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Voltammetric techniques for the assay of pharmaceuticals-A review

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 Analytical Biochemistry 408 (2011) 179–196

Contents lists available at ScienceDirect

Analytical Biochemistry
journal homepage: www.elsevier.com/locate/yabio

Review

Voltammetric techniques for the assay of pharmaceuticals—A review

Vinod K. Gupta a,b,⇑, Rajeev Jain c, Keisham Radhapyari c, Nimisha Jadon c, Shilpi Agarwal c
a
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee (UK) 247 667, India
b
Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
c
School of Studies in Chemistry, Jiwaji University, Gwalior 474011, India

Vinod K. Gupta Rajeev Jain Keisham Radhapyari Nimisha Jadon Shilpi Agarwal

Dr. Vinod K. Gupta obtained his Ph.D. degree in chemistry from the University of Roorkee (now Indian Institute of Technology, Roorkee), Roorkee, India, in 1979. Since then he
is pursuing research at the same institute and currently is a Professor of physical chemistry. He has worked as postdoctoral fellow at University of Regensburg, Germany, in the
year 1993 as an EC fellow and was DAAD visiting professor at University of Chemnitz and Freie University of Berlin in the year 2002. He is a highly cited researcher in
Environmental Engineering and received the Indian Citation Laureate Award 2004. Dr. Gupta has published one book, 10 book chapters, 15 reviews and 275 research papers in
highly reputed journals. His papers have received more than 6500 citations with h index of 45. He is KFUPM Chair Professor at King Fahd University of Petroleum and Minerals,
Dhahran, Saudi Arabia. His research interests include chemical sensors and biosensors, waste water treatment, environmental and electro-analytical chemistry. He is Fellow of
the World Innovation Foundation (FWIF) and The National Academy of Sciences, India (FNASc).

Dr. Rajeev Jain obtained his Ph.D. degree in chemistry from the University of Roorkee (now Indian Institute of Technology, Roorkee), Roorkee, India, in 1978 and worked as Post
Doctoral Fellow and Research Associate at the same institute. He joined Jiwaji University, Gwalior, India in 1982 as lecturer and at present working as Professor of Analytical
Chemistry at the same University. He was awarded D.Sc. degree by Jiwaji University, Gwalior, India in 1990. He is a highly cited researcher in Electroanalytical Chemistry. Dr.
Jain has published over 270 research papers in journals of high impart factor. He has supervised over 60 Ph.D. students and one D.Sc. student. He is a widely traveled researcher
and has completed 15 research projects. His research interests include Electro-analytical behavior of pharmaceuticals, method development and validation, and waste water
treatment.

Dr. Keisham Radhapyari obtained her Ph.D degree in Chemistry from Jiwaji University, Gwalior, India in the year 2008. She joined North East Institute of Science and
Technology (NEIST), Jorhat, India as Young Scientist in Analytical Chemistry Division in the year 2009. She is working on development of biosensors electrodes for the
determination of organic compounds of pharmaceutical significance.

Dr. Nimisha Jadon is working as a research associate at Centre for Science & Environment (CSE), New Delhi, India. She has done her post-graduation in environmental
chemistry in 2002 and Ph.D. in chemistry in 2008, from Jiwaji University, Gwalior, India.

Shilpi Agarwal obtained her M. Sc. degree in Chemistry in the year 2004 and since 2006 persuing research in the areas of chromatography and electroanalytical chemistry at
School of Studies in Chemistry, Jiwaji University, Gwalior, India. She successfully completed the research work and submitted the thesis for the award of Ph.D. degree in the year
2010.

Analytical Chemistry plays a critical role in the development of
a compound from its synthesis stage to its marketing stage as a
part of a drug formulation and analysis. The instrumental methods
⇑ Corresponding author at: Department of Chemistry, Indian Institute of
Technology Roorkee, Roorkee (UK) 247 667, India. Fax: +91 1332 273560.
E-mail addresses: vinodfcy@gmail.com, vinodfcy@iitr.ernet.in (V.K. Gupta).
for quantitation which are most commonly used in a pharmaceuti-
cal laboratory fall into four basic categories: chromatography,
spectrophotometric, electrochemical, and radiometric analysis
[1]. Electroanalytical chemistry along with the use of oxidation–
reduction reactions and other charge-transfer phenomena had its
origins eight decades ago. It is one of the fundamental subdisci-
plines of analytical chemistry.

0003-2697/$ - see front matter Ó 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.ab.2010.09.027
180 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196
In the 1920s, Czech scientist Jaroslav Heyrovsky discovered
voltammetry, a form of electrochemistry, in which samples were
analyzed by measuring current as a function of the applied elec-
trical potential. A quarter century later, on October 26, 1959,
Jaroslav Heyrovsky was awarded the Nobel Prize in Chemistry
for his discovery of the polarographic methods of analysis [2].
In the last eight decades, voltammetric methods have become a
popular tool for the study of electrochemical reactions [3], for
the study of electrochemically generated free radicals [4], in
model studies of enzymatic catalysis [5], in coordination chemis-
try [6], in solar energy conversion [7], in environmental monitor-
ing [8], in industrial quality control [9], and in the determination
of trace concentrations of biological and clinically important
compounds [10,11].
Till now, the commonly employed techniques for the deter-
mination of the drug in bulk form, pharmaceutical formulation,
and biological fluids are based on HPLC [12], LC/MS [13], spec-
troscopy [14], and microbiological assays [15]. Such techniques
for the measurement of biological concentration are necessary
in a clinical environment to ensure that adequate drug levels
can be maintained while avoiding toxic concentrations of such
drugs. The problems encountered using such methods are either
the need for derivatization or the need for time-consuming
extraction procedures. Since these techniques have expensive
instrumentation and running costs, the use of simpler, faster,
and cheaper, yet sensitive, electrochemical techniques can be
interesting alternatives, especially those based on electroanalyti-
cal techniques.
Electrochemistry has many advantages, making it an appealing
choice for pharmaceutical analysis [16,17]. Electrochemistry has
always provided analytical techniques characterized by instru-
mental simplicity, moderate cost, and portability. These techniques
have introduced the most promising methods for specific applica-
tions [18–24]. Due to similarity in the electrochemical and biolog-
ical reactions, it can be assumed that the oxidation/reduction
mechanisms taking place at the electrode and in the body share
similar principles. Biologically important molecules can be investi-
gated electroanalytically by voltammetry in order to determine the
molecule in different ways. Additional applications of electro-
chemistry include the determination of electrode mechanisms.
The redox properties of drugs can give us insight into their meta-
bolic fate in in vivo redox processes or pharmacological activity
[25].
Further, the electroanalytical techniques have been shown to be
excellent for the determination of pharmaceutical compounds in
different matrices. Many of the active constituents of formulations,
in contrast to excipients, can be readily oxidized. The selectivity of
this method is normally excellent because the analyte can be read-
ily identified by its voltammetric peak potential. Advances in
experimental electrochemical techniques in the field of analysis
of drugs are because of their simplicity, low cost, and relatively
short analysis time compared to other techniques. The use of var-
ious electrodes, viz. mercury [26–42], solids [9,43–61], and modi-
fied electrodes [20,62–70], for electroanalytical measurements
has increased in recent years because of their applicability to the
determination of active compounds that undergo oxidation reac-
tions, which is a matter of great importance in the field of clinical
and pharmaceutical analysis.
Ozkan and co-workers [71] critically reviewed the application
of modern electroanalytical techniques (potentiometry, on-line or
hyphenated voltammetry, voltammetry) in the analysis of pharma-
ceuticals and biological fluids. The authors reviewed about 200
papers starting from 1995 to 2000. The use and advantages of tech-
niques to pharmaceutical compounds in dosage forms and biolog-
ical media were discussed. However, the review did not clearly
provide the matrix in which pharmaceuticals were analyzed. Fur-
thermore, important information, like the peak potential of the
electroactive substance, was not included.
The present study reviews the various applications of voltam-
metry to pharmaceutical analysis covering the period from 2001
to 2010. The present review includes the voltammetric determina-
tion of pharmaceuticals of various classes, viz. antibiotics [72–79],
antiemetics [46,47], antiamoebic [80], hypolipidemic [81–83],
antipsychotic [84,85], cardiovascular [86–89], hypoglycemic [90],
analgesics [91–95], coagulants [96], antiplatelet [97], anthelmintic
[98], sedatives [58,99], gastrointestinal [34,100], antidepressant
[101,102], antiarrhythmic [103], opioid analgesics [104], vitamins
[105–107], anticholinesterase [108], antiadrenergic [109], antipar-
kinsonian [110], antiallergics [111], and others. The review is
divided into four sections. The first deals with various applications
of nonstripping voltammetric techniques using linear sweep
voltammetry (LSV),1 cyclic voltammetry (CV), differential pulse
voltammetric (DPV), and square-wave voltammetry (SWV) in phar-
maceutical analysis. The second section covers the application of
sensitive stripping techniques in pharmaceutical analysis. The third
part deals with the effectiveness of surfactants in the electroanalysis
of biological compounds and drugs. Finally, the fourth section of the
review is devoted to the use of chemically modified electrodes in the
analysis of pharmaceuticals. The third and fourth sections of this re-
view were not taken in detail by Ozkan and co-workers. Additionally,
another interesting feature of this review, which is worth noting, is
that the names of drugs along with the peak potential (Ep) and
matrix are sorted in ascending order in Tables 1 and 2. This makes
the table user friendly.
1
Abbreviations used: AAdSV, anodic adsorptive stripping voltammetry; AC,
acetaminophen; AdCSV, adsorptive cathodic stripping voltammetry; AdLSCSV,
adsorptive linear sweep cathodic stripping voltammetry; AdS, adsorptive stripping;
AdSACV, adsorptive stripping alternating current voltammetry; AdSDPV, adsorptive
stripping differential pulse voltammetry; AdSLSV, adsorptive stripping linear sweep
voltammetry; AdSSWV, adsorptive stripping square-wave voltammetry; AdSSWV,
adsorptive stripping square-wave voltammetry; AdSV, adsorptive stripping voltam-
metry; AMPC, ampicillin; ASDPV, anodic stripping differential pulse voltammetry;
5-ASA, 5-aminosalicyclic acid; ASV, anodic stripping voltammetry; Au, gold; BUS,
buspirone hydrochloride; BR, Britton-Robinsons; BDD, boron diamond doped; BF,
bulk form; BS, blood sample; CAdSDPV, cathodic adsorptive stripping differential
pulse voltammetry; CAdSV, cathodic adsorptive stripping voltammetry; CGME,
controlled growth mercury electrode; CP, carbon paste; CP, carbon paste; CSSWV,
cathodic stripping square-wave voltammetry; CSV, cathodic stripping voltammetry;
CV, cyclic voltammetry; CTAB, cetyl trimethylammonium bromide; DC, direct
current; DME, dropping mercury electrode; DPAdCSV, differential pulse adsorptive
cathodic stripping voltammetry; DPAdSV, differential pulse adsorptive stripping
voltammetry; DPAdV, differential pulse adsorptive voltammetry; DPCAdS, differential
pulse cathodic adsorptive stripping; DPCSV, differential pulse cathodic stripping
voltammetry; DPP, differential pulse polarography; DPSV, differential pulse stripping
voltammetry; DPV, differential pulse voltammetry; ENRO, enrofloxacin; FDCMCPE,
ferrocenedicarboxylic acid; GC, glassy carbon; GCRDE, glassy carbon rotating disk
electrode; GE, graphite electrode; GNP, gold nanoparticle; HB, human blood; HMDE,
hanging mercury drop electrode; HS, human serum; HU, human urine; ISO,
isorhamnetin; LSAAdSV, linear sweep anodic adsorptive stripping voltammetry;
LSAdCSV, linear sweep adsorptive cathodic stripping voltammetry; LSAdSV, linear
sweep adsorptive stripping voltammetry; LSSV, linear sweep stripping voltammetry;
LSV, linear sweep voltammetry; MCP, modified carbon paste; MGC, modified glassy
carbon; MGE, modified graphite electrode; MWCNT, multiwalled carbon nanotube;
NA, noradrenalin; NGITO, nanogold indium tin oxide; NGMITO, nanogold modified
indium tin oxide; NPV, normal pulse voltammetry; OMC, ordered mesoporous
carbon; OSWSV, Osteryoung square-wave stripping voltammetry; OSWV, Osteryoung
square-wave voltammetry; PIR, Piribedil; PF, pharmaceutical formulation; PGE, pencil
graphite electrode; Pt, platinum; SDS, sodium dodecyl sulfate; SMDE, static mercury
drop electrode; SODASV, second-order differential anodic stripping voltammetry; SP,
spiked plasma; SWAdASV, square-wave adsorptive anodic stripping voltammetry;
SWAdCSV, square-wave adsorptive cathodic stripping voltammetry; SWAdSV,
square-wave adsorptive stripping voltammetry; SWASV, square-wave anodic strip-
ping voltammetry; SWCAdS, square-wave cathodic adsorptive stripping; SWCSV,
square-wave cathodic stripping voltammetry; SWSV, square-wave stripping voltam-
metry; SWV, square-wave voltammetry; TC, tetracycline; TX-100, Triton X-100; ZP,
zopiclone.
 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196 181

