Anda di halaman 1dari 19

See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/46426449

Voltammetric techniques for the assay of pharmaceuticals-A review

Article  in  Analytical Biochemistry · January 2011


DOI: 10.1016/j.ab.2010.09.027 · Source: PubMed

CITATIONS READS

277 1,837

5 authors, including:

Vinod K Gupta Rajeev Jain


University of Johannesburg Jiwaji University
798 PUBLICATIONS   54,597 CITATIONS    319 PUBLICATIONS   5,496 CITATIONS   

SEE PROFILE SEE PROFILE

Keisham Radhapyari Nimisha Jadon


Central Ground Water Board, India Jiwaji University
28 PUBLICATIONS   840 CITATIONS    30 PUBLICATIONS   821 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Study on water quality trends in ground water of Digboi, Assam View project

Synthesis of silver nanoparticles using Silybum marianum seed extract View project

All content following this page was uploaded by Keisham Radhapyari on 08 December 2018.

The user has requested enhancement of the downloaded file.


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 for quantitation which are most commonly used in a pharmaceuti-
a compound from its synthesis stage to its marketing stage as a cal laboratory fall into four basic categories: chromatography,
part of a drug formulation and analysis. The instrumental methods spectrophotometric, electrochemical, and radiometric analysis
[1]. Electroanalytical chemistry along with the use of oxidation–
⇑ Corresponding author at: Department of Chemistry, Indian Institute of reduction reactions and other charge-transfer phenomena had its
Technology Roorkee, Roorkee (UK) 247 667, India. Fax: +91 1332 273560. origins eight decades ago. It is one of the fundamental subdisci-
E-mail addresses: vinodfcy@gmail.com, vinodfcy@iitr.ernet.in (V.K. Gupta). 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 thermore, important information, like the peak potential of the
voltammetry, a form of electrochemistry, in which samples were electroactive substance, was not included.
analyzed by measuring current as a function of the applied elec- The present study reviews the various applications of voltam-
trical potential. A quarter century later, on October 26, 1959, metry to pharmaceutical analysis covering the period from 2001
Jaroslav Heyrovsky was awarded the Nobel Prize in Chemistry to 2010. The present review includes the voltammetric determina-
for his discovery of the polarographic methods of analysis [2]. tion of pharmaceuticals of various classes, viz. antibiotics [72–79],
In the last eight decades, voltammetric methods have become a antiemetics [46,47], antiamoebic [80], hypolipidemic [81–83],
popular tool for the study of electrochemical reactions [3], for antipsychotic [84,85], cardiovascular [86–89], hypoglycemic [90],
the study of electrochemically generated free radicals [4], in analgesics [91–95], coagulants [96], antiplatelet [97], anthelmintic
model studies of enzymatic catalysis [5], in coordination chemis- [98], sedatives [58,99], gastrointestinal [34,100], antidepressant
try [6], in solar energy conversion [7], in environmental monitor- [101,102], antiarrhythmic [103], opioid analgesics [104], vitamins
ing [8], in industrial quality control [9], and in the determination [105–107], anticholinesterase [108], antiadrenergic [109], antipar-
of trace concentrations of biological and clinically important kinsonian [110], antiallergics [111], and others. The review is
compounds [10,11]. divided into four sections. The first deals with various applications
Till now, the commonly employed techniques for the deter- of nonstripping voltammetric techniques using linear sweep
mination of the drug in bulk form, pharmaceutical formulation, voltammetry (LSV),1 cyclic voltammetry (CV), differential pulse
and biological fluids are based on HPLC [12], LC/MS [13], spec- voltammetric (DPV), and square-wave voltammetry (SWV) in phar-
troscopy [14], and microbiological assays [15]. Such techniques maceutical analysis. The second section covers the application of
for the measurement of biological concentration are necessary sensitive stripping techniques in pharmaceutical analysis. The third
in a clinical environment to ensure that adequate drug levels part deals with the effectiveness of surfactants in the electroanalysis
can be maintained while avoiding toxic concentrations of such of biological compounds and drugs. Finally, the fourth section of the
drugs. The problems encountered using such methods are either review is devoted to the use of chemically modified electrodes in the
the need for derivatization or the need for time-consuming analysis of pharmaceuticals. The third and fourth sections of this re-
extraction procedures. Since these techniques have expensive view were not taken in detail by Ozkan and co-workers. Additionally,
instrumentation and running costs, the use of simpler, faster, another interesting feature of this review, which is worth noting, is
and cheaper, yet sensitive, electrochemical techniques can be that the names of drugs along with the peak potential (Ep) and
interesting alternatives, especially those based on electroanalyti- matrix are sorted in ascending order in Tables 1 and 2. This makes
cal techniques. the table user friendly.
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 1
Abbreviations used: AAdSV, anodic adsorptive stripping voltammetry; AC,
have introduced the most promising methods for specific applica- acetaminophen; AdCSV, adsorptive cathodic stripping voltammetry; AdLSCSV,
tions [18–24]. Due to similarity in the electrochemical and biolog- adsorptive linear sweep cathodic stripping voltammetry; AdS, adsorptive stripping;
ical reactions, it can be assumed that the oxidation/reduction AdSACV, adsorptive stripping alternating current voltammetry; AdSDPV, adsorptive
stripping differential pulse voltammetry; AdSLSV, adsorptive stripping linear sweep
mechanisms taking place at the electrode and in the body share
voltammetry; AdSSWV, adsorptive stripping square-wave voltammetry; AdSSWV,
similar principles. Biologically important molecules can be investi- adsorptive stripping square-wave voltammetry; AdSV, adsorptive stripping voltam-
gated electroanalytically by voltammetry in order to determine the metry; AMPC, ampicillin; ASDPV, anodic stripping differential pulse voltammetry;
molecule in different ways. Additional applications of electro- 5-ASA, 5-aminosalicyclic acid; ASV, anodic stripping voltammetry; Au, gold; BUS,
chemistry include the determination of electrode mechanisms. buspirone hydrochloride; BR, Britton-Robinsons; BDD, boron diamond doped; BF,
bulk form; BS, blood sample; CAdSDPV, cathodic adsorptive stripping differential
The redox properties of drugs can give us insight into their meta-
pulse voltammetry; CAdSV, cathodic adsorptive stripping voltammetry; CGME,
bolic fate in in vivo redox processes or pharmacological activity controlled growth mercury electrode; CP, carbon paste; CP, carbon paste; CSSWV,
[25]. cathodic stripping square-wave voltammetry; CSV, cathodic stripping voltammetry;
Further, the electroanalytical techniques have been shown to be CV, cyclic voltammetry; CTAB, cetyl trimethylammonium bromide; DC, direct
excellent for the determination of pharmaceutical compounds in current; DME, dropping mercury electrode; DPAdCSV, differential pulse adsorptive
cathodic stripping voltammetry; DPAdSV, differential pulse adsorptive stripping
different matrices. Many of the active constituents of formulations, voltammetry; DPAdV, differential pulse adsorptive voltammetry; DPCAdS, differential
in contrast to excipients, can be readily oxidized. The selectivity of pulse cathodic adsorptive stripping; DPCSV, differential pulse cathodic stripping
this method is normally excellent because the analyte can be read- voltammetry; DPP, differential pulse polarography; DPSV, differential pulse stripping
ily identified by its voltammetric peak potential. Advances in voltammetry; DPV, differential pulse voltammetry; ENRO, enrofloxacin; FDCMCPE,
ferrocenedicarboxylic acid; GC, glassy carbon; GCRDE, glassy carbon rotating disk
experimental electrochemical techniques in the field of analysis
electrode; GE, graphite electrode; GNP, gold nanoparticle; HB, human blood; HMDE,
of drugs are because of their simplicity, low cost, and relatively hanging mercury drop electrode; HS, human serum; HU, human urine; ISO,
short analysis time compared to other techniques. The use of var- isorhamnetin; LSAAdSV, linear sweep anodic adsorptive stripping voltammetry;
ious electrodes, viz. mercury [26–42], solids [9,43–61], and modi- LSAdCSV, linear sweep adsorptive cathodic stripping voltammetry; LSAdSV, linear
fied electrodes [20,62–70], for electroanalytical measurements sweep adsorptive stripping voltammetry; LSSV, linear sweep stripping voltammetry;
LSV, linear sweep voltammetry; MCP, modified carbon paste; MGC, modified glassy
has increased in recent years because of their applicability to the carbon; MGE, modified graphite electrode; MWCNT, multiwalled carbon nanotube;
determination of active compounds that undergo oxidation reac- NA, noradrenalin; NGITO, nanogold indium tin oxide; NGMITO, nanogold modified
tions, which is a matter of great importance in the field of clinical indium tin oxide; NPV, normal pulse voltammetry; OMC, ordered mesoporous
and pharmaceutical analysis. carbon; OSWSV, Osteryoung square-wave stripping voltammetry; OSWV, Osteryoung
square-wave voltammetry; PIR, Piribedil; PF, pharmaceutical formulation; PGE, pencil
Ozkan and co-workers [71] critically reviewed the application
graphite electrode; Pt, platinum; SDS, sodium dodecyl sulfate; SMDE, static mercury
of modern electroanalytical techniques (potentiometry, on-line or drop electrode; SODASV, second-order differential anodic stripping voltammetry; SP,
hyphenated voltammetry, voltammetry) in the analysis of pharma- spiked plasma; SWAdASV, square-wave adsorptive anodic stripping voltammetry;
ceuticals and biological fluids. The authors reviewed about 200 SWAdCSV, square-wave adsorptive cathodic stripping voltammetry; SWAdSV,
papers starting from 1995 to 2000. The use and advantages of tech- square-wave adsorptive stripping voltammetry; SWASV, square-wave anodic strip-
ping voltammetry; SWCAdS, square-wave cathodic adsorptive stripping; SWCSV,
niques to pharmaceutical compounds in dosage forms and biolog- square-wave cathodic stripping voltammetry; SWSV, square-wave stripping voltam-
ical media were discussed. However, the review did not clearly metry; SWV, square-wave voltammetry; TC, tetracycline; TX-100, Triton X-100; ZP,
provide the matrix in which pharmaceuticals were analyzed. Fur- 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 voltammetric and differential pulse voltammetric peak in acetoni-
trile using platinum and glassy carbon working electrodes. The Ip of
Cyclic and linear sweep voltammetry the DPV peak increases linearly within the concentration range
from 4.5  104 to 1.0  102 mol L1 of the investigated drug.
Cyclic voltammetry is often the first experiment performed in an The concentration of Ch-HCl in raw drug material and in its phar-
electrochemical study of a compound, a biological material, or an maceutical preparations was determined using the standard addi-
electrode surface. It is effectively used in the fields of environmental tion method, the Randles–Sevcik equation, and indirectly via its
electrochemistry, organic chemistry, inorganic chemistry, and bio- complexation with sodium tetraphenylborate (NaTPB). The ob-
chemistry. The effectiveness of CV results from its capability for rap- tained overall average recoveries were 101.44% and 100.49% with
idly observing the redox behavior over a wide potential range. The SD 0.45 and 0.38 (n = 4) for platinum and glassy carbon electrodes,
resulting voltammogram is analogous to a conventional spectrum respectively. The effect of scan rate, sample concentration, and
in the sense that it conveys information as a function of an energy supporting electrolyte on the Ip and Ep was also investigated [116].
scan. Cyclic voltammetry has become a popular tool since the last Loracarbef has antibacterial activity and is oxidizable at the
40 years for studying electrochemical reaction. CV is perhaps the glassy carbon electrode. The electrochemical oxidation of
most versatile electroanalytical technique in pharmaceutical analy- Loracarbef was investigated using cyclic, linear sweep, differential
sis [27,112]. It is often the first experiment performed in an electro- pulse, and square-wave voltammetric techniques. The results ob-
chemical study of drugs in raw material [113,114], pharmaceuticals tained from cyclic voltammetry indicate that the oxidation process
[50,52,58], and biological material [39]. of Loracarbef is irreversible and diffusion controlled on glassy
The formation and stability of the radical anion from PA-824 carbon electrodes. The dependence of peak currents and potentials
and its comparison with metronidazole were carried out by Bollo on pH, concentration, scan rate, and nature of the buffer was inves-
et al. [39] by using CV. Acuna et al. [112] used CV for studying tigated. According to the linear relation between the peak current
the kinetics of the hydrolytic decomposition of droxicam and for and the concentration, differential pulse and square-wave voltam-
establishing the possible pharmacological action of the drug in metric methods for Loracarbef quantitative determination were
an organism of the human being. Acetaminophen [18] in paracet- developed. Different parameters were tested to optimize the con-
amol tablets was determined by using CV in phosphate buffer with ditions for the determination of Loracarbef. The quantitative deter-
a good linear calibration range of 3–240 lg mL1. The CV method is mination of Loracarbef was proposed in 0.1 M H2SO4, which allows
in good agreement with the USPXXII official method. Wang et al. quantitation over the 6  106 to 2  104 M range. Precision,
[81], by employing CV along with bulk electrolysis, deduced the re- accuracy, reproducibility, sensitivity, and selectivity were checked.
dox reaction mechanisms of nicotinic acid and nicotinamide in The methods were proposed for the determination of Loracarbef in
which it was rationalized by the formation/disappearance of the pharmaceutical dosage forms [117].
new nitrogen–oxygen bonds in pyridine rings. Furthermore, LSV, along with CV, has received great interest for
Liu and co-workers had studied the electrochemical behavior of the elucidation of electrode processes and redox mechanisms.
isorhamnetin at a glassy carbon electrode by cyclic voltammetry. Un- Linear sweep voltammetry was used to study the influence of pH
der optimal conditions, the oxidation peak current showed a linear on the peak current and peak potential of 5-aminosalicyclic acid
dependence on the concentration of ISO in the range of 1.0  108 to (5-ASA) [16] in different buffer systems. The oxidative behavior
4.0  107 and 1.0  106 to 1.0  105 M. This method has been suc- has been investigated using a glassy carbon electrode. Santos
cessfully applied to the detection of ISO in tablets [115]. et al. [23] studied the electroanalytical behavior and methodology
Voltammetric methods have been used for the determination of for quantification of albendazole in pharmaceutical formulations.
chlorphenoxamine hydrochloride (Ch-HCl) in raw material and in The study reveals that the albendazole oxidation exhibited a stan-
its pharmaceutical preparations (Allergex and Allergex caffeine dard heterogeneous rate constant for the electrodic process equal
tablet). It was found that Ch-HCl gives a characteristic cyclic 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, method for fast determination of hydrochlorothiazide [141] in ur-
low cost, and simplicity [118], which was applied in studying the ine was developed which involved no clean-up procedure. A simple
electrochemical behavior of norfloxacin and its determination at dilution of the urine with buffer nearly eliminates its potential
poly (methyl red) film-coated glassy carbon electrodes. LSV is interferences.
highly suitable for investigating the electrochemical behavior of Another simple, precise, and affordable pulse differential vol-
rabeprazole [119], diethylstilbestrol [38], ethinyl estradiol [120], tammetric method was proposed for effective determination of
and fenbendazole [121]. hydroxychloroquine [54] in plaquenil tablets. It requires no com-
Some analytical data on the CV and LSV determination of organ- plex pretreatment of the active principle to be determined. Jain
ic compounds in pharmaceutical preparations and biological media et al. [98] have developed CV and DPP methods for the determina-
are listed in Table 1. The data were compiled from some selected tion of pyrantel pamoate in pharmaceutical formulation. A well-
literature sources since the period 1996. The measurements were defined cathodic wave and an anodic peak were observed for the
carried out using different electrodes. pyrantel pamoate in the entire pH range. The number of electrons
transferred in the reduction process was calculated and the reduc-
Pulse and square-wave voltammetry tion mechanism postulated. The peak current was found to be
linear over the concentration range 4  104 to 2  102 M with
A pulse technique was proposed by Barker and Gardner in order a detection limit of 2.45  105 M. Easy applicability and availabil-
to increase the sensitivity of the technique and to lower the detec- ity of low-cost instruments are the important advantages of DPV.
tion limits for electroactive species. Differential pulse voltammetry DPV/DPP is often the method of choice for therapeutic dose
has been extremely useful for the determination of trace amounts analysis because of the low limit of detection of approximately
of electroactive compound in pharmaceuticals [122–130] and bio- 108 M. Some of the important applications of DPV/DPP in the
logical fluids [55]. analysis of pharmaceutical and biological fluid have been tabulated
There are numerous studies related to the electrochemical as- in Table 1.
pects of antimicrobial drugs. Generally these are focused on the Square-wave voltammetry is a large amplitude differential
electroanalytical determination of antimicrobial drugs of impor- technique in which a waveform is composed of symmetrical
tance in medicine such as sparfloxacin [131,132] and pantoprazole square waves. Excellent sensitivity in SWV is gained from the fact
[133]. Various cephalosporins [127,134–137] have been success- that net current is large compared to either forward or backward
fully determined by electroanalytical methods with good sensitiv- current, coupled with effective discrimination against the charging
ity and accuracy. The DPV method was applied successfully to current. The peak currents obtained are about four times higher
individual tablet assays in order to verify the uniform content of than the differential pulse response.
bromhexine [138]. Torres et al. [21,22] have proposed a DPP meth- The major advantage of square-wave voltammetry is its speed.
od to determine acrivastine in human urine at the level obtained The effective scan rate is of the order of 500 mV s1. As a result, the
after the administration of normal clinical doses. The electroactiv- analysis time is drastically reduced. A complete voltammogram
ity of tamsulosin on a glassy carbon electrode was also established can be recorded within a few seconds, compared to 2–3 min in dif-
and studied for the first time [139] using DPV. The described ferential pulse voltammetry. So, the entire voltammogram can be
methods were rapid, requiring less than 5 min to perform. It recorded with a single mercury drop. In addition, SWV is also more
showed the possibility of monitoring this drug compound, making sensitive than DPV, because both forward and reverse currents are
the method useful for pharmacokinetic and pharmacodynamic measured in the former, but only the forward currents are mea-
purposes. sured in the latter. Frequencies of 1 to 100 square-wave cycles
The presence of the electroreducible conjugate diene groups ini- per second permit the use of extremely fast potential scan rates.
tiated the electrochemical study. Belal et al. [140] have developed a The analysis time is reduced; a complete voltammogram can be
promising DPP method that can be considered as an alternative recorded within a few seconds, compared to about 3 min time
substitute for the chromatographic methods. The most striking fea- required for DPV.
ture of the method when applied for urine analysis was that no The SWV method has been used for the sensitive determination
prior treatment of the sample was necessary before measurement. of many pharmaceuticals. Lumivudine [142] concentration in hu-
Another rapid and simple differential pulse anodic voltammetric 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 M nþ þ ne þ Hg ! MðHgÞ ½preconcentration
corresponding to the cytosine moiety over the HMDE. No pretreat- MðHgÞ ! Mnþ þ ne þ Hg ½stripping
ment and time-consuming extraction steps were adopted; hence it
could be adopted for pharmacokinetics studies as well as for qual- Important examples include determination of metoclopramide
ity control laboratory studies. The SWV method for determination [153] and prazosin [154].
of methimazole [143] was developed with a detection limit of
0.5 lM with good RSD (2.89%). The SWV method was applied for Cathodic stripping voltammetry (CSV)
the determination of resveratrol [144] in Chinese patent medicine
and diluted wine with good reproducibility, precision, and This method is the ‘‘mirror image” of ASV. It involves anodic
accuracy. deposition of the analyte followed by stripping in a negative poten-
The SW and DP voltammetric method was developed by Uslu tial scan (cathodic scan). The method is generally applied to organ-
et al. [145] for determination of antiviral drug valacyclovir in phar- ic compounds and anions that are capable of forming insoluble
maceuticals and human biological fluids. The drug was irreversibly salts with mercury. During the stripping step, as the potential
oxidized at a glassy carbon electrode in one or two oxidation steps, attains a value equal to the reduction potential of the analyte, it
which are pH dependent. LOD values were 1.04  107 and is stripped out in the form of anion.
4.6  108 M for DP and SWV, respectively. An anodic voltammet-
ric behavior and determination of cefixime in pharmaceutical An þ Hg ! HgA þ ne ½preconcentration
dosage forms and biological fluids were developed by Golcu et al. HgA þ ne ! An þ Hg ½stripping
[134]. The repeatability, reproducibility, precision, and accuracy
of the methods in all media were investigated. No electroactive The resulting reduction peak current provides the desired quan-
interferences from the excipients and endogenous substances were titative information. Other electrodes, like rotating silver disk elec-
found in the pharmaceutical dosage forms and in the biological trodes, can be used for halides. The method has a large number of
samples. applications in the field of organic and medicinal chemistry since a
Gao et al. [146] proposed a sensitive SWV method for the deter- large number of medicines can be analyzed with CSV [79,155–
mination of trepibutone in pharmaceutical formulation using a 157].
pencil graphite electrode (PGE). The PGE exhibits the best repro-
ducibility and highest sensitivity without any additional procedure Adsorptive stripping voltammetry (AdSV)
for the renewal of the electrode surface. In another study, a simple,
fast, and sensitive SWV method for the determination of trace Higher sensitivity and better selectivity compared to other
amounts of captopril [147] in pharmaceutical formulation and voltammetric techniques are the important features of AdSV. The
reconstituted serum was reported. Sodium sulfite was used as both principle advantages of the stripping voltammetric method are
supporting electrolyte and oxygen-removing agent. SW voltam- its speed and simplicity. Each voltammetric run takes a few sec-
metric methods have been developed for the determination of onds. It involves no clean-up procedures, and simple dilution of
abacavir [17], cilazapril–quinaprit–ramipril [148], dopamine the biological fluid with suitable solvent nearly eliminates most
[149], etodolac [150], nefazodone hydrochloride [151], and trapm- of the published chromatographic and spectroscopic methods
adol [152]. Various applications on pharmaceuticals and biological requiring lengthy and tedious extraction procedures, such as
samples using the above wave forms are illustrated in Table 1. 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-
Stripping voltammetric techniques tremely low detection limits can be reached. Compared with other
techniques the DPAdSV and SWAdSV methods are cheap and the
Electroanalytical techniques, especially modern stripping vol- measurements are not time consuming, leading to results for ana-
tammetry, have been used for the sensitive determination of a lytical purposes of certain drugs in pharmaceutical formulation
wide range of pharmaceuticals. Such techniques enjoy the advan- and biological fluids [158–163].
tages that there is no need for derivatization and that these meth- Adsorptive stripping voltammetry is the best known analytical
ods are less sensitive to matrix effects than other analytical method that incorporates an electrolytic preconcentration step.
techniques. This technique has the advantages of low detection limit, low
determination limit, high sensitivity, wide spectrum of the test
Anodic stripping voltammetry (ASV) material and analytes, relative simplicity, insignificant matrix ef-
fect, speed, and low cost of equipment. The AdSV technique is a
Anodic stripping voltammetry is the most widely used form of well-established and fast growing area with a number of possible
stripping analysis. In this case, the metals are preconcentrated by applications in the analysis of pharmaceutical and biological com-
electro-deposition onto a small-volume mercury electrode (thin pounds. Ghoneim et al. [164] studied the adsorptive behavior of
mercury film or a hanging mercury drop). The deposition is done norfloxacin onto a glassy carbon electrode in acetate buffer. The
at a potential usually 0.3–0.5 V more negative than peak potential phenomenon was put to analytical advantage in the design of an
for the metal ion to be determined. The metal ions are reduced at adsorptive stripping method for the determination of norfloxacin
the mercury electrode and concentrated as amalgam. The solution at low pbb levels, i.e., 107 to 108 M concentration. Its applicabil-
is stirred during preconcentration in order to achieve convection ity to the determination of norfloxacin levels in urine sample was
transport. The deposition period may vary from a few seconds to evaluated.
about 20 min depending on the sensitivity required. After precon- A SWAdS voltammetric procedure has been successfully used
centration, the potential is scanned anodically using linear or pulse to determine trimetazidine hydrochloride [165] drug in pharma-
ramps. During this scan, amalgamated metals are reoxidized and ceutical formulation and human urine. The method is simple,
stripped out of the electrode. As a result, current flows through sensitive, accurate, fast, and low cost and purging of the trimetaz-
the cell. This current is directly proportional to the concentration idine hydrochloride solutions with nitrogen is not required. The
of the metal in the solution: 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) 179–196 189

