Malaysian Journal of Analytical Sciences, Vol 27 No 3 (2023): 521 - 532

EXPLORATION OF NATURAL DEEP EUTECTIC SOLVENT AS THE ALTERNATIVE DISPERSIVE SOLVENT IN DLLME FOR THE EXTRACTION OF ANABOLIC STEROID DRUGS IN WATER

(Penerokaan Pelarut Eutektik Semulajadi Sebagai Alternatif Pelarut Serakan dalam DLLME untuk Pengekstrakan Ubat Steroid Anabolik dalam Air)

Azreen Asyikin Mhd Kamal^1*, Wan Nazihah Wan Ibrahim¹, Mohd Sufri Mastuli¹, Noorfatimah Yahaya²_, Sazlinda Kamaruzaman³, Sheela Chandren⁴, Nurul Auni Zainal Abidin⁵, and Nursyamsyila Mat Hadzir¹

¹Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

²Integrative Medicine Cluster, Advanced Medical and Dental Institute, Universiti Sains Malaysia, 13200 Kepala Batas, Penang, Malaysia

³Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, Serdang, Selangor, Malaysia

⁴Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia

⁵Faculty of Applied Sciences, Universiti Teknologi MARA, Negeri Sembilan Branch,72000 Kuala Pilah, Negeri Sembilan, Malaysia

*Corresponding author: wannazihah@uitm.edu.my

Received: 13 February 2023; Accepted: 18 April 2023; Published: 23 June 2023

Abstract

By combining hydrogen bond donors such as D-sorbitol, glucose, and sucrose with hydrogen bond acceptors like L-proline and lactic acid, a successful preparation of six new types of eco-friendly solvent known as natural deep eutectic solvents (NADES) was achieved. Their capability as dispersive solvent substituting hazardous and non-biodegradability organic solvents was explored in vortex-assisted dispersive liquid-liquid microextraction (VADLLME) method for determination of anabolic steroid drugs in aqueous samples. Optimization combination of hydrogen bond donor-hydrogen bond acceptor and their molar ratio were investigated, and the result showed high viscosity of lactic acid: sorbitol at a molar ratio of 2:1, whereby recorded the highest extraction efficiency towards the determination of nandrolone and testosterone. This optimum NADES combination was then performed in three significant VADLLME procedures, including the volume of NADES as the dispersive solvent, type, and volume of extraction solvent. The VADLLME optimal conditions are as follows: NADES dispersive solvent volume of 500 µL, chloroform as an extraction solvent and extraction solvent volume at 200 µL. Under the optimum conditions, good linearity was achieved (0.5 - 10 mg/L) with the coefficient of determination (R²) of 0.9990 and 0.9996 for the nandrolone and testosterone, respectively. The LOD values were recorded in the range of 0.0020 - 0.0117 mg/L, while LOQ values were recorded in the range of 0.0067 - 0.0392 mg/L, respectively. The developed NADES-VADLLME method was applied for the determination of nandrolone and testosterone in tap water samples, with relative recovery values ranging from 88.63 - 97.23%. Based on the results obtained, the developed method demonstrated excellent sensitivity for the extraction of nandrolone and testosterone in water samples. The prepared NADES showed great potential as an alternative green dispersive solvent for the extraction of anabolic steroids active contaminants in the aquatic system.

Keywords: natural deep eutectic solvents, dispersive liquid-liquid microextraction, anabolic steroid drugs, dispersive solvent, green analytical chemistry

Abstrak

Dengan menggabungkan penderma ikatan hidrogen seperti D-sorbitol, glukosa, dan sukrosa dengan penerima ikatan hidrogen seperti L-prolin dan asid laktik, penyediaan enam jenis pelarut mesra alam baharu dikenali sebagai pelarut eutektik dalam semulajadi (NADES) telah berjaya disediakan. Keupayaan mereka sebagai pelarut serakan menggantikan pelarut organik berbahaya dan tidak boleh terbiodegradasi telah diterokai dalam kaedah pengekstrakan mikro cecair-cecair serakan dibantu vorteks (VADLLME) untuk penentuan ubat steroid anabolik di dalam sampel akueus. Pengoptimuman gabungan penderma ikatan hidrogen dan nisbah molarnya telah disiasat dan hasilnya menunjukkan kelikatan asid latik:sorbitol yang tinggi pada nisbah molar 2:1 menunjukkan kecekapan pengkestrakan tertinggi terhadap penentuan nandrolon dan testosteron. Gabungan optimum NADES ini kemudiannya dilakukan dalam tiga prosedur utama VADLLME termasuk isipadu NADES sebagai pelarut serakan, jenis dan isipadu pelarut pengekstrakan. Keadaan optimum VADLLME seperti berikut: isipadu pelarut dispersif NADES 500 µL, kloroform sebagai pelarut pengekstrakan dan isipadu pelarut pengekstrakan pada 200 µL. Pada keadaan optimum, kelinearan yang baik telah dicapai (0.5 - 10 mg/L) dengan pekali penentuan (R²) masing-masing 0.9990 dan 0.9996 untuk nandrolon dan testosteron. Nilai LOD direkodkan dalam julat 0.0020 - 0.0117 mg/L manakala nilai LOQ masing-masing direkodkan dalam julat 0.0067 - 0.0392 mg/L. Kaedah NADES-VADLLME yang dibangunkan telah digunakan untuk penentuan nandrolon dan testosteron di dalam sampel air paip, dengan nilai pemulihan antara 88.63 - 97.23%. Berdasarkan keputusan yang diperoleh, kaedah yang dibangunkan menunjukkan sensitiviti yang sangat baik untuk pengestrakan nandrolon dan testosteron dalam sampel air. NADES yang disediakan menunjukkan potensi besar sebagai pelarut dispersif hijau alternatif untuk pengestrakan bahan cemar aktif steroid anabolik dalam sistem akuatik.

Kata kunci: pelarut eutektik dalam semulajadi, pengekstrakan mikro cecair-cecair serakan, ubat steroid anabolik, pelarut serakan, kimia analitikal hijau

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