Table 1
Pharmaceutical compounds determined by LSV/CV/DPV/SWV in bulk form, pharmaceutical formulation, and biological fluid with references and matrix studied.

Name of drug Indicator Detection/determination Methods Matrix Ep (V) References

electrode limit/conc. range
5-Aminosalicyclic acid GC 1  104 to 2  106 M LSV PF – [16]
DPV
7 4
Abacavir GC 8  10 to 2  10 M DPV, PF – [17]
1  105 to 1  104 M SWV HU
2  105 to 2  104 M HS
Acetaminophen GC 3.0 lg mL1 CV PF – [18]
Acetaminophen MGC 1.7  105 M CV PF, HS – [19]
Acetaminophen MGC 4  108 M CV PF – [20]
Acrivastine DME 0.11 mg L1 DPP PF, 0.6 [21]
HU 0.99
Acrivastine DME 0.03 lg mL1 DPP PF, HU 1.0 [22]
Albendazole GCRDE 2.4  105 M LSV PF +0.99 [23]
Amoxicillin MCP 24.8  106 M LSV PF – [24]
16.6  106 M DPV
8.49  106 M SWV
Ampicillin Modified carbon-paste electrode 2.34–30 mmol L1 and 40–700 mmol L1 DPV PF, HU 480 mV [269]
Ascorbic acid – 0.88 lg mL1 DPV PF – [122]
Atenolol MGC 0.16  10103 M SWV PF, HU 1.04 [62]
Atenolol NGMITO 0.13  106 M DPV PF, HU 0.47 [253]
0.90
Azithromycin GC 9.24  107 M CV/DPV PF 0.8 [123]
Azithromycin GC – CV [43]
Benorilate MCP 1  108 M DPV PF, HU 0.97 [63]
Bergenin MCP 7  108 M DPV PF, HU – [234]
Bromhexine GC 1.4  105 M DPV PF – [138]
Bisoprolol fumarate MGC 8.27  107 M DPV PF, HU 0.95 [225]
Bromocriptine GCE 0.01 lg mL1 DPV PF 0.6 [124]
Betahistine GCE 250 to 3500 lg mL1 SWV PF 1.5 [162]
Captopril SMDE 6.28  103 lg mL1 SWV PF, HS 0.7 [147]
Captopril CP 1.1  106 M CV, DPV PF, HS 0.65 [125]
Carvediol GC 0.10 lg mL1 CV, DPV PF – [126]
Catechol GC 3  106 M CV, DPV PF 0.4 V [216]
hydroxyquinone
8  106 M 0.3 V
Cefdinir DME 0.3  106 M DPP PF 0.6 [127]
Cefixime – 6.0  106 to 2.0  104 M DPV PF, HS, 0.85 [134]
HU
SWV
Cefixime HMDE 4.6  108 M DPV PF, 0.58 [135]
Cefpodoxime 8.52  108 M HS 0.67
Proxetil
Cefotaxime GC, CP 2  105 M to 1  104 M CV, SWV PF 1.15 [136]
2  104 M to 6  104 M
Cefotriaxone MGC 4.03  106 M CV, DPV HS – [137]
Chlorphenoxamine GCE, PE 4.5  104 to 1.0  102 mol L1 CV, DPV PF – [116]
Hydrochloride
Ciclopirox Olamine DME 0.2 lg mL1 DC, DPP PF 0.4 [272]
Cilazapril HMDE 0.5–8 lg mL1 SWV PF – [148]
Quinapril and ramipril 0.5–6 lg mL1
Cisatracurium CP 0.38 lg mL1 DPV HU, HS 0.45 [44]
Clofibric DME 4.7  106 M DPP BF – [26]
Ofloxacin 5.2  106 M
Diclofenac 0.8  106 M
Propranolol 0.5  106 M
Coenzyme Q10 GC 12 mg mL1 DPV PF 0.02 [45]
Diazepam DME, HMDE 9.6  109 M CV PF – [27]
Diazepam CP 0.021 lg mL1 DPV HP, 1.3 [258]
Temazepam 0.021 lg mL1 HU 0.87
Oxazepam 0.012 lg mL1 0.90
Diclofenac CP, GoE, CNP 8.0  106 M NPV BF 0.84 [91]
Diethylstilbestrol CP 1.0  108 M CV, LSV BF – [162]
Dipyridamole HMDE 1.88  108 M SWV PF – [28]
Domperidone GC 4.0  107 M DPV PF 0.64 [46]
Domperidone GC 6.1  107 M DPV PF – [47]
Dopamine Ordered mesoporous carbon (OMC)/ – – – – [265]
Nafion composite film
Donepezil GC 1  106 to 1  104 M DPV, PF, HS – [48]
SWV
Dopamine GC 0.08  106 M SWV PF – [149]
Dopamine CP 5  106 M DPV PF – [219]
Dopamine NGGC 4  109 M DPV PF 0.175, 0.146 [252]
Dopamine NGITO 0.5  109 M SWV PF, HS, 0.7, 0.24 [254]
HU

(continued on next page)

182 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196

Table 1 (continued)

