The Solid-Phase of the Dynamic Microextraction of Thymol and Carvacrol Using a Porous, Low-Cost and Unbreakable Disk Coated by Polythiophene/Multiwalled Carbon Nanotubes

  • Fatemeh Yazdankhah * Department of Chemistry, Lorestan University, Khoramabad, Iran
Keywords: Polythiophene/multiwalled carbon nanotubes (PTh/MWCNTs), Solid-phase dynamic extraction (SPDE), SPE disk, Thymol, Carvacrol


Background and Aim: In the present study, a stainless steel plate was penetrated and platinized, and it was used as the disk for the solid phase dynamic extraction (SPDE) method. The SPE disk was coated by polythiophene/multiwalled carbon nanotubes (PTh/MWCNTs) nanocomposite using in-situ electropolymerization method.Materials and Methods: A high-surface area, porous and unbreakable platinized SPE disk was used for the dynamic extraction and determination of thymol and carvacrol by high-performance liquid chromatography (HPLC) with UV detection. The effect of various variables, including the type of elution solvent, pH, ionic strength and extraction time was optimized by the use of the central composite design (CCD) method.Results: Under the response surface methodology, the present method has admissible calibration curves over wide linear ranges of 0.01-100 µg mL-1 with high coefficient of determination (0.9998) that firmly confirms the high pertinence of the present method to the quantification of analytes. Meanwhile, their limits of detection (LODs) were 0.007 and 0.005 µg mL-1, and the limits of quantification (LOQs) were 0.09 and 0.01 µg mL-1 for thymol and carvacrol, respectively. Moreover, the enrichment factor (EF) was 87 for thymol and 54 for carvacrol, and the preconcentration factor was 142.8 for thymol and carvacrol.Conclusion: The SPDE-PTh/MWCNTs-disk was used for the extraction of thymol and carvacrol in thyme samples, and satisfactory results were obtained


Nickavar B, MojabB F, Dolat-Abadi R. Analysis of the essential oils of two Thymus species from Iran Food Chem. 2005;90:609- 11.

Balavoine GG, Geletii YV. Peroxynitrite scavenging by different antioxidants. Part I: convenient assay. Nitric Oxide. 1999;3:40-54.

Du WX, Olsen CW, Avena-Bustillos RJ, McHugh TH, Levin CE, Friedman M. Storage stability and antibacterial activity against Escherichia coli O157: H7 of carvacrol in edible apple films made by two different casting methods. J Agric Food Chem. 2008;56:3082-8.

Kiyanpour V, Fakhariab AR, Alizadeh R, Asghari B, Jalali-Heravic M. Multivariate optimization of hydrodistillation-headspace solvent microextraction of thymol and carvacrol from Thymus transcaspicus. Talanta. 2009;79:695-9.

Bagamboula C, Uyttendaele M, Debevere J. Inhibitory effect of thyme and basil essential oils, carvacrol, thymol, estragol, linalool and p-cymene towards Shigella sonnei and S. flexneri Food Microbiol. 2004;21:33-42.

Sereshti H, Izadmanesh Y, Samadi S, Optimized ultrasonic assisted extraction-dispersive liquid–liquid microextraction coupled with gas chromatography for determination of essential oil of Oliveria decumbens Vent. J Chromatogr A. 2011;1218:4593-8.

Zare F, Ghaedi M, Daneshfar A, Solid phase extraction of antidepressant drugs amitriptyline and nortriptyline from plasma samples using core-shell nanoparticles of the type Fe3O4@ ZrO2@ N-cetylpyridinium, and their subsequent determination by HPLC with UV detection. Microchim Acta. 2015;182:1893-902.

Zare F, Ghaedi M, Daneshfar A. Application of an ionic-liquid combined with ultrasonic-assisted dispersion ofgold nanoparticles for micro-solid phase extraction of unmetabolized pyridoxine and folic acid in biological fluids prior to high-performance liquid chromatography. RSC Adv. 2015;5:70064-72.

Albuquerque BR, Prieto MA, Barreiro MF, Rodrigues A, Curran TP, Barros L, et al. Catechin-based extract optimization obtained from Arbutus unedo L. fruits using maceration/microwave/ultrasound extraction techniques. Ind Crops Prod. 2017;95:404-15.

Safdar M.N, Kausar T, Jabbar S, Mumtaz A, Ahad K, Saddozai AA. Extraction and quantification of polyphenols from kinnow (Citrus reticulate L.) peel using ultrasound and maceration techniques. J Food Drug Anal. 2017;25:488-500.

