Voltammetric techniques for the assay of

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 Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia c School of Studies in Chemistry, Jiwaji University, Gwalior 474011, India b

Vinod K. Gupta

Rajeev Jain

Keisham Radhapyari

Nimisha Jadon

Shilpi Agarwal

Dr. Vinod K. Gupta obtained his Ph.D. degree in chemistry from the University of Roorkee (now Indian Institute of Technology, Roorkee), Roorkee, India, in 1979. Since then he is pursuing research at the same institute and currently is a Professor of physical chemistry. He has worked as postdoctoral fellow at University of Regensburg, Germany, in the year 1993 as an EC fellow and was DAAD visiting professor at University of Chemnitz and Freie University of Berlin in the year 2002. He is a highly cited researcher in Environmental Engineering and received the Indian Citation Laureate Award 2004. Dr. Gupta has published one book, 10 book chapters, 15 reviews and 275 research papers in highly reputed journals. His papers have received more than 6500 citations with h index of 45. He is KFUPM Chair Professor at King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia. His research interests include chemical sensors and biosensors, waste water treatment, environmental and electro-analytical chemistry. He is Fellow of the World Innovation Foundation (FWIF) and The National Academy of Sciences, India (FNASc). Dr. Rajeev Jain obtained his Ph.D. degree in chemistry from the University of Roorkee (now Indian Institute of Technology, Roorkee), Roorkee, India, in 1978 and worked as Post Doctoral Fellow and Research Associate at the same institute. He joined Jiwaji University, Gwalior, India in 1982 as lecturer and at present working as Professor of Analytical Chemistry at the same University. He was awarded D.Sc. degree by Jiwaji University, Gwalior, India in 1990. He is a highly cited researcher in Electroanalytical Chemistry. Dr. Jain has published over 270 research papers in journals of high impart factor. He has supervised over 60 Ph.D. students and one D.Sc. student. He is a widely traveled researcher and has completed 15 research projects. His research interests include Electro-analytical behavior of pharmaceuticals, method development and validation, and waste water treatment. Dr. Keisham Radhapyari obtained her Ph.D degree in Chemistry from Jiwaji University, Gwalior, India in the year 2008. She joined North East Institute of Science and Technology (NEIST), Jorhat, India as Young Scientist in Analytical Chemistry Division in the year 2009. She is working on development of biosensors electrodes for the determination of organic compounds of pharmaceutical significance. Dr. Nimisha Jadon is working as a research associate at Centre for Science & Environment (CSE), New Delhi, India. She has done her post-graduation in environmental chemistry in 2002 and Ph.D. in chemistry in 2008, from Jiwaji University, Gwalior, India. Shilpi Agarwal obtained her M. Sc. degree in Chemistry in the year 2004 and since 2006 persuing research in the areas of chromatography and electroanalytical chemistry at School of Studies in Chemistry, Jiwaji University, Gwalior, India. She successfully completed the research work and submitted the thesis for the award of Ph.D. degree in the year 2010.

Analytical Chemistry plays a critical role in the development of a compound from its synthesis stage to its marketing stage as a part of a drug formulation and analysis. The instrumental methods ⇑ Corresponding author at: Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee (UK) 247 667, India. Fax: +91 1332 273560. E-mail addresses: [email protected], [email protected] (V.K. Gupta). 0003-2697/$ - see front matter Ó 2010 Elsevier Inc. All rights reserved. doi:10.1016/j.ab.2010.09.027

for quantitation which are most commonly used in a pharmaceutical laboratory fall into four basic categories: chromatography, spectrophotometric, electrochemical, and radiometric analysis [1]. Electroanalytical chemistry along with the use of oxidation– reduction reactions and other charge-transfer phenomena had its origins eight decades ago. It is one of the fundamental subdisciplines of analytical chemistry.

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

In the 1920s, Czech scientist Jaroslav Heyrovsky discovered voltammetry, a form of electrochemistry, in which samples were analyzed by measuring current as a function of the applied electrical potential. A quarter century later, on October 26, 1959, Jaroslav Heyrovsky was awarded the Nobel Prize in Chemistry for his discovery of the polarographic methods of analysis [2]. In the last eight decades, voltammetric methods have become a popular tool for the study of electrochemical reactions [3], for the study of electrochemically generated free radicals [4], in model studies of enzymatic catalysis [5], in coordination chemistry [6], in solar energy conversion [7], in environmental monitoring [8], in industrial quality control [9], and in the determination of trace concentrations of biological and clinically important compounds [10,11]. Till now, the commonly employed techniques for the determination of the drug in bulk form, pharmaceutical formulation, and biological fluids are based on HPLC [12], LC/MS [13], spectroscopy [14], and microbiological assays [15]. Such techniques for the measurement of biological concentration are necessary in a clinical environment to ensure that adequate drug levels can be maintained while avoiding toxic concentrations of such drugs. The problems encountered using such methods are either the need for derivatization or the need for time-consuming extraction procedures. Since these techniques have expensive instrumentation and running costs, the use of simpler, faster, and cheaper, yet sensitive, electrochemical techniques can be interesting alternatives, especially those based on electroanalytical techniques. Electrochemistry has many advantages, making it an appealing choice for pharmaceutical analysis [16,17]. Electrochemistry has always provided analytical techniques characterized by instrumental simplicity, moderate cost, and portability. These techniques have introduced the most promising methods for specific applications [18–24]. Due to similarity in the electrochemical and biological reactions, it can be assumed that the oxidation/reduction mechanisms taking place at the electrode and in the body share similar principles. Biologically important molecules can be investigated electroanalytically by voltammetry in order to determine the molecule in different ways. Additional applications of electrochemistry include the determination of electrode mechanisms. The redox properties of drugs can give us insight into their metabolic fate in in vivo redox processes or pharmacological activity [25]. Further, the electroanalytical techniques have been shown to be excellent for the determination of pharmaceutical compounds in different matrices. Many of the active constituents of formulations, in contrast to excipients, can be readily oxidized. The selectivity of this method is normally excellent because the analyte can be readily identified by its voltammetric peak potential. Advances in experimental electrochemical techniques in the field of analysis of drugs are because of their simplicity, low cost, and relatively short analysis time compared to other techniques. The use of various electrodes, viz. mercury [26–42], solids [9,43–61], and modified electrodes [20,62–70], for electroanalytical measurements has increased in recent years because of their applicability to the determination of active compounds that undergo oxidation reactions, which is a matter of great importance in the field of clinical and pharmaceutical analysis. Ozkan and co-workers [71] critically reviewed the application of modern electroanalytical techniques (potentiometry, on-line or hyphenated voltammetry, voltammetry) in the analysis of pharmaceuticals and biological fluids. The authors reviewed about 200 papers starting from 1995 to 2000. The use and advantages of techniques to pharmaceutical compounds in dosage forms and biological media were discussed. However, the review did not clearly provide the matrix in which pharmaceuticals were analyzed. Fur-

thermore, important information, like the peak potential of the electroactive substance, was not included. The present study reviews the various applications of voltammetry to pharmaceutical analysis covering the period from 2001 to 2010. The present review includes the voltammetric determination of pharmaceuticals of various classes, viz. antibiotics [72–79], antiemetics [46,47], antiamoebic [80], hypolipidemic [81–83], antipsychotic [84,85], cardiovascular [86–89], hypoglycemic [90], analgesics [91–95], coagulants [96], antiplatelet [97], anthelmintic [98], sedatives [58,99], gastrointestinal [34,100], antidepressant [101,102], antiarrhythmic [103], opioid analgesics [104], vitamins [105–107], anticholinesterase [108], antiadrenergic [109], antiparkinsonian [110], antiallergics [111], and others. The review is divided into four sections. The first deals with various applications of nonstripping voltammetric techniques using linear sweep voltammetry (LSV),1 cyclic voltammetry (CV), differential pulse voltammetric (DPV), and square-wave voltammetry (SWV) in pharmaceutical analysis. The second section covers the application of sensitive stripping techniques in pharmaceutical analysis. The third part deals with the effectiveness of surfactants in the electroanalysis of biological compounds and drugs. Finally, the fourth section of the review is devoted to the use of chemically modified electrodes in the analysis of pharmaceuticals. The third and fourth sections of this review were not taken in detail by Ozkan and co-workers. Additionally, another interesting feature of this review, which is worth noting, is that the names of drugs along with the peak potential (Ep) and matrix are sorted in ascending order in Tables 1 and 2. This makes the table user friendly.