Name of drug Indicator Detection/determination Methods Matrix Ep (V) References

electrode limit/conc. range
Serotonin 3  109 M
Dopamine MGE 0.35  105to 3.4  105 M SWV PF – [226]
Dopamine HMDE 0.02  106 M SWV PF 0.9 [29]
Dopamine MWCNT 2  107 M DPV PF 0.2 [227]
Dopamine MWCNT – SWV PF 0.2 [228]
Doxazosin RPE – DPV PF – [109]
D-Penicillamine MCP 6.04  105 M CV PF – [217]
6.15  106 M DPV
Droxicam HMDE – CV – – [112]
Enrofloxacin HMDE 10.0–80.0 nmol L1 with a detection SWV PF 0.10 V
limit of 0.33 nmol L1
Entacapone – – DC, DPV PF – [110]
Epinephrine MGE 6  108 M CV PF – [251]
Ethinylestradiol CP 3.0  108 M LSV PF 0.59 [120]
Ethopropazine GE 0.4–4  106 M CV BF 0.67 [113]
Etodolac GC 6.8  107 M DPV PF, HS – [150]
1. 1  106 M SWV
Etoposide CP 1  107 M DPV PF – [49]
Entacapone HDME 5  104 mol L1 to 1.8  105 mol L1 SWV,CV PF 0.25 221
Fenbendazole GC 5.2  105 M LSV PF +1.2 [121]
5  106 M DPV
5  105 M SWV
Finasteride DME 5  105 to 5  104 M DPP PF 1.25 [30]
Floctafenine HMDE 0.4 to 3.6 lg mL1 DC, DPP PF 1.05 to 1.27 [31]
Metopimazine 0.4 to 2.4 lg mL1
Fluoxetine GC 1  106 M DPV, PF 0.9 [9]
SWV
Flupenthixol GC 1.17  107 M DPV PF, HS – [51]
Fluvastatin sodium BDD 1.37  107 M DPV PF, HS – [259]
Ganciclovir GC 4.52  108 M SWV PF, HS +1.2 [51]
8.1  108 M DPV
Guaifenesin PE 20–60 lg mL1 CV PF 0.924 [52]
Hydrochlorothiazide GC 5 ng mL1, 14 ng mL1 DPV PF, HU +1.05 [53]
Hydroxychloroquine GC 11.2 lg mL1 DPV PF +1.4 [54]
Hyoscine Pt 1  106 to 1  103 M DPV PF, HS, – [55]
HU
Indinavir HMDE 8  107 to 8  106 M DPV PF, HS – [32]
8  107 to 1  105 M LSV
Inosine MCP 8.3  1010 M – PF, HS +0.20 [236]
Isoprenaline CP 8  105 M CV PF – [50]
Isoxsuptine GC 6  108 to 6  105 M DPV, PF, HS – [57]
Formoterol SWV
Isradipine DME 2.7  108 M DPP PF, HU, 0.6 [33]
HU
8 7
Isorhamnetin GC 1.0  10 to 4.0  10 M CV PF – [115]
Josamycin DME 1.9  106 M DC, DPP PF, HU 1.1 [140]
Lamivudine HMDE 8.65  108 and 6.36  108 M DPV, PF, HS 1.26 [142]
OSW
Lansoprazole SMDE 0.03 lg mL1 DPV PF – [34]
L-Dopa Carbidopa MCP 2.5  105 M DPV PF – [237]
3.7  106 M
Lidocaine BDD 10 lg L1 SWV PF 1.68 [260]
Melatonin CP 2.3  106 M CV PF – [58]
Meloxicam SMDE 0.38 to 15 lg mL1 CV, DC, PF, SP – [35]
DPP
Meloxicam MGC 1.5  109 M – PF, HS 1.088 [238]
Meloxicam HMDE 1  108 to 5  106 M DPV PF 1.088 [36]
Meloxicam DME 1  105 M DPV – – [37]
Metformin MWCNT 6.7  108 M – PF – [233]
Methimazole Pt 1  106 to 700  106 M SWV PF +0.8 [143]
Methyl prednisolone MGC 5.6  109 M DPV PF, HS, – [10]
HU
Methyl prednisolone NGITO 2.68  107 M DPV HS, HU 0.515 [255]
Citrate
1
Mosapride citrate Pt 0.05 lg mL SWV BF, PF 1.1 [218]
Nabumetone – 7.65  108 M DPV PF 1.2 [92]
3.6  108 M OSW
2.31  107 M DPV HS
2.53  107 M OSW
2.68  107 M DPV HU
2.5  107 M OSW
Natamycin CP 1.5  106 M DPV PF – [74]
Naproxen PE 0.24 lg mL1 DPV PF – [93]
Nefazodone HCl GC 2.1  107 M DPV PF, HS – [151]
 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196 183

Table 1 (continued)

Name of drug Indicator Detection/determination Methods Matrix Ep (V) References

electrode limit/conc. range
1.17  107 M SWV
Niocotinic acid and PGE 0.27  106 M CV PF 0.20 [81]
nicotinamide
0.33  106 M
Nilvadipine DME 0.2 –10 lg mL1 DPP PF, HU 0.4 [38]
1.5–20 lg mL1 DC
Nimusilide MGC 5.0  108 M DPV PF, HS 1.25 [235]
Nitroimidazopyran DME – CV PF 1.3 [39]
Norfloxacin PMRE 1  107 M LSV PF – [118]
Nitrofurantoin. HMDE 0.06 and 0.27 ng mL1 CV, PF – [173]
SWCAdSV
Nortriptyline HMDE 0.92 ng mL1 SWV,CV PF – [220]
Hydrochloride
Noradrenalin GCE DPV [266]
Nitrazepam DME 0.04 and 0.15 ng mL1 DPP PF – [224]
Olsalazine-Na GC 5.75  107 M DPV PF – [100]
Ornidazole DME 4.0  103 to 4.0  106 mo L1 DPV, CV PF – [223]
Pantoprazole GCE 4  107 M DPV PF, HP – [133]
Para-aminobenzoic MCP 0.1 lg mL1 DPV PF 0.98 [141]
acid
Paracetamol NGMITO 1.8  107 M DPV PF HU 0.83 [256]
Paracetamol MGC 0.05  106 to 1.5  106 M – PF, HU – [261]
Pefloxacin BDD, GC 2  106 to 2  104 M DPV, PF, HS 1.2 [262]
SWV
Pentoxifylline GC 4.42  1010 M DPV BF, PF – [273]
Phenylephrine MGC 3  108 M – PF – [239]
Pipamperone HMDE 3  106 M DPP PF 1.4 [128]
Piribedil GC 2  106 to 1  103 M DPV PF, HS 1.1 [104]
2  106 to 8  104 M SWV
Piroxicam CNP 0.1 lg mL1 DPV PF 0.5 [94]
Procaine MGC 2  107 M – PF – [232]
Propranolol SMDE 5  109 M DPP PF 0.275 [274]
Pyrantel pamoate DME 2.45  105 M CV, DPP PF 1.36 [98]
Pyridoxine HCl MCP 0.4 lg mL1 DPV PF [64]
Pyrantel pamoate Polymer membrane – – – – [264]
Pyridostigmine – – – – – [263]
bromide
Quercetin MWCNT 0.05–5 lM RDPV PF 0.155 V, 0.36 V, [229]
0.316 V
Rutine 0.1–10 lM
Quetiapine GC 4  108 M DPV HS [84]
1.33  107 M SWV
6.20  107 M DPV HU
5.92  107 M SWV
1.44  107 M DPV PF
1.31  107 M SWV
Rabeprazole GC 4  107 M CV, PF – [275]
LSV,DPV
Resveratrol HMDE 5.0  109 to 1.65  107 M CV PF, HU 0.7 [215]
SWV
7
Repaglinide CP 1.348  10 DPV PF, HS – [275]
GC 1.062  107 M
Rutine GC, CP, PE 106 to 105 M CV, LSV, PF – [96]
DPV
Salbutamol NGITO 75 ng mL1 SWV PF, HU, 0.575 [257]
HP
1
Salicylic acid GC 1–60 lg mL CV, DPV PF – [121]
Serotonin GC – SWV PF – [276]
Tryptophan MCP 1  107 M DPV PF, HU 0.9 [230]
Simvastatin GC 2.71  107 M DPV PF, HS – [82]
5.5  107 M SWV
Sinomenine MGC 5  108 M DPV HS 0.632 [240]
Sparfloxacin DME – DC, DPP BF – [131]
Sparfloxacin GC – DPV PF – [132]
Tamsulosin GC 3.34  107 DPV, PF, HS 1.3 [139]
2.45  107 M SWV
Terazosin GC 6  107 M CV, DPV PF 1.0 [188]
HCl 4.58  109 M
Terbinafine MGC 2.5  108 M DPV PF, HS 1.15 [241]
Tetracycline – – – – – [267]
Thalidomide SMDE, HMDE, GC – CV BF 0.65 [114]
Ticlopidine HMDE 5.17  107 M SWV PF 0.01 [97]
Tramadol – 2.2  106 M SWV PF – [152]
Trazodone HCl DME 0.104 lg mL1 DC PF, HU, 1.0 [101]

(continued on next page)

184 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196

Table 1 (continued)

Name of drug Indicator Detection/determination Methods Matrix Ep (V) References

electrode limit/conc. range
HP
0.314 lg mL1 DPP
Trepibutone PGE 20 ng mL1 SWV PF 0.06, 1.24 [146]
Trimebutine GC 0.3  106 M DPV PF 1.39 [129]
Tryptophan CP 1. 7  106 M DPV PF – [130]
Tryptophan MCP 1.0  107 M DPV PF 0.8 [230]
Tryptophan zeolite beta to the carbon paste 5.0–107 to 5.0–103 M PF – [174]
Tyrosine MGC 8  107 M CV, DPV PF 0.6 [231]
Uric acid MGC 5.27  107 M SWV HU 0.03 [242]
0.32
Valacyclovir GC 1.04  107 and 4.6  108 M DPV, PF, HS – [145]
SWV
Verapamil GC 1.61  107 M DPV PF, HS – [103]
OSWV
7
1.33  10 M
Vitamins B1 DME – DC, DPP PF 1.22 [105]
Vitamins B2 1.2
Vitamins B6 1.68
Vitamins 6 GC 1  107 M CV, LS, PF – [106]
DPV
Vitamins E – 0.03 mg mL1 – PF 0.756 [107]
Silymarin 0.01 mg mL1 0.444
Vitamins 12 MGC 1  109 M CV PF 0.41 [244]