ment. The detection limit of trimetazidine hydrochloride at glassy behavior of nitrofurantoin by using different voltammetric tech-
carbon electrodes in urine samples after medium exchange is low niques and to establish the methodology for its determination in
enough to reach the concentration levels expected in urine after the presence of surfactants. Voltammograms of the drug with
therapeutic doses. The present method could possibly be adopted cetrimide in phosphate buffers of pH 2–11 exhibited a single
for pharmacokinetic studies as well as quality control laborato- well-defined reduction peak which may be attributed to the reduc-
ries. The above such method has also been used successfully to tion of the ANO2 group. The reduction process is irreversible over
determine amlodipine besylate in tablets and biological fluids the entire pH range studied. The mechanism of reduction has been
[166]. The method is also selective for the determination of amlo- postulated on the basis of controlled potential electrolysis, coulom-
dipine besylate in the presence of its metabolites in biological etry, and spectral analysis. The proposed SWCAdSV voltammetric
fluids. method allows the determination of nitrofurantoin in linear con-
An adsorptive stripping voltammetric technique at HMDE has centration range 2  105 to 1  107 mol L1. The lower limit of
been described for the measurement of buspirone hydrochloride detection (LOD) and lower limit of quantification (LOQ) are 0.06
(BUS) and piribedil (PIR) [11]. The results are adequately accurate and 0.27 ng mL1, respectively [173].
and precise and demonstrate promising sensitivity. The proposed In this work, a simple and sensitive electroanalytical method was
method is suitable for routine analysis in control laboratories, to developed for the determination of enrofloxacin (ENRO) by adsorp-
be applied for the analysis of BUS and PIR in pure form and in tab- tive cathodic stripping voltammetry (ADSV) using Cu (II) as a
lets. The evaluation of the voltammetric method toward the anal- suitable probe. The complex of copper (II) with ENRO was accumu-
ysis of real plasma samples (in vivo study) and establishment of an lated at the surface of a hanging mercury drop electrode at 0.10 V
effective extraction procedure to separate different metabolites for 40 s. Then, the preconcentrated complex was reduced and the
was studied. A study of the reduction of ketoconazole [167] in peak current was measured using square-wave voltammetry. The
aqueous medium (pH 5.6) has been carried out at HMDE. The optimization of experimental variables was conducted by experi-
sensitivity is significantly enhanced by adsorption of drug on the mental design and support vector machine (SVM) modeling. The
electrode surface and after careful choice of the operating param- model was used to find optimized values for the factors such as
eters; extremely low detection limits can be reached. Compared pH, Cu (II) concentration, and accumulation potential. Under the
with other techniques the method is cheap and the measurement optimized conditions, the peak current at 0.30 V is proportional
is not time consuming. The proposed methods avoid the use of to the concentration of ENRO over the range of 10.0–80.0 nmol L1
organic solvents, which present high volatility and toxicity. A with a detection limit of 0.33 nmol L1. The influence of potential
square-wave adsorptive stripping voltammetric procedure for the interfering substances on the determination of ENRO was examined.
determination of antibacterial piromidic acid has been presented The method was successfully applied to determination of ENRO in
[168]. The set of values for the variables influencing these stripping plasma and pharmaceutical samples [174].
techniques, perchloric acid concentration, accumulation potential, Adsorptive stripping analysis using different waveforms has
and accumulation time, was optimized using response surface been applied for the determination of dilitiazem [175], diosmin
methodology (RSM). The proposed method was successfully ap- [176], enrofloxacin [177], ethinylestradiol [178], famotidine
plied to human urine at nanomole levels 1.65  109 M, and [179], flavoxate [180], flaxedil [181], gatofloxacin [182], glipizide
proved to be a simple, highly sensitive, highly accurate, fast, and [183], haloperidol [184], hydroxyzine [185], isoniazid [186], lamo-
low-cost method. trigine [187], lamivudine [188], lansoprazol [189,190], levonorge-
Radi [169] concerned with the voltammetric study of pantop- strel [191], lorazepam [192], meloxicam [193], metoclopramide
razole at HMDE used a rapid and sensitive square-wave voltam- [194,153], nalidixic acid [195], nicardipine [196], nitrofurantoin
metric technique. Determination of the antibiotic drug pefloxacin [197], nitroxynil [198], norethisterone [199], ofloxacin [200], pan-
in bulk form, tablets, and human serum using SWCAdSV has been toprazole [201], piroxicam [202], pravastatine [203], praziquantel
developed by Beltagi [170]. Voltammetric determination of cila- [204], rofecoxib [205], spironolactone [206], terazosin [207], ter-
zapril in pharmaceutical formulations using the DPAdSV method butaline [208], tetrazepam [209], tolmetin [210], triamcinolone
has the advantages of being simpler, faster, and less tedious than [211], trimethoprim [68], triprolidine [212], trobramycin [213],
other techniques [171]. and zafirlukast [214]. Lists of the selected pharmaceutical and bio-
A simple, sensitive, and validated method for the determina- logical compounds that can be determined using stripping tech-
tion of diflunisal by DPP and DPAdSV had been developed and niques along with the ranges of their respective detection or
applied to the pharmaceutical preparation [163]. The results determination limits or concentration range are given in Table 2.
obtained by the developed method were compared with the
spectrofluorometric method by using the variance analysis and Voltammetric methods using surfactants
no statistically significant difference was found. A method based
on controlled adsorptive preconcentration of cefminox on HMDE Surfactant has been widely used in the electrochemistry and
[76], followed by LSV, allows its determination in the concentra- electroanalysis for various purposes. Surfactants have proved to
tion range 8.3  108 to 1.5  106 M with a detection limit of be effective in the electroanalysis of biological compounds and
2.47  108 M. This method has been used for the direct determi- drugs. For example, the addition of surface-active agents to elec-
nation of cefminox in human urine with recoveries between 98% trolyte containing terazosin [215] enhanced the voltammetric peak
and 103% and precision around ±2%. response at GCE. It was recently shown that anionic surfactants
Yılmaz has investigated the voltammetric behavior and determi- could be used to improve the accumulation of some electroactive
nation of zopiclone (ZP) on glassy carbon electrodes using a variety organic molecules such as ethopropazine [113] at gold electrodes.
of voltammetric techniques. The limits of detection and quantitation In another study, the influence of micelles in the simultaneous
were 2.78  107 and 5.28  107 mol L1 for DPAdSV. The pro- determination of two components was also demonstrated, as in
posed technique was successfully applied to direct determination the case of catechol and hydroquinone [216]. Recently, the oxida-
of ZP in tablet dosage forms and spiked human urine samples [172]. tion peak currents of certain pharmaceuticals increasing
A simple, sensitive, and reproducible square-wave cathodic significantly in the presence of surfactants have been reported by
adsorptive stripping voltammetric method had been developed different studies [217,218].
for the determination of nitrofurantoin in a solubilized system. Jain and co-workers had studied the effect of changing the
The objective of the present paper was to investigate the redox 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- ibility. Excellent improvement in the electrochemical behavior of
hanced the reduction current signal. Another important study by biologically important compounds such as dopamine and ascorbic
Alarcon-Angeles et al. [219] showed that sodium dodecyl sulfate acid [227,228], quercetin and rutine [229], tryptophan [230],
(SDS) micelles can act as a masking agent useful for the selective glucose [231], procaine [232], and metformine [233] at CNTs has
determination of dopamine in the presence of ascorbic acid. The been demonstrated.
SDS micelles make it possible to obtain DPV where DA and AA sig- Multiwalled carbon nanotube (MWCNT)-modified CPE was
nals appear separated because the SDS micelles provide that the used to study the electrochemical behavior of bergenin [234].
DA adsorbs strongly on the CPE and an increase of the charge trans- The modified electrode showed an excellent electrocatalytic activ-
fer reaction for the electrochemical oxidation of dopamine. ity in lowering the anodic overpotential and remarkable enhance-
Jain and co-workers also studied the effect of adding surface- ment of the ipa of bergenin if compared with the electrochemical
active agents to electrolytes-containing nortriptyline hydrochlo- performances obtained at CPE.
ride on the voltammetric response at hanging mercury drop Wang et al. [235] suggest that cysteic acid/carbon nanotube
electrodes. Addition of Tween 20 to the nortriptyline hydrochlo- film will have significant electroanalytical utility in the future.
ride-containing electrolyte enhances the reduction current signal. The novel cysteic acid/CNT film material can be easily applied to
Application of Tween 20 in the electrochemical determination of other types of substrate electrodes and surfaces and this will fur-
nortriptyline hydrochloride using square-wave voltammetry at ther broaden the potential for applications.
the HMDE enhanced the detection limit of the analyte [220]. Similarly various pharmaceuticals [67,80,90,141,154,236–239,
A voltammetric method for the determination of entacapone 230,240–249,144,250] have been determined by different kinds of
based on the enhancement effect of Tween 20 had been developed. modified electrodes. Wang et al. [251] reported a new approach to
Addition of neutral surfactant (Tween 20) to the entacapone-con- construct a nano-Au self-assembly gold electrode which was used
taining electrolyte enhanced the reduction current signal while an- for determination of epinephrine.
ionic surfactant (sodium lauryl sulfate) and cationic surfactant Hu et al. [252] also reported the fabrication of a modified elec-
(cetrimide) showed an opposite effect. The analysis of entacapone trode based on the self-assembly of gold nanoparticles on cyste-
in its pharmaceutical formulation exhibited the mean recovery of amine film, which has been bound to the surface of a glassy
99% for the reduction peak [221]. carbon electrode. The modified electrode exhibited an excellent
Assay and electrochemical behavior of betahistine hydrochlo- reproducibility, sensibility, and stability for determination of dopa-
ride in Britton-Robinsons (BR) buffer of pH range 2.5–12.0 at a mine in the presence of high concentrations of ascorbic acid.
glassy carbon electrode have been investigated. Addition of anionic Goyal and co-workers have successfully studied the electro-
surfactant (sodium lauryl sulfate) to the betahistine hydrochloride chemical behavior of various pharmaceuticals [253–255] at a gold
solution-containing electrolyte enhanced the reduction current nanoparticle-modified indium tin oxide (nano Au/ITO) electrode.
signal while neutral surfactant (Tween 20) and cationic surfactant Gold nanoparticles exhibit attractive properties in electrode mod-
cetyl trimethylammonium bromide (CTAB) showed an opposite ef- ification by improving the electrode conductivity and enhancing
fect. Voltammograms of betahistine hydrochloride exhibited a sin- the analytical sensitivity and selectivity [256,257].
gle wave. The proposed method was successfully applied to the An entire electrochemical study of diazepam, temazepam, and
determination of betahistine hydrochloride in drug product. The oxazepam using modified carbon-paste electrodes was reported
results were compared with those obtained by the reference [258]. Boron-doped diamond electrodes have received much atten-
high-performance liquid chromatographic method. No significant tion for electrochemical determination [259,260] due to their
differences were found between results of proposed and reference attractive electrochemical properties over other electrodes.
methods [222]. Compared to classical carbon electrodes and other metallic
The voltammetric behavior of ornidazole had been studied in electrodes, diamond electrodes open up new opportunities for
different surfactant media, viz. anionic, cationic, and non-ionic sur- working under extreme conditions such as media (e.g., strongly
factants over the pH range 2.5 to 12.0 in phosphate buffer (0.2 M). acidic). Over the past two past decades electroanalytical tech-
Addition of non-ionic surfactant (Tween 20) to the ornidazole-con- niques based on modified polymer electrodes have attracted broad
taining electrolyte enhanced the reduction current signal while the interest from scientist engaged in pharmaceutical analysis
anionic surfactant sodium lauryl sulfate and cationic surfactant [261,262]. The modification of the electrode by Nafion film [19] en-
cetyltrimethylammonium bromide showed a small enhancement hanced the analytical signal intensity and simultaneously pro-
in peak current. The analysis of ornidazole in its pharmaceutical tected the surface of the working electrode, avoiding its fouling
formulation exhibited the mean recovery of 98% for the reduction by species present in the sample matrices, conferring greater sta-
peak [223]. bility to the electrode and higher reproducibility to the
Voltammetric behavior of nitrazepam had been studied in ace- determinations.
tonitrile and in the presence of anionic surfactant (sodium lauryl Fullerene science is one of the fastest growing areas of research
sulfate). It exhibit two well-defined cathodic peaks [224]. 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-
Voltammetric methods at modified electrodes ysis as observed in recent report for the electrochemical oxidation
of nandrolone [10] at fullerene C60-modified glassy carbon
Chemically modified electrodes are currently widely used due electrode.
to the various advantages they offer. The use of chemically modi- Jain et al. also reported a composite polymer surface coated on a
fied electrodes in electroanalysis offers several advantages, which tin oxide which offers dramatic improvement in the stability of
include lowering of the peak potential and increase in sensitivity voltammetric measurement of pyridostigmine bromide compared
along with improvement in selectivity in the application of phar- to individual tin oxide, polyaniline, or polypyrrole-coated elec-
maceutical analysis [137,217,225,226]. trodes [263].
Much attention has been given to the use of carbon nanotubes The voltammetric behavior of pyrantel pamoate was studied in
(CNTs) since its discovery in 1991. CNT-modified electrodes have the Britton-Robinson buffer system at a composite polymer mem-
proved to have excellent electroanalytical properties, such as wide brane working electrode. The cyclic voltammetric method has been
potential windows, low background current, and good biocompat- developed for the determination of drug in pharmaceutical formu-
Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196 191

