Indirect spectrophotometric method is described for quantification of five of 1,4-dihydropyridine (1,4-DHP) drugs using N-bromosuccinimide (NBS) with the aid of indigo carmine (INC) dye. The method is based on addition of known excess of NBS to an acidified solution of 1,4-DHP drugs and determining the residual of NBS through its ability to bleach the colour of the used dye; the amount of NBS that reacted corresponded to the amount of drugs. Beer’s law is obeyed in the concentration range 1.25–13.00？μg/mL. Good correlation coefficients (0.998-0.999) were found between the absorbance values and the corresponding concentrations. Limits of detections ranged from 0.141 to 0.500？μg/mL. The proposed method was successfully applied to the analysis of dosage forms; percent of recoveries ranged from 97.31 to 99.46% without interference from any common excipients. The statistical comparison by Student’s t-test and variance ratio F-test showed no significant difference between the proposed and official or reported methods. 1. Introduction 1,4-DHP derivatives are vasodilators with a great selectivity for vascular smooth muscles; they are primarily used for treatment of some of cardiovascular diseases such as hypertension, angina, and cardiac arrhythmias. Recently, they were used for the treatment of other pathological states, such as seizures and cerebral ischemic disorders [1, 2]. Many analytical methods were developed for determination of 1,4-DHP drugs, namely, nifedipine (NIF), nicardipine (NIC), nimodipine (NIM), felodipine (FEL), and amlodipine (AML) (Figure 1), in their pharmaceutical formulations and in biological fluids, such as titrimetric methods [3, 4], spectrometric methods (spectrophotometry [5–13] or spectrofluorimetry [12, 14–20]), electrochemical methods [21–23], liquid chromatographic methods [24–28], and gas chromatographic methods [29–32]. Figure 1: Chemical structure of the investigated 1,4-DHP drugs. Classical spectrophotometric measurements and their applications are considered as a routine analytical method in most quality control laboratories. Subsequently, the aim of this study to develop a simple, sensitive, and cost-effective method for determination of these drugs in pure and dosage forms using spectrophotometric technique. The method utilized NBS-INC reagents (Figure 2) and their developed offer the advantage of simplicity, sensitivity, speed, accuracy, and precision without the need for costly equipment/chemicals. Figure 2: Chemical structure of the chemical reagents. 2. Experimental 2.1. Instrumentation Absorbance measurements were
References
[1]
Y. Ikegaya, N. Nishiyama, and N. Matsuki, “L-type Ca2+ channel blocker inhibits mossy fiber sprouting and cognitive deficits following pilocarpine seizures in immature mice,” Neuroscience, vol. 98, no. 4, pp. 647–659, 2000.
[2]
Y. Murai, H. Uneyama, H. Ishibashi, K. Takahama, and N. Akaike, “Preferential inhibition of L- and N-type calcium channels in the rat hippocampal neurons by cilnidipine,” Brain Research, vol. 854, no. 1-2, pp. 6–10, 2000.
[3]
B. Kanakapura, C. Umakanthappa, and N. Paregowda, “Titrimetric and spectrophotometric assay of felodipine in tablets using bromate-bromide, Methyl Orange and Indigo Carmine reagents,” Journal of the Serbian Chemical Society, vol. 70, no. 7, pp. 969–978, 2005.
[4]
B. Kanakapura, C. Umakanthappa, and N. Paregowda, “Titrimetric and modified spectrophotometric methods for the determination of amlodipine besylate using bromate-bromide mixture and two dyes,” ScienceAsia, vol. 32, no. 3, pp. 271–278, 2006.
[5]
M. Nasr-Esfahani, M. Moghadam, and G. Valipour, “Rapid and efficient aromatization of Hantzsch 1,4-dihydropyridines with potassium peroxomonosulfate catalyzed by manganese(III) Schiff base complexes,” Journal of the Iranian Chemical Society, vol. 5, no. 2, pp. 244–251, 2008.
[6]
S. B. Wankhede, K. C. Raka, S. B. Wadkar, and S. S. Chitlange, “Spectrophotometric and HPLC methods for simultaneous estimation of amlodipine besilate, losartan potassium and hydrochlorothiazide in tablets,” Indian Journal of Pharmaceutical Sciences, vol. 72, no. 1, pp. 136–140, 2010.
[7]
M. A. Rontogianni, C. K. Markopoulou, and J. E. Koundourellis, “HPLC and chemometrically-assisted spectrophotometric estimation of two binary mixtures for combined hypertension therapy,” Journal of Liquid Chromatography and Related Technologies, vol. 29, no. 18, pp. 2701–2719, 2006.