Nonstripping voltammetric techniques
Cyclic and linear sweep voltammetry
Cyclic voltammetry is often the first experiment performed in an
electrochemical study of a compound, a biological material, or an
electrode surface. It is effectively used in the fields of environmental
electrochemistry, organic chemistry, inorganic chemistry, and bio-
chemistry. The effectiveness of CV results from its capability for rap-
idly observing the redox behavior over a wide potential range. The
resulting voltammogram is analogous to a conventional spectrum
in the sense that it conveys information as a function of an energy
scan. Cyclic voltammetry has become a popular tool since the last
40 years for studying electrochemical reaction. CV is perhaps the
most versatile electroanalytical technique in pharmaceutical analy-
sis [27,112]. It is often the first experiment performed in an electro-
chemical study of drugs in raw material [113,114], pharmaceuticals
[50,52,58], and biological material [39].
The formation and stability of the radical anion from PA-824
and its comparison with metronidazole were carried out by Bollo
et al. [39] by using CV. Acuna et al. [112] used CV for studying
the kinetics of the hydrolytic decomposition of droxicam and for
establishing the possible pharmacological action of the drug in
an organism of the human being. Acetaminophen [18] in paracet-
amol tablets was determined by using CV in phosphate buffer with
a good linear calibration range of 3–240 lg mL1. The CV method is
in good agreement with the USPXXII official method. Wang et al.
[81], by employing CV along with bulk electrolysis, deduced the re-
dox reaction mechanisms of nicotinic acid and nicotinamide in
which it was rationalized by the formation/disappearance of the
new nitrogen–oxygen bonds in pyridine rings.
Liu and co-workers had studied the electrochemical behavior of
isorhamnetin at a glassy carbon electrode by cyclic voltammetry. Un-
der optimal conditions, the oxidation peak current showed a linear
dependence on the concentration of ISO in the range of 1.0  108 to
4.0  107 and 1.0  106 to 1.0  105 M. This method has been suc-
cessfully applied to the detection of ISO in tablets [115].
Voltammetric methods have been used for the determination of
chlorphenoxamine hydrochloride (Ch-HCl) in raw material and in
its pharmaceutical preparations (Allergex and Allergex caffeine
tablet). It was found that Ch-HCl gives a characteristic cyclic
voltammetric and differential pulse voltammetric peak in acetoni-
trile using platinum and glassy carbon working electrodes. The Ip of
the DPV peak increases linearly within the concentration range
from 4.5  104 to 1.0  102 mol L1 of the investigated drug.
The concentration of Ch-HCl in raw drug material and in its phar-
maceutical preparations was determined using the standard addi-
tion method, the Randles–Sevcik equation, and indirectly via its
complexation with sodium tetraphenylborate (NaTPB). The ob-
tained overall average recoveries were 101.44% and 100.49% with
SD 0.45 and 0.38 (n = 4) for platinum and glassy carbon electrodes,
respectively. The effect of scan rate, sample concentration, and
supporting electrolyte on the Ip and Ep was also investigated [116].
Loracarbef has antibacterial activity and is oxidizable at the
glassy carbon electrode. The electrochemical oxidation of
Loracarbef was investigated using cyclic, linear sweep, differential
pulse, and square-wave voltammetric techniques. The results ob-
tained from cyclic voltammetry indicate that the oxidation process
of Loracarbef is irreversible and diffusion controlled on glassy
carbon electrodes. The dependence of peak currents and potentials
on pH, concentration, scan rate, and nature of the buffer was inves-
tigated. According to the linear relation between the peak current
and the concentration, differential pulse and square-wave voltam-
metric methods for Loracarbef quantitative determination were
developed. Different parameters were tested to optimize the con-
ditions for the determination of Loracarbef. The quantitative deter-
mination of Loracarbef was proposed in 0.1 M H2SO4, which allows
quantitation over the 6  106 to 2  104 M range. Precision,
accuracy, reproducibility, sensitivity, and selectivity were checked.
The methods were proposed for the determination of Loracarbef in
pharmaceutical dosage forms [117].
Furthermore, LSV, along with CV, has received great interest for
the elucidation of electrode processes and redox mechanisms.
Linear sweep voltammetry was used to study the influence of pH
on the peak current and peak potential of 5-aminosalicyclic acid
(5-ASA) [16] in different buffer systems. The oxidative behavior
has been investigated using a glassy carbon electrode. Santos
et al. [23] studied the electroanalytical behavior and methodology
for quantification of albendazole in pharmaceutical formulations.
The study reveals that the albendazole oxidation exhibited a stan-
dard heterogeneous rate constant for the electrodic process equal
to (1.51 ± 0.07)  105 cm s1, with a ana value equal to 0.76. LSV
 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196 185

Table 2
Pharmaceutical compounds determined by stripping technique in bulk form, pharmaceutical formulation, and biological fluid with references and matirx studied.

Name of drug Indicator electrode Detection/determination Methods Matrix Ep (V) References

limit/conc. range
Amfepramone HMDE 0.035 mg L1 (acidic) DPAdSV BF, PF – [40]
0.18 (alkaline)
Amiloride HMDE 7.1  109 M DPAdSV PF 11.25 [41]
Amiloride HMDE 1.9  1010 M SWAdSV PF – [42]
5.7  1010 M HS
Amlodipine GC 1.4  108 M SWAdSV PF 0.510 [166]
Atorvastatin – 4  109 M DPV PF, HP [83]
2  109 M SWAdSV
Atorvastatin calcium GC 2.11  107 M DPV PF, HS, HU – [59]
2.05  107 M SWV
Azithromycin CP 0.463 ppb SWV PF – [60]
Azithromycin GC 0.2 lg L1 DPAdSV PF, HU 0.82 [61]
Buspirone HCl HMDE 0.20 ng mL1 DPCSV PF, HP 1.23 [11]
Piribedil 0.19 ng mL1 1.22
Captopril HMDE 0.5 lg L1 SWCAdSV PF, BF – [86]
Captopril HMDE 0.3  109 M DPCAdSV PF, HS 0.40 [87]
Thiogeranine 0.8  109 M 0.15
Captopril Pt 9.2  107 M – PF 1.2 [88]
Carvedilol GC 2  107 to 2  105 M DPAdSV PF, HS – [158]
2  107 to 1  105 M SWAdSV
Cefazolin HMDE 2.6  1010 M SWAdSV BF, PF 1.1 [74]
Cefdinir HMDE 0.2 ng mL1 SWCAdSV PF 0.38 [75]
0.08 lg mL1 HU
Cefminox DME 1.76  106 M DPP HU 1.0 [76]
HMDE 2.47  108 M LSAdSV
Cefonicid HMDE 4  108 M AdSWSV HU 0.6 [77]
Cefoperazone HMDE 1.5  109 M SWSV PF – [78]
6  1010 M HS
2  109 M HP
Ceftiofur HMDE 6  1010 M CSV PF, HS 1.25 [79]
Celecoxib HMDE 0.4 ng mL1 SWCAdSV PF, HS 1.45 [95]
Cephalothin HMDE 3.3  109 M AdSV PF, HS, HU 0.62 [159]
Chlordiazepoxide HMDE 4.4  1010 M (DF) SWAdCSV PF, HS 1.2 [99]
6.6  1010 M (S)
Chlorhexidine GC film FME – – – 1.88 [65]
Chlorpromazine HCl GC 0.05–1.2 mg mL1 DPSV PF, HB 0.62 [85]
0.1–1 mg mL1 0.44
Promethazine HCl
Cilazapril HMDE 17.6 ng mL1 DPAdSV PF 1.33 [171]
Cilazapril HMDE 0.5–8 lg mL1 SWSV PF – [89]
Quinapril 0.5–6 lg mL1
Ramipril
5-Aminosalic acid MGrC – CV, SWV PF 0.54 [66]
Ciprofloxacin 1.2
Azithromycin 0.94
Citalopram HMDE 5  108 M SWAdSV PF 1.25 [102]
Creatine MHMDE 0.11 ng mL1 DPCSV PF, HS – [155]
Danazol HMDE 5.7  109 M SWAdSV PF 1.09 [160]
Dapsone GC 3.56 mg mL1 SWSV PF, HU 1.55 [161]
0.0036 mg mL1
Diethylstilbestrol CP 1  108 M CV PF 0.51 [162]
Diflunisal DME 5 lg mL1 DPP PF 0.31 [163]
HMDE 0.1 lg mL1 DPAdSV
Diltiazem – 6  109 M AdSV PF, HU 1.72 [175]
Diosmin GC 3.5  108 M AdSV PF 0.73 [176]
Enrofloxacin – 4 –25 ng mL1 AdSV PF, HU – [177]
Ethinylestradiol HMDE 5.9  1010 M AdCSV PF, HP 1.2 [178]
Famotidine – 6.2  1010 M LSAdSV PF, HU – [179]
4.9  1010 M SWAdSV
Flavoxate HCl HMDE 1  105 M DCP PF – [180]
5  106 M DPP
1  108 M LSAdSV
1  109 M SWAdSV
Flaxedil HMDE 3  109 M CAdSV PF, HU – [181]
Fluoroquinolones – 10 lg mL1, 50 ng mL1 CSV PF 1.02 to 1.13 [182]
Norfloxacin Enoxacin 0.93 to 1.07
Folic acid MGC 7  1010 M AdSV PF 0.88 [244]
Gatifloxacin HMDE 2  108 M AdSV PF, BS – [182]
Moxifloxacin
Lomefloxacin
Sparfloxacin
Glipizide HMDE 1.5  1010 M DPAdSV BF – [173]
Haloperidol 3.83  1010 M SWAdCSV BF 1.55 [184]

