Malaysian Journal of Analytical Sciences Vol 19 No 3 (2015): 481 – 492

 

 

 

NEW FUNCTIONALISED SOL-GEL HYBRID SORBENT COATING FOR STIR BAR SORPTIVE EXTRACTION OF SELECTED NON-STEROIDAL ANTI INFLAMMATORY DRUGS IN HUMAN URINE SAMPLES

 

(Bahan Salutan Baharu Hibrid Sol-Gel Terfungsi Untuk Pengekstrakan Erapan Bar Berputar Ubat  Anti-Radang Bukan Steroid Terpilih Dalam  Sampel Urin Manusia)

 

Mashkurah Abd Rahim¹ , Wan Aini Wan Ibrahim*^{1, 2}, Zainab Ramli^{1, 2},  Mohd Marsin Sanagi^{1, 2}

 

¹Separation Science and Technology Group (SepSTec),

Department of Chemistry, Faculty of Science,

²Ibnu Sina Institute for Scientific & Industrial Research (ISI-SIR),

 Universiti Teknologi Malaysia, 81310 UTM, Johor Bahru, Johor, Malaysia

 

*Corresponding author: wanaini@kimia.fs.utm.my, waini@utm.my

 

 

Received: 30 January 2015; Accepted: 1 April 2015

 

 

Abstract

A new sol-gel hybrid material, methyltrimethoxysilane-cyanopropyltriethoxysilane (MTMOS-CNPrTEOS) was successfully synthesized and used as a coating material in stir bar sorptive extraction (SBSE) of selected non-steroidal anti-inflammatory drugs (NSAIDs) in urine samples. The MTMOS-CNPrTEOS hybrid was synthesized by hydrolysis and condensation of MTMOS and CNPrTEOS in the presence of trifluoroacetic acid as catalyst via sol–gel method. Several factors influencing the synthesized sol-gel hybrid MTMOS-CNPrTEOS process such as mole ratio of MTMOS-CNPrTEOS, NaOH concentrations as etching solution, etching time, coating time and water content were investigated and optimized in this study. The optimum synthesis conditions obtained were 1:1 mol ratio of MTMOS-CNPrTEOS, 1 M NaOH as etching solution, 60 min etching time, 2 h coating time and 6 mmol water. The sol-gel hybrid MTMOS-CNPrTEOS synthesized under the optimum conditions was used to determine selected NSAIDs in human urine samples using normal stacking mode capillary electrophoresis with ultraviolet detection. MTMOS-CNPrTEOS SBSE method demonstrated good linearity (60 to 20,000 µg L^-1) with excellent coefficient of determination (r² > 0.9990). The sol-gel hybrid MTMOS-CNPrTEOS SBSE method showed low limit of detection (35 – 41 µg L^-1) with good precision (RSD < 6 %, n = 3) and excellent extraction recoveries (83.5 – 98.9%) for the selected NSAIDs. The sol-gel hybrid MTMOS-CNPrTEOS SBSE method demonstrated good potential as an alternative sorbent in SBSE method for NSAIDs.

 

Keywords: Sol-gel hybrid, stir bar sorptive extraction, non-steroidal anti-inflammatory drugs, normal stacking mode, capillary electrophoresis-UV detection

 

