ANZETSE ZIPPORAH FAITH

SHNM/00939/2021
TECHNICAL UNIVERSITY OF KENYA
SCHOOL OF HEALTH AND BIOMEDICAL SCIENCE
DEPARTMENT OF BIOMEDICAL SCIENCES AND TECHNOLOGY
CLINICAL CHEMISTRY: POTENTIOMETRY AND VOLTAMMETRY
TERESIA N.
14TH OCTOBER, 2021
 POTENTIOMETRY
A potentiometer is used to carry out potentiometry.
Potentiometry is a chemical titration method that does not use a colour indicator. It is used to
find the concentration of a solute in solution. It is applied in determination of electrolytes (K+,
Na+, Ca2+ and Cl-) in various body fluids such as blood samples.
Potentiometry measures the potential of an analyte like body fluids with the help of an
indicator electrode and a reference electrode. The reference electrode has a potential value
and it remains stable when put in the sample being tested. The indicator electrode then
measures the potential difference.
The concentration of an ion in a tested sample is given as millimoles of the ion per liter of
sample.
Ion selective potentiometry uses sensors such as:
▫ Glass membrane
▫ Solid phase
▫ Fluid membrane
▫ Carrier
▫ Gas sensitive
▫ Enzyme electrodes
The enzyme electrodes ion selective sensors have immobilized enzymes that are used in blood
glucose monitoring.
Ion selective potentiometry is divided into direct potentiometry and indirect potentiometry.
Most potentiometric instruments use indirect potentiometry but vitro analysers use direct
potentiometry.
Molarity is the measure of moles of an ion per mass of water in a sample. Normal concentration
is 0.93kg/L.
Direct potentiometry is used by blood gas machines and the sample is not diluted before
analysis. This makes it sensitive to molarity and thus not affected by changes in concentration
of proteins or lipids in a sample being tested.
Direct potentiometry can sense the presence of electrostatically hindered ions in a sample.
Indirect potentiometry is used by automated chemistry analyzers and involves dilution of the
sample before analysis. Only the water part of the sample is diluted leading to the method
being affected by presence of proteins and lipids in the sample.
The end results are lower than the normal molarity and hence risks such as falsely low sodium
ion concentration, pseudohyponatremia.

VOLTAMMETRY
Voltammetry is a technique used to detect neurochemicals such as neurotransmitters like
serotonin, that are capable of undergoing oxidation reactions.
It measures the activity and neurochemistry of cells as well as control or change their activity to
determine effects on behaviour.
An electrical potential is applied to an electrode to oxidize nearby molecules in the extracellular
space. For example, a carbon fiber microelectrode is inserted into the brain and a specific
voltage is applied. Prescence and concentration of neurochemicals s detected by determining
the change in current, whose magnitude is proportional to the number of molecules oxidized.
An advantage of voltammetry is that there is decreased disruption of surrounding tissue but a
disadvantage is that there is decreased chemical selectivity.
Forms of voltammetry are fast-scan cyclic voltammetry and amperometry.
Fast-scan cyclic voltammetry (FSCV) is used to monitor neurochemicals. It is also used to
measure dopamine levels.
Dopamine is a neurotransmitter that plays a role in movement, memory, pleasurable reward
and motivation. Its high or low levels are associated with severe neurological disorders.
FSCV provides a better understanding of how neurotransmitters act in the extracellular space
during basal conditions. Its application allows rapid production of a voltammogram and ensures
high temporal resolution as it has a very high scan rate.
Advantages of FSCV over amperometry are: chemical specificity, high resolution, it has non-
invasive probes that make it a powerful technique for detecting changing chemical
concentrations in vivo.
Amperometry is use in electrophysiology to study vesicle release using a carbon fiber electrode.
It is also used in electrochemical detection of neurotransmitters such as adenosine and
glutamate.
In amperometry, a carbon fiber electrode is brought close to the cell to record vesicle fusion. A
spike is caused by the transfer of electrons to the electrode. The size of the spike is used to
estimate the number of vesicles present.
Detection methods in amperometry are:
▫ Single-potential amperometry
▫ Pulsed amperometry
Single-potential amperometry is the simplest form of amperometry. It is also known as direct
current amperometry.
Pulsed amperometry is used to detect certain compounds that tend to spoil the surface of an
electrode making single-potential amperometry difficult.

References:
1. Ion selective potentiometry in clinical chemistry by J.D Kruse-Jarres
2. Theory and principles of potentiometry by UN Academy
3. Tietz textbook of Clinical Chemistry and molecular diagnostics (chapter 14, page 224-
249) by Paul D’Orazio
4. Guide to research techniques in neuroscience (chapter, 3 page 73-90) by Matt Carter
and Jennifer C. Shieh
5. Neuroeconomics (chapter 25, page 389-406) by Brian Knutson, Mauricio R. Delgado and
Paul E.M. Philips
6. Electrochemistry for bioanalysis (chapter 9, page 195-222) by Aya Abdalla