lation. A well-defined cathodic peak was observed for the pyrantel with a detection limit of 0.67 mmol L1 AMPC. The linear calibra-
pamoate in the entire pH range. The current increases steadily with tion was in the range of 2.34–30 and 40–700 mmol L1 AMPC using
diffusion scan rate and concentration. The results indicate that the the differential pulse voltammetric method. Finally, this method
process is irreversible and diffusion controlled. This composite film was also examined as a selective, simple, and precise electrochem-
showed good current response [264]. ical sensor for the determination of AMPC in real samples such as
Zheng and co-workers reported the selective, sensitive, and drugs and urine [162,270–279].
simultaneous determination of dopamine, ascorbic acid, and uric Several synthetic zeolites such as mazzite, mordenite, zeolite L,
acid on ordered mesoporous carbon (OMC)/Nafion composite film zeolite beta, and MCM-41 were tested as electrode modifiers in
[265]. voltammetric determination of tryptophan. It was found that the
Recently Nasirizadeh et al. had fabricated a highly efficient nor- addition of zeolite beta to the carbon paste would generate the
adrenalin (NA) biosensor on the basis of hematoxylin electrodepos- peak current of Trp because of its catalytic effect. The anodic peak
ited on a glassy carbon electrode, GCE. The peaks of differential pulse currents were proportional to Trp concentrations in the range of
voltammetric for NA and acetaminophen (AC) oxidation at the 5.0  107 to 5.0  103 M. The detection limit was 1.0  107 M.
hematoxylin biosensor surface are clearly separated from each other The influence of several species, especially amino acids, was tested.
when they coexited in the physiological pH (pH 7.0). It was, there- The proposed method was applied successfully to the determina-
fore, possible to simultaneously determine NA and AC in the samples tion of tryptophan in pharmaceutical formulations [174].
at a hematoxylin biosensor [266].
A voltammetric method was developed for the determination of Conclusion
tetracycline (TC) by using an ionic liquid (IL, 1,octyl,3,methylimida-
zolium, hexafluorophosphate)–multiwall carbon nanotube Modern electrochemical instrumentation, especially voltam-
(MWNT) film-coated glassy carbon electrode (GCE). Experiment metric techniques, provides reliable and reproducible data for the
showed that both IL and MWNT could facilitate the TC oxidation. quantification of analyte. Further, use of modified electrodes
Thus on the electrode TC exhibited a sensitive anode peak at proved to have excellent electroanalytical properties, such as wide
0.54 V (vs SCE) in pH 7.0 phosphate buffer solutions. Under the potential windows, low background current, and good biocompat-
optimized experimental conditions, the peak current was linear ibility. Also, addition of surface-active agents to electrolytes greatly
to TC concentration in the range of 1.1  107 to 2.2  105 M for enhances the voltammetric peak response, increasing sensitivity.
150 s accumulation. The electrode had good reproducibility. It The present review will be of great help for the analytical chemists
was successfully applied to the detection of TC in egg and pharma- using voltammetric methods for the determination of a given ana-
ceutical samples [267]. lyte in a complex matrix. The aim of the review is to assess the util-
The determination of sildenafil citrate using differential pulse ity of methods using various electrodes and surface-active agents
voltammetry and a cathodically pretreated boron-doped diamond for the determination of pharmaceuticals with low running cost,
electrode is described. The obtained analytical curve is linear in high speed, sensitivity, universality, and wide application. These
the sildenafil concentration range 7.3  107 to 7.3  106 mol L1 techniques are simple and in cases more sensitive to the usually
in a 0.1 mol L1 H2SO4, with a detection limit of 6.4  107 mol L1. applied chromatographic and spectroscopic techniques.
The proposed method, which is fast and simple to carry out, was
successfully applied in the determination of sildenafil citrate in Acknowledgments
Viagra1 pharmaceutical formulations, with results in close agree-
ment (at 95% confidence level) with those obtained using a com- The authors dedicate this paper to their reverend teacher and
parative HPLC method [268]. renowned Electrochemist (Late) Prof. Wahid. U. Malik and one of
The electrochemical response of sodium levothyroxine at a car- the authors; K. Radhapyari is thankful to the Department of Science
bon-paste electrode in the presence of 0.1 M HCl as supporting and Technology (DST), New Delhi, India, for the award of
electrolyte was investigated by cyclic voltammetry. It showed a fellowship.
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-
References
tration and scan rate of sodium levothyroxine was studied. The
scan rate effect showed that the electrode process is adsorption [1] P.T. Kissinger, W.R. Heineman, Laboratory Techniques in Electroanalytical
controlled. The effect of surfactants like sodium dodecyl sulfate, Chemistry, second ed., Dekker, New York, 1996.
cetyltrimethylammonium bromide, and Triton X-100 (TX-100) [2] J. Barek, A.G. Fogg, A. Merck, J. Zima, Polarography and voltammetry at
mercury electrodes, Crit. Rev. Anal. Chem. 31 (2001) 291–309.
were studied by mobilizing and immobilizing methods. The con- [3] S.R. Annapoorna, M.P. Rao, B. Sethuram, Multiple substituent effects in the
centration effect of all the three surfactants was studied. Among C@C reduction of phenyl styryl ketones: cyclic voltammetry as a tool, J.
these SDS showed excellent enhancement in both oxidation peak Electroanal. Chem. 490 (2000) 93–97.
[4] L.J. Nunez-Vergara, D. Farias, S. Bollo, J.A. Squella, An electrochemical
and reduction peak currents [269]. evidence of free radicals formation from flutamide and its reactivity with
A carbon-paste electrode spiked with ferrocenedicarboxylic endo/xenobiotics of pharmacological relevance, Bioelectrochemistry 53
acid (FDCMCPE) was constructed by incorporation of ferrocenedi- (2001) 103–110.
[5] L. Ye-Mei, C. Xian-Tang, L. Jun, L. Hui-Hong, Direct voltammetry and catalysis
carboxylic acid in a graphite powder–paraffin oil matrix. It has of hemoenzymes in methyl cellulose film, Electrochim. Acta 49 (2004) 3195–
been shown by direct current cyclic voltammetry and double-step 3200.
chronoamperometry that this electrode can catalyze the oxidation [6] V.K. Gupta, A.K. Singh, B. Gupta, A cerium (III) selective poly vinyl chloride
membrane based on a Schiff base complex of N,N-bis [2-
of ampicillin (AMPC) in aqueous buffered solution. It has been (salicylideneamino)ethyl] ethane-1,2-diamine, Anal. Chim. Acta 575 (2006)
found that under optimum conditions (pH 10.0) in cyclic voltam- 198–204.
metry, the oxidation of AMPC occurred at a potential of about [7] G. Angulo, A. Kapturkiewicz, A. Palmaerts, L. Lutsen, T.J. Cleij, D. Vanderzande,
Cyclic voltammetry studies of n-type polymers with non-alternant
480 mV on the surface of the modified carbon-paste electrode.
fluoranthene units, Electrochim. Acta 54 (2009) 1584–1588.
The kinetic parameters such as electron-transfer coefficient, a, [8] G. Macchi, The determination of ionic zinc in sea-water by anodic stripping
and rate constant for the chemical reaction between AMPC and re- voltammetry using ordinary capillary electrodes, J. Electroanal. Chem. 9
dox sites in FDCMCPE were also determined using electrochemical (1965) 290–298.
[9] R.P. Lencastre, C.D. Matos, J. Garrido, F. Borges, E.M. Garrido, Voltammetric
approaches. Under the optimized conditions, the electrocatalytic quantification of fluoxetine: application to quality control and quality
oxidation peak current of AMPC showed two linear dynamic ranges assurance processes, J. Food Drug Anal. 14 (2006) 242–251.
192 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196