Abstrak

Sol-gel hibrid baharu, metiltrimetoksisilana-sianopropiltrietoksisilana (MTMOS-CNPrTEOS) telah berjaya disintesis dan digunakan sebagai bahan baharu penyalutan untuk pengekstrakan erapan bar berputar (SBSE) dalam penentuan ubat anti-radang bukan steroid (NSAIDs) terpilih di dalam sampel urin manusia. Hibrid MTMOS-CNPrTEOS disintesis melalui hidrolisis dan kondensasi MTMOS dan CNPrTEOS dengan kehadiran asid trifluoroasetik sebagai mangkin melalui kaedah sol-gel. Beberapa faktor yang mempengaruhi proses penghasilan hibrid sol-gel MTMOS-CNPrTEOS seperti nisbah mol MTMOS-CNPrTEOS, kepekatan NaOH sebagai larutan punaran, masa punaran, masa salutan dan kandungan air dalam proses sol-gel telah dikaji dan dioptimumkan. Keadaan sintesis yang optimum ialah 1:1 nisbah mol MTMOS-CNPrTEOS, 1 M NaOH sebagai larutan punaran, 60 min masa punaran, 2 jam masa salutan dan 6 mmol air. Hibrid sol-gel MTMOS-CNPrTEOS yang disintesis di bawah keadaan optimum telah digunakan untuk menentukan NSAID terpilih dalam sampel urin manusia menggunakan mod normal tersusun elektroforesis rerambut dengan pengesan ultralembayung. Kaedah hibrid sol-gel MTMOS-CNPrTEOS SBSE menunjukkan kelinearan yang baik (60 - 20,000 μg L^-1) dengan pekali penentuan, r² > 0.9990 yang cemerlang. Kaedah hibrid sol-gel MTMOS-CNPrTEOS SBSE ini menunjukkan had pengesanan yang rendah (35 - 41 μg L^-1) dengan ketepatan yang baik (RSD < 6%, n = 3) dan pengembalian pengekstrakan yang cemerlang (83.5 – 98.9%) untuk NSAID terpilih. Kaedah hibrid sol-gel MTMOS-CNPrTEOS menunjukkan potensi tinggi sebagai pengerap alternatif untuk kaedah SBSE.

 

Kata kunci: Hibrid sol-gel, pengekstrakan bar berputar, ubat anti radang bukan steroid, mod tersusun normal, elektroforesis rerambut-pengesan ultralembayung

 

References

1.       Lisa, C. K. and Eliezer, M. R. (1994). Sol-gel optic: processing and application. Berlin: Springer International Series.

2.       Wan Ibrahim, W. A., Veloo, K. V., and Sanagi, M. M. (2012).  Novel sol-gel hybrid methyltrimethoxysilane-tetraethoxysilane as solid phase extraction sorbent for organophosphorus pesticides. J. Chromatogr. A, 1229:55-62.

3.       Rao, A. V. and Haranath, D. (1999). Effect of Methyltrimethoxysilane as a Synthesis Component on the Hydrophobicity and some physical properties of silica aerogels. Microporous Mesoporous Mater., 30: 267–273.

4.       Brambilla, R., Poisson, J., Miranda, M. S. L., Cardoso, M. B. and Butler, I. S. (2011). Sol-gel preparation of aminopropyl-silica-magnesia hybrid materials. J. Sol-Gel Sci. Tech., 2: 1–10.

5.       Wan Ibrahim, W. A., Abdul Keyon, A. S., Prastomo, N. and Atsunori, M. (2011). Synthesis and characterization of polydimethylsiloxane-cyanopropyltriethoxysilane-derived hybrid coating for stir bar sorptive extraction. J. Sol-Gel Sci. Technol., 59: 28–134.

6.       Wan Ibrahim, W. A., Wan Ismail, W. A. and Sanagi, M. M. (2013). Selective and Simultaneous Solid Phase Extraction of Polar and Non- Polar Organophosphorus Pesticides Using Sol-Gel Hybrid Silica-Based Sorbent. J. Tec., 62(3): 83–87.

7.       Colon, L. A., Guo, Y. and Fermier, A. (1997). Capillary Electrochromatography. Anal.Chem. 69: 461A–467A.

8.       Lopes, A. L. and Augusto, F. (2004). Preparation and characterization of polydimethylsiloxane/poly(vinylalcohol) coated solid phase microextraction fibers using sol–gel technology. J. Chromatogr. A. 1056: 13–19.

9.       Ebell, M. H. (2004). NSAIDs vs opiates for pain in acute renal colic. Am. Fam. Physician. 70(9): 1682–1690.

10.    Gajraj, N. M. (2003). The effect of cyclooxygenase-2 inhibitors on bone healing. Reg. Anesth. Pain. med. 28(5): 456–465.

11.    Chiang, J. and Huang, S. (2008). Simultaneous derivatization and extraction of amphetamine and methylenedioxyamphetamine in urine with headspace liquid-phase microextraction followed by gas chromatography-mass spectrometry. J. Chromatogr. B. 1185: 19–22.

12.    Pountos, I., Georgouli, T., Bird, H. and Giannoudis, P. V. (2011). Nonsteroidal anti-inflammatory drugs: prostaglandins, indications, and side effects. Int. J. Interferon. Cytokine Mediator. Res. 3: 19–27.

