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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


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5 authors, including:

Vinod K Gupta Rajeev Jain

University of Johannesburg Jiwaji University


Keisham Radhapyari Nimisha Jadon

Central Ground Water Board, India Jiwaji University


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Analytical Biochemistry 408 (2011) 179–196

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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
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee (UK) 247 667, India
Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
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

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

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:, (V.K. Gupta). plines of analytical chemistry.

0003-2697/$ - see front matter Ó 2010 Elsevier Inc. All rights reserved.
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]
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]
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]
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]
Cefixime HMDE 4.6  108 M DPV PF, 0.58 [135]
Cefpodoxime 8.52  108 M HS 0.67
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]
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]
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]

(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]
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]
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]
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]
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]
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]
Methyl prednisolone NGITO 2.68  107 M DPV HS, HU 0.515 [255]
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]
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]
Nortriptyline HMDE 0.92 ng mL1 SWV,CV PF – [220]
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]
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]
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]
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]
Resveratrol HMDE 5.0  109 to 1.65  107 M CV PF, HU 0.7 [215]
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]
Salbutamol NGITO 75 ng mL1 SWV PF, HU, 0.575 [257]
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
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]
Valacyclovir GC 1.04  107 and 4.6  108 M DPV, PF, HS – [145]
Verapamil GC 1.61  107 M DPV PF, HS – [103]
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]
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
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]
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]
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
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-
tration and scan rate of sodium levothyroxine was studied. The
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