Proceeding of The International Seminar on Chemistry 2008 (pp. 381-384) Usage of some surfactant types as mediator on cetirizine determination by using square wave voltammetry technique at carbon paste electrode
Nikmans Hattu1*, Buchari2, Indra Noviandri2, Sadijah Achmad2
1Research Division of Analytical Chemistry of Institut Teknologi Bandung
2Chemistry Study Program of Institut Teknologi Bandung
Abstract
Cetirizine is one of antihistamine (H1-receptor antagonist) drugs which many applied in medical and pharmacy. Allergy prevalence increases recently, so that usage of this drug also increases. Therefore, monitoring improvement need to be done. Usage of some surfactant types as mediator in increasing sensitivity of cetirizine determination has been done by using cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques. The optimum composition of carbon paste electrode is 70:30% for graphite and paraffin, respectively. Potential interval to determination of cetirizine is 0 - 400 mV. Optimization some parameters have also been done to obtain optimum values of measurement. The research found that optimum values such as accumulation potential, pulse amplitude, frequency and scan rate are 1 mV, 25 mV, 15 Hz and 15 mVs-1, respectively. Based on square wave voltammogram, cetyltrimethylammonium bromide (CTAB) shows the best performance as mediator. The result shows that increase of peak current is equal to 5.01 times as effect of CTAB influence. Keywords: antihistamine, carbon paste electrode, cetirizine, surfactant, voltammetry Introduction
analysis always done to get new methods. The new
method is expected to be more practical, quickly,
Antihistamine is one of drugs which many applied in
modestly but has reliable performance. Voltammetry
medical and pharmacy. Besides successfully used in
method many applied in electroanalysis to answer this
the therapy of allergic diseases, also used as anti-
challenge. A Working electrode is important factor in
cholinergic, anti-emetic, anti-phlogistic, sedatives,
voltammetry method. One of electrode which often
anti-serotonin and has local anesthetic activity (Akdis,
applied is carbon paste electrode, recently. Electrode
et.al., 2000 ; Juniper, et.al., 2005 ; Sicherer & Leung,
modified and usage of mediator meant to increase
2005). It’s often used as combination agents in cough
measurement response. The mediator which many
and cold drugs. Cetirizine is second generation
antihistamine. It is described as a long acting non-
Usage of surfactants in electroanalysis has many
sedating antihistamine with some mast-cell stabilizing
reported. Zhang, et.al.,(2002) has applied Cetyl-
trimethylammonium bromide (CTAB) as mediator on
In 3 last decades happened increasing of allergy
determination of Adriamycin. Chengguo, et.al., (2004)
prevalence. Not less than 22 % of people in the world
have also applied CTAB for determination of
every year, hit allergy symptoms that reducing
Thyroxine at carbon paste electrode, while
productivity and quality of life. The kinds of Allergy
Shengshui, et.al., (2002), by using modified nafion-
are rhinitis allergy, asthma, rhino-conjunctivitis,
glassy carbon has determined estrogen compounds
dermatitis syndrome and anaphylaxis. The World
(estradiol, estrone and estriol). Posac, et.al.,(1995),
Allergy Organization (WAO) notes more than US$ 20
even impregnation of Triton X-405 has into carbon
billion/year had been released just for handling
paste for determination of Aceclofenac. The result of
rhinitis allergy (Motala, 2005). The many application
researches shows improvement of analysis sensitivity
of antihistamine and allergy prevalence that is
increasing, causes usage of this drug also increases.
Based on these facts, in this research has been
Therefore, drug monitoring need to be improved. This
made carbon paste electrode to determine cetirizine by
thing is done that well guarantied drug quality control
Determination of cetirizine is done in surfactants
Some analytical methods such as chromatography
medium. Influence of some surfactant types is studied
and spectrophotometry has been applied to determine
to obtain the best of surfactants on increasing analysis
cetirizine. Even though, development of chemical
Proceeding of The International Seminar on Chemistry 2008 (pp. 381-384)
is done. All of these measurements apply optimum condition which has been obtained before.
Materials and Methods Results and Discussion
All the electrochemical measurements were carried
Cyclic voltammetry of cetirizine at the CPE
out with voltammetric analyzer (Epsilon BASi) and
voltammograms were recorded with a set of computer
The voltammetric responses of 1x10-2 mol/L cetirizine
from IBM. A three-electrode system, including carbon
in potassium chloride solution at the carbon paste
paste as working electrode, a platinum wire as
electrode were investigated by using cyclic
auxiliary electrode and Ag/AgCl electrode as
voltammetry technique. Voltammogram of cetirizine
reference electrode, was employed. All potentials
(Fig. 1) is measured at certain potential interval.
Determination of potential interval meant to know
working area which will be applied. In this research,
potential interval is applied to identify peak current of
1 x 10-2 mol/L cetirizine is 0.00 V to +0.30 V with
In this research using materials such as cetirizine
(pharmaceutical grade), potassium chloride, graphite, solid paraffin, copper wire, cetyltrimethylammonium
bromide (CTAB), sodium dodecyl sulfate (SDS),
sodium dodecylbenzene sulfonate (SDBS), and Triton
Preparation of carbon paste electrode (CPE)
The CPE was prepared by mixing solid paraffin and
graphite powder in a small petri dish, and this mixture
was then heated and homogenized. After that, the
paste was pressed manually into the cavity of the
electrode body, and the surface was smoothed against
clean paper. Unless otherwise stated, the paste was
Figure 1 Cyclic voltammogram of cetirizine
carefully removed prior to pressing a new portion into
the electrode after every measurement. Composition
Figure 1 shows cyclic voltammogram of cetirizine
optimization of CPE is also done to obtain result of
at potential interval from 0.00 V to +0.30 V.