[10] R.N. Goyal, V.K. Gupta, S. Chatterjee, Electrochemical investigations of [39] S. Bollo, L.J. Nunez-Vergara, J.A. Squella, Cyclic voltammetric determination of
corticosteroid isomers—testosterone and epitestosterone and their simultaneous free radical species from nitroimidazopyran: a new antituberculosis agent, J.
determination in human urine, Anal. Chim. Acta 657 (2010) 147–153. Electroanal. Chem. 562 (2004) 9–14.
[11] S.M. Sabry, M.H. Barary, M.H. Abdel-Hay, T.S. Belal, Adsorptive stripping [40] L.M. De Carvalho, P.C. Do Nascimento, D. Bohrer, D. Correia, A.V. De Bairros, S.G.
voltammetric behavior of azomethine group in pyrimidine-containing drugs, Pomblum, Voltammetric behavior of amfepramone (diethylpropion) at the
J. Pharm. Biomed. Anal. 34 (2004) 509–516. hanging mercury drop electrode and its analytical determination in
[12] L.G. Martinez, P.C. Falco, A.S. Cabeza, Comparison of several methods used for pharmaceutical formulations, J. Braz. Chem. Soc. 18 (2007) 789–812.
the determination of cephalosporins. Analysis of cephalexin in [41] G.B. El-Hefnawy, I.S. El-Hallag, E.M. Ghoneim, M.M. Ghoneim,
pharmaceutical samples, J. Pharm. Biomed. Anal. 29 (2002) 405–423. Electrochemical behavior and determination of amiloride drug in bulk form
[13] Chen Zhang-jing, J. Zhang, Yu Ji-cheng, Cao Guo-ying, Wu Xiao-jie, Shi Yao- and pharmaceutical formulation at mercury electrodes, J. Pharm. Biomed.
guo, Selective method for the determination of cefdinir in human plasma Anal. 34 (2004) 899–911.
using liquid chromatography electrospray ionization tandem mass [42] E. Hammam, Behavior and quantification studies of amiloride drug using
spectrometry, J. Chromatogr. B 834 (2006) 63–67. cyclic and square-wave adsorptive stripping voltammetry at a mercury
[14] N. Ozaltin, Determination of lansoprazole in pharmaceutical dosage forms by electrode, J. Pharm. Biomed. Anal. 34 (2004) 1109–1116.
two different spectroscopic methods, J. Pharm. Biomed. Anal. 20 (1999) 599– [43] Z. Mandic, Z. Weitner, M. Ilijas, Electrochemical oxidation of azithromycin
606. and its derivatives, J. Pharm. Biomed. Anal. 33 (2003) 647–654.
[15] A.S.L. Mendez, V. Weisheimer, T.P. Oppe, M. Steppe, E.E.S. Schapoval, [44] R. Fernandez Torres, M. Callejan Mochon, J.C. Jimenez Sanchez, M.A. Bello
Microbiological assay for the determination of meropenem in Lopez, A. Guiraum Perez, Electrochemical oxidation of cisatracurium on
pharmaceutical dosage form, J. Pharm. Biomed. Anal. 37 (2005) 649–653. carbon paste electrode and its analytical applications, Talanta 53 (2001)
[16] B. Nigovic, B. Simunic, Determination of 5-aminosalicylic acid in 1179–1185.
pharmaceutical formulation by differential pulse voltammetry, J. Pharm. [45] S. Michalkiewicz, Voltammetric determination of coenzyme Q10 in
Biomed. Anal. 31 (2003) 169–174. pharmaceutical dosage forms, Bioelectrochemistry 73 (2008) 30–36.
[17] B. Uslu, S.A. Ozkan, Anodic voltammetry of abacavir and its determination in [46] T. Wahdan, N.A. El-Ghany, Determination of domperidone in tablet dosage
pharmaceuticals and biological fluids, Electrochim. Acta 49 (2004) 4321– form by anodic differential pulse voltammetry, Il Farmaco 60 (2005) 830–
4329. 833.
[18] A.K. Jain, V.K. Gupta, S. Radi, L.P. Singh, J.R. Raisoni, A comparative study of [47] M.S. El-Shahawi, S. Bahaffi, T. El-Mogy, Analysis of domperidone in
Pb2+ sensors based on derivatized tetrapyrazole and calix[4]arene receptors, pharmaceutical formulations and wastewater by differential pulse
Electrochim. Acta 51 (12) (2006) 2547–2553. voltammetry at a glassy-carbon electrode, Anal. Bioanal. Chem. 387 (2007)
[19] M.L.S. Silva, M.B.Q. Garcia, J.L.F.C. Lima, E. Barrado, Modified tubular electrode 719–725.
in a multi-commutated flow system: determination of acetaminophen in [48] A. Golcu, S.A. Ozkan, Electroanalytical determination of donepezil HCl in
blood serum and pharmaceutical formulations, Anal. Chim. Acta 573 (2006) tablets and human serum by differential pulse and osteryoung square
383–390. wave voltammetry at a glassy carbon electrode, Pharmazie 61 (2006) 760–
[20] D. Sun, H. Zhang, Electrochemical determination of acetaminophen using a 765.
glassy carbon electrode coated with a single-wall carbon nanotube-dicetyl [49] A.E. Radi, N. Abd-Elghany, T. Wahdan, Electrochemical study of the
phosphate film, Microchim. Acta 158 (2007) 131–136. antineoplastic agent etoposide at carbon paste electrode and its
[21] R.F. Torres, M.C. Mochon, J.C. Jimenez Sanchez, M.A. Bello Lopez, A.G. Perez, determination in spiked human serum by differential pulse voltammetry,
Electrochemical behaviour and determination of acrivastine in pharmaceu- Chem. Pharm. Bull. 55 (2007) 1379–1382.
ticals and human urine, J. Pharm. Biomed. Anal. 30 (2002) 1215–1219. [50] B. Dogan, S.A. Ozkan, B. Uslu, Electrochemical characterization of flupentixol
[22] H. Abdine, F. Belal, Polarographic behaviour and determination of acrivastine and rapid determination of the drug in human serum and pharmaceuticals by
in capsules and human urine, Talanta 56 (2002) 97–104. voltammetry, Anal. Lett. 38 (2005) 641–656.
[23] A.L. Santos, R.M. Takeuchi, M.P. Mariotti, M.F. De Oliveira, M.V.B. Zanoni, N.R. [51] B. Uslu, B. Dogan, S.A. Ozkan, Electrochemical studies of ganciclovir at glassy
Stradiotto, Study of electrochemical oxidation and determination of carbon electrodes and its direct determination in serum and pharmaceutics
albendazole using a glassy carbon-rotating disk electrode, Il Farmaco 60 by square wave and differential pulse voltammetry, Anal. Chim. Acta 537
(2005) 671–674. (2005) 307–313.
[24] A.K. Jain, V.K. Gupta, L.P. Singh, U. Khurana, Macrocycle based membrane [52] I. Tapsoba, J.E. Belgaied, K. Boujlel, Voltammetric assay of Guaifenesin in
sensors for the determination of cobalt (II) ions, Analyst 122 (1997) 583–586. pharmaceutical formulation, J. Pharm. Biomed. Anal. 38 (2005) 162–165.
[25] J. Wang, Electroanalytical Techniques in Clinical Chemistry and Laboratory [53] O.A. Razak, Electrochemical study of hydrochlorothiazide and its
Medicine, VCH, New York, 1988. determination in urine and tablets, J. Pharm. Biomed. Anal. 34 (2004) 433–
[26] A. Ambrosi, R. Antiochia, L. Campanella, R. Dragone, I. Lavagnini, 440.
Electrochemical determination of pharmaceuticals in spiked water samples, [54] M.L.P.M. Arguelho, J.F. Andrade, N.R. Stradiotto, Electrochemical study of
J. Hazard. Mater. 122 (2005) 219–225. hydroxychloroquine and its determination in plaquenil by differential pulse
[27] W. Guo, H. Lin, L. Liu, J. Song, Polarographic determination of diazepam with voltammetry, J. Pharm. Biomed. Anal. 32 (2003) 269–273.
its parallel catalytic wave in the presence of persulfate, J. Pharm. Biomed. [55] K. Farhadi, A. Karimpour, Electrochemical behavior and determination of
Anal. 34 (2004) 1137–1144. hyoscine-N-butylbromide from pharmaceutical preparations, J. Chin. Chem.
[28] R.A. Toledo, M. Castilho, L.H. Mazo, Determination of dipyridamole in Soc. 54 (2007) 165–172.
pharmaceutical preparations using square wave voltammetry, J. Pharm. [56] V.G. Bonifacio, L.H. Marcolino, M.F.S. Teixeira, O. Fatibello-Filho,
Biomed. Anal. 36 (2005) 1113–1116. Voltammetric determination of isoprenaline in pharmaceutical preparations
[29] E. Winter, L. Codognoto, S. Rath, Electrochemical behavior of dopamine at a using a copper (II) hexacyanoferrate (III) modified carbon paste electrode,
mercury electrode in the presence of citrate: analytical applications, Anal. Microchem. J. 78 (2004) 55–61.
Lett. 40 (2007) 1197–1208. [57] B.T. Demircigil, S.A. Ozkan, O. Coruh, S. Yilmaz, Electrochemical behavior of
[30] A. Alvarez-Lueje, S. Brain-Isasi, L.J. Nunez-Vergara, J.A. Squella, Voltammetric formoterol fumarate and its determination in capsules for inhalation and
reduction of finasteride at mercury electrode and its determination in tablets, human serum using differential-pulse and square-wave voltammetry,
Talanta 75 (2008) 691–696. Electroanalysis 14 (2002) 122–127.
[31] A.A. Gazy, E.M. Hassan, M.H. Abdel-Hay, T.S. Belal, Differential pulse cathodic [58] B. Uslu, B.T. Demircigil, S.A. Ozkan, Z. Senturk, H.Y. Aboul-Enein,
voltammetric determination of floctafenine and metopimazine, J. Pharm. Simultaneous determination of melatonin and pyridoxine in tablet
Biomed. Anal. 43 (2007) 1535–1539. formulation by differential pulse voltammetry, Pharmazie 56 (2001) 938–
[32] B. Dogan, D. Canbaz, S.A. Ozkan, B. Uslu, Electrochemical methods for 941.
determination of protease inhibitor indinavir sulfate in pharmaceutics and [59] B. Dogan-Topal, B. Uslu, S.A. Ozkan, Investigation of electrochemical behavior
human serum, Pharmazie 61 (2006) 409–413. of lipid lowering agent atorvastatin calcium in aqueous media and its
[33] F. Belal, A. Al-Majed, S. Julkhuf, Voltammetric determination of isradipine in determination from pharmaceutical dosage forms and biological fluids using
dosage forms and spiked human plasma and urine, J. Pharm. Biomed. Anal. 31 boron-doped diamond and glassy carbon electrodes, Comb. Chem. High
(2003) 989–998. Throughput Screen. 10 (2007) 571–582.
[34] C. Yardimci, N. Ozaltin, Electrochemical studies and differential pulse [60] O. Abd El-Moaty Farghaly, N.A.L. Mohamed, Voltammetric determination of
polarographic analysis of lansoprazole in pharmaceuticals, Analyst 126 azithromycin at the carbon paste electrode, Talanta 62 (2004) 531–535.
(2001) 361–366. [61] B. Nigovic, Adsorptive stripping voltammetric determination of azithromycin
[35] S. Altınoz, E. Nemutlu, S. Kır, Polarographic behaviour of meloxicam and its at a glassy carbon electrode modified by electrochemical oxidation, Anal. Sci.
determination in tablet preparations and spiked plasma, Il Farmaco 57 (2002) 20 (2004) 639–643.
463–468. [62] R. Jain, V.K. Gupta, N. Jadon, K. Radhapyari, Adsorptive stripping voltammetric
[36] A.M. Beltagi, M.M. Ghoneim, A. Radi, Electrochemical reduction of meloxicam determination of pyridostigmine bromide in bulk and pharmaceutical
at mercury electrode and its determination in tablets, J. Pharm. Biomed. Anal. formulations, J. Electroanal. Chem. 648 (2010) 20–27.
27 (2002) 795–801. [63] C. Yin Wang, X. Ya Hu, Determination of benorilate in pharmaceutical
[37] G. Altiokka, Z. Atkosar, M. Tuncel, Pulse polarographic determination of formulations and its metabolite in urine at carbon paste electrode modified
meloxicam, Pharmazie 56 (2001) 184–185. by silver nanoparticles, Talanta 67 (2005) 625–633.
[38] F. Belal, H. Abdine, N. Zoman, Voltammetric determination of nilvadipine in [64] P.B. Desai, R.M. Kotkar, A.K. Srivastava, Electrochemical behaviour of
dosage forms and spiked human urine, J. Pharm. Biomed. Anal. 26 (2001) pyridoxine hydrochloride (vitamin B6) at carbon paste electrode modified
585–592. with crown ethers, J. Solid State Electrochem. 12 (2008) 1067–1075.
Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196 193