1 Abbreviations used: AAdSV, anodic adsorptive stripping voltammetry; AC, acetaminophen; AdCSV, adsorptive cathodic stripping voltammetry; AdLSCSV, adsorptive linear sweep cathodic stripping voltammetry; AdS, adsorptive stripping; AdSACV, adsorptive stripping alternating current voltammetry; AdSDPV, adsorptive stripping differential pulse voltammetry; AdSLSV, adsorptive stripping linear sweep voltammetry; AdSSWV, adsorptive stripping square-wave voltammetry; AdSSWV, adsorptive stripping square-wave voltammetry; AdSV, adsorptive stripping voltammetry; AMPC, ampicillin; ASDPV, anodic stripping differential pulse voltammetry; 5-ASA, 5-aminosalicyclic acid; ASV, anodic stripping voltammetry; Au, gold; BUS, buspirone hydrochloride; BR, Britton-Robinsons; BDD, boron diamond doped; BF, bulk form; BS, blood sample; CAdSDPV, cathodic adsorptive stripping differential pulse voltammetry; CAdSV, cathodic adsorptive stripping voltammetry; CGME, controlled growth mercury electrode; CP, carbon paste; CP, carbon paste; CSSWV, cathodic stripping square-wave voltammetry; CSV, cathodic stripping voltammetry; CV, cyclic voltammetry; CTAB, cetyl trimethylammonium bromide; DC, direct current; DME, dropping mercury electrode; DPAdCSV, differential pulse adsorptive cathodic stripping voltammetry; DPAdSV, differential pulse adsorptive stripping voltammetry; DPAdV, differential pulse adsorptive voltammetry; DPCAdS, differential pulse cathodic adsorptive stripping; DPCSV, differential pulse cathodic stripping voltammetry; DPP, differential pulse polarography; DPSV, differential pulse stripping voltammetry; DPV, differential pulse voltammetry; ENRO, enrofloxacin; FDCMCPE, ferrocenedicarboxylic acid; GC, glassy carbon; GCRDE, glassy carbon rotating disk electrode; GE, graphite electrode; GNP, gold nanoparticle; HB, human blood; HMDE, hanging mercury drop electrode; HS, human serum; HU, human urine; ISO, isorhamnetin; LSAAdSV, linear sweep anodic adsorptive stripping voltammetry; LSAdCSV, linear sweep adsorptive cathodic stripping voltammetry; LSAdSV, linear sweep adsorptive stripping voltammetry; LSSV, linear sweep stripping voltammetry; LSV, linear sweep voltammetry; MCP, modified carbon paste; MGC, modified glassy carbon; MGE, modified graphite electrode; MWCNT, multiwalled carbon nanotube; NA, noradrenalin; NGITO, nanogold indium tin oxide; NGMITO, nanogold modified indium tin oxide; NPV, normal pulse voltammetry; OMC, ordered mesoporous carbon; OSWSV, Osteryoung square-wave stripping voltammetry; OSWV, Osteryoung square-wave voltammetry; PIR, Piribedil; PF, pharmaceutical formulation; PGE, pencil graphite electrode; Pt, platinum; SDS, sodium dodecyl sulfate; SMDE, static mercury drop electrode; SODASV, second-order differential anodic stripping voltammetry; SP, spiked plasma; SWAdASV, square-wave adsorptive anodic stripping voltammetry; SWAdCSV, square-wave adsorptive cathodic stripping voltammetry; SWAdSV, square-wave adsorptive stripping voltammetry; SWASV, square-wave anodic stripping voltammetry; SWCAdS, square-wave cathodic adsorptive stripping; SWCSV, square-wave cathodic stripping voltammetry; SWSV, square-wave stripping voltammetry; SWV, square-wave voltammetry; TC, tetracycline; TX-100, Triton X-100; ZP, zopiclone.

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

Detection/determination limit/conc. range

Methods

Matrix

Ep (V)

References

5-Aminosalicyclic acid

GC

1  104 to 2  106 M

LSV DPV DPV, SWV

PF

–

[16]

PF HU HS PF PF, HS PF PF, HU PF, HU PF PF

–

[17]

– – – 0.6 0.99 1.0 +0.99 –

[18] [19] [20] [21]

480 mV – 1.04 0.47 0.90 0.8

[269] [122] [62] [253]

Abacavir

GC

Acetaminophen Acetaminophen Acetaminophen Acrivastine

GC MGC MGC DME

Acrivastine Albendazole Amoxicillin

DME GCRDE MCP

Ampicillin Ascorbic acid Atenolol Atenolol

7

4

8  10 to 2  10 M 1  105 to 1  104 M 2  105 to 2  104 M 3.0 lg mL1 1.7  105 M 4  108 M 0.11 mg L1

CV CV CV DPP

Modified carbon-paste electrode – MGC NGMITO

0.03 lg mL1 2.4  105 M 24.8  106 M 16.6  106 M 8.49  106 M 2.34–30 mmol L1 and 40–700 mmol L1 0.88 lg mL1 0.16  10103 M 0.13  106 M

DPP LSV LSV DPV SWV DPV DPV SWV DPV

Azithromycin Azithromycin Benorilate Bergenin Bromhexine Bisoprolol fumarate Bromocriptine Betahistine Captopril Captopril Carvediol Catechol hydroxyquinone

GC GC MCP MCP GC MGC GCE GCE SMDE CP GC GC

9.24  107 M – 1  108 M 7  108 M 1.4  105 M 8.27  107 M 0.01 lg mL1 250 to 3500 lg mL1 6.28  103 lg mL1 1.1  106 M 0.10 lg mL1 3  106 M

CV/DPV CV DPV DPV DPV DPV DPV SWV SWV CV, DPV CV, DPV CV, DPV

Cefdinir Cefixime

DME –

8  106 M 0.3  106 M 6.0  106 to 2.0  104 M

DPP DPV

Cefixime Cefpodoxime Proxetil Cefotaxime

HMDE

4.6  108 M 8.52  108 M

GC, CP

Cefotriaxone Chlorphenoxamine Hydrochloride Ciclopirox Olamine Cilazapril Quinapril and ramipril Cisatracurium Clofibric Ofloxacin Diclofenac Propranolol Coenzyme Q10 Diazepam Diazepam Temazepam Oxazepam Diclofenac Diethylstilbestrol Dipyridamole Domperidone Domperidone Dopamine

MGC GCE, PE

2  105 M to 1  104 M 2  104 M to 6  104 M 4.03  106 M 4.5  104 to 1.0  102 mol L1

DME HMDE CP DME

GC DME, HMDE CP

Donepezil

CP, GoE, CNP CP HMDE GC GC Ordered mesoporous carbon (OMC)/ Nafion composite film GC

Dopamine Dopamine Dopamine Dopamine

GC CP NGGC NGITO

0.2 lg mL1 0.5–8 lg mL1 0.5–6 lg mL1 0.38 lg mL1 4.7  106 M 5.2  106 M 0.8  106 M 0.5  106 M 12 mg mL1 9.6  109 M 0.021 lg mL1 0.021 lg mL1 0.012 lg mL1 8.0  106 M 1.0  108 M 1.88  108 M 4.0  107 M 6.1  107 M – 1  106 to 1  104 M 0.08  106 M 5  106 M 4  109 M 0.5  109 M

SWV DPV

PF, HU PF PF, HU PF, HU PF PF, PF, PF PF, PF PF PF, PF, PF PF

HU HU HU

HS HS

PF PF, HS, HU

[22] [23] [24]

0.97 – – 0.95 0.6 1.5 0.7 0.65 – 0.4 V

[123] [43] [63] [234] [138] [225] [124] [162] [147] [125] [126] [216]

0.3 V 0.6 0.85

[127] [134]

PF, HS

0.58 0.67

[135]

CV, SWV

PF

1.15

[136]

CV, DPV CV, DPV

HS PF

– –

[137] [116]

DC, DPP SWV

PF PF

0.4 –

[272] [148]

DPV DPP

HU, HS BF

0.45 –

[44] [26]

DPV CV DPV

PF PF HP, HU

[45] [27] [258]

NPV CV, LSV SWV DPV DPV –

BF BF PF PF PF –

0.02 – 1.3 0.87 0.90 0.84 – – 0.64 – –

[91] [162] [28] [46] [47] [265]

DPV, SWV SWV DPV DPV SWV

PF, HS

–

[48]

PF PF PF PF, HS, HU

– – 0.175, 0.146 0.7, 0.24

[149] [219] [252] [254]

(continued on next page)

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

Table 1 (continued) Name of drug

Indicator electrode

Detection/determination limit/conc. range 3  109 M 0.35  105to 3.4  105 M 0.02  106 M 2  107 M – – 6.04  105 M 6.15  106 M – 10.0–80.0 nmol L1 with a detection limit of 0.33 nmol L1 – 6  108 M 3.0  108 M 0.4–4  106 M 6.8  107 M 1. 1  106 M 1  107 M 5  104 mol L1 to 1.8  105 mol L1 5.2  105 M 5  106 M 5  105 M 5  105 to 5  104 M 0.4 to 3.6 lg mL1 0.4 to 2.4 lg mL1 1  106 M

Serotonin Dopamine Dopamine Dopamine Dopamine Doxazosin D-Penicillamine

MGE HMDE MWCNT MWCNT RPE MCP

Droxicam Enrofloxacin

HMDE HMDE

Entacapone Epinephrine Ethinylestradiol Ethopropazine Etodolac

– MGE CP GE GC

Etoposide Entacapone Fenbendazole

CP HDME GC

Finasteride Floctafenine Metopimazine Fluoxetine

DME HMDE GC

Flupenthixol Fluvastatin sodium Ganciclovir

GC BDD GC

Guaifenesin Hydrochlorothiazide Hydroxychloroquine Hyoscine

PE GC GC Pt

Indinavir

HMDE

Inosine Isoprenaline Isoxsuptine Formoterol Isradipine

MCP CP GC

8  107 to 8  106 M 8  107 to 1  105 M 8.3  1010 M 8  105 M 6  108 to 6  105 M

DME

2.7  108 M

1.17  107 M 1.37  107 M 4.52  108 M 8.1  108 M 20–60 lg mL1 5 ng mL1, 14 ng mL1 11.2 lg mL1 1  106 to 1  103 M

