Rapid detection of synthetic adulterants in Indonesian herbal medicines using ATR-FTIR spectroscopy combined with chemometrics

Year 2023, Volume: 27 Issue: 1, 184 - 196, 28.06.2025

Azminah Azminah Islamudin Ahmad Jihan Azmi Nur Fikri Muhammad Irsal Jumadil Nadia Aqilah Fakhriyyah Erza Sarini Abdullah Adelina Simamora Abdul Mun’im

Abstract

Herbal medicines have been gaining popularity as alternative medicines in recent years, including in Indonesia. Synthetic drug compounds can be illegally included in herbal medicines to achieve a faster effect. Detection of synthetic drugs in adulterated herbal products is important because of the negative side effects associated with short- and long-term use. Sildenafil, phenylbutazone, and sibutramine HCl are common adulterants in Indonesian herbal products intended to promote sexual arousal and performance, relieve muscle pain, and reduce weight. The aim of this study was the rapid and cost-effective detection of sildenafil citrate, phenylbutazone, and sibutramine HCl in Indonesian herbal products and herbal drug preparations by Attenuated Total Reflectance-Fourier Transmission Infrared Spectrometer (ATR-FTIR) spectroscopy combined with chemometrics. Herbs (aphrodisiac, muscle pain relieving and slimming herbs) and medicinal plants (Pasak Bumi (Eurycoma longifolia Jack.) roots, black pepper (Piper nigrum L.) leaves and West Indian Elm (Guazuma ulmifolia Lamk.) leaves) were intentionally adulterated with synthetic drug compounds in the range of 0-40% (w/w). ATR-FTIR spectra were recorded for all unadulterated and adulterated samples at 4000 - 650 cm-1. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied to analyze the spectra of the unadulterated and adulterated samples. All samples were successfully classified with respect to their synthetic compound content. The presence of sildenafil, phenylbutazone and sibutramine can be rapidly detected with simple and non-destructive sample preparation using ATR-FTIR spectroscopy in combination with chemometrics. In conclusion, this method can be used for screening sildenafil citrate, phenylbutazone and sibutramine HCl adulterants in herbal products and herbal powders.

Keywords

Adulteration , aphrodisiac herb , pain-relieving herb , principal component analysis , hierarchical cluster analysis