[8]
N. Rahman and S. N. Hejaz Azmi, “New spectrophotometric methods for the determination of nifedipine in pharmaceutical formulations,” Acta Biochimica Polonica, vol. 52, no. 4, pp. 915–922, 2005.
[9]
N. Rahman and S. N. H. Azmi, “Validated spectrophotometric method for the assay of nifediplne in bulk and commercial dosage forms,” ScienceAsia, vol. 32, no. 4, pp. 429–435, 2006.
[10]
B. Kanakapura, C. Umakanthappa, and N. Paregowda, “Spectrophotometric and high performance liquid chromatographic determination of amlodipine besylate in pharmaceuticals,” ScienceAsia, vol. 31, pp. 13–21, 2005.
[11]
K. R. Mahadik, G. B. Byale, H. N. More, and S. S. Kadam, “Spectrophotometric estimation of nifedipine and its formulation,” East-Pharm, pp. 34121–34122, 1991.
[12]
H. F. Askal, O. H. Abdelmageed, S. M. S. Ali, and M. A. El Hamd, “Spectrophotometric and spectrofluorimetric determination of 1, 4- dihydropyridine drugs using potassium permanganate and cerium (iv) ammonium sulphate,” Bulletin of Pharmaceutical Sciences, vol. 33, no. 2, pp. 201–215, 2010.
[13]
M. A. El Hamd, S. M. Derayea, O. H. Abdelmageed, and H. F. Askal, “A novel spectrophotometric method for determination of five 1, 4-dihydropyridine drugs in their tablets and capsules using vanillin reagent,” The American Journal of Analytical Chemistry, vol. 4, pp. 148–156, 2013.
[14]
H. H. Abdine, “Spectrofluorimetric determination of amlodipine,” Mansoura Journal of Pharmaceutical Sciences, vol. 25, no. 1, pp. 31–38, 2009.
[15]
A. B. Tabrizi, “A new spectrofluorimetric method for determination of nifedipine in pharmaceutical formulations,” Chemia Analityczna, vol. 52, no. 4, pp. 635–643, 2007.
[16]
M. I. Walash, F. Belal, N. El-Enany, and A. A. Abdelal, “Kinetic spectrofluorometric determination of certain calcium channel blockers via oxidation with cerium (IV) in pharmaceutical preparations,” International Journal of Biomedical Science, vol. 5, no. 2, pp. 146–157, 2009.
[17]
F. Belal, A. A. Al-Majed, S. Julkhuf, and N. Y. Khalil, “Spectrofluorometric determination of nimodipine in dosage forms and human urine,” Pharmazie, vol. 58, no. 12, pp. 874–876, 2003.
[18]
S. M. Al-Ghannam and A. M. Al-Olyan, “Spectrofluorometric determination of nicardipine, nifedipine and isradipine in pharmaceutical preparations and biological fluids,” Central European Journal of Chemistry, vol. 6, no. 2, pp. 222–228, 2008.
[19]
H. M. Abdel-Wadood, N. A. Mohamed, and A. M. Mahmoud, “Validated spectrofluorometric methods for determination of amlodipine besylate in tablets,” Spectrochimica Acta A, vol. 70, no. 3, pp. 564–570, 2008.
[20]
S. M. Derayea, H. F. Askal, O. H. Abdelmageed, and M. A. El Hamd, “Spectrophotometric determination of amlodipine and nicardipine in pharmaceutical formulations via binary complex formation with eosin Y,” Journal of Applied Pharmaceutical Science, vol. 2, no. 6, pp. 84–89, 2012.
[21]
R. J. B. Diez-Caballero, L. L. de la Torre, J. F. A. Valentin, and A. A. Garcia, “Adsorptive stripping voltammetry for the determination of nifedipine in human serum,” Talanta, vol. 36, no. 4, pp. 501–504, 1989.
[22]
M. M. Ghoneim, A. Tawfik, and P. Y. Khashaba, “Cathodic adsorptive stripping square-wave voltammetric determination of nifedipine drug in bulk, pharmaceutical formulation and human serum,” Analytical and Bioanalytical Chemistry, vol. 375, no. 3, pp. 369–375, 2003.
[23]
N. ？zaltin, C. Yardimci, and I. Süslü, “Determination of nifedipine in human plasma by square wave adsorptive stripping voltammetry,” Journal of Pharmaceutical and Biomedical Analysis, vol. 30, no. 3, pp. 573–582, 2002.
