Screening antifungal activity of Mentha sp. by two-dimensional gas chromatography combined to multivariate data prosessing
Prata, Paloma Santana; Augusto, Fabio; Fukuda, Karina; Aleme, Helga G.; Duarte, Renata M.T.; Duarte, Marta C.T.; Sartoratto, Adilson; Poppi, Ronei J.
Palavras-chave: GC×GC, secondary metabolites, antifungal properties, multivariate analyses, Mentha.
Resumo: Combination of Comprehensive Two-Dimensional Gas Chromatography (GC×GC) and multivariate data processing was evaluated to model and predict the antifungal activity of essential oils of Menth sp. Metabolites secondary in leaves of various species and cultivars of Mentha were isolated by hydrodistillation and the antimycotic activity of these essential oils against to a pathogenic yeast (Candida dubliniensis) was estimated and expressed after determination of their Minimum Inhibitory Concentrations (MIC). In this work, these samples were analyzed by GC×GC with flame ionization detection (-FID) and mass spectrometry (-QMS). A model correlating MIC against C. dubliniensis to GC×GC-FID chromatograms was obtained to using N-way Partial Least Square Discriminant Analysis (N-PLS-DA) Calibration. This model, when applied to chromatograms obtained for validation samples was able to successfully predict to presence or absence of antimycotic activity in 92% of the cases. In addition, GC×GC-QMS chromatogram inspected allowed the preliminary identification of secondary metabolites responsible for activity model: linalool, carvone, pulegone, piperitone and piperitone oxide. This demonstrates the potential of GC×GC-FID – a simple and inexpensive technique – combined with chemometrics techniques as a powerful tool to infer the biochemical properties of complex mixtures of metabolites.
 Jalali-Heravi M, Parastar H (2011) Recent trends in application of multivariate curve resolution approaches for improving gas chromatography–mass spectrometry analysis of essential oils. Talanta 85:835-849.
 van de Braak SAAJ, Leijten GCJJ (1999) Essential Oils and Oleoresins: a Survey in the Netherlands and Other Major Markets in the European Union. CBI, Rotterdam.
 Burt S (2004) Essential oils: their antibacterial properties and potential applications in foods – a review. Int. J. Food Microbiol. 94:223 – 253.
 A.M. Janssen AM, Scheffer JJC, Svendsen AB (1987) Antimicrobial activity of essential oils: a 1976-86 literature review. Aspects of the test methods. Planta Med. 53:395-398.
 Hammer KA, Carson CF, Riley TV (1999) Antimicrobial activity of essential oils and other plant extracts. J Appl. Microbiol. 86:985-990.
 Rios JL, Recio MC, Villar A (1988) Screening methods for natural products with antimicrobial activity: A review of the literature. J. Ethnopharmacol. 23:127-149.
 Bakkali F, Averbeck S, Averbeck D, Idaomar M (2008) Biological effects of essential oils – a review. Food Chem. Toxicol. 46:446:475.
 Ait-Ouazzou A, Lorán A Arakrak A, Laglaouib A, Rota C, Herrera A, Pagána R, Conchelloa P. (2012) Evaluation of the chemical composition and antimicrobial activity of Mentha pulegium, Juniperus phoenicea, and Cyperus longus essential oils from Morocco. Food Res. Int. 45:313-319.
 Franz CM (2010) Essential oil research: past, present and future. Flavour Fragr. J. 25:112-113.
 Bicchi C, Cagliero C, Rubiolo P (2011) New trends in the analysis of the volatile fraction of matrices of vegetable origin: a short overview. A review. Flavour Fragr. J. 26:321-325.
 Marriott PJ, Shellie R, Cornwell C (2001) Gas chromatographic technologies for the analysis of essential oils. J. Chromatogr. A 936:1- 22.
 Shellie R, Mondello L, Marriott P, Dugo G (2002) Characterisation of lavender essential oils by using gas chromatography – mass spectrometry with correlation of linear retention indices and comparison with comprehensive two-dimensional gas chromatography. J. Chromatogr. A 970:225-234.
 Eyres G, Dufour JP, Hallifax G, Sotheeswaran S, Marriott PJ (2005) Identification of character-impact odorants in coriander and wild coriander leaves using gas chromatography-olfactometry (GCO) and comprehensive two-dimensional gas chromatography-time-offlight mass spectrometry (GC×GC-TOFMS). J. Sep. Sci. 28:1061-1074.
