Fluorescence Spectrometric Determination of Drugs Containing -Methylene Sulfone/Sulfonamide Functional Groups Using N1-Methylnicotinamide Chloride as a Fluorogenic Agent
A simple spectrofluorometric method has been developed, adapted, and validated for the quantitative estimation of drugs containing -methylene sulfone/sulfonamide functional groups using N1-methylnicotinamide chloride (NMNCl) as fluorogenic agent. The proposed method has been applied successfully to the determination of methyl sulfonyl methane (MSM) (1), tinidazole (2), rofecoxib (3), and nimesulide (4) in pure forms, laboratory-prepared mixtures, pharmaceutical dosage forms, spiked human plasma samples, and in volunteer's blood. The method showed linearity over concentration ranging from 1 to 150? g/mL, 10 to 1000?ng/mL, 1 to 1800?ng/mL, and 30 to 2100?ng/mL for standard solutions of 1, 2, 3, and 4, respectively, and over concentration ranging from 5 to 150? g/mL, 10 to 1000?ng/mL, 10 to 1700?ng/mL, and 30 to 2350?ng/mL in spiked human plasma samples of 1, 2, 3, and 4, respectively. The method showed good accuracy, specificity, and precision in both laboratory-prepared mixtures and in spiked human plasma samples. The proposed method is simple, does not need sophisticated instruments, and is suitable for quality control application, bioavailability, and bioequivalency studies. Besides, its detection limits are comparable to other sophisticated chromatographic methods. 1. Introduction Encouraged by the successful application of the NMNCl methodology to the determination of a similar α-methylene carbonyl functional group containing drugs, namely, warfarin [1], pentoxifylline, propafenone hydrochloride and acebutolol hydrochloride [2], the almost isosteric α-methylene sulfoxide group, such as proton pump inhibitors (PPIs) and the cyclic α-methylene carbonyl group, such as ketamine hydrochloride, griseofulvin, and levonorgestrel (unpublished results), we decided to investigate the possibility of extending the application of such methodology to drugs containing the isosteric α-methylene sulfone/sulfonamide functional groups, namely, methyl sulfonyl methane (MSM) (1), tinidazole (2), rofecoxib (3), and nimesulide (4). Methyl sulfonyl methane (MSM) (1) is a relatively new dietary supplement form of sulfur that is found in our living tissues. MSM supports healthy connective tissues like tendons, ligaments, and muscle. Thus, it is important in conditions such as arthritis, muscle pains, and bursitis. MSM should be considered an integral part of any health care practice because of its physiological action, indirect importance, and current/future uses [3–5]. In this report, MSM was used as a model compound and was found to react successfully with NMNCl
References
[1]
M. A. Eldawy, M. M. Mabrouk, and R. A. Elbarbary, “Spectrofluorimetric determination of warfarin sodium by using N1-methylnicotinamide chloride as a fluorigenic agent,” Journal of Association of Official Analytical Chemists International, vol. 88, pp. 455–461, 2005.
[2]
M. A. El Dawy, M. M. Mabrouk, and R. A. El Barbary, “Spectrofluorimetric determination of drugs containing active methylene group using N-methyl nicotinamide chloride as a fluorigenic agent,” Chemical and Pharmaceutical Bulletin, vol. 54, no. 7, pp. 1026–1029, 2006.
[3]
D. Mitchell, S. J. Bock, and M. S. M. Sulfur, “Natural Health and Longevity Resource Center,” October 2010, http://www.all-natural.com/msm.html.
[4]
MSM, “Life Extension Foundation,” October 2010, http://www.lef.org/newshop/items/item00451.html.
[5]
MSM, “Natural Ways to Health,” October 2010, http://www.naturalways.com/MSM.htm.
[6]
C. Arsene, I. Barnes, K. H. Becker, and R. Mocanu, “FT-IR product study on the photo-oxidation of dimethyl sulphide in the presence of NO—temperature dependence,” Atmospheric Environment, vol. 35, no. 22, pp. 3769–3780, 2001.
[7]
Y. C. Ling, T. J. Vickers, and C. K. Mann, “Background correction in raman spectroscopic determination of dimethylsulfone, sulfate, and bisulfate,” Applied Spectroscopy, vol. 39, pp. 463–470, 1983.
[8]
H. Berresheim, D. J. Tanner, and F. L. Eisele, “Method for real-time detection of dimethyl sulfone in ambient air,” Analytical Chemistry, vol. 65, no. 21, pp. 3168–3170, 1993.
[9]
R. F. Lang and C. J. Brown, “Determination of dimethyl sulfoxide and dimethyl sulfone in air,” Analytical Chemistry, vol. 63, no. 2, pp. 185–189, 1991.
[10]
A. C. Mehta, S. Peaker, C. Acomb, and R. T. Calvert, “Rapid gas chromatographic determination of dimethyl sulphoxide and its metabolite dimethyl sulphone in plasma and urine,” Journal of Chromatography—Biomedical Applications, vol. 383, no. 2, pp. 400–404, 1986.
