Solid phase microextraction and gas chromatography: A combination of high potential

Rocha, Silvia M.; Salvador, Ângelo C.; Martins, Cátia; Barbosa, Corália Barbosa; Santos, Magda; Petronilho, Silvia

Palavras-chave: SPME, GC, GC×GC, volatile compounds, food products, natural products, metabolomics.

Resumo: Solid phase microextraction (SPME) combined with gas chromatography (GC) represents a powerful tool regarding several fields of application, which may be used to establish global volatile sample profiling or to quantify target analytes. This combination has been used in many fields, such as in the characterization of natural products, foods, and biofluids, screening of contaminants, evaluation of industrial processes, and in the environmental or clinical studies, among others. These studies typically involve the analysis of complex samples, containing numerous molecules, with different physicochemical characteristics, in com awide range of concentrations. Thus, the experimental parameters, including the sample preparation and extraction, and subsequent chromatographic analysis, should be optimized for each specific case, according to the physicochemical characteristics of the sample(s) and analyte(s). This paper covers a set of examples selected to highlight the challenges related to method implementation, and particular attention was devoted to applications in the fields of natural products, food and metabolomics, which really demonstrate the high potential of microextraction and gas chromatography techniques.

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Referências Bibliográficas

1. Dettmer K, Aronov PA, Hammock BD. Mass spectrometry-based metabolomics. Mass Spectrometry Reviews 2007; 26(1):51-78. PMid:16921475 PMCid:PMC1904337. http://dx.doi.org/10.1002/ mas.20108

2. S.ousa FL, Horta S, Santos M, Rocha SM, Trindade T. Release behavior of trans,trans-farnesol entrapped in amorphous silica capsules. Results in Pharma Sciences 2012; 2(1):52-56. http://dx.doi.org/10.1016/j. rinphs.2012.07.001

3. G.órecki T, Panić O, Oldridge N. Recent Advances in Comprehensive Two‐Dimensional Gas Chromatography (GC×GC). Journal of Liquid Chromatography & Related Technologies 2006; 29(7-8):1077-1104. http:// dx.doi.org/10.1080/10826070600574762

4. M.arriott PJ, Massil T, Hugel H. Molecular structure retention relationships in comprehensive two-dimensional gas chromatography. Journal of Separation Science 2004; 27(15-16):1273- 84. PMid:15587276. http://dx.doi.org/10.1002/ jssc.200401917

5. F.erreira LR, Lima S, Neves P, Antunes MM, Rocha SM, Pillinger M, et al. Aqueous phase reactions of pentoses in the presence of nanocrystalline zeolite beta: Identification of by-products and kinetic modelling. Chemical Engineering Journal 2013; 215-216:772-783. http://dx.doi.org/10.1016/j.cej.2012.11.022

6. A.ntunes MM, Lima S, Fernandes A, Candeias J, Pillinger M, Rocha SM, et al. Catalytic dehydration of d-xylose to 2-furfuraldehyde in the presence of Zr-(W,Al) mixed oxides. Tracing by-products using two-dimensional gas chromatography-time-of-flight mass spectrometry. Catalysis Today 2012; 195(1):127- 135. http://dx.doi.org/10.1016/j.cattod.2012.03.066

7. N.eves P, Lima S, Pillinger M, Rocha S.M, Rocha J, Valente A.A. Conversion of furfuryl alcohol to ethyl levulinate using porous aluminosilicate acid catalysts. Catalysis Today 2013; 218-219:76-84. http://dx.doi. org/10.1016/j.cattod.2013.04.035

8. N.eves P, Antunes MM, Russo PA, Abrantes JP, Lima S, Fernandes A, et al. Production of biomass-derived furanic ethers and levulinate esters using heterogeneous acid catalysts. Green Chemistry 2013; 15:3367-3376. http://dx.doi.org/10.1039/c3gc41908h

9. P.etronilho S, Maraschin M, Delgadillo I, Coimbra MA, Rocha SM. Antunes MM. Sesquiterpenic composition of the inflorescences of Brazilian chamomile (Matricaria recutita L.): Impact of the agricultural practices. Industrial Crops and Products 2011; 34(3):1482-1490. http://dx.doi. org/10.1016/j.indcrop.2011.05.005 10 Petronilho S, Barros AS, Coimbra MA, Rocha SM. Efficient Use of Non-renewable Natural Resources for Quality Wine through Sustainable Viticulture. In: Raza A, editor. Agricultural Systems in the 21st Century – Global Agriculture Developements. Nova Science Publishers, Inc; 2013. chapt. 9, p. 195-230.