(continued on next page)

186 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196

Table 2 (continued)

Name of drug Indicator electrode Detection/determination Methods Matrix Ep (V) References

limit/conc. range
3.3  109 M HS
5.46  109 M HU
Hydroxyzine GC 1.5  108 M SWAdASV PF, HS – [185]
Hymecromone MGC 8  108 M AdSV PF 0.82 [245]
Indapamide MCP 5  109 M ASDPV PF, HS [246]
Isoniazid HMDE 1.18  1010 M (B) SWAdSV BF, PF 1.1 [186]
4.9  109 M (S)
8  108 M (U)
Isoniazid MGC  108 M DPSV PF – [67]
Ketoconazole HMDE 5.3  1011 M AdSDPV PF, HU 1.6 [167]
Lamotrigine HMDE 4.38  109 M DPAdSV PF, HP 0.7 [187]
5.02  109 M SWAdSV
Lamotrigine CSPE, MCE 3.72  107 M DPAdSV PF 1.06 [247]
Lamivudine HMDE 69 ng mL1 CAdSWSV PF 1.2, 1.8 [188]
Lansoprazole HMDE – AdSSWV PF – [189]
Lansoprazole CP 1  108 M DPSV PF – [190]
Omeprazole 2.5  108 M
Levonorgestrel HMDE 4.88  1010 M SWAdCSV BF, PF, HS – [191]
Loracarbef GC 6–106 to 2–104 M range CV, DPV, SQW PF – [117]
Loratadine HMDE 1.6  107 M (DF) CAdSV PF, HP – [111]
1.25  107 M (P)
Lorazepam HMDE 0.019 lg mL1 DPAdCSV PF, HU, HP – [192]
Meloxicam GC 0.02  106 to 10  106 M LSAdSV PF, HU, HS 1.8 [193]
Metoclopramide CP 0.067 to 0.269 ng mL1 SWASV PF, HU 0.90 [194]
Metoclopramide NME 8  1011 M ASV HS – [153]
Metronidazole MGC 6  109 M DPV PF 0.71 [80]
Nalidixic acid HMDE 3.3  109 M CAdSV PF, HU, HS 1.2 [195]
Nicardipine HMDE 2.08  1010 M AdSV HB, HU – [196]
Nifuroxime MGC 68  108 M DPSV PF – [248]
Nitrofurantoin HMDE 1.32  1010 M SWV BF 0.7 [197]
2.86  1010 M HS
5.77  1010 M HU
Nitroxynil HMDE 3.0  105 M DCP PF 0.4 [198]
1.3  108 M DPAdSV
8.4  1010 M SWAdSV
Norethisterone HMDE 1.5  109 M SWAdCSV PF – [199]
Norfloxacin GC lg mL1 AdSSWV HU 0.92 [164]
Ofloxacin HMDE – LSSV PF, bird feed stuffs – [200]
Norfloxacin
Ciprofloxacin
Oxcarbazepine HMDE 1.74  107 M SWAdSV PF 1.0 [277]
Oxybutynin HMDE 0.1 lg mL1 SWCAdSV PF – [108]
0.23 lg mL1 DPCAdSV
Pantoprazole CP 2  108 M DPAdSV [201]
Pantoprazole HMDE 5  1010 M SWAdCSV PF 1.25 [169]
Pefloxacin HMDE 1.6  1010 M SWAdCSV PF 1.07 [170]
4.5  1010 M HS
Piromidic acid HMDE 1.65  109 M SWAdSV HU 0.5 [168]
Piroxicam HMDE 5.4  1011 M SWAdSV PF, HS – [202]
4.32  1010 M
Pravastatin HMDE 8  108 to 5  107 M CV, SWAdSV PF 1.22 to 1.44 [203]
Praziquantel HMDE 1.14  109 M CAdSDPV PF, HF, HP – [204]
Prazosin MGC 3.2  1010 M ASV – – [154]
Procaine hydrochloride MCP 5  108 M DPAdV PF, HU 1.0 [250]
Resveratrol – 1.65  107 to 5  109 M SWV PF – [278]
Riboflavin MCP 0.2 ng mL1 SWASV PF 0.15 [209]
Rofecoxib HMDE – AdSSWV PF – [183]
Sertraline HMDE 1.5  107 M SWCSV PF – [103]
Sildenafil citrate Cathodically pretreated 6.4–107 mol L1 DPP PF – [264]
boron-doped diamond
electrode
Sodium Levothyroxine Carbon-paste electrode – CV – 0.78 [172]
Spironolactone HMDE 1.72  1010 M AdSV PF, HS, HU 1.0 [184]
Terazosin HMDE 1.5  1011 M SWAdCSV PF, HS – [185]
5.3  1011 M
Terbutaline GC 6  109 M SWAdASV PF HS – [245]
1.41  108 M
Testosterone LFE 9  109 M AdSV PF, HU 1.1 [278]
Tetrazepam DME, HMDE 5  106 M DPP BF, PF, HS – [209]
3  107 M DPAdCSV
1  108 M LSAdCSV
3  109 M SWAdCSV
Tolmetin HMDE 2  109 M SWAdCSV BF – [210]
5  109 M HS
 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196 187

Table 2 (continued)

Name of drug Indicator electrode Detection/determination Methods Matrix Ep (V) References

limit/conc. range
Triamcinolone acetate HMDE 3  1010 M SWAdCSV PF – [211]
7.5  1010 M HS
Trimetazidine HCl GC 2  108 M SWAdSV PF 0.75 [165]
1.7 lg mL1 HU
Trimethoprim HMDE 3 ng mL1 SWAdCSV PF 1.3 [279]
Trimethoprim MGC 3.5  109 M AdSV PF, HU 1.275 [68]
Triprolidine HMDE 2.64 ng mL1 DCV PF 1.35 [212]
6.24 ng mL1 DPV
8.80 ng mL1 SWV
8.80 ng mL1 NPV
Trobramycin HMDE 3.44  109 M AdSLSV PF, HU, HS 1.40 [213]
Troxerutin MCP 5.0  109 M – PF – [69]
Verapamil HMDE 0.246 ng mL1 CAdSV BF 1.84 [162]
0.491 ng mL1 HU
Vitamin E MCP 0.056 lg L1 SWSV PF 0.6 [70]
Zafirlukast GC 4  107 M SWAdSV PF 1.3 [214]
Zopiclone (ZP) GC 2.78  107 and 5.28  107 mol L1 DPAdSV PF, HU – [172]