8

7

Methods

Matrix

Ep (V)

References

SWV SWV DPV SWV DPV CV DPV CV SWV

PF PF PF PF PF PF

– 0.9 0.2 0.2 – –

[226] [29] [227] [228] [109] [217]

– PF

– 0.10 V

[112]

DC, DPV CV LSV CV DPV SWV DPV SWV,CV LSV DPV SWV DPP DC, DPP

PF PF PF BF PF, HS

– – 0.59 0.67 –

[110] [251] [120] [113] [150]

PF PF PF

– 0.25 +1.2

[49] 221 [121]

PF PF

1.25 1.05 to 1.27

[30] [31]

DPV, SWV DPV DPV SWV DPV CV DPV DPV DPV

PF

0.9

[9]

PF, HS PF, HS PF, HS

– – +1.2

[51] [259] [51]

PF PF, HU PF PF, HS, HU PF, HS

0.924 +1.05 +1.4 –

[52] [53] [54] [55]

–

[32]

PF, HS PF PF, HS

+0.20 – –

[236] [50] [57]

PF, HU, HU PF PF, HU PF, HS

0.6

[33]

– 1.1 1.26

[115] [140] [142]

PF PF

– –

[34] [237]

PF PF PF, SP

1.68 – –

[260] [58] [35]

PF, HS PF – PF PF PF, HS, HU HS, HU

1.088 1.088 – – +0.8 –

[238] [36] [37] [233] [143] [10]

0.515

[255]

BF, PF PF

1.1 1.2

[218] [92]

– – –

[74] [93] [151]

DPV LSV – CV DPV, SWV DPP

Isorhamnetin Josamycin Lamivudine

GC DME HMDE

1.0  10 to 4.0  10 M 1.9  106 M 8.65  108 and 6.36  108 M

Lansoprazole L-Dopa Carbidopa

SMDE MCP

Lidocaine Melatonin Meloxicam

BDD CP SMDE

0.03 lg mL1 2.5  105 M 3.7  106 M 10 lg L1 2.3  106 M 0.38 to 15 lg mL1

Meloxicam Meloxicam Meloxicam Metformin Methimazole Methyl prednisolone

MGC HMDE DME MWCNT Pt MGC

1.5  109 M 1  108 to 5  106 M 1  105 M 6.7  108 M 1  106 to 700  106 M 5.6  109 M

SWV CV CV, DC, DPP – DPV DPV – SWV DPV

Methyl prednisolone Citrate Mosapride citrate Nabumetone

NGITO

2.68  107 M

DPV

Natamycin Naproxen Nefazodone HCl

Pt –

CP PE GC

1

0.05 lg mL 7.65  108 M 3.6  108 M 2.31  107 M 2.53  107 M 2.68  107 M 2.5  107 M 1.5  106 M 0.24 lg mL1 2.1  107 M

CV DC, DPP DPV, OSW DPV DPV

SWV DPV OSW DPV OSW DPV OSW DPV DPV DPV

HS HU PF PF PF, HS

183

Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196 Table 1 (continued) Name of drug

Indicator electrode

Detection/determination limit/conc. range

Methods

Matrix

Ep (V)

References

Niocotinic acid and nicotinamide

PGE

1.17  107 M 0.27  106 M

SWV CV

PF

0.20

[81]

Nilvadipine

DME

0.4

[38]

MGC DME PMRE HMDE

PF, HS PF PF PF

1.25 1.3 – –

[235] [39] [118] [173]

Nortriptyline Hydrochloride Noradrenalin Nitrazepam Olsalazine-Na Ornidazole Pantoprazole Para-aminobenzoic acid Paracetamol Paracetamol Pefloxacin

HMDE

0.92 ng mL1

DPP DC DPV CV LSV CV, SWCAdSV SWV,CV

PF, HU

Nimusilide Nitroimidazopyran Norfloxacin Nitrofurantoin.

0.33  106 M 0.2 –10 lg mL1 1.5–20 lg mL1 5.0  108 M – 1  107 M 0.06 and 0.27 ng mL1

PF

–

[220]

GCE DME GC DME GCE MCP

0.04 and 0.15 ng mL1 5.75  107 M 4.0  103 to 4.0  106 mo L1 4  107 M 0.1 lg mL1

DPV DPP DPV DPV, CV DPV DPV

PF PF PF PF, HP PF

– – – – 0.98

[266] [224] [100] [223] [133] [141]

NGMITO MGC BDD, GC

1.8  107 M 0.05  106 to 1.5  106 M 2  106 to 2  104 M

PF HU PF, HU PF, HS

0.83 – 1.2

[256] [261] [262]

Pentoxifylline Phenylephrine Pipamperone Piribedil

GC MGC HMDE GC

BF, PF PF PF PF, HS

– – 1.4 1.1

[273] [239] [128] [104]

Piroxicam Procaine Propranolol Pyrantel pamoate Pyridoxine HCl Pyrantel pamoate Pyridostigmine bromide Quercetin

CNP MGC SMDE DME MCP Polymer membrane –

4.42  1010 M 3  108 M 3  106 M 2  106 to 1  103 M 2  106 to 8  104 M 0.1 lg mL1 2  107 M 5  109 M 2.45  105 M 0.4 lg mL1 – –

DPV – DPV, SWV DPV – DPP DPV SWV DPV – DPP CV, DPP DPV – –

PF PF PF PF PF – –

0.5 – 0.275 1.36

[94] [232] [274] [98] [64] [264] [263]

MWCNT

0.05–5 lM

RDPV

PF

0.155 V, 0.36 V, 0.316 V

DPV SWV DPV SWV DPV SWV CV, LSV,DPV CV SWV DPV

HS

Rabeprazole

GC

0.1–10 lM 4  108 M 1.33  107 M 6.20  107 M 5.92  107 M 1.44  107 M 1.31  107 M 4  107 M

Resveratrol

HMDE

5.0  109 to 1.65  107 M

Rutine Quetiapine

Repaglinide

GC

7

Rutine

CP GC GC, CP, PE

1.348  10 1.062  107 M 106 to 105 M

Salbutamol

NGITO

75 ng mL1

Salicylic acid Serotonin Tryptophan Simvastatin

GC GC MCP GC

Sinomenine Sparfloxacin Sparfloxacin Tamsulosin

MGC DME GC GC

Terazosin HCl Terbinafine Tetracycline Thalidomide Ticlopidine Tramadol Trazodone HCl

GC MGC – SMDE, HMDE, GC HMDE – DME

1

1–60 lg mL – 1  107 M 2.71  107 M 5.5  107 M 5  108 M – – 3.34  107 2.45  107 M 6  107 M 4.58  109 M 2.5  108 M – – 5.17  107 M 2.2  106 M 0.104 lg mL1

CV, LSV, DPV SWV CV, DPV SWV DPV DPV SWV DPV DC, DPP DPV DPV, SWV CV, DPV DPV – CV SWV SWV DC

– –

[229]

[84]

HU PF PF

–

[275]

PF, HU

0.7

[215]

PF, HS

–

[275]

PF

–

[96]

PF, HU, HP PF PF PF, HU PF, HS

0.575

[257]

– – 0.9 –

[121] [276] [230] [82]

HS BF PF PF, HS

0.632 – – 1.3

[240] [131] [132] [139]

PF

1.0

[188]

PF, HS – BF PF PF PF, HU,

1.15 – 0.65 0.01 – 1.0

[241] [267] [114] [97] [152] [101] (continued on next page)

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Table 1 (continued) Name of drug

Indicator electrode

Detection/determination limit/conc. range

Methods

Trepibutone Trimebutine Tryptophan Tryptophan Tryptophan Tyrosine Uric acid

PGE GC CP MCP zeolite beta to the carbon paste MGC MGC

0.314 lg mL1 20 ng mL1 0.3  106 M 1. 7  106 M 1.0  107 M 5.0–107 to 5.0–103 M 8  107 M 5.27  107 M

DPP SWV DPV DPV DPV

Valacyclovir

GC

1.04  107 and 4.6  108 M

Verapamil

GC

1.61  107 M

Matrix

Ep (V)

References

[146] [129] [130] [230] [174] [231] [242]

PF, HS

0.06, 1.24 1.39 – 0.8 – 0.6 0.03 0.32 –

PF, HS

–

[103]

DC, DPP

PF

[105]

CV, LS, DPV –

PF

1.22 1.2 1.68 –

[107]