 Cordero C, Bicchi C, Galli M, Galli S, Rubiolo P (2008) Evaluation of different internal-diameter column combinations in comprehensive two-dimensional gas chromatography in flavour and fragrance analysis. J. Sep. Sci. 31:3437-3450.
 Gogus F, Ozel MZ, Lewis AC (2006) Extraction of essential oils of leaves and flowers of Achillea monocephala by superheated water. Flavour Fragr. J. 21:122-128.
 Escandar GM, Faber NKM, Goicoechea HC, de la Pena AM, Olivieri AC, Poppi RJ (2007) Second and third-order multivariate calibration: Data, algorithms and applications. Trends Anal. Chem. 26:752-765.
 M.M.C. Ferreira, A.M. Antunes, M.S. Melgo, P.L.O. Volpe (1999) Quimiometria I: calibração multivariada, um tutorial. Quim. Nova 22(5):724-731.
 L.R. Snyder, J. C. Hoggard, T. J. Montine, Synovec RE (2010) Development and Application of a Comprehensive Two-Dimensional Gas Chromatography with Time-of-Flight Mass Spectrometry Method for the Analysis of L-Methylamino-Alanine in Human Tissue. J. Chromatogr. A 1217:4639-4647.
 van Mispelaar VG, Tas AC, Smilde AK, Schoenmakers PJ, van Asten AC (2003) Quantitative analysis of target components by comprehensive two-dimensional gas chromatography. J. Chromatogr. A 1019:15-29.
 Johnson KJ, Synovec RE (2002) Pattern Recognition of Jet Fuels: Comprehensive GC×GC with ANOVA-Based Feature Selection and Principal Component Analysis. Chem. Intell. Lab. Syst. 60:225-237.
 Vaz-Freire LT, Silva MDRG, Freitas AMC (2009) Comprehensive two-dimensional gas chromatography for fingerprint pattern recognition in olive oils produced by two different techniques in Portuguese olive varieties Galega Vulgar, Cobrançosa e Carrasquenha. Anal. Chim. Acta 633:263-270.
 Schmarr HG, Bernhardt J (2010) Profiling analysis of volatile compounds from fruits using comprehensive two-dimensional gas chromatography and image processing techniques. J. Chromatogr. A 1217:565-574.
 Godoy LAF, Pedroso MP, Ferreira EC, Augusto F, Poppi RJ (2011) Prediction of the physicochemical properties of gasoline by comprehensive two-dimensional gas chromatography and multivariate data processing. J. Chromatogr. A 1218:1663-1667.
 C. Kohlert, I. van Rensen, R. März, G. Schindler, E.U. Graefe, M. Veit (2000) Bioavailability and Pharmacokinetics of Natural Volatile Terpenes in Animals and Humans. Planta Med. 66:495-505.
 Iscan G, Kirimer N, Kurkcuoglu M, Husnu K, Baser C, Demirci F (2002) Antimicrobial Screening on Mentha piperita Essential Oils. J. Agric. Food Chem. 50:3943-3946.
 Mkaddem M, Bouajila J, Ennajar M, Lebrihi A, Mathieu F, Romdhane A (2009) Chemical composition and antimicrobial and antioxidant activities of essential oils and various extracts of Juniperus phoenicea L. (Cupressacees). J. Food Sci. 74:358-371
 J.P.S. Guedes, J.A.C. Medeiros, R.S.S. Silva, J.M.B. Sousa, M.L. Conceição, E.L. Souza (2016) The efficacy of Mentha arvensis L. and M. piperita L. essential oils in reducing pathogenic bacteria and maintaining quality characteristics in cashew, guava, mango, and pineapple juices. J. Food Microbiol. 238:183-192
 S.K. Verma, P. Goswami, R.S. Verma, R.C. Padalia, A. Chauhan, V.R. Singh, M.P. Daroka (2016) Chemical composition and antimicrobial activity of bergamot-mint (Mentha citrata Ehrh.) essential oils isolated from the herbage and aqueous distillate using different methods. Ind. Crops Prod. 91:152-160.