[65] W. Lai-Hao, T. Shu-Jen, Voltammetric behavior of chlorhexidine at a film [93] N. Adhoum, L. Monser, M. Toumi, K. Boujlel, Determination of naproxen in
mercury electrodes and its determination in cosmetics and oral hygiene pharmaceuticals by differential pulse voltammetry at a platinum electrode,
products, Anal. Chim. Acta 441 (2001) 107–116. Anal. Chim. Acta 495 (2003) 69–75.
[66] S. Komorsky-Lovric, B. Nigovic, Identification of 5-aminosalicylic acid, [94] A. Abbaspour, R. Mirzajani, Electrochemical monitoring of piroxicam in
ciprofloxacin and azithromycin by abrasive stripping voltammetry, J. different pharmaceutical forms with multi-walled carbon nanotubes paste
Pharm. Biomed. Anal. 36 (2004) 81–89. electrode, J. Pharm. Biomed. Anal. 44 (2007) 41–48.
[67] G. Yang, C. Wang, R. Zhang, C. Wang, Q. Qu, X. Hu, Poly (amidosulfonic acid) [95] M.M. Ghoneim, A.M. Beltagi, Adsorptive stripping voltammetric
modified glassy carbon electrode for determination of isoniazid in determination of the anti-inflammatory drug celecoxib in pharmaceutical
pharmaceuticals, Bioelectrochemistry 73 (2008) 37–42. formulation and human serum, Talanta 60 (2003) 911–921.
[68] M. Korolczuk, K. Tyszczuk, Adsorptive stripping voltammetry of [96] R.N. Goyal, V.K. Gupta, S. Chatterjee, Voltammetric biosensors for the
trimethoprim at an in situ plated lead film electrode, Chem. Anal. 52 (2007) determination of paracetamol at carbon nanotube modified pyrolytic
1015–1024. graphite electrode, Sens. Actuators B 149 (2010) 252–258.
[69] X. Yang, F. Wang, S. Hu, The electrochemical oxidation of troxerutin and its [97] E. Turkoz, A.N. Omar, Determination of ticlopidine in pharmaceutical
sensitive determination in pharmaceutical dosage forms at PVP modified products, Anal. Lett. 40 (2007) 2231–2240.
carbon paste electrode, Colloids Surf. B 52 (2006) 8–11. [98] R. Jain, N. Jadon, K. Radhapyari, Determination of antihelminthic drug
[70] Y.L. Suw, Voltammetric analysis of DL-a-ocopherol with a paste electrode, J. pyrantel pamoate in bulk and pharmaceutical formulations using electro-
Sci. Food Agric. 88 (2008) 1272–1275. analytical methods, Talanta 70 (2006) 383–386.
[71] S.A. Ozkan, B. Uslu, H.Y. Aboul-Enein, Analysis of pharmaceuticals and [99] G.B. El-Hefnawey, I.S. El-Hallag, E.M. Ghoneim, M.M. Ghoneim, Voltammetric
biological fluids using modern electroanalytical techniques, Crit. Rev. Anal. behavior, quantification of the sedative-hypnotic drug chlordiazepoxide in
Chem. 33 (2003) 155–181. bulk form, pharmaceutical formulation and human serum at a mercury
[72] C. Aki, S. Yilmaz, Y. Dilgin, S. Yagmur, E. Suren, Electrochemical study of electrode, J. Pharm. Biomed. Anal. 34 (2004) 75–86.
natamycin (Pimaricin)—analytical application to pharmaceutical dosage [100] B. Uslu, S. Yilmaz, S.A. Ozkan, Determination of olsalazine sodium in
forms by differential pulse voltammetry, Pharmazie 60 (2005) 747–750. pharmaceuticals by different pulse voltammetry, Pharmazie 56 (2001)
[73] A.A.J. Torriero, J.M. Luco, L. Sereno, J. Raba, Voltammetric determination of 629–632.
salicylic acid in pharmaceuticals formulations of acetylsalicylic acid, Talanta [101] N. EL-Enany, F. Belal, M.S. Rizk, Voltammetric analysis of trazodone HCl in
62 (2004) 247–254. pharmaceuticals and biological fluids, J. Pharm. Biomed. Anal. 30 (2002) 219–
[74] H.S. El-Desoky, E.M. Ghoneim, M.M. Ghoneim, Voltammetric behavior and 226.
assay of the antibiotic drug cefazolin sodium in bulk form and [102] H.P.A. Nouws, C. Delerue-Matos, A.A. Barros, Electrochemical determination
pharmaceutical formulation at a mercury electrode, J. Pharm. Biomed. Anal. of citalopram by adsorptive stripping voltammetry—determination in
39 (2005) 1051–1056. pharmaceutical products, Anal. Lett. 39 (2006) 1907–1915.
[75] R. Jain, K. Radhapyari, N. Jadon, Electrochemical evaluation and [103] S. Demircan, S. Kir, S.A. Ozkan, Electroanalytical characterization of verapamil
determination of cefdinir in dosage form and biological fluid at mercury and its voltammetric determination in pharmaceuticals and human serum,
electrode, J. Electrochem. Soc. 154 (2007) F199–F202. Anal. Lett. 40 (2007) 1177–1195.
[76] A. Hilali, J.C. Jimenez, M. Callejon, M.A. Bello, A. Guiraum, Electrochemical [104] B. Uslu, S.A. Ozkan, Electroanalytical characteristics of piribedil and its
reduction of cefminox at the mercury electrode and its voltammetric differential pulse and square wave voltammetric determination in
determination in urine, Talanta 59 (2003) 137–146. pharmaceuticals and human serum, J. Pharm. Biomed. Anal. 31 (2003) 481–
[77] A. Radi, T. Wahdan, N.A. El-Ghany, Determination of cefonicid in human urine 489.
by adsorptive square-wave stripping voltammetry, J. Pharm. Biomed. Anal. 31 [105] I. Siddiqui, K.S. Pitre, Voltammetric determination of vitamins in a
(2003) 1041–1046. pharmaceutical formulation, J. Pharm. Biomed. Anal. 26 (2001) 1009–
[78] E. Hammam, M.A. El-Attar, A.M. Beltagi, Voltammetric studies on the 1111.
antibiotic drug cefoperazone: quantification and pharmacokinetic studies, J. [106] Y. Wu, F. Song, Voltammetric investigation of vitamin B6 at a glassy carbon
Pharm. Biomed. Anal. 42 (2006) 523–527. electrode and its application in determination, Bull. Korean Chem. Soc. 29
[79] A.M. Jacques Barbosa, M.A. Goncalves Trindade, V. Souza Ferreira, Cathodic (2008) 38–42.
stripping voltammetry determination of ceftiofur antibiotic in formulations [107] E.M. Hassan, E.F. Khamis, E.I. El-Kimary, M.A. Barary, Development of a
and bovine serum, Anal. Lett. 39 (2006) 1143–1158. differential pulse voltammetric method for the determination of
[80] S. Lu, K. Wu, X. Dang, S. Hu, Electrochemical reduction and voltammetric silymarin/vitamin E acetate mixture in pharmaceuticals, Talanta 74
determination of metronidazole at a nanomaterial thin film coated glassy (2008) 773–778.
carbon electrode, Talanta 63 (2004) 653–657. [108] R. Jain, K. Radhapyari, N. Jadon, Adsorptive stripping voltammetric behavior
[81] X. Wang, N. Yang, Q. Wan, Cyclic voltammetric response of nicotinic acid and and determination of anticholinergic agent oxybutynin chloride on a mercury
nicotinamide on a polycrystalline gold electrode, Electrochim. Acta 52 (2006) electrode, J. Colloid Interface Sci. 314 (2007) 572–575.
361–368. [109] G. Altiokka, Voltammetric determination of doxazosin in tablets using
[82] O. Coruh, S.A. Ozkan, Determination of the antihyperlipidemic simvastatin by rotating platinum electrode, J. Pharm. Biomed. Anal. 25 (2001) 387–391.
various voltammetric techniques in tablets and serum sample, Pharmazie 61 [110] M.L. Abasq, P. Courtel, G. Burgot, Determination of entacapone by differential
(2006) 285–290. pulse polarography in pharmaceutical formulation, Anal. Lett. 41 (2008) 56–
[83] N. Erk, Development of electrochemical methods for determination of 62.
atorvastatin and analytical application to pharmaceutical products and [111] M.M. Ghoneim, M.M. Mabrouk, A.M. Hassanein, A. Tawfik, Polarographic
spiked human plasma, Crit. Rev. Anal. Chem. 34 (2004) 1–6. behaviour of loratadine and its direct determination in pharmaceutical
[84] S.A. Ozkan, B. Dogan, B. Uslu, Voltammetric analysis of the novel atypical formulation and human plasma by cathodic adsorptive stripping
antipsychotic drug quetiapine in human serum and urine, Microchim. Acta voltammetry, J. Pharm. Biomed. Anal. 25 (2001) 933–939.
153 (2006) 27–32. [112] J.A. Acuna, C. de la Fuente, M.D. Vazquez, M.L. Tascon, M.I. Gomez, F. Mata,
[85] Y. Wang, L. Ni, S. Kokot, Voltammetric determination of chlorpromazine P.S. Batanero, Electrochemical behaviour of droxicam: kinetic study in
hydrochloride and promethazine hydrochloride with the use of multivariate aqueous-organic media, J. Pharm. Biomed. Anal. 29 (2002) 617–622.
calibration, Anal. Chim. Acta 439 (2001) 159–168. [113] L. Huang, L. Bu, F. Zhao, B. Zeng, Voltammetric behavior of ethopropazine and
[86] X. Ioannides, A. Economou, A. Voulgaropoulos, A study of the determination the influence of sodium dodecylsulfate on its accumulation on gold
of the hypertensive drug captopril by square wave cathodic adsorptive electrodes, J. Solid State Electrochem. 8 (2004) 976–981.
stripping voltammetry, J. Pharm. Biomed. Anal. 33 (2003) 309–316. [114] T. Liu, M. Li, Q. Li, Electrochemical behavior of thalidomide, J. Pharm. Biomed.
[87] A.A. Ensafi, R. Hajian, A highly selective mercury (II) ion-selective membrane Anal. 29 (2002) 761–770.
sensor, J. Braz. Chem. Soc. 19 (2008) 405–412. [115] A.-L. Liu, S.-B. Zhang, W. Chen, L.-Y. Huang, X.-H. Lin, X.-H. Xia, Study of the
[88] G.K. Ziyatdinova, G.K. Budnikov, Pogorel’tsev VI, Determination of captopril electrochemical behavior of isorhamnetin on a glassy carbon electrode and
in pharmaceutical forms by stripping voltammetry, J. Anal. Chem. 61 (2006) its application, Talanta 77 (2008) 314–317.
798–800. [116] N.T. Abdel-Ghani, G.M. Abu-Elenien, S.H. Hussein, Differential pulse
[89] J.A. Prieto, R.M. Jimenez, R.M. Alonso, Square wave voltammetric voltammetric determination of chlorphenoxamine hydrochloride and its
determination of the angiotensin-converting enzyme inhibitors cilazapril, pharmaceutical preparations using platinum and glassy carbon electrodes, J.
quinapril and ramipril in pharmaceutical formulations, Il Farmaco 58 (2003) Appl. Electrochem. 40 (2010) 499–505.
343–346. [117] B.D. Topal, A. Golcu, S.A. Ozkan, Electrochemical investigation and
[90] D.P. Santos, M.F. Bergamini, V.A.F.F.M. Santos, M. Furlan, M.V.B. Zanoni, determination of the antibacterial loracarbef by voltammetric methods,
Preconcentration of rutin at a poly glutamic acid modified electrode and its Anal. Lett. 42 (2009) 689–705.
determination by square wave voltammetry, Anal. Lett. 40 (2007) 3430– [118] K.J. Huang, C.X. Xu, W.Z. Xie, Electrochemical behavior of norfloxacin and its
3442. determination at poly (methyl red) film coated glassy carbon electrode, Bull.
[91] M.C. Blanco-Lopez, L. Fernandez-Liano, M.J. Lobo-castanon, A.J. Miranda- Korean Chem. Soc. 29 (2008) 988–992.
Ordieres, P.T. Blauco, Voltammetry of diclofenac at graphite, carbon [119] A. Radi, N. Abd El-Ghany, T. Wahdan, Voltammetric behaviour of rabeprazole
composites, and molecularly imprinted polymer-composite electrodes, at a glassy carbon electrode and its determination in tablet dosage form, Il
Anal. Lett. 37 (2004) 915–927. Farmaco 59 (2004) 515–518.
[92] Y. Altun, B. Dogan, S.A. Ozkan, B. Uslu, Development and validation of [120] L. Chunya, Voltammetric determination of ethinylestradiol at a carbon paste
voltammetric techniques for nabumeton in pharmaceutical dosage form, electrode in the presence of cetyl pyridine bromine, Bioelectrochemistry 70
human serum and urine, Acta Chim. Slov. 54 (2007) 287–294. (2007) 263–271.
194 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196