CV

PF

0.756 0.444 0.41

HP

7

Vitamins Vitamins Vitamins Vitamins

B1 B2 B6 6

Vitamins E Silymarin Vitamins 12

1.33  10 –

GC

1  107 M

–

0.03 mg mL1 0.01 mg mL1 1  109 M

Nonstripping voltammetric techniques Cyclic and linear sweep voltammetry Cyclic voltammetry is often the first experiment performed in an electrochemical study of a compound, a biological material, or an electrode surface. It is effectively used in the fields of environmental electrochemistry, organic chemistry, inorganic chemistry, and biochemistry. The effectiveness of CV results from its capability for rapidly observing the redox behavior over a wide potential range. The resulting voltammogram is analogous to a conventional spectrum in the sense that it conveys information as a function of an energy scan. Cyclic voltammetry has become a popular tool since the last 40 years for studying electrochemical reaction. CV is perhaps the most versatile electroanalytical technique in pharmaceutical analysis [27,112]. It is often the first experiment performed in an electrochemical study of drugs in raw material [113,114], pharmaceuticals [50,52,58], and biological material [39]. The formation and stability of the radical anion from PA-824 and its comparison with metronidazole were carried out by Bollo et al. [39] by using CV. Acuna et al. [112] used CV for studying the kinetics of the hydrolytic decomposition of droxicam and for establishing the possible pharmacological action of the drug in an organism of the human being. Acetaminophen [18] in paracetamol tablets was determined by using CV in phosphate buffer with a good linear calibration range of 3–240 lg mL1. The CV method is in good agreement with the USPXXII official method. Wang et al. [81], by employing CV along with bulk electrolysis, deduced the redox reaction mechanisms of nicotinic acid and nicotinamide in which it was rationalized by the formation/disappearance of the new nitrogen–oxygen bonds in pyridine rings. Liu and co-workers had studied the electrochemical behavior of isorhamnetin at a glassy carbon electrode by cyclic voltammetry. Under optimal conditions, the oxidation peak current showed a linear dependence on the concentration of ISO in the range of 1.0  108 to 4.0  107 and 1.0  106 to 1.0  105 M. This method has been successfully applied to the detection of ISO in tablets [115]. Voltammetric methods have been used for the determination of chlorphenoxamine hydrochloride (Ch-HCl) in raw material and in its pharmaceutical preparations (Allergex and Allergex caffeine tablet). It was found that Ch-HCl gives a characteristic cyclic

DPV, SWV DPV OSWV

[145]

M

DME

MGC

CV, DPV SWV

PF PF PF PF PF PF HU

PF

[106]

[244]

voltammetric and differential pulse voltammetric peak in acetonitrile using platinum and glassy carbon working electrodes. The Ip of the DPV peak increases linearly within the concentration range from 4.5  104 to 1.0  102 mol L1 of the investigated drug. The concentration of Ch-HCl in raw drug material and in its pharmaceutical preparations was determined using the standard addition method, the Randles–Sevcik equation, and indirectly via its complexation with sodium tetraphenylborate (NaTPB). The obtained overall average recoveries were 101.44% and 100.49% with SD 0.45 and 0.38 (n = 4) for platinum and glassy carbon electrodes, respectively. The effect of scan rate, sample concentration, and supporting electrolyte on the Ip and Ep was also investigated [116]. Loracarbef has antibacterial activity and is oxidizable at the glassy carbon electrode. The electrochemical oxidation of Loracarbef was investigated using cyclic, linear sweep, differential pulse, and square-wave voltammetric techniques. The results obtained from cyclic voltammetry indicate that the oxidation process of Loracarbef is irreversible and diffusion controlled on glassy carbon electrodes. The dependence of peak currents and potentials on pH, concentration, scan rate, and nature of the buffer was investigated. According to the linear relation between the peak current and the concentration, differential pulse and square-wave voltammetric methods for Loracarbef quantitative determination were developed. Different parameters were tested to optimize the conditions for the determination of Loracarbef. The quantitative determination of Loracarbef was proposed in 0.1 M H2SO4, which allows quantitation over the 6  106 to 2  104 M range. Precision, accuracy, reproducibility, sensitivity, and selectivity were checked. The methods were proposed for the determination of Loracarbef in pharmaceutical dosage forms [117]. Furthermore, LSV, along with CV, has received great interest for the elucidation of electrode processes and redox mechanisms. Linear sweep voltammetry was used to study the influence of pH on the peak current and peak potential of 5-aminosalicyclic acid (5-ASA) [16] in different buffer systems. The oxidative behavior has been investigated using a glassy carbon electrode. Santos et al. [23] studied the electroanalytical behavior and methodology for quantification of albendazole in pharmaceutical formulations. The study reveals that the albendazole oxidation exhibited a standard heterogeneous rate constant for the electrodic process equal to (1.51 ± 0.07)  105 cm s1, with a ana value equal to 0.76. LSV

185

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

Methods

Matrix

Ep (V)

References

Amfepramone

HMDE

DPAdSV

BF, PF

–

[40]

Amiloride Amiloride

HMDE HMDE

DPAdSV SWAdSV

[41] [42]

GC –

PF PF HS PF PF, HP

11.25 –

Amlodipine Atorvastatin

0.510

[166] [83]

Atorvastatin calcium

GC

PF, HS, HU

–

[59]

Azithromycin Azithromycin Buspirone HCl Piribedil Captopril Captopril Thiogeranine Captopril Carvedilol

CP GC HMDE

PF PF, HU PF, HP

– 0.82 1.23 1.22 – 0.40 0.15 1.2 –

[60] [61] [11]

Pt GC

Cefazolin Cefdinir

HMDE HMDE

[74] [75]

1.0

[76]

Cefonicid Cefoperazone

DME HMDE HMDE HMDE

BF, PF PF HU HU

1.1 0.38

Cefminox

[77] [78]

HMDE HMDE HMDE HMDE

CSV SWCAdSV AdSV SWAdCSV

HU PF HS HP PF, HS PF, HS PF, HS, HU PF, HS

0.6 –

Ceftiofur Celecoxib Cephalothin Chlordiazepoxide

1.25 1.45 0.62 1.2

[79] [95] [159] [99]

Chlorhexidine Chlorpromazine HCl

GC film FME GC

0.035 mg L1 (acidic) 0.18 (alkaline) 7.1  109 M 1.9  1010 M 5.7  1010 M 1.4  108 M 4  109 M 2  109 M 2.11  107 M 2.05  107 M 0.463 ppb 0.2 lg L1 0.20 ng mL1 0.19 ng mL1 0.5 lg L1 0.3  109 M 0.8  109 M 9.2  107 M 2  107 to 2  105 M 2  107 to 1  105 M 2.6  1010 M 0.2 ng mL1 0.08 lg mL1 1.76  106 M 2.47  108 M 4  108 M 1.5  109 M 6  1010 M 2  109 M 6  1010 M 0.4 ng mL1 3.3  109 M 4.4  1010 M (DF) 6.6  1010 M (S) – 0.05–1.2 mg mL1 0.1–1 mg mL1

– DPSV

– PF, HB

1.88 0.62 0.44

[65] [85]

Promethazine HCl Cilazapril Cilazapril Quinapril Ramipril 5-Aminosalic acid Ciprofloxacin Azithromycin Citalopram Creatine Danazol Dapsone

HMDE HMDE

SWAdSV DPV SWAdSV DPV SWV SWV DPAdSV DPCSV SWCAdSV DPCAdSV

PF, BF PF, HS

– DPAdSV SWAdSV SWAdSV SWCAdSV

PF PF, HS

DPP LSAdSV AdSWSV SWSV

[86] [87] [88] [158]

HMDE HMDE

17.6 ng mL1 0.5–8 lg mL1 0.5–6 lg mL1

DPAdSV SWSV

PF PF

1.33 –

[171] [89]

MGrC

–

CV, SWV

PF

[66]

HMDE MHMDE HMDE GC

SWAdSV DPCSV SWAdSV SWSV

PF PF, HS PF PF, HU

0.54 1.2 0.94 1.25 – 1.09 1.55

CV DPP DPAdSV AdSV AdSV AdSV AdCSV LSAdSV SWAdSV DCP DPP LSAdSV SWAdSV CAdSV CSV

PF PF

0.51 0.31

[162] [163]

1.72 0.73 – 1.2 –

[175] [176] [177] [178] [179]

PF

–

[180]

PF, HU PF

[181] [182] [244] [182]

[173] [184]

Diltiazem Diosmin Enrofloxacin Ethinylestradiol Famotidine

CP DME HMDE – GC – HMDE –

Flavoxate HCl

HMDE

Flaxedil Fluoroquinolones Norfloxacin Enoxacin Folic acid Gatifloxacin Moxifloxacin Lomefloxacin Sparfloxacin Glipizide Haloperidol

HMDE –

5  108 M 0.11 ng mL1 5.7  109 M 3.56 mg mL1 0.0036 mg mL1 1  108 M 5 lg mL1 0.1 lg mL1 6  109 M 3.5  108 M 4 –25 ng mL1 5.9  1010 M 6.2  1010 M 4.9  1010 M 1  105 M 5  106 M 1  108 M 1  109 M 3  109 M 10 lg mL1, 50 ng mL1

MGC HMDE

7  1010 M 2  108 M

AdSV AdSV

PF PF, BS

– 1.02 to 1.13 0.93 to 1.07 0.88 –

HMDE

1.5  1010 M 3.83  1010 M

DPAdSV SWAdCSV

BF BF

– 1.55

Diethylstilbestrol Diflunisal

PF, PF PF, PF, PF,

HU HU HP HU

[102] [155] [160] [161]

