Malaysian Journal of Analytical Sciences Vol 20 No 1 (2016): 51 -  63

 

 

 

NEW METHYLTRIMETHOXYSILANE-(3-MERCAPTOPROPYL)-TRIMETHOXYSILANE COATED HOLLOW FIBER-SOLID PHASE MICROEXTRACTION FOR HEXANAL AND HEPTANAL ANALYSIS

 

(Pengekstrakan Mikro Fasa Pepejal-Gentian Berongga Tersalut Metiltrimetoksisilana-

(3-merkaptopropil)trimetoksisilana Baharu bagi  Analisis Heksanal dan Heptanal)

 

Siti Munirah Abd Wahib¹, Wan Aini Wan Ibrahim^1,2*, Mohd Marsin Sanagi³

 

¹Separation Science and Technology Group (SepSTec), Department of Chemistry, Faculty of Science

²Frontier Materials Research Alliance

³Ibnu Sina Institute for Scientific and Industrial Research

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

 

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

 

 

Received: 9 December 2014; Accepted: 16 October 2015

 

 

Abstract

Determination of volatile organic compounds (VOCs) in various matrices is often accomplished using solid phase microextraction (SPME) as a superior mode of extraction. Alternatively, another configuration of solid phase microextraction (SPME) namely hollow fiber-solid phase microextraction (HF-SPME) is a great approach to redress some limitations of the ordinary SPME fibers including fiber breakage, coating stripping and sample carry over. The HF-SPME technique highlights the use of hollow polypropylene (PP) membrane to hold and protect the adsorbent inside its lumen. Unlike the conventional SPME, the inexpensive HF device can be disposed after single use. Introducing extracting phase via sol-gel technology has gained great interest owing to its simple preparation method and promising way to obtain materials with good characteristics. In the present work, a new hybrid silica material based on methyltrimethoxysilane-(3-mercaptopropyl)trimethoxysilane (MTMOS-MPTMOS) was introduced as a new extractant of HF-SPME and the effectiveness of the proposed method was tested for analysis of hexanal and heptanal as the target VOC analytes. Preparation of the HF-SPME MTMOS-MPTMOS was simple in which the hybrid material was synthesized via sol-gel method and was self-polymerized in small segments of HF. Parameters affecting the efficiency of the HF-SPME MTMOS-MPTMOS in extracting both aldehydes were thoroughly investigated and analyzed by gas chromatography-flame ionization detection (GC-FID). It was found that the highest efficiency was achieved as the extraction was conducted in 30 min at a stirring rate of 1000 rpm in a 10 mL of sample solution whereby the back-extraction was performed via vortex for 3 min using 100 µL methanol as desorption solvent. Under the optimal conditions, linearity was observed over a range of 0.020-10.00 µg mL^-1 with detection limits of 0.015 µg mL^-1 and 0.010 µg mL^-1 for hexanal and heptanal, respectively. The applicability of the HF-SPME MTMOS-MPTMOS for analysis of hexanal and heptanal in human urine sample was proven from the quantitative recoveries (> 90%) achieved. The HF-SPME MTMOS-MPTMOS offers an attractive alternative for rapid and convenient extraction tool and showed good potential for analysis of hexanal and heptanal from aqueous samples.

 

Keywords:  hollow fiber-solid phase microextraction, sol-gel hybrid, methyltrimethoxysilane, (3-mercaptopropyl)tri-methoxysilane,  hexanal, heptanal

 

Abstrak

Penentuan sebatian organik meruap (VOC) dalam pelbagai matriks sering dicapai dengan pengekstrakan mikro fasa pepejal (SPME) sebagai mod unggul pengekstrakan. Sebagai alternatif, pengekstrakan mikro fasa pepejal-gentian berongga (HF-SPME) adalah pendekatan yang baik untuk mengatasi kekangan gentian SPME biasa termasuk kerapuhan gentian, salutan tertanggal dan baki sampel suntikan tertinggal. Teknik HF-SPME mengetengahkan penggunaan membran polipropilena (PP) berongga untuk memegang dan melindungi fasa pengekstrak dalam lumen HF. Tidak seperti konvensional SPME, alat HF yang murah boleh dibuang selepas sekali penggunaan. Menghasilkan fasa pengekstrak melalui teknologi sol-gel telah mendapat perhatian luas kerana kaedah penyediaan yang mudah dan cara yang memberangsangkan untuk menghasilkan bahan dengan ciri-ciri yang baik. Dalam kajian semasa, bahan silika hibrid baharu berdasarkan metiltrimetoksisilana-(3-merkaptopropil)trimetoksisilana (MTMOS-MPTMOS) telah diperkenalkan sebagai bahan penjerap baharu HF-SPME dan keberkesanan kaedah yang dicadangkan telah diuji terhadap analisis heksanal dan heptanal sebagai analit VOC sasaran. Penyediaan HF-SPME MTMOS-MPTMOS adalah mudah yang mana bahan hibrid ini telah disintesis menggunakan kaedah sol-gel dan telah diswapolimer di dalam segmen kecil HF. Parameter yang mempengaruhi kecekapan HF-SPME MTMOS-MPTMOS dalam mengekstrak kedua-dua aldehid telah dikaji dengan teliti dan dianalisis menggunakan kromatografi gas-pengesan pengionan nyala (GC-FID). Kecekapan tertinggi telah dicapai apabila pengekstrakan dijalankan selama 30 min pada kadar kacauan 1000 rpm di dalam 10 mL larutan sampel yang mana pengekstrakan-kembali dilakukan melalui vorteks selama 3 min menggunakan 100 µL metanol sebagai pelarut penyahjerapan. Pada keadaan optimum, julat linear ialah 0.020-10.00 µg mL^-1 dengan had pengesanan bagi heksanal dan heptanal masing-masing ialah 0.015 µg mL^-1 and 0.010 µg mL^-1. Kesesuaian HF-SPME MTMOS-MPTMOS untuk analisis heksanal dan heptanal dalam sampel air kencing manusia terbukti dengan perolehan kuantitatif yang dicapai (> 90%). HF-SPME MTMOS-MPTMOS menawarkan alternatif menarik sebagai alat pengekstrakan yang cepat dan mudah serta menunjukkan potensi yang baik untuk analisis heksanal dan heptanal daripada sampel akueus.

 

Kata kunci:      pengekstrakan mikro fasa pepejal-gentian berongga, hibrid sol-gel, metiltrimetoksisilana, (3-merkaptopropil)-trimetoksisilana, heksanal, heptanal

 

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