[24]
M. V. Vertzoni, C. Reppas, and H. A. Archontaki, “Sensitive and simple liquid chromatographic method with ultraviolet detection for the determination of nifedipine in canine plasma,” Analytica Chimica Acta, vol. 573-574, pp. 298–304, 2006.
[25]
X.-D. Wang, J.-L. Li, Y. Lu et al., “Rapid and simultaneous determination of nifedipine and dehydronifedipine in human plasma by liquid chromatography-tandem mass spectrometry: application to a clinical herb-drug interaction study,” Journal of Chromatography B, vol. 852, no. 1-2, pp. 534–544, 2007.
[26]
H. S. Abou-Auda, T. A. Najjar, K. I. Al-Khamis, B. M. Al-Hadiya, N. M. Ghilzai, and N. F. Al-Fawzan, “Liquid chromatographic assay of nifedipine in human plasma and its application to pharmacokinetic studies,” Journal of Pharmaceutical and Biomedical Analysis, vol. 22, no. 2, pp. 241–249, 2000.
[27]
A.-E. F. Nassar, “Online hydrogen-deuterium exchange and a tandem-quadrupole time-of-flight mass spectrometer coupled with liquid chromatography for metabolite identification in drug metabolism,” Journal of Chromatographic Science, vol. 41, no. 8, pp. 398–404, 2003.
[28]
L. H. Miglioran？a, R. E. Barrientos-Astigarraga, B. S. Schug, H. H. Blume, A. S. Pereira, and G. De Nucci, “Felodipine quantification in human plasma by high-performance liquid chromatography coupled to tandem mass spectrometry,” Journal of Chromatography B, vol. 814, no. 2, pp. 217–223, 2005.
[29]
M. T. Rosseel and M. G. Bogaert, “Determination of nifedipine in human plasma by capillary gas chromatography with nitrogen detection,” Journal of Chromatography, vol. 279, pp. 675–680, 1983.
[30]
J. Martens, P. Banditt, and F. P. Meyer, “Determination of nifedipine in human serum by gas chromatography-mass spectrometry: validation of the method and its use in bioavailability studies,” Journal of Chromatography B, vol. 660, no. 2, pp. 297–302, 1994.
[31]
A. T. Wu, I. J. Massey, and S. Kushinsky, “Capillary column gas chromatographic method using electron-capture detection for the simultaneous determination of nicardipine and its pyridine metabolite II in plasma,” Journal of Chromatography B, vol. 59, no. 1, pp. 65–73, 1987.
[32]
R. Nishioka, I. Umeda, N. Oi, S. Tabata, and K. Uno, “Determination of felodipine and its metabolites in plasma using capillary gas chromatography with electron-capture detection and their identification by gas chromatography-mass spectrometry,” Journal of Chromatography, vol. 565, no. 1-2, pp. 237–246, 1991.
[33]
N. K. Mathur and C. K. Narang, Determination of Organic Compounds with N-Bromosuccinamide and Allied Reagents, Academic Press, London, UK, 1975.
[34]
G. A. Saleh, “Two selective spectrophotometric methods for the determination of amoxicillin and cefadroxil,” Analyst, vol. 121, no. 5, pp. 641–645, 1996.
[35]
I. H. Refaat, Contribution To the Analysis of Some Phenothiazines, Assiut University, Assiut, Egypt, 1983.
[36]
P. Job, Advanced Physicochemical Experiments, Analytical Chemistry, Oliner and Boyd, 1964.
[37]
H. Huang and H. Li, “Ultra-violet spectrophotometric determination of the content of nicardipine preparations,” Yaowu Fenxi Zazhi, vol. 10, no. 6, pp. 359–360, 1990.
[38]
K. Basavaiah, U. Chandrashekar, and H. C. Prameela, “Sensitive spectrophotometric determination of amlodipine and felodipine using iron(III) and ferricyanide,” Farmaco, vol. 58, no. 2, pp. 141–148, 2003.
[39]
D. C. Washington, The American Pharmaceutical Association, vol. 1, 31th edition, 2008.
[40]
M. Haase, “Stability testing on vaccines: results of activities of the international conference on harmonization (ICH) of technical requirements for registration of pharmaceuticals for human use,” Biologicals, vol. 22, no. 4, pp. 373–375, 1994.
[41]
IUPAC, “Nomenclature, symbols, units and their usage in spectrochemical analysis. II. Data interpretation analytical chemistry division,” Spectrochimica Acta B, vol. 33, p. 242, 1978.
[42]
The British Pharmacopoeia, Majesty's Stationary Office, vol. 1, London, UK, 2009.
[43]
The British Pharmacopoeia, Majesty's Stationary Office, vol. 2, London, UK, 2009.