(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

Hydroxyzine Hymecromone Indapamide Isoniazid

GC MGC MCP HMDE

Isoniazid Ketoconazole Lamotrigine

MGC HMDE HMDE

Lamotrigine Lamivudine Lansoprazole Lansoprazole Omeprazole Levonorgestrel Loracarbef Loratadine

CSPE, MCE HMDE HMDE CP

Lorazepam Meloxicam Metoclopramide Metoclopramide Metronidazole Nalidixic acid Nicardipine Nifuroxime Nitrofurantoin

HMDE GC CP NME MGC HMDE HMDE MGC HMDE

Nitroxynil

HMDE

Norethisterone Norfloxacin Ofloxacin Norfloxacin Ciprofloxacin Oxcarbazepine Oxybutynin

HMDE GC HMDE

Pantoprazole Pantoprazole Pefloxacin

CP HMDE HMDE

Piromidic acid Piroxicam

HMDE HMDE

Pravastatin Praziquantel Prazosin Procaine hydrochloride Resveratrol Riboflavin Rofecoxib Sertraline Sildenafil citrate

Sodium Levothyroxine Spironolactone Terazosin

HMDE HMDE MGC MCP – MCP HMDE HMDE Cathodically pretreated boron-doped diamond electrode Carbon-paste electrode HMDE HMDE

Terbutaline

GC

Testosterone Tetrazepam

LFE DME, HMDE

Tolmetin

HMDE

HMDE GC HMDE

HMDE HMDE

Detection/determination limit/conc. range 3.3  109 M 5.46  109 M 1.5  108 M 8  108 M 5  109 M 1.18  1010 M (B) 4.9  109 M (S) 8  108 M (U)  108 M 5.3  1011 M 4.38  109 M 5.02  109 M 3.72  107 M 69 ng mL1 – 1  108 M 2.5  108 M 4.88  1010 M 6–106 to 2–104 M range 1.6  107 M (DF) 1.25  107 M (P) 0.019 lg mL1 0.02  106 to 10  106 M 0.067 to 0.269 ng mL1 8  1011 M 6  109 M 3.3  109 M 2.08  1010 M 68  108 M 1.32  1010 M 2.86  1010 M 5.77  1010 M 3.0  105 M 1.3  108 M 8.4  1010 M 1.5  109 M lg mL1 –

Methods

Matrix

Ep (V)

References

SWAdASV AdSV ASDPV SWAdSV

HS HU PF, HS PF PF, HS BF, PF

– 0.82 1.1

[185] [245] [246] [186]

DPSV AdSDPV DPAdSV SWAdSV DPAdSV CAdSWSV AdSSWV DPSV

PF PF, HU PF, HP

– 1.6 0.7

[67] [167] [187]

PF PF PF PF

1.06 1.2, 1.8 – –

[247] [188] [189] [190]

SWAdCSV CV, DPV, SQW CAdSV

BF, PF, HS PF PF, HP

– – –

[191] [117] [111]

DPAdCSV LSAdSV SWASV ASV DPV CAdSV AdSV DPSV SWV

PF, HU, HP PF, HU, HS PF, HU HS PF PF, HU, HS HB, HU PF BF HS HU PF

– 1.8 0.90 – 0.71 1.2 – – 0.7

[192] [193] [194] [153] [80] [195] [196] [248] [197]

0.4

[198]

PF HU PF, bird feed stuffs

– 0.92 –

[199] [164] [200]

PF PF

1.0 –

[277] [108]

1.25 1.07

[201] [169] [170]

SWAdSV SWAdSV

PF PF HS HU PF, HS

0.5 –

[168] [202]

DCP DPAdSV SWAdSV SWAdCSV AdSSWV LSSV

1.74  107 M 0.1 lg mL1 0.23 lg mL1 2  108 M 5  1010 M 1.6  1010 M 4.5  1010 M 1.65  109 M 5.4  1011 M 4.32  1010 M 8  108 to 5  107 M 1.14  109 M 3.2  1010 M 5  108 M 1.65  107 to 5  109 M 0.2 ng mL1 – 1.5  107 M 6.4–107 mol L1

SWAdSV SWCAdSV DPCAdSV DPAdSV SWAdCSV SWAdCSV

CV, SWAdSV CAdSDPV ASV DPAdV SWV SWASV AdSSWV SWCSV DPP

PF PF, HF, HP – PF, HU PF PF PF PF PF

1.22 to 1.44 – – 1.0 – 0.15 – – –

[203] [204] [154] [250] [278] [209] [183] [103] [264]

– 1.72  1010 M 1.5  1011 M 5.3  1011 M 6  109 M 1.41  108 M 9  109 M 5  106 M 3  107 M 1  108 M 3  109 M 2  109 M 5  109 M

CV AdSV SWAdCSV

– PF, HS, HU PF, HS

0.78 1.0 –

[172] [184] [185]

SWAdASV

PF HS

–

[245]

AdSV DPP DPAdCSV LSAdCSV SWAdCSV SWAdCSV

PF, HU BF, PF, HS

1.1 –

[278] [209]

BF HS

–

[210]

187

Review / V.K. Gupta et al. / Anal. Biochem. 408 (2011) 179–196 Table 2 (continued) Name of drug

Indicator electrode

Detection/determination limit/conc. range

Methods

Matrix

Ep (V)

References

Triamcinolone acetate

HMDE

SWAdCSV

[211]

GC

0.75

[165]

Trimethoprim Trimethoprim Triprolidine

HMDE MGC HMDE

PF HS PF HU PF PF, HU PF

–

Trimetazidine HCl

1.3 1.275 1.35

[279] [68] [212]

Trobramycin Troxerutin Verapamil

HMDE MCP HMDE

1.40 – 1.84

[213] [69] [162]

Vitamin E Zafirlukast Zopiclone (ZP)

MCP GC GC

3  1010 M 7.5  1010 M 2  108 M 1.7 lg mL1 3 ng mL1 3.5  109 M 2.64 ng mL1 6.24 ng mL1 8.80 ng mL1 8.80 ng mL1 3.44  109 M 5.0  109 M 0.246 ng mL1 0.491 ng mL1 0.056 lg L1 4  107 M 2.78  107 and 5.28  107 mol L1

0.6 1.3 –

[70] [214] [172]

possessed advantages such as low detection limit, fast response, low cost, and simplicity [118], which was applied in studying the electrochemical behavior of norfloxacin and its determination at poly (methyl red) film-coated glassy carbon electrodes. LSV is highly suitable for investigating the electrochemical behavior of rabeprazole [119], diethylstilbestrol [38], ethinyl estradiol [120], and fenbendazole [121]. Some analytical data on the CV and LSV determination of organic compounds in pharmaceutical preparations and biological media are listed in Table 1. The data were compiled from some selected literature sources since the period 1996. The measurements were carried out using different electrodes. Pulse and square-wave voltammetry A pulse technique was proposed by Barker and Gardner in order to increase the sensitivity of the technique and to lower the detection limits for electroactive species. Differential pulse voltammetry has been extremely useful for the determination of trace amounts of electroactive compound in pharmaceuticals [122–130] and biological fluids [55]. There are numerous studies related to the electrochemical aspects of antimicrobial drugs. Generally these are focused on the electroanalytical determination of antimicrobial drugs of importance in medicine such as sparfloxacin [131,132] and pantoprazole [133]. Various cephalosporins [127,134–137] have been successfully determined by electroanalytical methods with good sensitivity and accuracy. The DPV method was applied successfully to individual tablet assays in order to verify the uniform content of bromhexine [138]. Torres et al. [21,22] have proposed a DPP method to determine acrivastine in human urine at the level obtained after the administration of normal clinical doses. The electroactivity of tamsulosin on a glassy carbon electrode was also established and studied for the first time [139] using DPV. The described methods were rapid, requiring less than 5 min to perform. It showed the possibility of monitoring this drug compound, making the method useful for pharmacokinetic and pharmacodynamic purposes. The presence of the electroreducible conjugate diene groups initiated the electrochemical study. Belal et al. [140] have developed a promising DPP method that can be considered as an alternative substitute for the chromatographic methods. The most striking feature of the method when applied for urine analysis was that no prior treatment of the sample was necessary before measurement. Another rapid and simple differential pulse anodic voltammetric