 F. Brahmi, A. Abdenour, M. Bruno, P. Silva, P. Alessandra, F. Danilo, Y.G. Drifa, E.M. Fahmi, M. Khodir, C. Mohamed (2016) Chemical composition and in vitro antimicrobial, insecticidal and antioxidant activities of the essential oils of Mentha pulegium L. and Mentha rotundifolia (L.) Huds growing in Algeria. Ind. Crops Prod. 88:96-105.
 M. Chraibi, A. Farah, S. Lebrazi, O.E. Amine, M. I. Houssaini, K.F. Benbrahim (2016) Antimycobacterial natural products from Moroccan medicinal plants: Chemical composition, bacteriostatic and bactericidal profile of Thymus satureioides and Mentha pulegium essential oils. Asian Pac. J. Trop. Biomed. 6(10):836-840.
 Dimandja JM, Stanfill SB, Grainger J, Patterson Jr. DG (2000) Application of comprehensive two-dimensional gas chromatography (GC×GC) to the qualitative analysis of essential oils. J. High Resolut. Chromatogr. 23:208-214.
 Eloff JNP (1998) A sensitive and quick microplate method to determine the minimal inhibitory concentration of plant extracts for bacteria. Planta Med. 64:711-713.
 Pedroso MP, Ferreira EC, Hantao LW, Bogusz S, Augusto F (2011) Identification of volatiles from pineapple (Ananas comosus L.) pulp by comprehensive two-dimensional gas chromatography and gas chromatography/mass spectrometry. J. Sep. Sci. 34:1547-1554
 Adams RP (2001), Identification of Essential Oil Components by Gas Chromatography / Mass Spectroscopy. Allured, Carol Stream, IL.
 Brereton RG (2000) Introduction to Multivariate Calibration in Analytical Chemistry. Analyst 125:2125-2154.
 Godoy LAF, Ferreira EC, Pedroso MP, Fidelis CHV, Augusto F, Poppi RJ (2008) Quantification of Kerosene in Gasoline by Comprehensive Two-Dimensional Gas Chromatography and N-Way Multivariate Analysis. Anal. Lett. 41:1603-1614.
 de Godoy LAF, Pedroso MP, Hantao LW, Poppi RJ, Augusto F (2011) Quantitative analysis by comprehensive two-dimensional gas chromatography using interval Multi-way Partial Least Squares calibration. Talanta 83:1302-1307.
 Fraga CG, Prazen BJ, Synovec RE (2001) Objective Data Alignment and Chemometric Analysis of Comprehensive Two-Dimensional Separations with Run-to-Run Peak Shifting on Both Dimensions. Anal. Chem. 73:5833-5840.
 Pedroso MP, Godoy LAF, Ferreira EC, Poppi RJ, Augusto F (2008) Identification of gasoline adulteration using comprehensive twodimensional gas chromatography combined to multivariate data processing. J. Chromatogr. A 1201:176-182.
 Wold S, Sjöström M, Eriksson L (2001) PLS regression: A basic tool of chemometrics. Chem. Intell. Lab. Sys. 58:109-130.
 Freire MM, Jham GN, Dhingra OD, Jardim CM, Barcelos RC, Valente VMM (2012) Composition, antifungal activity and main fungitoxic components of the essential oil of Mentha piperita. J. Food Saf. 32:29-36.
 Rodrigues L, Duarte A, Figueiredo AC, Brito L, Teixeira G, Moldão M, Monteiro A (2011) Chemical composition and antibacterial activity of the essential oils from the medicinal plant Mentha cervina L. grown in Portugal. Med. Chem. Res. 21:3485:3490.
 Massart DL, Vandeginste BGM, Deming SN, Michotte Y, Kaufman L (1988) Chemometrics: a Textbook. Elsevier, Amsterdam.
 Pietrella D, Angiolella L, Vavala E, Rachini A, Mondello F, Ragno R, Bistoni F, Vecchiarelli A (2011) Beneficial effect of Mentha suaveolens essential oil in the treatment of vaginal candidiasis assessed by real-time monitoring of infection. BMC Complement. Altern. Med. 11:1-10.
 d’Auria FD, Tecca M, Strippoli V, Salvatore G, Battinelli L, Mazzanti G. (2005) Antifungal activity of Lavandula angustifolia essential oil against Candida albicans yeast and mycelial form. Med. Mycol. 43:391-398.
 Mahmoud ALE (1994) Antifungal action and anti-aflatoxigenic properties of some essential oil constituents. Lett. Appl. Microbiol. 19:110-113.