[121] M.F. de Oliveira, N.R. Stradiotto, Voltammetric determination of [150] S. Yılmaz, B. Uslu, S.A. Ozkan, Anodic oxidation of etodolac and its square
fenbendazole in veterinarian formulations, J. Pharm. Biomed. Anal. 30 wave and differential pulse voltammetric determination in pharmaceuticals
(2002) 279–282. and human serum, Talanta 54 (2001) 351–360.
[122] S. Erdurak-Kilic, B. Uslu, B. Dogan, U. Ozgen, M. Coskun, Anodic voltammetric [151] B. Uslu, S.A. Ozkan, Electrochemical characterisation of nefazodone
behavior of ascorbic acid and its selective determination in pharmaceutical hydrochloride and voltammetric determination of the drug in
dosage forms and some Rosa species of Turkey, J. Anal. Chem. 61 (2006) pharmaceuticals and human serum, Anal. Chim. Acta 462 (2002) 49–57.
1113–1120. [152] E.M.P.J. Garrido, J.M.P.J. Garrido, F. Borges, C. Delerue-Matos, Development of
[123] B. Nigovic, B. Simunic, Voltammetric assay of azithromycin in pharmaceutical electrochemical methods for determination of tramadol—analytical
dosage forms, J. Pharm. Biomed. Anal. 32 (2003) 197–202. application to pharmaceutical dosage forms, J. Pharm. Biomed. Anal. 32
[124] A. Radi, M.S. El-Shahawi, T. Elmogy, Differential pulse voltammetric (2003) 975–981.
determination of the dopaminergic agonist bromocriptine at glassy carbon [153] Z. Wang, H. Zhang, S. Zhou, W. Dong, Determination of trace metoclopramide
electrode, J. Pharm. Biomed. Anal. 37 (2005) 195–199. by anodic stripping voltammetry with Nafion modified glassy carbon
[125] S. Shahrokhian, M. Karimi, H. Khajehsharifi, Carbon-paste electrode modified electrode, Talanta 53 (2001) 1133–1138.
with cobalt-5-nitrolsalophen as a sensitive voltammetric sensor for detection [154] R.N. Goyal, V.K. Gupta, S. Chatterjee, A sensitive voltammetric sensor for
of captopril, Sens. Actuators B l109 (2005) 278–284. determination of synthetic corticosteroid triamcinolone, abused for doping,
[126] A. Radi, T. Elmogy, Differential pulse voltammetric determination of Biosens. Bioelectron. 24 (2009) 3562–3568.
carvedilol in tablets dosage form using glassy carbon electrode, II Farmaco [155] D. Lakshmi, P.S. Sharma, B.B. Prasad, Imprinted polymer-modified hanging
60 (2005) 43–46. mercury drop electrode for differential pulse cathodic stripping voltammetric
[127] R. Jain, V.K. Gupta, N. Jadon, K. Radhapyari, Voltammetric determination of analysis of creatine, Biosens. Bioelectron. 22 (2007) 3302–3308.
cefixime in pharmaceuticals and biological fluids, Anal. Biochem. 407 (2010) [156] M.Y. Khuhawar, F.M.A. Rind, A. Rajper, Determination of
79–88. phenylpropanolamine in pharmaceutical preparations by second derivative
[128] J.E. Belgaied, H. Trabelsi, Differential-pulse polarography determination of spectrophotometry, J. Food Drug Anal. 13 (2005) 388–391.
pipamperone in pharmaceutical formulations, J. Pharm. Biomed. Anal. 30 [157] H.P.A. Nouws, C. Delerue-Matos, A.A. Barros, J.A. Rodrigues, Electroanalytical
(2002) 1417–1423. study of the antidepressant sertraline, J. Pharm. Biomed. Anal. 39 (2005) 290–
[129] N. Adhoum, L. Monser, Determination of trimebutine in pharmaceuticals by 293.
differential pulse voltammetry at a glassy carbon electrode, J. Pharm. Biomed. [158] B. Dogan, S.A. Ozkan, Electrochemical behavior of carvedilol and its
Anal. 38 (2005) 619–623. adsorptive stripping determination in dosage forms and biological fluids,
[130] A.R. Fiorucci, E.T.G. Cavalheiro, The use of carbon paste electrode in the direct Electroanalysis 17 (2005) 2074–2083.
voltammetric determination of tryptophan in pharmaceutical formulations, J. [159] A.H. Al-ghamdi, M.A. Al-shadokhy, A.A. Al-warthan, Electrochemical
Pharm. Biomed. Anal. 28 (2002) 909–915. determination of cephalothin antibiotic by adsorptive stripping
[131] S. Jain, N.K. Jain, K.S. Pitre, Electrochemical analysis of sparfloxacin in voltammetric technique, J. Pharm. Biomed. Anal. 35 (2004) 1001–1009.
pharmaceutical formulation and biochemical screening of its Co (II) complex, [160] A.H. Alghamdi, F.F. Belal, M.A. Al-Omar, Square-wave adsorptive stripping
J. Pharm. Biomed. Anal. 29 (2002) 795–801. voltammetric determination of danazol in capsules, J. Pharm. Biomed. Anal.
[132] K. Girish Kumar, P. Augustine, R. Poduval, S. John, Voltammetric studies of 41 (2006) 989–993.
sparfloxacin and application to its determination in pharmaceuticals, [161] P. Manisankar, A. Sarpudeen, S. Viswanathan, Electroanalysis of dapsone, an
Pharmazie 61 (2006) 291–292. anti-leprotic drug, J. Pharm. Biomed. Anal. 26 (2001) 873–881.
[133] E. Nevin, Differential pulse anodic voltammetric determination of [162] S. Zhang, K. Wu, S. Hu, Voltammetric determination of diethylstilbestrol at
pantoprazole in pharmaceutical dosage forms and human plasma using carbon paste electrode using cetylpyridine bromide as medium, Talanta 58
glassy carbon electrode, Anal. Biochem. 323 (2003) 48–53. (2002) 747–754.
[134] A. Golcu, B. Dogan, S.A. Ozkan, Anodic voltammetric behavior and [163] F. Sayın, S. Kır, Analysis of diflunisal by electrochemical methods, J. Pharm.
determination of cefixime in pharmaceutical dosage forms and biological Biomed. Anal. 25 (2001) 153–163.
fluids, Talanta 67 (2005) 703–712. [164] M.M. Ghoneim, P.Y. Khashaba, A.M. Beltagi, Determination of trimetazidine
[135] T.M. Reddy, M. Sreedhar, S.J. Reddy, Voltammetric behavior of cefixime and HCl by adsorptive stripping square-wave voltammetry at a glassy carbon
cefpodoxime proxetil and determination in pharmaceutical formulations and electrode, J. Pharm. Biomed. Anal. 27 (2002) 235–241.
urine, J. Pharm. Biomed. Anal. 31 (2003) 811–818. [165] A.A. Kader Gazy, Determination of amlodipine besylate by adsorptive square-
[136] M.M. Aleksic, V. Kapetanovic, Voltammetric determination of cefotaxime in wave anodic stripping voltammetry on glassy carbon electrode in tablets and
urine, J. Electroanal. Chem. 593 (2006) 258–266. biological fluids, Talanta 62 (2004) 575–625.
[137] V.K. Gupta, A.K. Singh, Manoj K. Pal, Desipramine hydrochloride selective [166] P. Arranz, A. Arranz, J.M. Moreda, A. Cid, J.F. Arranz, Stripping voltammetric
poly (vinyl chloride) based sensor, Electrochim. Acta 55 (2010) 1068–1073. and polarographic techniques for the determination of anti-fungal
[138] M. Turchan, P. Jara-Ulloa, S. Bollo, L.J. Nunez-Vergara, J.A. Squella, A. Alvarez- ketoconazole on the mercury electrode, J. Pharm. Biomed. Anal. 33 (2003)
Lueje, Voltammetric behaviour of bromhexine and its determination in 589–596.
pharmaceuticals, Talanta 73 (2007) 913–919. [167] A.G. Cabanillas, J.M.O. Burguillos, M.A. Martinez Canas, M.I. Rodriguez
[139] S.A. Ozkan, B. Uslu, H.Y. Aboul-Enein, Voltammetric investigation of Caceres, F.S. Lopez, Square wave adsorptive stripping voltammetric
tamsulosin, Talanta 61 (2003) 147–156. determination of piromidic acid. Application in urine, J. Pharm. Biomed.
[140] F. Belal, A. Al-Majed, K.E.E. Ibrahim, N.Y. Khalil, Voltammetric determination Anal. 33 (2003) 553–558.
of josamycin (a macrolide antibiotic) in dosage forms and spiked human [168] V.K. Gupta, R. Jain, N. Jadon, K. Radhapyari, Adsorption of pyrantel pamoate
urine, J. Pharm. Biomed. Anal. 30 (2002) 705–713. on mercury from aqueous solutions: studies by stripping voltammetry, J.
[141] R.M. Kotkar, A.K. Srivastava, Voltammetric determination of para- Colloid Interface Sci. 350 (2010) 330–335.
aminobenzoic acid using carbon paste electrode modified with macrocyclic [169] A. Radi, Anodic voltammetric assay of lansoprazole and omeprazole on a
compounds, Sens. Actuators B 119 (2006) 524–530. carbon paste electrode, J. Pharm. Biomed. Anal. 31 (2003) 1007–1012.
[142] B. Dogan, B. Uslu, S. Suzen, S.A. Ozkan, Electrochemical evaluation of [170] A.M. Beltagi, Determination of the antibiotic drug pefloxacin in bulk
nucleoside analogue lamivudine in pharmaceutical dosage forms and form, tablets and human serum using square wave cathodic adsorptive
human serum, Electroanalysis 17 (2005) 1886–1894. stripping voltammetry, J. Pharm. Biomed. Anal. 31 (2003) 1079–1082.
[143] M. Aslanoglu, N. Peker, Potentiometric and voltammetric determination of [171] U. Tamer, N.P. Ozcicek, O. Atay, A. Yıldız, Voltammetric determination of
methimazole, J. Pharm. Biomed. Anal. 33 (2003) 1143–1147. cilazapril in pharmaceutical formulations, J. Pharm. Biomed. Anal. 29 (2002)
[144] H. Zhang, L. Xu, J. Zheng, Anodic voltammetric behavior of resveratrol and its 43–50.
electroanalytical determination in pharmaceutical dosage form and urine, [172] S. Yılmaz, Adsorptive stripping voltammetric determination of zopiclone in
Talanta 71 (2007) 19–24. tablet dosage forms and human urine, Colloids Surf. B 71 (2009) 79–83.
[145] B. Uslu, S.A. Ozkan, Z. Senturk, Electrooxidation of the antiviral drug [173] R. Jain, A. Dwivedi, R. Mishra, Stripping voltammetric behaviour of toxic drug
valacyclovir and its square-wave and differential pulse voltammetric nitrofurantoin, J. Hazard. Mater. 169 (2009) 667–672.
determination in pharmaceuticals and human biological fluids, Anal. Chim. [174] M. Arvand, M.A. Zanjanchi, A. Islamnezhad, Zeolite-modified carbon-paste
Acta 555 (2006) 341–347. electrode as a selective voltammetric sensor for detection of tryptophan in
[146] W. Gao, J. Song, N. Wu, Voltammetric behavior and square-wave pharmaceutical preparations, Anal. Lett. 42 (2009) 727–732.
voltammetric determination of trepibutone at a pencil graphite electrode, J. [175] M.A. Ghandour, E.A. Kasim, A.M.M. Ali, M.T. El-Haty, M.M. Ahmed, Adsorptive
Electroanal. Chem. 576 (2005) 1–7. stripping voltammetric determination of antihypertensive agent: diltiazem, J.
[147] H. Parham, B. Zargar, Square-wave voltammetric (SWV) determination of Pharm. Biomed. Anal. 25 (2001) 443–451.
captopril in reconstituted serum and pharmaceutical formulations, Talanta [176] M.S. El-Shahawi, A.S. Bashammakh, T. El-Mogy, Determination of trace levels
65 (2005) 776–780. of diosmin in a pharmaceutical preparation by adsorptive stripping
[148] J.A. Prieto, R.M. Jimenez, R.M. Alonso, Square wave voltammetric voltammetry at a glassy carbon electrode, Anal. Sci. 22 (2006) 1351–1354.
determination of the angiotensin-converting enzyme inhibitors cilazapril, [177] A. Navalon, R. Blanc, L. Reyes, N. Navas, J.L. Vílchez, Determination of the
quinapril and ramipril in pharmaceutical formulations, II Farmaco 58 (2003) antibacterial enrofloxacin by differential-pulse adsorptive stripping
343–350. voltammetry, Anal. Chim. Acta 454 (2002) 83–91.
[149] S. Shahrokhian, S. Bozorgzadeh, Electrochemical oxidation of dopamine in the [178] E.M. Ghoneim, H.S. El-Desoky, M.M. Ghoneim, Adsorptive cathodic stripping
presence of sulfhydryl compounds: application to the square-wave voltammetric assay of the estrogen drug ethinylestradiol in pharmaceutical
voltammetric detection of penicillamine and cysteine, Electrochim. Acta 51 formulation and human plasma at a mercury electrode, J. Pharm. Biomed.
(2006) 4271–4276. Anal. 40 (2006) 255–261.
Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196 195