Oxidation and reduction peak current were located at
A 10 mL volume of 0.1 mol/L potassium chloride
containing a known concentration of cetirizine was
To obtain carbon paste electrode with the best
added into the electrochemical cell and purged with
performance, optimization of electrode composition is
purified nitrogen for 5 minutes to remove oxygen, and
done. Composition ratio of graphite versus paraffin is
nitrogen gas was passed over the solution during the
made in various 50:50, 60:40, 70:30, 80:20, and 90:10
experiment. After cetirizine was accumulated under an
%. The result found that the highest peak current is
open-circuit for a certain time while stirring the
obtained at composition ratio of graphite versus
solution, cyclic voltammogram was recorded from
0.00 V to +0.30 V at scan rate, 50 mV/s. All of the
measurements carried out at room temperature.
Optimum parameter to determination cetirizine by Optimization and influences of surfactants
Optimization of parameters in SWV technique is done
Optimization of measurement parameter in square
to get highest peak current. These parameter are step
wave voltammetry technique is done to obtain the best
potential (step E, mV), pulse amplitude (mV),
performance of analysis, such as accumulation
potential, pulse amplitude and frequency.
In the same procedure above, influence of some
surfactant types to improvement of analysis sensitivity
Proceeding of The International Seminar on Chemistry 2008 (pp. 381-384)
concentration range (below the critical micelle
concentration (CMC)), but the degree of enhancement
Figure 2 Composition optimum of the CPE
The potential wave form consists of a square
wave of constant amplitude superimposed on a
staircase wave form. The current is measured at the
end of each half-cycle, and the current measured on
Figure 4 Frequency optimization
the reverse half-cycle (ir) is subtracted from the
current measured on the forward half-cycle (if)
Among these surfactants, the oxidation peak
(Fig.3). This difference current (if - ir) is displayed as
current of cetirizine is the highest and the background
current is the smallest in the presence of low concentration of CTAB. CTAB with hydrophobic C-H chain and hydrophilic head group can adsorb strongly at the surface of the carbon paste electrode via their hydrophobic interactions. Consequently, adsorbed CTAB induces cetirizine to adsorb at the electrode
concentration of cetirizine. So the oxidation peak current of cetirizine increases significantly in the presence of CTAB. In the experimental, the CTAB concentration is 1.0 x 10-4 mol/L.
Figure 3 Potential wave form for square wave 3.0
The result of optimization of some parameters
influencing peak current of analysis is obtained at step
potential, pulse amplitude, and frequency were 1 mV,
25 mV and 15 Hz, respectively. Figure 4 shows level of peak current is obtained at various frequencies. The
scan rate cannot be directly investigated by the
researcher in this technique, and is determined by step
potential (step E) x square wave frequency. Thereby,
scan rate optimum is obtained at 15 mV/s.
Figure 5 Voltamogram of surfactant influence
The influences of surfactants, such as cationic
The average peak current on determination of
cetirizine in presence of triton X-100, CTAB, SDS
(CTAB), anionic surfactant: sodium dodecyl sulfate
and SDBS are 2.20, 3.88, 2.88, and 2,62 x 10-6 A
(SDS) and sodium dodecyl benzene sulfonate (SDBS)
(Fig.6). This research also find that improvement of
and nonionic surfactant: triton X-100, on the oxidation
peak current of cetirizine in presence of surfactant to
peak current of cetirizine were examined. It is
peak current of cetirizine without surfactant are 2.84
observed that all these surfactants can improve the
times, 5.01 times, 3.72 times, and 3,38 times for
oxidation peak current of cetirizine during a certain
Proceeding of The International Seminar on Chemistry 2008 (pp. 381-384)
respectively. The relative standard deviations (RSD)
Acknowledgements
is obtained on determination of cetirizine in presence
of surfactants are 0.55% - 2.24% (n=10). This fact
The authors would like to thank Direktorat Jenderal
shows reproducibility of this method is good to
Pendidikan Tinggi Depdiknas RI for the financial
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Sedative and Hypnotic Withdrawal Worksheet Instrument: Modified CIWA-A Patient: The trigger point for this protocol is 6. Symptoms & Intoxication Signs: Nystagmus Give only one score for each block. Withdrawal Signs: Hallucinations DBP > 100 Sitting/Standing Orthostasis Sedative and Hypnotic Withdrawal Worksheet Instrument: Modified CIWA-A Inst
Timothy J. Alikakos, MD, FACC Robert B Johnson, MD, FACC Board Certified Board Certified Cardiovascular Disease Cardiovascular Disease Interventional Cardiology Interventional Vascular Medicine C a r d i o v a s c u l a r S p e c i a l i s t s , S C Patient Instructions for Nuclear Stress Testing: Please follow Instructions carefully
Proceeding of The International Seminar on Chemistry 2008 (pp. 381-384)
concentration range (below the critical micelle
concentration (CMC)), but the degree of enhancement
Figure 2 Composition optimum of the CPE