11. R.ocha SM, Freitas R, Cardoso P, Santos M, Martins R, Figueira E. Exploring the potentialities of comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry to distinguish bivalve species: Comparison of two clam species (Venerupis decussata and Venerupis philippinarum). Journal of Chromatography A 2013; 1315:152-161. PMid:24084002. http://dx.doi. org/10.1016/j.chroma.2013.09.049

12. J.alali HT, Petronilho S, Villaverde JJ, Coimbra MA, Domingues MRM, Ebrahimian ZJ, et al. Assessment of the sesquiterpenic profile of Ferula gummosa oleo-gum-resin (galbanum) from Iran. Contributes to its valuation as a potential source of sesquiterpenic compounds. Industrial Crops and Products 2013; 44:185-191. http://dx.doi. org/10.1016/j.indcrop.2012.10.031

13. P.etronilho S, Rocha SM, Ramírez-Chávez E, Molina- Torres J, Rios-Chavez P. Assessment of the terpenic profile of Callistemon citrinus (Curtis) Skeels from Mexico. Industrial Crops and Products 2013; 46:369- 379. http://dx.doi.org/10.1016/j.indcrop.2013.02.012

14. J.alali HT, Petronilho S, Villaverde JJ, Coimbra MA, Domingues MRM, Ebrahimian ZJ, et al. Deeper insight into the monoterpenic composition of Ferula gummosa oleo-gum-resin from Iran. Industrial Crops and Products 2012; 36(1):500-507. http://dx.doi. org/10.1016/j.indcrop.2011.11.001

15. S.antos M. Composição terpénica e actividade anti-oxidante de plantas e infusões [tese]. Aveiro: Universidade de Aveiro; 2010.

16. C.oelho E, Rocha SM, Delgadillo I, Coimbra MA. Headspace-SPME applied to varietal volatile components evolution during Vitis vinifera L. cv. ‘Baga’ ripening. Analytica Chimica Acta 2006; 563(1-2):204- 214. http://dx.doi.org/10.1016/j.aca.2005.11.018

17. R.ocha SM, Coelho E, Zrostlíková J, Delgadillo I, Coimbra MA. Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry of monoterpenoids as a powerful tool for grape origin traceability. Journal of Chromatography A 2007; 1161(1-2):292-299. PMid:17585921. http:// dx.doi.org/10.1016/j.chroma.2007.05.093

18. C.oelho E, Rocha SM, Barros AS, Delgadillo I, Coimbra MA. Coimbra. Screening of variety- and pre-fermentation-related volatile compounds during ripening of white grapes to define their evolution profile. Analytica Chimica Acta 2007; 597(2):257- 264. PMid:17683737. http://dx.doi.org/10.1016/j. aca.2007.07.010

19. P.etronilho S, Maraschin M, Coimbra MA, Rocha SM. In vitro and in vivo studies of natural products: A challenge for their valuation. The case study of chamomile (Matricaria recutita L.). Industrial Crops and Products 2012; 40(1):1-12. http://dx.doi. org/10.1016/j.indcrop.2012.02.041

20. Silva I, Rocha SM, Coimbra MA, Marriott PJ. Headspace solid-phase microextraction combined with comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry for the determination of volatile compounds from marine salt. Journal of Chromatography A 2010; 1217(34):5511-5521. PMid:20633884. http:// dx.doi.org/10.1016/j.chroma.2010.06.050

21. S.ilva I, Rocha SM, Coimbra MA. Headspace solid phase microextraction and gas chromatography– quadrupole mass spectrometry methodology for analysis of volatile compounds of marine salt as potential origin biomarkers. Analytica Chimica Acta 2009; 635(2):167-174. PMid:19216874. http:// dx.doi.org/10.1016/j.aca.2009.01.011