possessed advantages such as low detection limit, fast response,
low cost, and simplicity [118], which was applied in studying the
electrochemical behavior of norfloxacin and its determination at
poly (methyl red) film-coated glassy carbon electrodes. LSV is
highly suitable for investigating the electrochemical behavior of
rabeprazole [119], diethylstilbestrol [38], ethinyl estradiol [120],
and fenbendazole [121].
Some analytical data on the CV and LSV determination of organ-
ic compounds in pharmaceutical preparations and biological media
are listed in Table 1. The data were compiled from some selected
literature sources since the period 1996. The measurements were
carried out using different electrodes.
Pulse and square-wave voltammetry
A pulse technique was proposed by Barker and Gardner in order
to increase the sensitivity of the technique and to lower the detec-
tion limits for electroactive species. Differential pulse voltammetry
has been extremely useful for the determination of trace amounts
of electroactive compound in pharmaceuticals [122–130] and bio-
logical fluids [55].
There are numerous studies related to the electrochemical as-
pects of antimicrobial drugs. Generally these are focused on the
electroanalytical determination of antimicrobial drugs of impor-
tance in medicine such as sparfloxacin [131,132] and pantoprazole
[133]. Various cephalosporins [127,134–137] have been success-
fully determined by electroanalytical methods with good sensitiv-
ity and accuracy. The DPV method was applied successfully to
individual tablet assays in order to verify the uniform content of
bromhexine [138]. Torres et al. [21,22] have proposed a DPP meth-
od to determine acrivastine in human urine at the level obtained
after the administration of normal clinical doses. The electroactiv-
ity of tamsulosin on a glassy carbon electrode was also established
and studied for the first time [139] using DPV. The described
methods were rapid, requiring less than 5 min to perform. It
showed the possibility of monitoring this drug compound, making
the method useful for pharmacokinetic and pharmacodynamic
purposes.
The presence of the electroreducible conjugate diene groups ini-
tiated the electrochemical study. Belal et al. [140] have developed a
promising DPP method that can be considered as an alternative
substitute for the chromatographic methods. The most striking fea-
ture of the method when applied for urine analysis was that no
prior treatment of the sample was necessary before measurement.
Another rapid and simple differential pulse anodic voltammetric
method for fast determination of hydrochlorothiazide [141] in ur-
ine was developed which involved no clean-up procedure. A simple
dilution of the urine with buffer nearly eliminates its potential
interferences.
Another simple, precise, and affordable pulse differential vol-
tammetric method was proposed for effective determination of
hydroxychloroquine [54] in plaquenil tablets. It requires no com-
plex pretreatment of the active principle to be determined. Jain
et al. [98] have developed CV and DPP methods for the determina-
tion of pyrantel pamoate in pharmaceutical formulation. A well-
defined cathodic wave and an anodic peak were observed for the
pyrantel pamoate in the entire pH range. The number of electrons
transferred in the reduction process was calculated and the reduc-
tion mechanism postulated. The peak current was found to be
linear over the concentration range 4  104 to 2  102 M with
a detection limit of 2.45  105 M. Easy applicability and availabil-
ity of low-cost instruments are the important advantages of DPV.
DPV/DPP is often the method of choice for therapeutic dose
analysis because of the low limit of detection of approximately
108 M. Some of the important applications of DPV/DPP in the
analysis of pharmaceutical and biological fluid have been tabulated
in Table 1.
Square-wave voltammetry is a large amplitude differential
technique in which a waveform is composed of symmetrical
square waves. Excellent sensitivity in SWV is gained from the fact
that net current is large compared to either forward or backward
current, coupled with effective discrimination against the charging
current. The peak currents obtained are about four times higher
than the differential pulse response.
The major advantage of square-wave voltammetry is its speed.
The effective scan rate is of the order of 500 mV s1. As a result, the
analysis time is drastically reduced. A complete voltammogram
can be recorded within a few seconds, compared to 2–3 min in dif-
ferential pulse voltammetry. So, the entire voltammogram can be
recorded with a single mercury drop. In addition, SWV is also more
sensitive than DPV, because both forward and reverse currents are
measured in the former, but only the forward currents are mea-
sured in the latter. Frequencies of 1 to 100 square-wave cycles
per second permit the use of extremely fast potential scan rates.
The analysis time is reduced; a complete voltammogram can be
recorded within a few seconds, compared to about 3 min time
required for DPV.
The SWV method has been used for the sensitive determination
of many pharmaceuticals. Lumivudine [142] concentration in hu-
man serum and in pharmaceuticals was determined by using SW
188 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196
voltammetric techniques on the basis of their reduction process
corresponding to the cytosine moiety over the HMDE. No pretreat-
ment and time-consuming extraction steps were adopted; hence it
could be adopted for pharmacokinetics studies as well as for qual-
ity control laboratory studies. The SWV method for determination
of methimazole [143] was developed with a detection limit of
0.5 lM with good RSD (2.89%). The SWV method was applied for
the determination of resveratrol [144] in Chinese patent medicine
and diluted wine with good reproducibility, precision, and
accuracy.
The SW and DP voltammetric method was developed by Uslu
et al. [145] for determination of antiviral drug valacyclovir in phar-
maceuticals and human biological fluids. The drug was irreversibly
oxidized at a glassy carbon electrode in one or two oxidation steps,
which are pH dependent. LOD values were 1.04  107 and
4.6  108 M for DP and SWV, respectively. An anodic voltammet-
ric behavior and determination of cefixime in pharmaceutical
dosage forms and biological fluids were developed by Golcu et al.
[134]. The repeatability, reproducibility, precision, and accuracy
of the methods in all media were investigated. No electroactive
interferences from the excipients and endogenous substances were
found in the pharmaceutical dosage forms and in the biological
samples.
Gao et al. [146] proposed a sensitive SWV method for the deter-
mination of trepibutone in pharmaceutical formulation using a
pencil graphite electrode (PGE). The PGE exhibits the best repro-
ducibility and highest sensitivity without any additional procedure
for the renewal of the electrode surface. In another study, a simple,
fast, and sensitive SWV method for the determination of trace
amounts of captopril [147] in pharmaceutical formulation and
reconstituted serum was reported. Sodium sulfite was used as both
supporting electrolyte and oxygen-removing agent. SW voltam-
metric methods have been developed for the determination of
abacavir [17], cilazapril–quinaprit–ramipril [148], dopamine
[149], etodolac [150], nefazodone hydrochloride [151], and trapm-
adol [152]. Various applications on pharmaceuticals and biological
samples using the above wave forms are illustrated in Table 1.
Stripping voltammetric techniques
Electroanalytical techniques, especially modern stripping vol-
tammetry, have been used for the sensitive determination of a
wide range of pharmaceuticals. Such techniques enjoy the advan-
tages that there is no need for derivatization and that these meth-
ods are less sensitive to matrix effects than other analytical
techniques.
Anodic stripping voltammetry (ASV)
Anodic stripping voltammetry is the most widely used form of
stripping analysis. In this case, the metals are preconcentrated by
electro-deposition onto a small-volume mercury electrode (thin
mercury film or a hanging mercury drop). The deposition is done
at a potential usually 0.3–0.5 V more negative than peak potential
for the metal ion to be determined. The metal ions are reduced at
the mercury electrode and concentrated as amalgam. The solution
is stirred during preconcentration in order to achieve convection
transport. The deposition period may vary from a few seconds to
about 20 min depending on the sensitivity required. After precon-
centration, the potential is scanned anodically using linear or pulse
ramps. During this scan, amalgamated metals are reoxidized and
stripped out of the electrode. As a result, current flows through
the cell. This current is directly proportional to the concentration
of the metal in the solution:
M nþ þ ne þ Hg ! MðHgÞ ½preconcentration
MðHgÞ ! Mnþ þ ne þ Hg ½stripping
Important examples include determination of metoclopramide
[153] and prazosin [154].
Cathodic stripping voltammetry (CSV)
This method is the ‘‘mirror image” of ASV. It involves anodic
deposition of the analyte followed by stripping in a negative poten-
tial scan (cathodic scan). The method is generally applied to organ-
ic compounds and anions that are capable of forming insoluble
salts with mercury. During the stripping step, as the potential
attains a value equal to the reduction potential of the analyte, it
is stripped out in the form of anion.
An þ Hg ! HgA þ ne ½preconcentration
HgA þ ne ! An þ Hg ½stripping
The resulting reduction peak current provides the desired quan-
titative information. Other electrodes, like rotating silver disk elec-
trodes, can be used for halides. The method has a large number of
applications in the field of organic and medicinal chemistry since a
large number of medicines can be analyzed with CSV [79,155–
157].
Adsorptive stripping voltammetry (AdSV)
Higher sensitivity and better selectivity compared to other
voltammetric techniques are the important features of AdSV. The
principle advantages of the stripping voltammetric method are
its speed and simplicity. Each voltammetric run takes a few sec-
onds. It involves no clean-up procedures, and simple dilution of
the biological fluid with suitable solvent nearly eliminates most
of the published chromatographic and spectroscopic methods
requiring lengthy and tedious extraction procedures, such as
liquid–liquid and solid-phase extraction. The sensitivity is signifi-
cantly enhanced by adsorption of the drug on the electrode surface
[75,108] and after careful choice of the operating parameters ex-
tremely low detection limits can be reached. Compared with other
techniques the DPAdSV and SWAdSV methods are cheap and the
measurements are not time consuming, leading to results for ana-
lytical purposes of certain drugs in pharmaceutical formulation
and biological fluids [158–163].
Adsorptive stripping voltammetry is the best known analytical
method that incorporates an electrolytic preconcentration step.
This technique has the advantages of low detection limit, low
determination limit, high sensitivity, wide spectrum of the test
material and analytes, relative simplicity, insignificant matrix ef-
fect, speed, and low cost of equipment. The AdSV technique is a
well-established and fast growing area with a number of possible
applications in the analysis of pharmaceutical and biological com-
pounds. Ghoneim et al. [164] studied the adsorptive behavior of