[11]
N. Moreira, P. Guedes De Pinho, and I. Vasconcelos, “Method for analysis of heavy sulphur compounds using gas chromatography with flame photometric detection,” Analytica Chimica Acta, vol. 513, no. 1, pp. 183–189, 2004.
[12]
J. L. Liu, S. Li, Z. H. Li, and H. Ma, “Capillary gas-chromatographic separation and determination of dimethyl sulfoxide and dimethyl sulfone,” Lihua Jianyan Huaxue Fence, vol. 38, pp. 283–284, 2002.
[13]
A. Willse, A. M. Belcher, G. Preti et al., “Identification of major histocompatibility complex-regulated body odorants by statistical analysis of a comparative gas chromatography/mass spectrometry experiment,” Analytical Chemistry, vol. 77, no. 8, pp. 2348–2361, 2005.
[14]
A. C. Silva Ferreira, P. Rodrigues, T. Hogg, and P. G. De Pinho, “Influence of some technological parameters on the formation of dimethyl sulfide, 2-mercaptoethanol, methionol, and dimethyl sulfone in port wines,” Journal of Agricultural and Food Chemistry, vol. 51, no. 3, pp. 727–732, 2003.
[15]
D. T. T. Vu, “SPME/GC-MS characterization of volatiles associated with methamphetamine: toward the development of a pseudomethamphetamine training material,” Journal of Forensic Sciences, vol. 46, no. 5, pp. 1014–1024, 2001.
[16]
C. Pérès, C. Denoyer, P. Tournayre, and J. L. Berdagué, “Fast characterization of cheeses by dynamic headspace-mass spectrometry,” Analytical Chemistry, vol. 74, no. 6, pp. 1386–1392, 2002.
[17]
D. Saccù, P. Bogoni, and G. Procida, “Aloe exudate: characterization by reversed phase HPLC and headspace GC-MS,” Journal of Agricultural and Food Chemistry, vol. 49, no. 10, pp. 4526–4530, 2001.
[18]
E. Valero, J. Sanz, and I. Martínez-Castro, “Direct thermal desorption in the analysis of cheese volatiles by gas chromatography and gas chromatography-mass spectrometry: comparison with simultaneous distillation-extraction and dynamic headspace,” Journal of Chromatographic Science, vol. 39, no. 6, pp. 222–228, 2001.
[19]
British Pharmacopoeia, Her-Majesty's Stationary Office, London, UK, 2005.
[20]
United States Pharmacopoeia, vol. 28, United States Pharmacopoeia Convention, Washington, DC, USA, 2005.
[21]
J. Z. Wang, B. Liu, and X. Q. Sun, “Determination of tinidazole by fluorimetry,” Fenxi Ceshi Xuebao, vol. 23, pp. 76–79, 2004.
[22]
X. C. Fu, G. P. Wang, Y. H. Wang, and W. Q. Liang, “A predictive model for the release of slightly water-soluble drugs from HPMC matrices,” Pharmazie, vol. 59, no. 8, pp. 624–626, 2004.
[23]
C. H. Yang, “Voltammetric determination of tinidazole using a glassy carbon electrode modified with single-wall carbon nanotubes,” Analytical Sciences, vol. 20, no. 5, pp. 821–824, 2004.
[24]
A. P. Argekar and J. G. Sawant, “Simultaneous determination of ciprofloxacin hydrochloride and tinidazole in tablets by HPTLC,” Journal of Planar Chromatography—Modern TLC, vol. 12, no. 3, pp. 202–206, 1999.
[25]
A. P. Argekar and S. G. Powar, “Simultaneous determination of diloxanide furoate and tinidazole in tablets by high-performance thin-layer chromatography,” Journal of Planar Chromatography—Modern TLC, vol. 12, no. 6, pp. 452–455, 1999.
[26]
H. Sun, F. Wang, L. Ai, C. Guo, and R. Chen, “Validated method for determination of eight banned nitroimidazole residues in natural casings by LC/MS/MS with Solid-Phase Extraction,” Journal of Association of Official Analytical Chemists International, vol. 92, no. 2, pp. 612–621, 2009.
[27]
Y. J. Yang, X. Y. Li, and H. Y. Li, “HPLC determination of related substances and content of tinidazole colon targeting tablets,” Yaowu Fenxi Zazhi, vol. 24, pp. 614–616, 2004.
[28]
G. S. Sadana and M. V. Gaonkar, Indian Drugs, vol. 22, pp. 241–246, 1989.
[29]
Y. Cheng, E. Ho, B. Subramanyam, and J. L. Tseng, “Measurements of drug-protein binding by using immobilized human serum albumin liquid chromatography-mass spectrometry,” Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, vol. 809, no. 1, pp. 67–73, 2004.
[30]
Vioxx? (rofecoxib) Information Center. Merk & Co., Inc, October 2010 http://www.merck.com/newsroom/vioxx_withdrawal.
[31]
Vioxx information, “Defective drugs, eJustice,” October 2009, http://www.adrugrecall.com/vioxx/information.html.
[32]
M. A. Shehata, A. Ashour, N. Y. Hassan, A. S. Fayed, and B. A. El-Zeany, “Liquid chromatography and chemometric methods for determination of rofecoxib in presence of its photodegradate and alkaline degradation products,” Analytica Chimica Acta, vol. 519, no. 1, pp. 23–30, 2004.
