, temperature and other physical or
chemical properties of the radionuclide.
 The half-life of a radionuclide is the time required for the sample
activity to decrease to half of its initial value.
t1/2 = 0.693/λ
log No
Log N Slop = -λ /2.303
t
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Radioactive decay …
Q. 60
Co is a long-lived isotope (t1/2 = 5.3 years) that frequently is used
as a radiotracer. The activity in a 5.00-mL sample of a solution of
60
Co was found to be 2.1 x 107 disintegrations/s. What is the molar
concentration of 60Co in the sample? (hint: Avogadro No = 6.022
x 1023 atoms/mol)
A 0.693
N  where ,  
 t1 / 2
A  t1 / 2
N  
0.693
N ( No atom)
mole  
6.02  10 23 atom / mol
mol
M  
L
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Unit of radioactivity
Unit of radioactivity
 The fundamental SI unit of activity is the Becquerel (Bq).
 One Bq is equal to one disintegration per second (dps).
1 Bq = 1 dps
 The older historical unit of activity Curie (Ci)
1 μCi (= 3.7 x 104 dis/s = 3.7 x 104 Bq),
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Measurement of radioactivity
 Radioactivity is measured using a particle energy to produces
a pulse of electric current in a detector.
 Quantitative information about decay rates is obtained by counting these
pulses for a specific period.
 Three type of detectors

A. Gas filled detectors => Geiger counter
B. Scintillation counters
C. Semiconductor detectors
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Measurement of radioactivity
Measurement of radioactivity is achieved by:

1. Liquid-scintillation counters:
 An instrument for counting radioactive particles based on their ability
to initiate fluorescence in another substance
 Uses a fluorescent material to convert radioactive particles into easily
measurable photons.
 When radiation interacts with certain substances called fluors, it produces a flash of
light called scintillation.
 The scintillation is then detected using a sensing element, amplified and recorded by
counting. (counts per second/ minute)
 Used to assay α-and β-emitting radio-nuclides

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Measurement of radioactivity …
Then, principal components:-
a)Solvent
1 o
solvent - toluene, xylene, or 1,2,4-Trimethylbenzene
 The charged particle dissipates its energy in the solvent
2 o
solvent
 such as dioxane to improve solubility of aqueous samples
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b) Solute
1 o
fluor solute: 2,5-Diphenyloxazole (DPO) that emits UV
light at ~380 nm.

 a fraction of this energy is converted into fluorescence in the
primary solute.
 2o scintillator : (2,2′-p-phenylenebis[4-methyl-5-
phenyloxazole] dimethyl)to shift the wavelength (λ) of photons
emitted (~380 nm) to the λ response of some photomultiplier
tubes (PMT, ~420nm).
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 Summary
=> RA cpd → dissolve in solvent → solvent mol. exited by RA cpd
→ 1o flour added to the solution & take the energy from the sol n
→ the flour will exited & the solvent return to Go
→ the 1o flour come to the Go & emit UV radiation (Cpm @ ≈ 380nm)
→ add the 2o flour → the 2o flour will exited b/s of UV radiation
→ emit visible radiation → counted by PMT (Cpm @ ≈ 420 nm)

( the No of fluorescence per minute or second)
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2. Gas filled detector: /Geiger muller counting

 The detection and quantitation of nuclear radiation are
based on its interaction with inert gas (Ar) contained in
the detector
 When radioactive particles enter the tube, they ionize
the inert gas, producing a large number of Ar+/e– ion
pairs. Movement of the electrons toward an anode and
the Ar+ toward a cathode generates a measurable electric
current.
 The ionization current produced in an ionization
chamber is proportional to the intensity of the radiation.
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Application of radioactive isotope

Radio isotopes are extensively used in:
A. Medicine
for diagnosis:
o The radiopharmaceuticals accumulated in an organ of interest emit
radiations which are used for imaging of the organs.
for therapeutic – eg. treatment of cancer

o Are radio labeled molecules designed to deliver therapeutic
doses of ionizing radiation to specific diseased sites.
 posses the ability to destroy diseased tissues.
 Sterilization
B. Analytical application - For drug analysis
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Quantitative application
Radiochemical methods of analysis:

 are considerably more sensitive than other chemical methods.
 it is possible to attain quantitation levels lower than ppb levels of elements.
 In most cases, can be done without separation of the analyte.

 Radiochemical methods of analysis include:
 Direct Analysis of Radioactive Analytes
 The sample’s activity can be used to calculate the number of radioactive
particles that are present in the sample.
 Activation analysis
 Tracer methods - Isotope dilution
 Radioimmunoassay techniques
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Neutron Activation Analysis

 A means of inducing radioactivity in a nonradioactive sample by
bombarding the sample with neutrons.
 The radioactive element formed by neutron activation decays to a
stable isotope by emitting gamma rays and, if necessary, other
nuclear particles.
 The rate of gamma-ray emission is proportional to the analyte’s
initial concentration in the sample.
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Neutron Activation Analysis …
 For example, when a sample containing nonradioactive 27

13 Al is
placed in a nuclear reactor and irradiated with neutrons, the
following nuclear reaction results.
 When irradiation is complete, the sample is removed from the

nuclear reactor, allowed to cool and the rate of gamma-ray emission
is measured.
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• Reading Assignment
Isotope dilution
Radioimmunoassay techniques

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1

▫ Radiation is a general property of all radiopharmaceuticals,

 Natural radioactive - radioactive process can be spontaneous in some naturally

1. Alpha (α) particle

2. Beta (β) particle:

 Have high penetration power

3. Gamma -Rays (γ)

 Has high penetration power & high energy EMR

 X-Ray emission is formed from electronic transitions in which

N = No e- λt log N = log No – λt/2.303

 Where: A = activity (dps)

N = No of radioactive atom present in the

 Three type of detectors

Measurement of radioactivity is achieved by:

 Used to assay α-and β-emitting radio-nuclides

light at ~380 nm.

→ the flour will exited & the solvent return to Go

→ the 1o flour come to the Go & emit UV radiation (Cpm @ ≈ 380nm)

→ add the 2o flour → the 2o flour will exited b/s of UV radiation

→ emit visible radiation → counted by PMT (Cpm @ ≈ 420 nm)

2. Gas filled detector: /Geiger muller counting

Application of radioactive isotope

for therapeutic – eg. treatment of cancer

Radiochemical methods of analysis:

 In most cases, can be done without separation of the analyte.

Neutron Activation Analysis

Neutron Activation Analysis …

 For example, when a sample containing nonradioactive 27

 When irradiation is complete, the sample is removed from the

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