norfloxacin onto a glassy carbon electrode in acetate buffer. The
phenomenon was put to analytical advantage in the design of an
adsorptive stripping method for the determination of norfloxacin
at low pbb levels, i.e., 107 to 108 M concentration. Its applicabil-
ity to the determination of norfloxacin levels in urine sample was
evaluated.
A SWAdS voltammetric procedure has been successfully used
to determine trimetazidine hydrochloride [165] drug in pharma-
ceutical formulation and human urine. The method is simple,
sensitive, accurate, fast, and low cost and purging of the trimetaz-
idine hydrochloride solutions with nitrogen is not required. The
electrochemical renewal of the electrode surface in acetate buffer
is efficient and ensures the reproducibility of individual measure-
 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196
ment. The detection limit of trimetazidine hydrochloride at glassy
carbon electrodes in urine samples after medium exchange is low
enough to reach the concentration levels expected in urine after
therapeutic doses. The present method could possibly be adopted
for pharmacokinetic studies as well as quality control laborato-
ries. The above such method has also been used successfully to
determine amlodipine besylate in tablets and biological fluids
[166]. The method is also selective for the determination of amlo-
dipine besylate in the presence of its metabolites in biological
fluids.
An adsorptive stripping voltammetric technique at HMDE has
been described for the measurement of buspirone hydrochloride
(BUS) and piribedil (PIR) [11]. The results are adequately accurate
and precise and demonstrate promising sensitivity. The proposed
method is suitable for routine analysis in control laboratories, to
be applied for the analysis of BUS and PIR in pure form and in tab-
lets. The evaluation of the voltammetric method toward the anal-
ysis of real plasma samples (in vivo study) and establishment of an
effective extraction procedure to separate different metabolites
was studied. A study of the reduction of ketoconazole [167] in
aqueous medium (pH 5.6) has been carried out at HMDE. The
sensitivity is significantly enhanced by adsorption of drug on the
electrode surface and after careful choice of the operating param-
eters; extremely low detection limits can be reached. Compared
with other techniques the method is cheap and the measurement
is not time consuming. The proposed methods avoid the use of
organic solvents, which present high volatility and toxicity. A
square-wave adsorptive stripping voltammetric procedure for the
determination of antibacterial piromidic acid has been presented
[168]. The set of values for the variables influencing these stripping
techniques, perchloric acid concentration, accumulation potential,
and accumulation time, was optimized using response surface
methodology (RSM). The proposed method was successfully ap-
plied to human urine at nanomole levels 1.65  109 M, and
proved to be a simple, highly sensitive, highly accurate, fast, and
low-cost method.
Radi [169] concerned with the voltammetric study of pantop-
razole at HMDE used a rapid and sensitive square-wave voltam-
metric technique. Determination of the antibiotic drug pefloxacin
in bulk form, tablets, and human serum using SWCAdSV has been
developed by Beltagi [170]. Voltammetric determination of cila-
zapril in pharmaceutical formulations using the DPAdSV method
has the advantages of being simpler, faster, and less tedious than
other techniques [171].
A simple, sensitive, and validated method for the determina-
tion of diflunisal by DPP and DPAdSV had been developed and
applied to the pharmaceutical preparation [163]. The results
obtained by the developed method were compared with the
spectrofluorometric method by using the variance analysis and
no statistically significant difference was found. A method based
on controlled adsorptive preconcentration of cefminox on HMDE
[76], followed by LSV, allows its determination in the concentra-
tion range 8.3  108 to 1.5  106 M with a detection limit of
2.47  108 M. This method has been used for the direct determi-
nation of cefminox in human urine with recoveries between 98%
and 103% and precision around ±2%.
Yılmaz has investigated the voltammetric behavior and determi-
nation of zopiclone (ZP) on glassy carbon electrodes using a variety
of voltammetric techniques. The limits of detection and quantitation
were 2.78  107 and 5.28  107 mol L1 for DPAdSV. The pro-
posed technique was successfully applied to direct determination
of ZP in tablet dosage forms and spiked human urine samples [172].
A simple, sensitive, and reproducible square-wave cathodic
adsorptive stripping voltammetric method had been developed
for the determination of nitrofurantoin in a solubilized system.
The objective of the present paper was to investigate the redox
189
behavior of nitrofurantoin by using different voltammetric tech-
niques and to establish the methodology for its determination in
the presence of surfactants. Voltammograms of the drug with
cetrimide in phosphate buffers of pH 2–11 exhibited a single
well-defined reduction peak which may be attributed to the reduc-
tion of the ANO2 group. The reduction process is irreversible over
the entire pH range studied. The mechanism of reduction has been
postulated on the basis of controlled potential electrolysis, coulom-
etry, and spectral analysis. The proposed SWCAdSV voltammetric
method allows the determination of nitrofurantoin in linear con-
centration range 2  105 to 1  107 mol L1. The lower limit of
detection (LOD) and lower limit of quantification (LOQ) are 0.06
and 0.27 ng mL1, respectively [173].
In this work, a simple and sensitive electroanalytical method was
developed for the determination of enrofloxacin (ENRO) by adsorp-
tive cathodic stripping voltammetry (ADSV) using Cu (II) as a
suitable probe. The complex of copper (II) with ENRO was accumu-
lated at the surface of a hanging mercury drop electrode at 0.10 V
for 40 s. Then, the preconcentrated complex was reduced and the
peak current was measured using square-wave voltammetry. The
optimization of experimental variables was conducted by experi-
mental design and support vector machine (SVM) modeling. The
model was used to find optimized values for the factors such as
pH, Cu (II) concentration, and accumulation potential. Under the
optimized conditions, the peak current at 0.30 V is proportional
to the concentration of ENRO over the range of 10.0–80.0 nmol L1
with a detection limit of 0.33 nmol L1. The influence of potential
interfering substances on the determination of ENRO was examined.
The method was successfully applied to determination of ENRO in
plasma and pharmaceutical samples [174].
Adsorptive stripping analysis using different waveforms has
been applied for the determination of dilitiazem [175], diosmin
[176], enrofloxacin [177], ethinylestradiol [178], famotidine
[179], flavoxate [180], flaxedil [181], gatofloxacin [182], glipizide
[183], haloperidol [184], hydroxyzine [185], isoniazid [186], lamo-
trigine [187], lamivudine [188], lansoprazol [189,190], levonorge-
strel [191], lorazepam [192], meloxicam [193], metoclopramide
[194,153], nalidixic acid [195], nicardipine [196], nitrofurantoin
[197], nitroxynil [198], norethisterone [199], ofloxacin [200], pan-
toprazole [201], piroxicam [202], pravastatine [203], praziquantel
[204], rofecoxib [205], spironolactone [206], terazosin [207], ter-
butaline [208], tetrazepam [209], tolmetin [210], triamcinolone
[211], trimethoprim [68], triprolidine [212], trobramycin [213],
and zafirlukast [214]. Lists of the selected pharmaceutical and bio-
logical compounds that can be determined using stripping tech-
niques along with the ranges of their respective detection or
determination limits or concentration range are given in Table 2.
Voltammetric methods using surfactants
Surfactant has been widely used in the electrochemistry and
electroanalysis for various purposes. Surfactants have proved to
be effective in the electroanalysis of biological compounds and
drugs. For example, the addition of surface-active agents to elec-
trolyte containing terazosin [215] enhanced the voltammetric peak
response at GCE. It was recently shown that anionic surfactants
could be used to improve the accumulation of some electroactive
organic molecules such as ethopropazine [113] at gold electrodes.
In another study, the influence of micelles in the simultaneous
determination of two components was also demonstrated, as in
the case of catechol and hydroquinone [216]. Recently, the oxida-
tion peak currents of certain pharmaceuticals increasing
significantly in the presence of surfactants have been reported by
different studies [217,218].
Jain and co-workers had studied the effect of changing the
charge of the surfactant, viz. anionic, neutral, and cationic on the
190 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196
cefdinir peak current [127]; the addition of cationic surfactant en-
hanced the reduction current signal. Another important study by
Alarcon-Angeles et al. [219] showed that sodium dodecyl sulfate
(SDS) micelles can act as a masking agent useful for the selective
determination of dopamine in the presence of ascorbic acid. The
SDS micelles make it possible to obtain DPV where DA and AA sig-
nals appear separated because the SDS micelles provide that the
DA adsorbs strongly on the CPE and an increase of the charge trans-
fer reaction for the electrochemical oxidation of dopamine.
Jain and co-workers also studied the effect of adding surface-
active agents to electrolytes-containing nortriptyline hydrochlo-
ride on the voltammetric response at hanging mercury drop
electrodes. Addition of Tween 20 to the nortriptyline hydrochlo-
ride-containing electrolyte enhances the reduction current signal.
Application of Tween 20 in the electrochemical determination of
nortriptyline hydrochloride using square-wave voltammetry at
the HMDE enhanced the detection limit of the analyte [220].
A voltammetric method for the determination of entacapone
based on the enhancement effect of Tween 20 had been developed.
Addition of neutral surfactant (Tween 20) to the entacapone-con-
taining electrolyte enhanced the reduction current signal while an-
ionic surfactant (sodium lauryl sulfate) and cationic surfactant
(cetrimide) showed an opposite effect. The analysis of entacapone
in its pharmaceutical formulation exhibited the mean recovery of
99% for the reduction peak [221].
Assay and electrochemical behavior of betahistine hydrochlo-
ride in Britton-Robinsons (BR) buffer of pH range 2.5–12.0 at a
glassy carbon electrode have been investigated. Addition of anionic
surfactant (sodium lauryl sulfate) to the betahistine hydrochloride
solution-containing electrolyte enhanced the reduction current
signal while neutral surfactant (Tween 20) and cationic surfactant
cetyl trimethylammonium bromide (CTAB) showed an opposite ef-
fect. Voltammograms of betahistine hydrochloride exhibited a sin-
gle wave. The proposed method was successfully applied to the
determination of betahistine hydrochloride in drug product. The
results were compared with those obtained by the reference
high-performance liquid chromatographic method. No significant
differences were found between results of proposed and reference
methods [222].
The voltammetric behavior of ornidazole had been studied in
different surfactant media, viz. anionic, cationic, and non-ionic sur-
factants over the pH range 2.5 to 12.0 in phosphate buffer (0.2 M).