[33]
N. Erk and T. G. Altuntas, “Comparison of derivative spectrophotometric and liquid chromatographic methods for the determination of rofecoxib,” Pharmazie, vol. 59, no. 6, pp. 453–456, 2004.
[34]
A. Duran, B. Bek?e, and H. N. Do?an, “Quantitative determination of rofecoxib in pharmaceutical preparations,” Pharmazie, vol. 59, no. 1, pp. 71–72, 2004.
[35]
N. Kaul, S. R. Dhaneshwar, H. Agrawal, A. Kakad, and B. Patil, “Application of HPLC and HPTLC for the simultaneous determination of tizanidine and rofecoxib in pharmaceutical dosage form,” Journal of Pharmaceutical and Biomedical Analysis, vol. 37, no. 1, pp. 27–38, 2005.
[36]
M. Amini, M. P. Hamedani, M. Vosooghi, M. Nabavi, and A. Shafiee, “Pre-column derivatization of rofecoxib for determination in serum by HPLC,” Analytical and Bioanalytical Chemistry, vol. 382, no. 5, pp. 1265–1268, 2005.
[37]
P. R. Tiller, L. A. Romanyshyn, and U. D. Neue, “Fast LC/MS in the analysis of small molecules,” Analytical and Bioanalytical Chemistry, vol. 377, no. 5, pp. 788–802, 2003.
[38]
Nimesulide, “Pharmaceutical Industry, India,” October 2010, http://www.pharma-india.com/nimesulide.html.
[39]
British Pharmacopoeia, Her-Majesty's Stationary Office, London, UK, 2005.
[40]
Nimesulide Information, “Helsinn Healthcare SA,” October 2010, http://www.nimesulide.net/nimesulide.htm.
[41]
M. Blanco, M. A. Romero, and M. Alcalà, “Strategies for constructing the calibration set for a near infrared spectroscopic quantitation method,” Talanta, vol. 64, no. 3, pp. 597–602, 2004.
[42]
D. Mrinalini, A. Madgulkar, D. Juvale, B. Awate, and A. Zambre, “Simultaneous spectrophotometric estimation of nimesulide and chlorzoxazone in tablet dosage form,” Indian Drugs, vol. 38, no. 11, pp. 576–579, 2001.
[43]
H. Ferreira, M. Lúcio, B. De Castro, P. Gameiro, J. L. F. C. Lima, and S. Reis, “Partition and location of nimesulide in EPC liposomes: a spectrophotometric and fluorescence study,” Analytical and Bioanalytical Chemistry, vol. 377, no. 2, pp. 293–298, 2003.
[44]
S. G. Navalgund, P. S. Prabhu, P. S. Sahasrabudhe, H. K. Deepa, and R. T. Sane, “A simple colorimetric method for the determination of nimesulide from its pharmaceutical preparation,” Indian Drugs, vol. 37, no. 4, pp. 209–210, 2000.
[45]
R. I. L. Catarino, A. C. L. Concei??o, M. B. Q. Garcia, M. L. S. Gon?alves, J. L. F. C. Lima, and M. M. C. Dos Santos, “Flow amperometric determination of pharmaceuticals with on-line electrode surface renewal,” Journal of Pharmaceutical and Biomedical Analysis, vol. 33, no. 4, pp. 571–580, 2003.
[46]
S. Furlanetto, S. Orlandini, G. Aldini, R. Gotti, E. Dreassi, and S. Pinzauti, “Designing experiments to optimise and validate the adsorptive stripping voltammetric determination of nimesulide,” Analytica Chimica Acta, vol. 413, no. 1-2, pp. 229–239, 2000.
[47]
C. M. B. Rolim, V. Porta, and S. Storpirtis, “Quantitation of nimesulide in human plasma by high-performance liquid chromatography with ultraviolet absorbance detection and its application to a bioequivalence study,” Arzneimittel-Forschung, vol. 57, no. 8, pp. 537–541, 2007.
[48]
A. Maltese, F. Maugeri, and C. Bucolo, “Rapid determination of nimesulide in rabbit aqueous humor by liquid chromatography,” Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, vol. 804, no. 2, pp. 441–443, 2004.
[49]
R. E. Barrientos-Astigarraga, Y. B. Vannuchi, M. Sucupira, R. A. Moreno, M. N. Muscará, and G. De Nucci, “Quantification of nimesulide in human plasma by high-performance liquid chromatography/tandem mass spectrometry. Application to bioequivalence studies,” Journal of Mass Spectrometry, vol. 36, no. 12, pp. 1281–1286, 2001.
[50]
H. Nakamura and Z. Tamura, “Fluorometric assay of α-methylene carbonyl compounds with N-methylnicotinamide chloride,” Analytical Chemistry, vol. 50, no. 14, pp. 2047–2051, 1978.
[51]
“Validation of Analytical Procedures: Text and Methodology ICH,” October 2010, http://www.ich.org/cache/compo/363-272-1.html#Q2A.