References

• BPOM-RI. Peraturan Kepala Badan Pengawas Obat dan Makanan Republik Indonesia Nomor 12 Tahun 2014 tentang Persyaratan Mutu Obat Tradisional. 2014.
• [2] BPOM Announces 54 Traditional Medicines Containing Medicinal Chemicals (BKO). Media Konsumen 2015 30 November 2015.
• [3] BPOM-RI. Peraturan Kepala Badan Pengawas Obat dan Makanan Republik Indonesia Nomor 5 Tahun 2016 tentang Penarikan dan Pemusnahan Obat Tradisional yang Tidak Memenuhi Persyaratan. 2016.
• [4] Indonesia’s health minister regulations permenkes-no-26-tahun-2018. [CrossRef]
• [5] Thompson TJU, Gauthier M, Islam M. The application of a new method of Fourier Transform Infrared Spectroscopy to the analysis of burned bone. J Archeol Sci. 2009;36(3):910–4. [CrossRef]
• [6] da Silva C, Prasniewski A, Calegari MA, de Lima VA, Oldoni TLC. Determination of total phenolic compounds and antioxidant activity of ethanolic extracts of propolis using ATR – FT-IR spectroscopy and chemometrics. Food Anal Methods. 2018;11:2013–21. [CrossRef]
• [7] Cao Z, Wang Z, Shang Z, Zhao J. Classification and identification of Rhodobryum roseum Limpr. and its adulterants based on fourier-transform infrared spectroscopy (FTIR) and chemometrics. PLoS One. 2017;12(2):e0172359. [CrossRef]
• [8] Ahmad I, Fikri JAN, Arifianti AE, Abdullah S, Mun’im A. The combination of ATR-FTIR and chemometrics for rapid analysis of essential oil from Myrtaceae plants – A review Journal of Applied Pharmaceutical Science. 2022;12(6),030-42. [CrossRef]
• [9] Cebi N, Yilmaz MT, Sagdic O. A rapid ATR-FTIR spectroscopic method for detection of sibutramine adulteration in tea and coffee based on hierarchical cluster and principal component analyses. Food Chem. 2017;229,517. [CrossRef]
• [10] Gad HA, El-Ahmady SH, Abou-Shoer MI, Al-Azizi MM. Application of chemometrics in authentication of herbal medicines: A review. Phytochem. 2012;2012:1–24. [CrossRef]
• [11] Kucharska-Ambrożej K, Karpinska J. The application of spectroscopic techniques in combination with chemometrics for detection adulteration of some herbs and spices. Microchemical Journal. 2020;153,104278. [CrossRef]
• [12] Champagne AB, Emmel KV. Rapid screening test for adulteration in raw materials of dietary supplements. Vibrational Spectroscopy. 2011; 55:216-223. [CrossRef]
• [13] Lin M, Rasco BA, Cavinato AG, Al-Holy M. Infrared (IR) spectroscopy-near infrared spectroscopy and mid-infrared spectroscopy. In: Infrared spectroscopy for food quality analysis and control. London, Nederland: Elsevier Inc.; 2009. [CrossRef]
• [14] Anzanello MJ, Ortiz RS, Limbergerb RP, Mayorga P. A multivariate-based wavenumber selection method for classifying medicines into authentic or counterfeit classes. J Pharm Biomed Anal. 2013;83:209–14. [CrossRef]
• [15] Mateescu C, Popescu AM, Radu GL, Onisei T, Raducanu AE. Spectroscopic and spectrometric methods used for the screening of certain herbal food supplements suspected of adulteration. Adv Pharm Bull. 2017;7(2):251–9. [CrossRef]
• [16] Kurniaty R, Khairan K, Lelifajri L. Analysis of sildenafil and its derivatives in jamu (herbal medicines) using LC/MS/MS spectroscopy. J Nat. 2018;18(3):115–21. [CrossRef]
• [17] Waters LJ, Hanrahan JP, Tobin JM, Finch CV, Parkes GMB, Ahmad SA, Mohammad F, Saleem M. Enhancing the dissolution of phenylbutazone using Syloid® based mesoporous silicas for oral equine applications. Journal of Pharmaceutical Analysis. 2018;8(3):181-186. [CrossRef]
• [18] Coates J. Interpretation of infrared spectra, a practical approach. Encycl Anal Chem. 2006;10815–37. [CrossRef]
• [19] Popescu AM, Radu GL. Detection of adulterants by FTIR and GC-MS in herbal slimming food supplements. UPB Sci Bull. 2015;77:221–30. [CrossRef]
• [20] Farag NF, El-Ahmady SH, Abdelrahman EH, Naumann A, Schulz H, Azzam SM, El-Kashoury E-SA. Characterization of essential oils from Myrtaceae species using ATR-IR vibrational spectroscopy coupled to chemometrics. Ind Crop Prod. 2018;124:870–7. [CrossRef]
• [21] Maluf DF, Pontarolo R, Cordeiro GA, Nagata N, Peralta-Zamora P. Determination of sibutramine in pharmaceutical forms through diffuse reflectance infrared spectroscopy and multivariate calibration. Quim New. 2010;33(3):649–52. [CrossRef]
• [22] Eliaerts J, Dardenne P, Meert N, Van Durme F, Samyn N, Janssens K, De Wael K. Rapid classification and quantification of cocaine in seized powders with ATR-FTIR and chemometrics. Drug Test Anal. 2017;9(10):1480–9. [CrossRef]
• [23] Bunaciu AA, Aboul-Enein HY. Adulterated drug analysis using FTIR spectroscopy. Appl Spectrosc Rev. 2020;0(0):1–15. [CrossRef]