SWAdSV SWAdCSV AdSV DCV DPV SWV NPV AdSLSV – CAdSV SWSV SWAdSV DPAdSV

PF, HU, HS PF BF HU PF PF PF, HU

method for fast determination of hydrochlorothiazide [141] in urine was developed which involved no clean-up procedure. A simple dilution of the urine with buffer nearly eliminates its potential interferences. Another simple, precise, and affordable pulse differential voltammetric method was proposed for effective determination of hydroxychloroquine [54] in plaquenil tablets. It requires no complex pretreatment of the active principle to be determined. Jain et al. [98] have developed CV and DPP methods for the determination of pyrantel pamoate in pharmaceutical formulation. A welldefined cathodic wave and an anodic peak were observed for the pyrantel pamoate in the entire pH range. The number of electrons transferred in the reduction process was calculated and the reduction mechanism postulated. The peak current was found to be linear over the concentration range 4  104 to 2  102 M with a detection limit of 2.45  105 M. Easy applicability and availability of low-cost instruments are the important advantages of DPV. DPV/DPP is often the method of choice for therapeutic dose analysis because of the low limit of detection of approximately 108 M. Some of the important applications of DPV/DPP in the analysis of pharmaceutical and biological fluid have been tabulated in Table 1. Square-wave voltammetry is a large amplitude differential technique in which a waveform is composed of symmetrical square waves. Excellent sensitivity in SWV is gained from the fact that net current is large compared to either forward or backward current, coupled with effective discrimination against the charging current. The peak currents obtained are about four times higher than the differential pulse response. The major advantage of square-wave voltammetry is its speed. The effective scan rate is of the order of 500 mV s1. As a result, the analysis time is drastically reduced. A complete voltammogram can be recorded within a few seconds, compared to 2–3 min in differential pulse voltammetry. So, the entire voltammogram can be recorded with a single mercury drop. In addition, SWV is also more sensitive than DPV, because both forward and reverse currents are measured in the former, but only the forward currents are measured in the latter. Frequencies of 1 to 100 square-wave cycles per second permit the use of extremely fast potential scan rates. The analysis time is reduced; a complete voltammogram can be recorded within a few seconds, compared to about 3 min time required for DPV. The SWV method has been used for the sensitive determination of many pharmaceuticals. Lumivudine [142] concentration in human serum and in pharmaceuticals was determined by using SW

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voltammetric techniques on the basis of their reduction process corresponding to the cytosine moiety over the HMDE. No pretreatment and time-consuming extraction steps were adopted; hence it could be adopted for pharmacokinetics studies as well as for quality control laboratory studies. The SWV method for determination of methimazole [143] was developed with a detection limit of 0.5 lM with good RSD (2.89%). The SWV method was applied for the determination of resveratrol [144] in Chinese patent medicine and diluted wine with good reproducibility, precision, and accuracy. The SW and DP voltammetric method was developed by Uslu et al. [145] for determination of antiviral drug valacyclovir in pharmaceuticals and human biological fluids. The drug was irreversibly oxidized at a glassy carbon electrode in one or two oxidation steps, which are pH dependent. LOD values were 1.04  107 and 4.6  108 M for DP and SWV, respectively. An anodic voltammetric behavior and determination of cefixime in pharmaceutical dosage forms and biological fluids were developed by Golcu et al. [134]. The repeatability, reproducibility, precision, and accuracy of the methods in all media were investigated. No electroactive interferences from the excipients and endogenous substances were found in the pharmaceutical dosage forms and in the biological samples. Gao et al. [146] proposed a sensitive SWV method for the determination of trepibutone in pharmaceutical formulation using a pencil graphite electrode (PGE). The PGE exhibits the best reproducibility and highest sensitivity without any additional procedure for the renewal of the electrode surface. In another study, a simple, fast, and sensitive SWV method for the determination of trace amounts of captopril [147] in pharmaceutical formulation and reconstituted serum was reported. Sodium sulfite was used as both supporting electrolyte and oxygen-removing agent. SW voltammetric methods have been developed for the determination of abacavir [17], cilazapril–quinaprit–ramipril [148], dopamine [149], etodolac [150], nefazodone hydrochloride [151], and trapmadol [152]. Various applications on pharmaceuticals and biological samples using the above wave forms are illustrated in Table 1.

Stripping voltammetric techniques Electroanalytical techniques, especially modern stripping voltammetry, have been used for the sensitive determination of a wide range of pharmaceuticals. Such techniques enjoy the advantages that there is no need for derivatization and that these methods are less sensitive to matrix effects than other analytical techniques. Anodic stripping voltammetry (ASV) Anodic stripping voltammetry is the most widely used form of stripping analysis. In this case, the metals are preconcentrated by electro-deposition onto a small-volume mercury electrode (thin mercury film or a hanging mercury drop). The deposition is done at a potential usually 0.3–0.5 V more negative than peak potential for the metal ion to be determined. The metal ions are reduced at the mercury electrode and concentrated as amalgam. The solution is stirred during preconcentration in order to achieve convection transport. The deposition period may vary from a few seconds to about 20 min depending on the sensitivity required. After preconcentration, the potential is scanned anodically using linear or pulse ramps. During this scan, amalgamated metals are reoxidized and stripped out of the electrode. As a result, current flows through the cell. This current is directly proportional to the concentration of the metal in the solution:

M nþ þ ne þ Hg ! MðHgÞ ½preconcentration MðHgÞ ! Mnþ þ ne þ Hg ½stripping Important examples include determination of metoclopramide [153] and prazosin [154]. Cathodic stripping voltammetry (CSV) This method is the ‘‘mirror image” of ASV. It involves anodic deposition of the analyte followed by stripping in a negative potential scan (cathodic scan). The method is generally applied to organic compounds and anions that are capable of forming insoluble salts with mercury. During the stripping step, as the potential attains a value equal to the reduction potential of the analyte, it is stripped out in the form of anion.

An þ Hg ! HgA þ ne ½preconcentration HgA þ ne ! An þ Hg ½stripping The resulting reduction peak current provides the desired quantitative information. Other electrodes, like rotating silver disk electrodes, can be used for halides. The method has a large number of applications in the field of organic and medicinal chemistry since a large number of medicines can be analyzed with CSV [79,155– 157]. Adsorptive stripping voltammetry (AdSV) Higher sensitivity and better selectivity compared to other voltammetric techniques are the important features of AdSV. The principle advantages of the stripping voltammetric method are its speed and simplicity. Each voltammetric run takes a few seconds. It involves no clean-up procedures, and simple dilution of the biological fluid with suitable solvent nearly eliminates most of the published chromatographic and spectroscopic methods requiring lengthy and tedious extraction procedures, such as liquid–liquid and solid-phase extraction. The sensitivity is significantly enhanced by adsorption of the drug on the electrode surface [75,108] and after careful choice of the operating parameters extremely low detection limits can be reached. Compared with other techniques the DPAdSV and SWAdSV methods are cheap and the measurements are not time consuming, leading to results for analytical purposes of certain drugs in pharmaceutical formulation and biological fluids [158–163]. Adsorptive stripping voltammetry is the best known analytical method that incorporates an electrolytic preconcentration step. This technique has the advantages of low detection limit, low determination limit, high sensitivity, wide spectrum of the test material and analytes, relative simplicity, insignificant matrix effect, speed, and low cost of equipment. The AdSV technique is a well-established and fast growing area with a number of possible applications in the analysis of pharmaceutical and biological compounds. Ghoneim et al. [164] studied the adsorptive behavior of norfloxacin onto a glassy carbon electrode in acetate buffer. The phenomenon was put to analytical advantage in the design of an adsorptive stripping method for the determination of norfloxacin at low pbb levels, i.e., 107 to 108 M concentration. Its applicability to the determination of norfloxacin levels in urine sample was evaluated. A SWAdS voltammetric procedure has been successfully used to determine trimetazidine hydrochloride [165] drug in pharmaceutical formulation and human urine. The method is simple, sensitive, accurate, fast, and low cost and purging of the trimetazidine hydrochloride solutions with nitrogen is not required. The electrochemical renewal of the electrode surface in acetate buffer is efficient and ensures the reproducibility of individual measure-

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

ment. The detection limit of trimetazidine hydrochloride at glassy carbon electrodes in urine samples after medium exchange is low enough to reach the concentration levels expected in urine after therapeutic doses. The present method could possibly be adopted for pharmacokinetic studies as well as quality control laboratories. The above such method has also been used successfully to determine amlodipine besylate in tablets and biological fluids [166]. The method is also selective for the determination of amlodipine besylate in the presence of its metabolites in biological fluids. An adsorptive stripping voltammetric technique at HMDE has been described for the measurement of buspirone hydrochloride (BUS) and piribedil (PIR) [11]. The results are adequately accurate and precise and demonstrate promising sensitivity. The proposed method is suitable for routine analysis in control laboratories, to be applied for the analysis of BUS and PIR in pure form and in tablets. The evaluation of the voltammetric method toward the analysis of real plasma samples (in vivo study) and establishment of an effective extraction procedure to separate different metabolites was studied. A study of the reduction of ketoconazole [167] in aqueous medium (pH 5.6) has been carried out at HMDE. The sensitivity is significantly enhanced by adsorption of drug on the electrode surface and after careful choice of the operating parameters; extremely low detection limits can be reached. Compared with other techniques the method is cheap and the measurement is not time consuming. The proposed methods avoid the use of organic solvents, which present high volatility and toxicity. A square-wave adsorptive stripping voltammetric procedure for the determination of antibacterial piromidic acid has been presented [168]. The set of values for the variables influencing these stripping techniques, perchloric acid concentration, accumulation potential, and accumulation time, was optimized using response surface methodology (RSM). The proposed method was successfully applied to human urine at nanomole levels 1.65  109 M, and proved to be a simple, highly sensitive, highly accurate, fast, and low-cost method. Radi [169] concerned with the voltammetric study of pantoprazole at HMDE used a rapid and sensitive square-wave voltammetric technique. Determination of the antibiotic drug pefloxacin in bulk form, tablets, and human serum using SWCAdSV has been developed by Beltagi [170]. Voltammetric determination of cilazapril in pharmaceutical formulations using the DPAdSV method has the advantages of being simpler, faster, and less tedious than other techniques [171]. A simple, sensitive, and validated method for the determination of diflunisal by DPP and DPAdSV had been developed and applied to the pharmaceutical preparation [163]. The results obtained by the developed method were compared with the spectrofluorometric method by using the variance analysis and no statistically significant difference was found. A method based on controlled adsorptive preconcentration of cefminox on HMDE [76], followed by LSV, allows its determination in the concentration range 8.3  108 to 1.5  106 M with a detection limit of 2.47  108 M. This method has been used for the direct determination of cefminox in human urine with recoveries between 98% and 103% and precision around ±2%. Yılmaz has investigated the voltammetric behavior and determination of zopiclone (ZP) on glassy carbon electrodes using a variety of voltammetric techniques. The limits of detection and quantitation were 2.78  107 and 5.28  107 mol L1 for DPAdSV. The proposed technique was successfully applied to direct determination of ZP in tablet dosage forms and spiked human urine samples [172]. A simple, sensitive, and reproducible square-wave cathodic adsorptive stripping voltammetric method had been developed for the determination of nitrofurantoin in a solubilized system. The objective of the present paper was to investigate the redox