13.    Albero, B., Sanchez-Brunete, C. and L. Tadeo, J. (2003). Determination of Organophosphorus Pesticides in Fruit Juices by Matrix Solid-Phase Dispersion and Gas Chromatography. J. Agric. Food Chem. 51: 6915–6921.

14.    Lin, W. C., Chen, H. C. and Ding, W. H. (2005). Determination of pharmaceutical residues in waters by solid-phase extraction and large-volume on-line derivatization with gas chromatography-mass spectrometry. J. Chromatogr. A. 1065(2): 279–285.

15.    Basheer, C., Alnedhary, A. A., Rao, B. S. M., Valliyaveettil, S. and Lee, H. K. (2006). Development and application of porous membrane-protected carbon nanotube micro-solid-phase extraction combined with gas chromatography/mass spectrometry. Anal. Chem. 78(8):  2853–2858.

16.    He, Y. and Kang, Y. J. (2006). Single drop liquid-liquid-liquid microextraction of methamphetamine and amphetamine in urine. J. Chromatogr. A. 1133: 35–40.

17.    Allen, D. L. and Oliver, J. S. (2000). The use of supercritical fluid extraction for the determination of amphetamines in hair. Forensic Sci. Int.107(1-3), 191–199.

18.    Fan, Y., Feng, Y. Q., Zhang, J. T., Da, S. L. and Zhang, M. (2005). Poly(methacrylic acid-ethylene glycol dimethacrylate) monolith in-tube solid phase microextraction coupled to high performance liquid chromatography and analysis of amphetamines in urine samples. J. Chromatogr. A. 1074: 9–16.

19.    Chou, C. C. and Lee, M. R. (2005). Solid phase microextraction with liquid chromatography–electrospray ionization–tandem mass spectrometry for analysis of amphetamine and methamphetamine in serum. Anal. Chim. Acta. 538: 49–56.

20.    Zhou, J. and Zeng, Z. (2006). Novel fiber coated with β-cyclodextrin derivatives used for headspace solid-phase microextraction of ephedrine and methamphetamine in human urine. Anal. Chim. Acta. 556(2): 400–406.

21.    Segro, S. S., Cabezas, Y. and Malik, A. (2009). Ultra-high-stability, pH-resistant sol-gel titania poly(tetrahydrofuran) coating for capillary microextraction on-line coupled to high-performance liquid chromatography. J. Chromatogr. A. 1216(20): 4329–4338.

22.    Moner-Girona, M., Roig, A. and Molins, E. (2003). Sol-Gel Route to Direct Formation of Silica Aerogel Microparticles. J. Sol-gel Sci. Techol. 26: 645–649.

23.    Guido, K., Caseri, W., Bourgeat-Lami, E., Zhu, J. and A. Wilkie, C. (2007). Hybrid material: Synthesis, characterization and application. Guido, K., Ed., 2^nd edition,  Wiley-Vch Verlag GmbH.

24.    Pandey, S. and Mishra, B. S. (2011). Sol-gel derived organic-inorganic hybrid materials : synthesis , characterizations and applications. J. Sol-gel Sci Technol. 57: 126-138.

25.    Khan, B. A., Farid, A., Asi, M. R., Shah, H. and Badshah, A. K. (2009). Determination of residues of trichlorfon and dimethoate on guava using HPLC. Food Chem. 114(1): 286–288.

26.    Kaplan, S. L. and Rose, P. W. (1991). Plasma surface treatment of plastics to enhance adhesion. Int. J. Adhes. Adhes. 11(2): 109–113.

27.    Momose, Y., Noguchi, M. and Okazaki, S. (1989). Ar, O and CF₄ plasma treatment of poly-(vinylidene fluoride), polyimide and polyamidoimide and its relationship to wettability. Nucl. Inst. Methods Phy. Res. 39: 805–808.

28.    Gerenser, L. J. (1993). XPS studies of in situ plasma-modified polymer surfaces. J. Adhes. Tech. 7(10): 1019–1040.

29.    Varinder, K., Ashok, K. M. and Neelam, V. (2006). Applications of solid - phase microextraction for the determination of metall ic and organometallic species. Wiley Inter Science publication.

30.    Nicolaon, G.A. and Teichner, S,J. (1968). New preparation process for silica xerogels and aerogels and their textural properties. Bull. Soc. Chim. France 5: 1900–1906.