ISSN 1061-9348, Journal of Analytical Chemistry, 2012, Vol. 67, No. 11, pp. 869–879. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © G.K. Ziyatdinova, E.R. Ziganshina, H.C. Budnikov, 2012, published in Zhurnal Analiticheskoi Khimii, 2012, Vol. 67, No. 11, pp. 968–979.
869
Surfactants are able to manifest themselves in
polarograms of test solutions, which is usually related
to changes in the properties of the double electric
layer. Even at the dawn of the development of polarog-
raphy and voltammetry, neutral organic surfactants
were used for the suppression of polarographic max-
ima. Aliphatic alcohols with six to eight carbon atoms
appeared as capacitive peaks in voltammograms at
mercury electrodes; this made it possible to use them
for developing determination methods based on the
so-called depression of differential capacitance. These
studies have been reviewed in many books on electro-
chemistry and voltammetry, for example [1].
The effects of surfactant adsorption appeared not
only on the suppression of polarographic maxima but
also on the inhibition of the electrochemical steps of
the process to cause a shift of wave or peak potentials
in voltammograms to higher values or splitting of a
multi-electron wave into several steps. The analytical
applications of these adsorption effects were of limited
utility. In particular, they were used for determining
the residual amounts of surfactants in aqueous test
samples. Currently, studies of this kind are mainly of
historical interest. However, the adsorption effects of
analyte species are widely used in order to increase the
sensitivity of their determination.
The variety of currently available surfactants and
hence their properties makes it possible to use this
group of compounds for controlling analytical signals
in voltammetry and, consequently, to increase the sen-
sitivity and selectivity of amperometric response to a
particular analyte.
It is well known that amphiphilic organic mole-
cules can occur in various forms in aqueous solutions;
this fact long ago came to the attention of chemists.
These forms are related to the properties of surfactants
containing negatively (–S –S –СOO
–
) or posi-
tively charged groups or a polar oxyeth-
ylene chain (–OC
2
H
4
)
n
and a long nonpolar hydrocar-
bon radical having from 8 to 18 carbon atoms. In
water, surfactant molecules primarily occupy its sur-
face to form a monomolecular layer, and the aggre-
gates of surfactant molecules (micelles) are spontane-
ously formed upon reaching a critical micelle concen-
tration (CMC). Because of this, the solutions of
surfactants can be classified as self-organizing systems
[2, 3].
All surfactants are divided into the three classes:
anionic, cationic, and nonionic surfactants.
Anionic surfactants: sodium dodecylsulfate (SDS)
and sodium dodecylbenzenesulfonate.
Cationic surfactants: N-dodecylpyridinium bro-
mide, cetylpyridinium bromide (CPB), and cetyltrim-
ethylammonium bromide (CTAB).
Nonionic surfactants: Brij
35, Triton X-100, and
Tween 20.
The physicochemical properties and processes in
the solutions of surfactants were considered in detail
earlier [4, 5].
Surfactants are in active current use in spectro-
scopic techniques [6], titrimetry, various versions of
chromatography [7], extraction, capillary and gel
electrophoresis, and other methods for the separation
and determination of organic and inorganic sub-
stances. These problems were considered in detail by
Shtykov [8]. In the past decades, surfactants have been
used in electroanalytical techniques [9–12].
Application of surfactant-containing media to the
voltammetry of biologically active compounds. Aque-
ous micellar solutions and microemulsions, in partic-
O
3
,
-
O
4
,
-
N CH
3
( )
3
+
– ( )
Application of Surfactants in Voltammetric Analysis
G. K. Ziyatdinova, E. R. Ziganshina, and H. C. Budnikov
A.M. Butlerov Institute of Chemistry, Kazan (Volga Region) Federal University,
ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
Received November 8, 2011; in final form, February 3, 2012
Abstract—The possibilities of applying surfactants to the voltammetry of various biologically active com-
pounds are generalized. Attention is focused on micellar solutions and surfactant-modified electrodes in the
determination of a number of organic compounds, including antioxidants. It is demonstrated that the use of
surfactants makes it possible to improve analytical characteristics and, in some cases, to simultaneously deter-
mine different analytes.
Keywords: surfactants, electrochemical methods, modified electrodes, biologically active compounds, phar-
maceutical preparations
DOI: 10.1134/S106193481211010X
REVIEWS