Malaysian Journal of Analytical Sciences, Vol 28 No 3 (2024): 664 - 680

AUTHENTICATION OF CLOVE LEAF OIL IN PRODUCTS

(Syzygium aromaticum (L.) Merr. & L. M. Perry) USING GC-MS AND FTIR METHODS COMBINED WITH CHEMOMETRIC

Pengesahan Minyak Daun Cengkih (Syzygium aromaticum (L.) Merr. & L. M. Perry) dalam Produk Menggunakan Kaedah GC-MS dan FTIR Yang Digabungkan dengan Kemometri

Any Guntarti¹, Laela Hayu Nurani^1*, Putri Lestari¹, Citra Ariani Edityaningrum¹, Lalu Muhammad Irham¹,

and Abdul Rohman^2,3

¹Faculty of Pharmacy, Universitas Ahmad Dahlan Yogyakarta 55164, Indonesia

²Center of Excellence, Institute for Halal Industry and Systems, Universitas Gadjah Mada, Yogyakarta 55281, Indonesia

³Faculty of Pharmacy, Universitas Gajah Mada, Yogyakarta 55281, Indonesia

^*Corresponding author: laela.farmasi@pharm.uad.ac.id

Received: 24 January 2024; Accepted: 26 March 2024; Published: 29 June 2024

Abstract

The production cost and market demand for clove oil are significantly high due to its great commercial value and benefits. However, the extraction yield of clove oil is very low at around 1%, causing the act of adulteration of essential oils to reduce production costs. Therefore, this study aims to determine the addition of adulterants in essential oils using the authentication technique. The samples used are clove oil from dry leaf distillation, products A, B, and C on the market. The GC-MS and FTIR methods combined with PCA (Principal Component Analysis) and PLS (Partial Least Square) multivariate calibration analysis were selected in the authentication to detect clove oil adulteration. The constituent’s presence in distilled clove oil from GC-MS analysis was eugenol (49.63%), β-Caryophyllene (28.25%), alpha-Humulene (8.92%), alpha-Copaene (2.15%), delta-Cadinene (1.61%), and Caryophyllene oxide (1.50%). Six concentrations were prepared for FT-IR analysis of clove leaf oil and turpentine oil mixture, which was estimated by PLS and PCA chemometrics. Turpentine oil was used as counterfeit, which was usually added to clove oil products. The PLS analysis of FTIR obtained optimized wavenumbers, 2960-2860 cm^-1. The equation y=0.9998x+0.0096 had an R² value of 0.9998, as well as RMSEC, RMSECV, and RMSEP values of 0.22%, 0.76%, and 1.20%, respectively. The PCA analysis can categorize the oil based on the main component types of distilled clove leaf oil, turpentine oil, and market oil, namely products A, B, and C. The results showed that product A oil was in the same quadrant as distilled clove leaf oil. Moreover, no clove leaf oil product had similar physical and chemical characteristics to turpentine oil.

Keywords: authentication, clove leaf oil, Fourier transform infrared, gas chromatography-mass spectrometry, turpentine oil

Abstrak

Minyak cengkih mempunyai nilai dan faedah komersial yang besar, pada masa ini permintaan untuk ketersediaan minyak cengkih di pasaran adalah sangat tinggi namun, hasil perahan minyak cengkih adalah sangat rendah, iaitu sekitar 1% dan mengakibatkan kos pengeluaran minyak cengkih yang agak tinggi. Ini menyebabkan pemalsuan minyak pati untuk mengurangkan kos pengeluaran dan mengekalkan jumlah minyak pati. Satu teknik yang boleh digunakan untuk mengesan kehadiran bahan tiruan dalam minyak pati adalah melalui pengesahan. Kaedah GC-MS dan FTIR digabungkan dengan analisis penentukuran multivariat PCA (analisis prinsip utama) dan PLS (partial least square) telah dipilih dengan tujuan untuk mengesan tindakan pemalsuan pada minyak cengkih. Kandungan minyak daun cengkih suling daripada hasil analisis GC-MS iaitu eugenol 49.63% β-Caryophyllene 28.25%, alpha-Humulene 8.92%, alpha-Copaene 2.15%, delta-Cadiene 1.61% dan Caryophyllene oksida 1.50%. Analisis FT-IR dijalankan dengan membuat 6 siri kepekatan campuran minyak daun cengkih dan minyak turpentin dan kemudiannya dianalisis dengan kemometrik PLS dan PCA. Keputusan analisis PLS daripada FTIR menunjukkan bahawa nombor gelombang yang dioptimumkan ialah 2960-2860 cm^-1. Persamaan yang terhasil ialah y = 0.9998x + 0.0096 dengan nilai R² 0.9998; Nilai RMSEC (0.22%; nilai RMSECV 0.76%; dan nilai RMSEP 1.20%. Hasil analisis PCA mampu mengklasifikasikan minyak berdasarkan jenis komponen utama minyak suling daun cengkih, minyak turpentin, dan minyak daun di pasaran (A, B, dan C), di mana minyak produk A berada dalam kuadran yang sama dengan minyak daun cengkih suling dan tiada produk minyak daun cengkih yang mempunyai ciri fizikal dan kimia yang serupa dengan minyak turpentin.

Kata kunci: pengesahan, inframerah transformasi Fourier, kromatografi gas-spektometri jisim, minyak daun cengkih, minyak terpentin

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