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behavior of nitrofurantoin by using different voltammetric techniques and to establish the methodology for its determination in the presence of surfactants. Voltammograms of the drug with cetrimide in phosphate buffers of pH 2–11 exhibited a single well-defined reduction peak which may be attributed to the reduction of the ANO2 group. The reduction process is irreversible over the entire pH range studied. The mechanism of reduction has been postulated on the basis of controlled potential electrolysis, coulometry, and spectral analysis. The proposed SWCAdSV voltammetric method allows the determination of nitrofurantoin in linear concentration range 2  105 to 1  107 mol L1. The lower limit of detection (LOD) and lower limit of quantification (LOQ) are 0.06 and 0.27 ng mL1, respectively [173]. In this work, a simple and sensitive electroanalytical method was developed for the determination of enrofloxacin (ENRO) by adsorptive cathodic stripping voltammetry (ADSV) using Cu (II) as a suitable probe. The complex of copper (II) with ENRO was accumulated at the surface of a hanging mercury drop electrode at 0.10 V for 40 s. Then, the preconcentrated complex was reduced and the peak current was measured using square-wave voltammetry. The optimization of experimental variables was conducted by experimental design and support vector machine (SVM) modeling. The model was used to find optimized values for the factors such as pH, Cu (II) concentration, and accumulation potential. Under the optimized conditions, the peak current at 0.30 V is proportional to the concentration of ENRO over the range of 10.0–80.0 nmol L1 with a detection limit of 0.33 nmol L1. The influence of potential interfering substances on the determination of ENRO was examined. The method was successfully applied to determination of ENRO in plasma and pharmaceutical samples [174]. Adsorptive stripping analysis using different waveforms has been applied for the determination of dilitiazem [175], diosmin [176], enrofloxacin [177], ethinylestradiol [178], famotidine [179], flavoxate [180], flaxedil [181], gatofloxacin [182], glipizide [183], haloperidol [184], hydroxyzine [185], isoniazid [186], lamotrigine [187], lamivudine [188], lansoprazol [189,190], levonorgestrel [191], lorazepam [192], meloxicam [193], metoclopramide [194,153], nalidixic acid [195], nicardipine [196], nitrofurantoin [197], nitroxynil [198], norethisterone [199], ofloxacin [200], pantoprazole [201], piroxicam [202], pravastatine [203], praziquantel [204], rofecoxib [205], spironolactone [206], terazosin [207], terbutaline [208], tetrazepam [209], tolmetin [210], triamcinolone [211], trimethoprim [68], triprolidine [212], trobramycin [213], and zafirlukast [214]. Lists of the selected pharmaceutical and biological compounds that can be determined using stripping techniques along with the ranges of their respective detection or determination limits or concentration range are given in Table 2. Voltammetric methods using surfactants Surfactant has been widely used in the electrochemistry and electroanalysis for various purposes. Surfactants have proved to be effective in the electroanalysis of biological compounds and drugs. For example, the addition of surface-active agents to electrolyte containing terazosin [215] enhanced the voltammetric peak response at GCE. It was recently shown that anionic surfactants could be used to improve the accumulation of some electroactive organic molecules such as ethopropazine [113] at gold electrodes. In another study, the influence of micelles in the simultaneous determination of two components was also demonstrated, as in the case of catechol and hydroquinone [216]. Recently, the oxidation peak currents of certain pharmaceuticals increasing significantly in the presence of surfactants have been reported by different studies [217,218]. Jain and co-workers had studied the effect of changing the charge of the surfactant, viz. anionic, neutral, and cationic on the

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cefdinir peak current [127]; the addition of cationic surfactant enhanced the reduction current signal. Another important study by Alarcon-Angeles et al. [219] showed that sodium dodecyl sulfate (SDS) micelles can act as a masking agent useful for the selective determination of dopamine in the presence of ascorbic acid. The SDS micelles make it possible to obtain DPV where DA and AA signals appear separated because the SDS micelles provide that the DA adsorbs strongly on the CPE and an increase of the charge transfer reaction for the electrochemical oxidation of dopamine. Jain and co-workers also studied the effect of adding surfaceactive agents to electrolytes-containing nortriptyline hydrochloride on the voltammetric response at hanging mercury drop electrodes. Addition of Tween 20 to the nortriptyline hydrochloride-containing electrolyte enhances the reduction current signal. Application of Tween 20 in the electrochemical determination of nortriptyline hydrochloride using square-wave voltammetry at the HMDE enhanced the detection limit of the analyte [220]. A voltammetric method for the determination of entacapone based on the enhancement effect of Tween 20 had been developed. Addition of neutral surfactant (Tween 20) to the entacapone-containing electrolyte enhanced the reduction current signal while anionic surfactant (sodium lauryl sulfate) and cationic surfactant (cetrimide) showed an opposite effect. The analysis of entacapone in its pharmaceutical formulation exhibited the mean recovery of 99% for the reduction peak [221]. Assay and electrochemical behavior of betahistine hydrochloride in Britton-Robinsons (BR) buffer of pH range 2.5–12.0 at a glassy carbon electrode have been investigated. Addition of anionic surfactant (sodium lauryl sulfate) to the betahistine hydrochloride solution-containing electrolyte enhanced the reduction current signal while neutral surfactant (Tween 20) and cationic surfactant cetyl trimethylammonium bromide (CTAB) showed an opposite effect. Voltammograms of betahistine hydrochloride exhibited a single wave. The proposed method was successfully applied to the determination of betahistine hydrochloride in drug product. The results were compared with those obtained by the reference high-performance liquid chromatographic method. No significant differences were found between results of proposed and reference methods [222]. The voltammetric behavior of ornidazole had been studied in different surfactant media, viz. anionic, cationic, and non-ionic surfactants over the pH range 2.5 to 12.0 in phosphate buffer (0.2 M). Addition of non-ionic surfactant (Tween 20) to the ornidazole-containing electrolyte enhanced the reduction current signal while the anionic surfactant sodium lauryl sulfate and cationic surfactant cetyltrimethylammonium bromide showed a small enhancement in peak current. The analysis of ornidazole in its pharmaceutical formulation exhibited the mean recovery of 98% for the reduction peak [223]. Voltammetric behavior of nitrazepam had been studied in acetonitrile and in the presence of anionic surfactant (sodium lauryl sulfate). It exhibit two well-defined cathodic peaks [224].

Voltammetric methods at modified electrodes Chemically modified electrodes are currently widely used due to the various advantages they offer. The use of chemically modified electrodes in electroanalysis offers several advantages, which include lowering of the peak potential and increase in sensitivity along with improvement in selectivity in the application of pharmaceutical analysis [137,217,225,226]. Much attention has been given to the use of carbon nanotubes (CNTs) since its discovery in 1991. CNT-modified electrodes have proved to have excellent electroanalytical properties, such as wide potential windows, low background current, and good biocompat-