Addition of non-ionic surfactant (Tween 20) to the ornidazole-con-
taining electrolyte enhanced the reduction current signal while the
anionic surfactant sodium lauryl sulfate and cationic surfactant
cetyltrimethylammonium bromide showed a small enhancement
in peak current. The analysis of ornidazole in its pharmaceutical
formulation exhibited the mean recovery of 98% for the reduction
peak [223].
Voltammetric behavior of nitrazepam had been studied in ace-
tonitrile and in the presence of anionic surfactant (sodium lauryl
sulfate). It exhibit two well-defined cathodic peaks [224].
Voltammetric methods at modified electrodes
Chemically modified electrodes are currently widely used due
to the various advantages they offer. The use of chemically modi-
fied electrodes in electroanalysis offers several advantages, which
include lowering of the peak potential and increase in sensitivity
along with improvement in selectivity in the application of phar-
maceutical analysis [137,217,225,226].
Much attention has been given to the use of carbon nanotubes
(CNTs) since its discovery in 1991. CNT-modified electrodes have
proved to have excellent electroanalytical properties, such as wide
potential windows, low background current, and good biocompat-
ibility. Excellent improvement in the electrochemical behavior of
biologically important compounds such as dopamine and ascorbic
acid [227,228], quercetin and rutine [229], tryptophan [230],
glucose [231], procaine [232], and metformine [233] at CNTs has
been demonstrated.
Multiwalled carbon nanotube (MWCNT)-modified CPE was
used to study the electrochemical behavior of bergenin [234].
The modified electrode showed an excellent electrocatalytic activ-
ity in lowering the anodic overpotential and remarkable enhance-
ment of the ipa of bergenin if compared with the electrochemical
performances obtained at CPE.
Wang et al. [235] suggest that cysteic acid/carbon nanotube
film will have significant electroanalytical utility in the future.
The novel cysteic acid/CNT film material can be easily applied to
other types of substrate electrodes and surfaces and this will fur-
ther broaden the potential for applications.
Similarly various pharmaceuticals [67,80,90,141,154,236–239,
230,240–249,144,250] have been determined by different kinds of
modified electrodes. Wang et al. [251] reported a new approach to
construct a nano-Au self-assembly gold electrode which was used
for determination of epinephrine.
Hu et al. [252] also reported the fabrication of a modified elec-
trode based on the self-assembly of gold nanoparticles on cyste-
amine film, which has been bound to the surface of a glassy
carbon electrode. The modified electrode exhibited an excellent
reproducibility, sensibility, and stability for determination of dopa-
mine in the presence of high concentrations of ascorbic acid.
Goyal and co-workers have successfully studied the electro-
chemical behavior of various pharmaceuticals [253–255] at a gold
nanoparticle-modified indium tin oxide (nano Au/ITO) electrode.
Gold nanoparticles exhibit attractive properties in electrode mod-
ification by improving the electrode conductivity and enhancing
the analytical sensitivity and selectivity [256,257].
An entire electrochemical study of diazepam, temazepam, and
oxazepam using modified carbon-paste electrodes was reported
[258]. Boron-doped diamond electrodes have received much atten-
tion for electrochemical determination [259,260] due to their
attractive electrochemical properties over other electrodes.
Compared to classical carbon electrodes and other metallic
electrodes, diamond electrodes open up new opportunities for
working under extreme conditions such as media (e.g., strongly
acidic). Over the past two past decades electroanalytical tech-
niques based on modified polymer electrodes have attracted broad
interest from scientist engaged in pharmaceutical analysis
[261,262]. The modification of the electrode by Nafion film [19] en-
hanced the analytical signal intensity and simultaneously pro-
tected the surface of the working electrode, avoiding its fouling
by species present in the sample matrices, conferring greater sta-
bility to the electrode and higher reproducibility to the
determinations.
Fullerene science is one of the fastest growing areas of research
in chemistry, physics, and material science. One possible field of
their application can be their use as mediators in electrochemistry,
that is, for the chemical modification of electrodes in electrocatal-
ysis as observed in recent report for the electrochemical oxidation
of nandrolone [10] at fullerene C60-modified glassy carbon
electrode.
Jain et al. also reported a composite polymer surface coated on a
tin oxide which offers dramatic improvement in the stability of
voltammetric measurement of pyridostigmine bromide compared
to individual tin oxide, polyaniline, or polypyrrole-coated elec-
trodes [263].
The voltammetric behavior of pyrantel pamoate was studied in
the Britton-Robinson buffer system at a composite polymer mem-
brane working electrode. The cyclic voltammetric method has been
developed for the determination of drug in pharmaceutical formu-
 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196
lation. A well-defined cathodic peak was observed for the pyrantel
pamoate in the entire pH range. The current increases steadily with
diffusion scan rate and concentration. The results indicate that the
process is irreversible and diffusion controlled. This composite film
showed good current response [264].
Zheng and co-workers reported the selective, sensitive, and
simultaneous determination of dopamine, ascorbic acid, and uric
acid on ordered mesoporous carbon (OMC)/Nafion composite film
[265].
Recently Nasirizadeh et al. had fabricated a highly efficient nor-
adrenalin (NA) biosensor on the basis of hematoxylin electrodepos-
ited on a glassy carbon electrode, GCE. The peaks of differential pulse
voltammetric for NA and acetaminophen (AC) oxidation at the
hematoxylin biosensor surface are clearly separated from each other
when they coexited in the physiological pH (pH 7.0). It was, there-
fore, possible to simultaneously determine NA and AC in the samples
at a hematoxylin biosensor [266].
A voltammetric method was developed for the determination of
tetracycline (TC) by using an ionic liquid (IL, 1,octyl,3,methylimida-
zolium, hexafluorophosphate)–multiwall carbon nanotube
(MWNT) film-coated glassy carbon electrode (GCE). Experiment
showed that both IL and MWNT could facilitate the TC oxidation.
Thus on the electrode TC exhibited a sensitive anode peak at
0.54 V (vs SCE) in pH 7.0 phosphate buffer solutions. Under the
optimized experimental conditions, the peak current was linear
to TC concentration in the range of 1.1  107 to 2.2  105 M for
150 s accumulation. The electrode had good reproducibility. It
was successfully applied to the detection of TC in egg and pharma-
ceutical samples [267].
The determination of sildenafil citrate using differential pulse
voltammetry and a cathodically pretreated boron-doped diamond
electrode is described. The obtained analytical curve is linear in
the sildenafil concentration range 7.3  107 to 7.3  106 mol L1
in a 0.1 mol L1 H2SO4, with a detection limit of 6.4  107 mol L1.
The proposed method, which is fast and simple to carry out, was
successfully applied in the determination of sildenafil citrate in
Viagra1 pharmaceutical formulations, with results in close agree-
ment (at 95% confidence level) with those obtained using a com-
parative HPLC method [268].
The electrochemical response of sodium levothyroxine at a car-
bon-paste electrode in the presence of 0.1 M HCl as supporting
electrolyte was investigated by cyclic voltammetry. It showed a
well-defined oxidation peak at 0.78 V and a sensitive and indis-
cernible reduction peaks at 0.53 and 0.32 V. The effect of concen-
tration and scan rate of sodium levothyroxine was studied. The
scan rate effect showed that the electrode process is adsorption
controlled. The effect of surfactants like sodium dodecyl sulfate,
cetyltrimethylammonium bromide, and Triton X-100 (TX-100)
were studied by mobilizing and immobilizing methods. The con-
centration effect of all the three surfactants was studied. Among
these SDS showed excellent enhancement in both oxidation peak
and reduction peak currents [269].
A carbon-paste electrode spiked with ferrocenedicarboxylic
acid (FDCMCPE) was constructed by incorporation of ferrocenedi-
carboxylic acid in a graphite powder–paraffin oil matrix. It has
been shown by direct current cyclic voltammetry and double-step
chronoamperometry that this electrode can catalyze the oxidation
of ampicillin (AMPC) in aqueous buffered solution. It has been
found that under optimum conditions (pH 10.0) in cyclic voltam-
metry, the oxidation of AMPC occurred at a potential of about
480 mV on the surface of the modified carbon-paste electrode.
The kinetic parameters such as electron-transfer coefficient, a,
and rate constant for the chemical reaction between AMPC and re-
dox sites in FDCMCPE were also determined using electrochemical
approaches. Under the optimized conditions, the electrocatalytic
oxidation peak current of AMPC showed two linear dynamic ranges
191
with a detection limit of 0.67 mmol L1 AMPC. The linear calibra-
tion was in the range of 2.34–30 and 40–700 mmol L1 AMPC using
the differential pulse voltammetric method. Finally, this method
was also examined as a selective, simple, and precise electrochem-
ical sensor for the determination of AMPC in real samples such as
drugs and urine [162,270–279].
Several synthetic zeolites such as mazzite, mordenite, zeolite L,
zeolite beta, and MCM-41 were tested as electrode modifiers in
voltammetric determination of tryptophan. It was found that the
addition of zeolite beta to the carbon paste would generate the
peak current of Trp because of its catalytic effect. The anodic peak
currents were proportional to Trp concentrations in the range of
5.0  107 to 5.0  103 M. The detection limit was 1.0  107 M.
The influence of several species, especially amino acids, was tested.
The proposed method was applied successfully to the determina-
tion of tryptophan in pharmaceutical formulations [174].
Conclusion
Modern electrochemical instrumentation, especially voltam-
metric techniques, provides reliable and reproducible data for the
quantification of analyte. Further, use of modified electrodes
proved to have excellent electroanalytical properties, such as wide
potential windows, low background current, and good biocompat-
ibility. Also, addition of surface-active agents to electrolytes greatly
enhances the voltammetric peak response, increasing sensitivity.
The present review will be of great help for the analytical chemists
using voltammetric methods for the determination of a given ana-
lyte in a complex matrix. The aim of the review is to assess the util-
ity of methods using various electrodes and surface-active agents
for the determination of pharmaceuticals with low running cost,
high speed, sensitivity, universality, and wide application. These
techniques are simple and in cases more sensitive to the usually
applied chromatographic and spectroscopic techniques.
Acknowledgments
The authors dedicate this paper to their reverend teacher and
renowned Electrochemist (Late) Prof. Wahid. U. Malik and one of
the authors; K. Radhapyari is thankful to the Department of Science
and Technology (DST), New Delhi, India, for the award of
fellowship.
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