Malaysian Journal of Analytical Sciences, Vol 28 No 1 (2024): 141 - 156

MODIFIED CHRYSIN-BASED BIOSORBENT FOR THE DISPERSIVE MICRO-SOLID PHASE EXTRACTION OF SELECTED PHENOLIC ACIDS FROM STINGLESS BEE HONEY

(Biopenjerap yang Diubahsuai berasaskan Krisin untuk Pengekstrakan Fasa Pepejal-mikro Asid Fenolik Terpilih secara Serakan daripada Madu Lebah Tanpa Sengat)

NyukTing Ng¹, Aemi Syazwani Abdul Keyon^1,2*, Wan Aini Wan Ibrahim^1*, Mohd Marsin Sanagi¹

and Faridah Mohd Marsin³

¹Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia

²Centre for Sustainable Nanomaterials, Ibnu Sina Institute for Scientific and Industrial Research, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia

³Jabatan Kimia Malaysia Negeri Pahang, Jalan Dato’ Bahaman, Alor Akar, 25662 Kuantan, Pahang, Malaysia

^*Corresponding author: aemi@utm.my; waini@utm.my

Received: 13 September 2023; Accepted: 30 December 2023; Published: 28 February 2024

Abstract

This study focuses on the preparation, characterisation, and application of a chrysin-based biosorbent (TA-CHY) for extracting protocatechuic acid (PCA) and vanillic acid (VA) from stingless bee honey (SBH) using a dispersive micro-solid phase extraction method. The extracted analytes were separated using high-performance liquid chromatography and detected using an ultraviolet detector. TA-CHY was prepared by depositing tannic acid onto the amino-functionalized chrysin. Its point of zero charge was determined at pH 6.8. Fourier transform infrared spectroscopy analysis had identified the presence of C=N, C=C, O-H, SiOR and C-O groups in TA-CHY, while aggregate formation was observed on TA-CHY through scanning electron microscopy. Energy dispersive X-ray study revealed the elemental composition of TA-CHY was 52.9% of C, 34.0% of O, 6.80% of Si and 6.3% of N. Its specific surface area was found to be 5.913 m²/g via Brunauer-Emmett-Teller surface area analysis. Optimised extraction parameters were 1 min extraction time, 300 µL methanol as desorption solvent, 15 min desorption time, sample pH of 2, no NaCl salt addition, 0.20 g biosorbent mass and 2 mL ethanol as dispersant solvent. The developed method was validated using matrix-match calibration where real SBH samples spiked with PCA and VA in the concentration range of 0.5-50 mg/L. The method exhibited satisfactory analytical performance characteristics, with a limit of detection ranging from 0.81 to 1.37 mg/kg, a limit of quantification ranging from 2.69 to 4.56 mg/kg, relative recoveries ranging from 79.38% to 113.38%, and precision with relative standard deviation values ranging from 0.29% to 10.83%. Importantly, the proposed method obtained a score of 71 on the analytical Eco-Scale, indicating its acceptability as a green method.

Keywords: chrysin, biosorbent, dispersive micro-solid phase extraction, phenolic acids, stingless bee honey

Abstrak

Kajian ini memberi tumpuan pada penyediaan, pencirian, dan penggunaan biopenjerap berasaskan krisin (TA-CHY) untuk mengekstrak asid protokatekuik (PCA) dan asid vanillik (VA) daripada madu lebah (SBH) tanpa sengat dengan menggunakan kaedah pengekstrakan fasa pepejal-mikro secara serakan. Analit yang diekstrak telah diasingkan menggunakan kromatografi cecair berprestasi tinggi dan dikesan menggunakan pengesan ultraungu. Biopenjerap TA-CHY telah disediakan dengan mendepositkan asid tannik pada krisin yang telah diberikan fungsi amino. Cas sifar titiknya telah ditentukan pada pH 6.8. Analisis spektroskopi inframerah transformasi Fourier telah mengenalpasti kehadiran kumpulan C=N, C=C, O-H, SiOR dan C-O dalam TA-CHY manakala pembentukan agregat diperhatikan pada TA-CHY melalui mikroskop pengimbas electron. Kajian tenaga penyerakan sinar-X mendedahkan komposisi unsur bagi TA-CHY ialah 52.9% C, 34.0% O, 6.80% Si dan 6.3% N. Luas permukaan spesifiknya didapati sebanyak 5.913 m²/g melalui analisis kawasan permukaan Brunauer-Emmett-Teller. Parameter pengekstrakan yang dioptimumkan ialah 1 minit masa pengekstrakan, 300 µL metanol sebagai pelarut desorpsi, 15 minit masa desorpsi, pH sampel 2, tiada penambahan garam NaCl, 0.20 g jisim biopenjerap dan 2 mL etanol sebagai pelarut penyerakan. Kaedah yang dibangunkan telah disahkan menggunakan kalibrasi padanan-matriks dengan sampel SBH tulen dengan menambah PCA dan VA dalam lingkungan kepekatan 0.5-50 mg/L. Kaedah ini menunjukkan ciri prestasi analisis yang memuaskan, dengan had pengesanan antara 0.81 dan 1.37 mg/kg, had kuantitatif antara 2.69 dan 4.56 mg/kg, pemulihan relatif antara 79.38% dan 113.38%, dan ketepatan dengan sisihan piawai relatif, antara 0.29% dan 10.83%. Kaedah yang dicadangkan telah memperoleh markah 71 pada skala-Eko analitik yang menunjukkan kebolehterimaannya sebagai kaedah hijau adalah sangat penting.

Kata kunci: krisin, biopenjerap, pengekstrakan fasa pepejal-mikro secara serakan, asid fenolik, madu lebah tanpa sengat

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