[179] S. Skrzypek, W. Ciesielski, A. Sokołowski, S. Yilmaz, D. Kazmierczak, Square [206] A.H. Al-Ghamdi, A.F. Al-Ghamdi, M.A. Al-Omar, Electrochemical studies and
wave adsorptive stripping voltammetric determination of famotidine in square-wave adsorptive stripping voltammetry of spironolactone drug, Anal.
urine, Talanta 66 (2005) 1146–1151. Lett. 41 (2008) 90–103.
[180] M.M. Ghoneim, M.A. El-Attar, S.A. Razeq, Voltammetric quantitation at the [207] M.M. Ghoneim, M.A. El Ries, E. Hammam, A.M. Beltagi, A validated stripping
mercury electrode of the anticholinergic drug flavoxate hydrochloride in voltammetric procedure for quantification of the anti-hypertensive and
bulk and in a pharmaceutical formulation, Cent. Eur. J. Chem. 5 (2007) benign prostatic hyperplasia drug terazosin in tablets and human serum,
496–507. Talanta 64 (2004) 703–710.
[181] A.M.M. Ali, M.A. Ghandour, M.M. Abd-El Fattah, Cathodic adsorptive stripping [208] A.M. Beltagi, H.S. El-Desoky, M.M. Ghoneim, Quantification of terbutaline in
voltammetric determination of muscle relaxant: gallamine triethiodide pharmaceutical formulation and human serum by adsorptive stripping
(flaxedil), J. Pharm. Biomed. Anal. 25 (2001) 31–37. voltammetry at a glassy carbon electrode, Chem. Pharm. Bull. 55 (2007)
[182] N.T. Abdel Ghani, M.A. El-Ries, M.A. El-Shall, Validated polarographic 1018–1023.
methods for the determination of certain antibacterial drugs, Anal. Sci. 23 [209] M.M. Ghoneim, H.S. El-Desoky, M.A. El-Ries, A.M. Abd-Elaziz, Electrochemical
(2007) 1053–1059. determination of muscle relaxant drug tetrazepam in bulk form,
[183] E.M. Ghoneim, M.A. El-Attar, E. Hammam, P.Y. Khashaba, Stripping pharmaceutical formulation, and human serum, Chem. Papers 62 (2008)
voltammetric quantification of the anti-diabetic drug glipizide in bulk form 127–134.
and pharmaceutical formulation, J. Pharm. Biomed. Anal. 43 (2007) 1465– [210] A.M.R. Beltagi, M.A. El-Attar, E.M. Ghoneim, Adsorptive stripping
1469. voltammetric determination of the anti-inflammatory drug tolmetin in
[184] H.S. El-Desoky, M.M. Ghoneim, Assay of the anti-psychotic drug haloperidol bulk form, pharmaceutical formulation and human serum, Cent. Eur. J.
in bulk form, pharmaceutical formulation and biological fluids using square- Chem. 5 (2007) 835–845.
wave adsorptive stripping voltammetry at a mercury electrode, J. Pharm. [211] E. Hammam, Determination of triamcinolone acetonide in pharmaceutical
Biomed. Anal. 38 (2005) 543–550. formulation and human serum by adsorptive cathodic stripping
[185] A.M. Beltagi, O.M. Abdallah, M.M. Ghoneim, Development of a voltammetric voltammetry, Chem. Anal. 52 (2007) 43–53.
procedure for assay of the antihistamine drug hydroxyzine at a glassy carbon [212] S.I.M. Zayed, I.H.I. Habib, Adsorptive stripping voltammetric determination of
electrode: quantification and pharmacokinetic studies, Talanta 74 (2008) triprolidine hydrochloride in pharmaceutical tablets, Il Farmaco 60 (2005)
851–859. 621–625.
[186] M.M. Ghoneim, K.Y. El-Baradie, A. Tawfik, Electrochemical behavior of the [213] N. Sun, W. Mo, Z.L. Shen, B.X. Hu, Adsorptive stripping voltammetric
antituberculosis drug isoniazid and its square-wave adsorptive stripping technique for the rapid determination of tobramycin on the hanging
voltammetric estimation in bulk form, tablets and biological fluids at a mercury electrode, J. Pharm. Biomed. Anal. 38 (2005) 256–263.
mercury electrode, J. Pharm. Biomed. Anal. 33 (2003) 673–685. [214] I. Suslu, S. Altınoz, Electrochemical characteristics of zafirlukast and its
[187] M.E.B. Calvo, O.D. Renedo, M.J.A. Martínez, Optimization of the experimental determination in pharmaceutical formulations by voltammetric methods, J.
parameters in the determination of lamotrigine by adsorptive stripping Pharm. Biomed. Anal. 39 (2005) 535–542.
voltammetry, Anal. Chim. Acta 549 (2005) 74–77. [215] N.F. Atta, S.A. Darwish, S.E. Khalli, A. Galal, Effect of surfactants on the
[188] R. Jain, N. Jadon, K. Radhapyari, Cathodic adsorptive stripping voltammetric voltammetric response and determination of an antihypertensive drug,
studies on lamivudine: an antiretroviral drug, J. Colloid Interface Sci. 313 Talanta 72 (2007) 1438–1445.
(2007) 254–266. [216] J. Peng, Gao Zuo-Ning, Influence of micelles on the electrochemical behaviors
[189] A. Radi, Adsorptive stripping square-wave voltammetric study of the of catechol and hydroquinone and their simultaneous determination, Anal.
degradation of lansoprazole in aqueous solutions, Microchem. J. 73 (2002) Bioanal. Chem. 384 (2006) 1525–1532.
349–354. [217] J.B. Raoof, R. Ojani, F. Chekin, Electrochemical analysis of D-penicillamine
[190] A.K. Jain, V.K. Gupta, L.P. Singh, A solid membrane sensor for Hg2+ ions, Bull. using a carbon paste electrode modified with ferrocene carboxylic acid,
Electrochem. 12 (1996) 418–420. Electroanalysis 19 (2007) 1883–1889.
[191] M.M. Ghoneim, W. Baumann, E. Hammam, A. Tawfik, Voltammetric behavior [218] R. Jain, K. Radhapyari, N. Jadon, Electrochemical studies and determination of
and assay of the contraceptive drug levonorgestrel in bulk, tablets, and gastroprokinetic drug mosapride citrate in bulk form and pharmaceutical
human serum at a mercury electrode, Talanta 64 (2004) 857–864. dosage form, J. Electrochem. Soc. 155 (2008) F104–F112.
[192] J. Ghasemi, A. Niazi, R. Ghorbani, Determination of trace amounts of [219] G. Alarcon-Angeles, S. Corona-Avendano, M. Palomar-Pardave, A. Rojas-
lorazepam by adsorptive cathodic differential pulse stripping method in Hernandez, M. Romero-Romo, M.T. Ramirez-Silva, Selective electrochemical
pharmaceutical formulations and biological fluids, Anal. Lett. 39 (2006) determination of dopamine in the presence of ascorbic acid using sodium
1159–1169. dodecyl sulfate micelles as masking agent, Electrochim. Acta 53 (2008) 3013–
[193] K. Farhadi, A. Karimpour, Electrochemical determination of meloxicam in 3020.
pharmaceutical preparation and biological fluids using oxidized glassy [220] R. Jain, A. Dwivedi, R. Mishra, Adsorptive stripping voltammetric behavior of
carbon electrodes, Chem. Pharm. Bull. 55 (2007) 638–642. nortriptyline hydrochloride and its determination in surfactant media,
[194] O.A. Farghaly, M.A. Taher, A.H. Naggar, A.Y. El-Sayed, Square wave anodic Langmuir 25 (2009) 10364–10369.
stripping voltammetric determination of metoclopramide in tablet and urine [221] R. Jain, R.K. Yadav, A. Dwivedi, Square-wave adsorptive stripping
at carbon paste electrode, J. Pharm. Biomed. Anal. 38 (2005) 14–18. voltammetric behaviour of entacapone at HMDE and its determination in
[195] I.S. Ibrahim, I.S. Shehatta, M.R. Sultan, Cathodic adsorptive stripping the presence of surfactants, Colloids Surf. A 359 (2010) 25–30.
voltammetric determination of nalidixic acid in pharmaceuticals, human [222] R. Jain, R.K. Yadav, J.A. Rather, Voltammetric assay of anti-vertigo drug
urine and serum, Talanta 56 (2002) 471–474. betahistine hydrochloride in sodium lauryl sulphate, Colloids Surf. A 366
[196] D. Obendorf, G. Stubauer, Adsorptive stripping voltammetry of nicardipine at (2010) 63–67.
a HMDE; determination of trace levels nicardipine in blood and urine, J. [223] R. Jain, A. Dwivedi, R. Mishra, Effect of surfactant on voltammetric behaviour
Pharm. Biomed. Anal. 13 (1995) 1339–1348. of ornidazole, Colloids Surf. A 337 (2009) 74–79.
[197] E. Hammam, Determination of nitrofurantoin drug in pharmaceutical [224] R. Jain, A. Dwivedi, R. Mishra, Voltammetric behaviour of nitrazepam in
formulation and biological fluids by square-wave cathodic adsorptive solubilized system, J. Sci. Ind. Res. 68 (2009) 540–547.
stripping voltammetry, J. Pharm. Biomed. Anal. 30 (2002) 651–659. [225] V.K. Gupta, R.N. Goyal, R.A. Sharma, Novel alizarin sensor for determination
[198] M.M. Ghoneim, M. El-Ries, A.M. Hassanein, A.M. Abd-Elaziz, Voltammetric of vanadium, zirconium and molybdenum, Int. J. Electrochem. Sci. 4 (2009)
assay of the anthelmintic veterinary drug nitroxynil in bulk form and 156–172.
formulation at a mercury electrode, J. Pharm. Biomed. Anal. 41 (2006) 1268– [226] L. Codognoto, E. Winter, J.A.R. Paschoal, H.B. Suffredini, M.F. Cabral, S.A.S.
1272. Machado, S. Rath, Electrochemical behavior of dopamine at a 3,30 -
[199] M.M. Ghoneim, A.M. Abushoffa, Y.I. Moharram, H.S. El-Desoky, dithiodipropionic acid self-assembled monolayers, Talanta 72 (2007) 427–
Voltammetry and quantification of the contraceptive drug norethisterone 433.
in bulk form and pharmaceutical formulation, J. Pharm. Biomed. Anal. 43 [227] Z. Ping, W. Fang-Hui, Z.T. Guang-Chao, W. Xian-Wen, Selective response of
(2007) 499–505. dopamine in the presence of ascorbic acid at multi-walled carbon nanotube
[200] Y. Ni, Y. Wang, S. Kokot, Simultaneous determination of three fluoroquinolones modified gold electrode, Bioelectrochemistry 67 (2005) 109–112.
by linear sweep stripping voltammetry with the aid of chemometrics, Talanta [228] M. Zhang, K. Gong, H. Zhang, L. Mao, Layer-by-layer assembled carbon
69 (2006) 216–225. nanotubes for selective determination of dopamine in the presence of
[201] A. Radi, Determination of pantoprazole by adsorptive stripping voltammetry ascorbic acid, Biosens. Bioelectron. 20 (2005) 1270–1276.
at carbon paste electrode, Il Farmaco 58 (2003) 535–539. [229] X.Q. Lin, J.B. He, Z. Gen Zha, Simultaneous determination of quercetin and
[202] A.M. Beltagi, O.M. Abdallah, M.M. Ghoneim, Determination of piroxicam in rutin at a multi-wall carbon-nanotube paste electrodes by reversing
pharmaceutical formulations and human serum by square-wave stripping differential pulse voltammetry, Sens. Actuators B 119 (2006) 608–614.
voltammetry, Chem. Anal. 52 (2007) 387–392. [230] S. Shahrokhian, L. Fotouhi, Carbon paste electrode incorporating multi-walled
[203] B. Nigovic, Electrochemical properties and square-wave voltammetric carbon nanotube/cobalt salophen for sensitive voltammetric determination
determination of pravastatin, Anal. Bioanal. Chem. 384 (2006) 431–437. of tryptophan, Sens. Actuators B 123 (2007) 942–949.
[204] M.M. Ghoneim, M.M. Mabrouk, A. Tawfik, Direct determination of [231] K.J. Huang, D.F. Luo, W.Z. Xie, Y.S. Yu, Sensitive voltammetric determination of
praziquantel in pharmaceutical formulations and human plasma by tyrosine using multi-walled carbon nanotubes/4-aminobenzeresulfonic acid
cathodic adsorptive stripping differential-pulse voltammetry, J. Pharm. film-coated glassy carbon electrode, Colloids Surf. B 61 (2008) 176–179.
Biomed. Anal. 30 (2002) 1311–1318. [232] K. Wu, H. Wang, F. Chen, S. Hu, Electrochemistry and voltammetry of
[205] A. Radi, Adsorptive stripping square-wave voltammetric behavior of procaine using a carbon nanotube film coated electrode, Bioelectrochemistry
rofecoxib, Microchem. J. 72 (2002) 35–41. 68 (2006) 144–149.
196 Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196