ibility. Excellent improvement in the electrochemical behavior of biologically important compounds such as dopamine and ascorbic acid [227,228], quercetin and rutine [229], tryptophan [230], glucose [231], procaine [232], and metformine [233] at CNTs has been demonstrated. Multiwalled carbon nanotube (MWCNT)-modified CPE was used to study the electrochemical behavior of bergenin [234]. The modified electrode showed an excellent electrocatalytic activity in lowering the anodic overpotential and remarkable enhancement of the ipa of bergenin if compared with the electrochemical performances obtained at CPE. Wang et al. [235] suggest that cysteic acid/carbon nanotube film will have significant electroanalytical utility in the future. The novel cysteic acid/CNT film material can be easily applied to other types of substrate electrodes and surfaces and this will further broaden the potential for applications. Similarly various pharmaceuticals [67,80,90,141,154,236–239, 230,240–249,144,250] have been determined by different kinds of modified electrodes. Wang et al. [251] reported a new approach to construct a nano-Au self-assembly gold electrode which was used for determination of epinephrine. Hu et al. [252] also reported the fabrication of a modified electrode based on the self-assembly of gold nanoparticles on cysteamine film, which has been bound to the surface of a glassy carbon electrode. The modified electrode exhibited an excellent reproducibility, sensibility, and stability for determination of dopamine in the presence of high concentrations of ascorbic acid. Goyal and co-workers have successfully studied the electrochemical behavior of various pharmaceuticals [253–255] at a gold nanoparticle-modified indium tin oxide (nano Au/ITO) electrode. Gold nanoparticles exhibit attractive properties in electrode modification by improving the electrode conductivity and enhancing the analytical sensitivity and selectivity [256,257]. An entire electrochemical study of diazepam, temazepam, and oxazepam using modified carbon-paste electrodes was reported [258]. Boron-doped diamond electrodes have received much attention for electrochemical determination [259,260] due to their attractive electrochemical properties over other electrodes. Compared to classical carbon electrodes and other metallic electrodes, diamond electrodes open up new opportunities for working under extreme conditions such as media (e.g., strongly acidic). Over the past two past decades electroanalytical techniques based on modified polymer electrodes have attracted broad interest from scientist engaged in pharmaceutical analysis [261,262]. The modification of the electrode by Nafion film [19] enhanced the analytical signal intensity and simultaneously protected the surface of the working electrode, avoiding its fouling by species present in the sample matrices, conferring greater stability to the electrode and higher reproducibility to the determinations. Fullerene science is one of the fastest growing areas of research in chemistry, physics, and material science. One possible field of their application can be their use as mediators in electrochemistry, that is, for the chemical modification of electrodes in electrocatalysis as observed in recent report for the electrochemical oxidation of nandrolone [10] at fullerene C60-modified glassy carbon electrode. Jain et al. also reported a composite polymer surface coated on a tin oxide which offers dramatic improvement in the stability of voltammetric measurement of pyridostigmine bromide compared to individual tin oxide, polyaniline, or polypyrrole-coated electrodes [263]. The voltammetric behavior of pyrantel pamoate was studied in the Britton-Robinson buffer system at a composite polymer membrane working electrode. The cyclic voltammetric method has been developed for the determination of drug in pharmaceutical formu-

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lation. A well-defined cathodic peak was observed for the pyrantel pamoate in the entire pH range. The current increases steadily with diffusion scan rate and concentration. The results indicate that the process is irreversible and diffusion controlled. This composite film showed good current response [264]. Zheng and co-workers reported the selective, sensitive, and simultaneous determination of dopamine, ascorbic acid, and uric acid on ordered mesoporous carbon (OMC)/Nafion composite film [265]. Recently Nasirizadeh et al. had fabricated a highly efficient noradrenalin (NA) biosensor on the basis of hematoxylin electrodeposited on a glassy carbon electrode, GCE. The peaks of differential pulse voltammetric for NA and acetaminophen (AC) oxidation at the hematoxylin biosensor surface are clearly separated from each other when they coexited in the physiological pH (pH 7.0). It was, therefore, possible to simultaneously determine NA and AC in the samples at a hematoxylin biosensor [266]. A voltammetric method was developed for the determination of tetracycline (TC) by using an ionic liquid (IL, 1,octyl,3,methylimidazolium, hexafluorophosphate)–multiwall carbon nanotube (MWNT) film-coated glassy carbon electrode (GCE). Experiment showed that both IL and MWNT could facilitate the TC oxidation. Thus on the electrode TC exhibited a sensitive anode peak at 0.54 V (vs SCE) in pH 7.0 phosphate buffer solutions. Under the optimized experimental conditions, the peak current was linear to TC concentration in the range of 1.1  107 to 2.2  105 M for 150 s accumulation. The electrode had good reproducibility. It was successfully applied to the detection of TC in egg and pharmaceutical samples [267]. The determination of sildenafil citrate using differential pulse voltammetry and a cathodically pretreated boron-doped diamond electrode is described. The obtained analytical curve is linear in the sildenafil concentration range 7.3  107 to 7.3  106 mol L1 in a 0.1 mol L1 H2SO4, with a detection limit of 6.4  107 mol L1. The proposed method, which is fast and simple to carry out, was successfully applied in the determination of sildenafil citrate in Viagra1 pharmaceutical formulations, with results in close agreement (at 95% confidence level) with those obtained using a comparative HPLC method [268]. The electrochemical response of sodium levothyroxine at a carbon-paste electrode in the presence of 0.1 M HCl as supporting electrolyte was investigated by cyclic voltammetry. It showed a well-defined oxidation peak at 0.78 V and a sensitive and indiscernible reduction peaks at 0.53 and 0.32 V. The effect of concentration and scan rate of sodium levothyroxine was studied. The scan rate effect showed that the electrode process is adsorption controlled. The effect of surfactants like sodium dodecyl sulfate, cetyltrimethylammonium bromide, and Triton X-100 (TX-100) were studied by mobilizing and immobilizing methods. The concentration effect of all the three surfactants was studied. Among these SDS showed excellent enhancement in both oxidation peak and reduction peak currents [269]. A carbon-paste electrode spiked with ferrocenedicarboxylic acid (FDCMCPE) was constructed by incorporation of ferrocenedicarboxylic acid in a graphite powder–paraffin oil matrix. It has been shown by direct current cyclic voltammetry and double-step chronoamperometry that this electrode can catalyze the oxidation of ampicillin (AMPC) in aqueous buffered solution. It has been found that under optimum conditions (pH 10.0) in cyclic voltammetry, the oxidation of AMPC occurred at a potential of about 480 mV on the surface of the modified carbon-paste electrode. The kinetic parameters such as electron-transfer coefficient, a, and rate constant for the chemical reaction between AMPC and redox sites in FDCMCPE were also determined using electrochemical approaches. Under the optimized conditions, the electrocatalytic oxidation peak current of AMPC showed two linear dynamic ranges

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with a detection limit of 0.67 mmol L1 AMPC. The linear calibration was in the range of 2.34–30 and 40–700 mmol L1 AMPC using the differential pulse voltammetric method. Finally, this method was also examined as a selective, simple, and precise electrochemical sensor for the determination of AMPC in real samples such as drugs and urine [162,270–279]. Several synthetic zeolites such as mazzite, mordenite, zeolite L, zeolite beta, and MCM-41 were tested as electrode modifiers in voltammetric determination of tryptophan. It was found that the addition of zeolite beta to the carbon paste would generate the peak current of Trp because of its catalytic effect. The anodic peak currents were proportional to Trp concentrations in the range of 5.0  107 to 5.0  103 M. The detection limit was 1.0  107 M. The influence of several species, especially amino acids, was tested. The proposed method was applied successfully to the determination of tryptophan in pharmaceutical formulations [174]. Conclusion Modern electrochemical instrumentation, especially voltammetric techniques, provides reliable and reproducible data for the quantification of analyte. Further, use of modified electrodes proved to have excellent electroanalytical properties, such as wide potential windows, low background current, and good biocompatibility. Also, addition of surface-active agents to electrolytes greatly enhances the voltammetric peak response, increasing sensitivity. The present review will be of great help for the analytical chemists using voltammetric methods for the determination of a given analyte in a complex matrix. The aim of the review is to assess the utility of methods using various electrodes and surface-active agents for the determination of pharmaceuticals with low running cost, high speed, sensitivity, universality, and wide application. These techniques are simple and in cases more sensitive to the usually applied chromatographic and spectroscopic techniques. Acknowledgments The authors dedicate this paper to their reverend teacher and renowned Electrochemist (Late) Prof. Wahid. U. Malik and one of the authors; K. Radhapyari is thankful to the Department of Science and Technology (DST), New Delhi, India, for the award of fellowship. References [1] P.T. Kissinger, W.R. Heineman, Laboratory Techniques in Electroanalytical Chemistry, second ed., Dekker, New York, 1996. [2] J. Barek, A.G. Fogg, A. Merck, J. Zima, Polarography and voltammetry at mercury electrodes, Crit. Rev. Anal. Chem. 31 (2001) 291–309. [3] S.R. Annapoorna, M.P. Rao, B. Sethuram, Multiple substituent effects in the C@C reduction of phenyl styryl ketones: cyclic voltammetry as a tool, J. Electroanal. Chem. 490 (2000) 93–97. [4] L.J. Nunez-Vergara, D. Farias, S. Bollo, J.A. Squella, An electrochemical evidence of free radicals formation from flutamide and its reactivity with endo/xenobiotics of pharmacological relevance, Bioelectrochemistry 53 (2001) 103–110. [5] L. Ye-Mei, C. Xian-Tang, L. Jun, L. Hui-Hong, Direct voltammetry and catalysis of hemoenzymes in methyl cellulose film, Electrochim. Acta 49 (2004) 3195– 3200. [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(salicylideneamino)ethyl] ethane-1,2-diamine, Anal. Chim. Acta 575 (2006) 198–204. [7] G. Angulo, A. Kapturkiewicz, A. Palmaerts, L. Lutsen, T.J. Cleij, D. Vanderzande, Cyclic voltammetry studies of n-type polymers with non-alternant fluoranthene units, Electrochim. Acta 54 (2009) 1584–1588. [8] G. Macchi, The determination of ionic zinc in sea-water by anodic stripping voltammetry using ordinary capillary electrodes, J. Electroanal. Chem. 9 (1965) 290–298. [9] R.P. Lencastre, C.D. Matos, J. Garrido, F. Borges, E.M. Garrido, Voltammetric quantification of fluoxetine: application to quality control and quality assurance processes, J. Food Drug Anal. 14 (2006) 242–251.

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