Ćujić N, Šavikin K, Janković T, Pljevljakušić D, Zdunić G, Ibrić S. Optimization of polyphenols extraction from dried chokeberry using maceration as traditional technique. Food Chem. 2016;194:135-42.

Ghiasvand AR, Dowlatshah S, Nouraei N, Heidari N, Yazdankhah F. A solid-phase microextraction platinized stainless steel fiber coated with a multiwalled carbon nanotube-polyaniline nanocomposite film for the extraction of thymol and carvacrol in medicinal plants and honey. J Chromatogr A. 2015;1406:87-93.

Roosta M, Ghaedi M, Daneshfar A, Sahraei R, Ultrasound assisted microextraction-nano material solid phase dispersion for extraction and determination of thymol and carvacrol in pharmaceutical samples: Experimental design methodology. J Chromatogr B. 2015;975:34-39.

Ghaedi M, Roosta M, Khodadoust S, Daneshfar A. Application of optimized vortex-assisted surfactant-enhanced dllme for preconcentration of thymol and carvacrol, and their determination by HPLC-UV: response surface methodology. J Chromatogr Sci. 2015;53:1222-31.

Ghiasvand AR, Moradi F, Sharghi H, Hasaninejad AR. Determination of silver (I) by electrothermal-AAS in a microdroplet formed from a homogeneous liquid-liquid extraction system using tetraspirocyclohexylcalix pyrroles. Anal Sci. 2005;21:387-90.

Płotka-Wasylka J, Szczepańska N, Guardia M, Namieśnik J. Modern trends in solid phase extraction: new sorbent media. Trends Anal Chem. 2016; 77:23-43.

Thurman E, Snavely K. Advances in solid-phase extraction disks for environmental chemistry. Trends Anal Chem. 2000;19:18-26.

Yin YM, Chen YP, Wang XF, Liu Y, Liu HL, Xia Xie M. Dummy molecularly imprinted polymers on silica particles for selective solid-phase extraction of tetrabromobisphenol A from water samples. J Chromatogr A. 2012;1220:7-13.

Martin-Esteban A, Molecularly imprinted polymers: new molecular recognition materials for selective solid-phase extraction of organic compounds. Fresenius. J Anal Chem. 2001;370:795-802.

Jordan TB, Nichols DS, Kerr NI. Selection of SPE cartridge for automated solid-phase extraction of pesticides from water followed by liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem. 2009; 394:2257-66.

Mashhadizadeh M.H, Pestehb M, Talakeshb M, Sheikhshoaiec I, Ardakani M.M, Ali-Karimie M, Solid phase extraction of copper (II) by sorption on octadecyl silica membrane disk modified with a new Schiff base and determination with atomic absorption spectrometry. Spectrochim Acta B. 2008;63:885-8.

Poole CF. New trends in solid-phase extraction. Trends Anal Chem. 2003;22:362-73.

Gómez M.J, Petrovićbc M, Fernández-Albaa A.R, Barcelób D. Determination of pharmaceuticals of various therapeutic classes by solid-phase extraction and liquid chromatography–tandem mass spectrometry analysis in hospital effluent wastewaters. J Chromatogr A. 2006;1114:224-33..

Tamayo F, Turiel E, Martín-Esteban A. Molecularly imprinted polymers for solid-phase extraction and solid-phase microextraction: recent developments and future trends. J Chromatogr A. 2007;1152:32-40.

Safaei-Ghomi J, Ebrahimabadi AH, Djafari-Bidgoli Z, Hossein ZB. GC/MS analysis and in vitro antioxidant activity of essential oil and methanol extracts of Thymus caramanicus Jalas and its main constituent carvacrol. Food Chem. 2009;115:1524-8.

Vinas P, Soler-Romera M.J, Hernández-Córdoba M. Liquid chromatographic determination of phenol, thymol and carvacrol in honey using fluorimetric detection. Talanta. 2006;69:1063-7.

Hajimehdipoor H, Shekarchi M, Khanavi M, Adib N, Amri M. A validated high performance liquid chromatography method for the analysis of thymol and carvacrol in Thymus vulgaris L. volatile oil. Pharmacogn Mag. 2010;6:154.

Arthur CL, Pawliszyn J. Solid phase microextraction with thermal desorptionusing fused silica optical fibers, Anal Chem, 1990;62:2145–8.

Psillakis E, Kalogerakis N. Developments in single-drop microextraction. Trend Anal Chem. 2002;21:54–64.

Original Article