[233] X.J. Tian, J.F. Song, Catalytic action of copper (II) ion on electrochemical [256] V.K. Gupta, P. Kumar, Cadmium (II)—selective sensors based on
oxidation of metformine and voltammetric determination of metformine in dibenzo-24-crown-8 in PVC matrix, Anal. Chim. Acta 389 (1999)
pharmaceuticals, J. Pharm. Biomed. Anal. 44 (2007) 1192–1196. 205–212.
[234] Q. Zhuang, J. Chen, J. Chen, X. Lin, Electrocatalytical properties of bergenin on [257] A.K. Singh, V.K. Gupta, B. Gupta, Chromium (III) selective membrane sensors
a multi-wall carbon nanotubes modified carbon paste electrode and its based on Schiff bases as chelating ionophores, Anal. Chim. Acta 585 (1)
determination in tablets, Sens. Actuators B 128 (2008) 500–506. (2007) 171–178.
[235] C. Wang, X. Shao, Q. Liu, Q. Qu, G. Yang, X. Hu, Differential pulse voltammetric [258] M.E. Lozano-Chaves, J.M. Palacios-Santander, L.M. Cubillana-Aguilera, I.
determination of nimesulide in pharmaceutical formulation and human Naranjo-Rodriguez, J.L. Hidalgo-Hidalgo-de-Cisneros, Modified carbon-paste
serum at glassy carbon electrode modified by cysteic acid/CNTs based on electrodes as sensors for the determination of 1,4-benzodiazepines:
electrochemical oxidation of l-cysteine, J. Pharm. Biomed. Anal. 42 (2006) application to the determination of diazepam and oxazepam in biological
237–244. fluids, Sens. Actuators B 115 (2006) 575–583.
[236] Li. Liu, Song Jun-feng, Yu Peng-fei, Cui Bin, A novel electrochemical sensing [259] B. Dogan, S. Tuncel, B. Uslu, S.A. Ozkan, Selective electrochemical behavior of
system for inosine and its application for inosine determination in highly conductive boron-doped diamond electrodes for fluvastatin sodium
pharmaceuticals and human serum, Electrochem. Commun. 8 (2006) 1521– oxidation, Diamond Relat. Mater. 16 (2007) 1695–1704.
1526. [260] R.T.S. Oliveira, G.R. Salazar-Banda, V.S. Ferreira, S.C. Oliveira, L.A. Avaca,
[237] R.N. Goyal, V.K. Gupta, Neeta Bachheti, Voltammetric determination of Electroanalytical determination of lidocaine in pharmaceutical preparations
adenosine and guanosine using fullerene-C60-modified glassy carbon using boron-doped diamond electrodes, Electroanalysis 19 (2007) 1189–
electrode, Talanta 71 (3) (2007) 1110–1117. 1195.
[238] R.N. Goyal, V.K. Gupta, M. Oyama, N. Bachheti, Differential pulse voltammetric [261] V.K. Gupta, A.K. Jain, L.P. Singh, U. Khurana, Porphyrins as carrier in PVC
determination of atenolol in pharmaceutical formulations and urine using based membrane potentiometric sensors for nickel (II), Anal. Chim. Acta 355
nanogold modified indium tin oxide (ITO) electrode, Electrochem. Commun. 8 (1997) 33–41.
(1) (2006) 65–70. [262] B. Uslu, B.D. Topal, S.A. Ozkan, Electroanalytical investigation and
[239] Z. Yuan-hai, Z. Zhi-ling, Z. Wei, P. Dai-wen, Voltammetric behavior and determination of pefloxacin in pharmaceuticals and serum at boron-
determination of phenylephrine at a glassy carbon electrode modified with doped diamond and glassy carbon electrodes, Talanta 74 (2008) 1191–
multi-wall carbon nanotubes, Sens. Actuators B 119 (2006) 308–314. 1195.
[240] C. Wang, J. Guan, Q. Qu, G. Yang, X. Hu, Voltammetric determination of [263] R.N. Goyal, M. Oyama, V.K. Gupta, S.P. Singh, S. Chatterjee, Sensors for 5-
sinomenine in biological fluid using a glassy carbon electrode modified by a hydroxytryptamine and 5-hydroxyindole acetic acid based on nanomaterial
composite film of polycysteic acid and carbon nanotubes, Comb. Chem. High modified electrodes, Sens. Actuators B 134 (2008) 816–821.
Throughput Screen. 10 (2007) 595–603. [264] R.N. Goal, V.K. Gupta, Sanghamitra Chatterjee, Simultaneous determination
[241] C. Wang, Y. Mao, D. Wang, G. Yang, Q. Qu, X. Hu, Voltammetric determination of adenosine and inosine using single-wall carbon nanotubes modified
of terbinafine in biological fluid at glassy carbon electrode modified by pyrolytic graphite electrode, Talanta 76 (3) (2008) 663–669.
cysteic acid/carbon nanotubes composite film, Bioelectrochemistry 72 (2008) [265] D. Zheng, J. Ye, L. Zhou, Y. Zhang, C. Yu, Simultaneous determination of
107–115. dopamine, ascorbic acid and uric acid on ordered mesoporous carbon/Nafion
[242] M. Aslanoglu, A. Kutluay, S. Abbasoglu, S. Karabulut, A poly (3- composite film, J. Electroanal. Chem. 625 (2009) 82–87.
acetylthiophene) modified glassy carbon electrode for selective [266] N. Nasirizadeh, H.R. Zare, Differential pulse voltammetric simultaneous
voltammetric measurement of uric acid in urine sample, Chem. Pharm. determination of noradrenalin and acetaminophen using a hematoxylin
Bull. 56 (2008) 282–286. biosensor, Talanta 80 (2009) 656–663.
[243] N. Yang, Q. Wan, X. Wang, Voltammetry of vitamin B12 on a thin self- [267] G. Guo, F. Zhao, F. Xiao, B. Zeng, Voltammetric determination of tetracycline
assembled monolayer modified electrode, Electrochim. Acta 50 (2005) 2175– by using multi-wall carbon nanotube-ionic liquid film coated glassy carbon
2185. electrode, Int. J. Electrochem. Sci. 4 (2009) 1365–1369.
[244] M. Korolczuk, K. Tyszczuk, Determination of folic acid by adsorptive [268] E.F. Batista, E.R. Sartori, R.A. Medeiros, R.C. Rocha-Filho, O. Fatibello-Filho,
stripping voltammetry at a lead film electrode, Electroanalysis 19 (2007) Differential pulse voltammetric determination of sildenafil citrate (ViagraÒ)
1959–1962. in pharmaceutical formulations using a boron-doped diamond electrode,
[245] A.K. Jain, V.K. Gupta, L.P. Singh, P. Srivastava, J.R. Raisoni, Anion recognition Anal. Lett. 43 (2010) 1046–1054.
through novel C-thiophenecalix[4]resorcinarene: PVC based sensor for [269] S. Chitravathi, B.E. Kumaraswamy, E. Niranjana, U. Chandra, G.P. Mamatha,
chromate ions, Talanta 65 (3) (2005) 716–721. B.S. Sherigara, An electrochemical cell configuration incorporating an ion
[246] A. Radi, Stripping voltammetric determination of indapamide in serum at conducting membrane separator between reference and working electrode,
castor oil-based carbon paste electrodes, J. Pharm. Biomed. Anal. 24 (2001) Int. J. Electrochem. Sci. 4 (2009) 223–237.
413–425. [270] M.A. Khalilzadeh, F. Khaleghi, F. Gholami, H. Karimi-Maleh, Electrocatalytic
[247] M.E. Burgoa Calvo, O. Dominguez Renedo, M.J. Arcos Martinez, Determination determination of ampicillin using carbon-paste electrode modified with
of lamotrigine by adsorptive stripping voltammetry using silver ferrocendicarboxylic acid, Anal. Lett. 42 (2009) 584–599.
nanoparticle-modified carbon screen-printed electrodes, Talanta 74 (2007) [271] E.A. Kasim, M.A. Ghandour, M.T. El-haty, M.M. Ahmed, Determination of
59–64. verapamil by adsorptive stripping voltammetry in urine and pharmaceutical
[248] N. Diab, A. AbuZuhri, W. Schuhmann, Sequential-injection stripping analysis formulations, J. Pharm. Biomed. Anal. 30 (2002) 921–929.
of nifuroxime using DNA-modified glassy carbon electrodes, [272] F. Ibrahim, N. El-Enany, Anodic polarographic determination of ciclopirox
Bioelectrochemistry 61 (2003) 57–63. olamine in pure and certain pharmaceutical preparations, J. Pharm. Biomed.
[249] C.Y. Wang, X.Y. Hu, G.D. Jin, Z.Z. Leng, Differential pulse adsorption Anal. 32 (2003) 353–359.
voltammetry for determination of procaine hydrochloride at a pumice [273] R.N. Hegde, S.T. Nandibewoor, Electrochemical oxidation of pentoxifylline
modified carbon paste electrode in pharmaceutical preparations and urine, and its analysis in pure and pharmaceutical formulations at a glassy carbon
J. Pharm. Biomed. Anal. 30 (2002) 131–139. electrode, Anal. Lett. 41 (2008) 977–991.
[250] R.M. Kotkar, P.B. Desai, A.K. Srivastava, Behavior of riboflavin on plain carbon [274] M.A. El-Ries, M.M. Abou-Sekkina, A.A. Wassel, Polarographic determination
paste and aza macrocycles based chemically modified electrodes, Sens. of propranolol in pharmaceutical formulation, J. Pharm. Biomed. Anal. 30
Actuators B 124 (2007) 90–98. (2002) 837–841.
[251] L. Wang, J. Bai, P. Huang, H. Wang, L. Zhang, Y. Zhao, Self-assembly of gold [275] M.A.N. El-Ries, G.G. Mohamed, A.K. Attia, Electrochemical determination
nanoparticles for the voltammetric sensing of epinephrine, Electrochem. of the antidiabetic drug repaglinide, Yakugaku Zasshi 128 (2008) 171–
Commun. 8 (2006) 1035–1041. 175.
[252] G.Z. Hu, D.P. Zhang, W.L. Wu, Z.S. Yang, Selective determination of dopamine [276] B. Hoyer, N. Jensen, Stabilization of the voltammetric serotonin signal by
in the presence of high concentration of ascorbic acid using nano-Au self- surfactants, Electrochem. Commun. 8 (2006) 323–328.
assembly glassy carbon electrode, Colloids Surf. B 62 (2008) 199–205. [277] M.E.B. Calvo, O.D. Renedo, M.J.A. Martinez, Determination of
[253] R.N. Goyal, V.K. Gupta, N. Bachheti, Gold nanoparticles modified indium tin oxcarbazepine by square wave adsorptive stripping voltammetry in
oxide electrode for the simultaneous determination of dopamine and pharmaceutical preparations, J. Pharm. Biomed. Anal. 43 (2007) 1156–
seroton: application in pharmaceutical formulations and biological fluids, 1160.
Talanta 72 (2007) 976–983. [278] K. Tyszczuk, Application of an in situ plated lead film electrode to the analysis
[254] R.N. Goyal, V.K. Gupta, N. Bachheti, Fullerene-C60-modified electrode as a of testosterone by adsorptive stripping voltammetry, Anal. Bioanal. Chem.
sensitive voltammetric sensor for detection of nandrolone, Anal. Chim. Acta 390 (2008) 1951–1956.
597 (1) (2007) 82–89. [279] H.M. Carapuca, D.J. Cabral, L.S. Rocha, Adsorptive stripping voltammetry
[255] R.N. Goyal, V.K. Gupta, M. Oyama, N. Bachheti, Differential pulse of trimethoprim: mechanistic studies and application to the fast deter-
voltammetric determination of paracetamol at nanogold modified indium mination in pharmaceutical suspensions, J. Pharm. Biomed. Anal. 38
tin oxide electrode, Electrochem. Commun. 7 (2005) 803–807. (2005) 364–369.

View publication stats