22. S.ilva I, Rocha SM, Coimbra MA. Quantification and potential aroma contribution of β-ionone in marine salt. Flavour and Fragrance Journal 2010; 25(2):93-97. http://dx.doi.org/10.1002/ffj.1975

23. R.ocha S, Maeztu L, Barros A, Cid C, Coimbra MA. Screening and distinction of coffee brews based on headspace solid phase microextraction/ gas chromatography/principal component analysis. Journal of the Science of Food and Agriculture 2004; 84(1):43-51. http://dx.doi. org/10.1002/jsfa.1607

24. R.ocha SM, Coutinho P, Delgadillo I, Dias Cardoso A, Coimbra MA.Effect of enzymatic aroma release on the volatile compounds of white wines presenting different aroma potentials. Journal of the Science of Food and Agriculture 2005; 85(2):199-205. http:// dx.doi.org/10.1002/jsfa.1937

25. N.unes C, Coimbra MA, Saraiva J, Rocha SM. Study of the volatile components of a candied plum and estimation of their contribution to the aroma. Food Chemistry 2008; 111(4):897-905. http://dx.doi. org/10.1016/j.foodchem.2008.05.003

26. S.antos MC, Nunes C, Rocha MAM, Rodrigues A, Rocha SM, Saraiva JA, et al. Impact of high pressure treatments on the physicochemical properties of a sulphur dioxide-free white wine during bottle storage: Evidence for Maillard reaction acceleration. Innovative Food Science and Emerging Technologies 2013; 20:51- 58. http://dx.doi.org/10.1016/j.ifset.2013.07.001

27. P.erestrelo R, Barros AS, Câmara JS, Rocha SM. In-Depth Search Focused on Furans, Lactones, Volatile Phenols, and Acetals As Potential Age Markers of Madeira Wines by Comprehensive Two-Dimensional Gas Chromatography with Time-of-Flight Mass Spectrometry Combined with Solid Phase Microextraction. Journal of Agricultural and Food Chemistry 2011; 59(7):3186-3204. PMid:21375340. http://dx.doi.org/10.1021/jf104219t

28. P.erestrelo R, Barros AS, Rocha SM, Câmara JS. Optimisation of solid-phase microextraction combined with gas chromatography–mass spectrometry based methodology to establish the global volatile signature in pulp and skin of Vitis vinifera L. grape varieties. Talanta 2011; 85(3):1483- 1493. PMid:21807213. http://dx.doi.org/10.1016/j. talanta.2011.06.025

29. P.erestrelo R, Petronilho S, Câmara JS, Rocha SM. Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction as a powerful tool for quantification of ethyl carbamate in fortified wines. The case study of Madeira wine. Journal of Chromatography A 2010; 1217(20):3441-3445. PMid:20388567. http:// dx.doi.org/10.1016/j.chroma.2010.03.027

30. Martins CSF. Estratégias para a redução de carbamato de etilo em vinhos Madeira [tese]. Aveiro: Universidade de Aveiro; 2011.

31. S.alvador ÂC, Baptista I, Barros AS, Gomes NCM, Cunha Â, Almeida A, et al. Can Volatile Organic Metabolites Be Used to Simultaneously Assess Microbial and Mite Contamination Level in Cereal Grains and Coffee Beans?. PLoS ONE 2013; 8(4):e59338. PMid:23613710 PMCid:PMC3628908. http://dx.doi.org/10.1371/ journal.pone.0059338

32. A.lmstetter M, Oefner P, Dettmer K. Comprehensive two-dimensional gas chromatography in metabolomics. Analytical and Bioanalytical Chemistry 2012; 402(6):1993-2013. PMid:22249417. http://dx.doi.org/10.1007/s00216-011-5630-y

33. K.uehnbaum NL, Britz-McKibbin P. New Advances in Separation Science for Metabolomics: Resolving Chemical Diversity in a Post-Genomic Era. Chemical Reviews 2013; 113(4):2437-2468. PMid:23506082. http://dx.doi.org/10.1021/cr300484s

34. M.artins M, Henriques M, Azeredo J, Rocha SM, Coimbra MA, Oliveira R. Candida species extracellular alcohols: production and effect in sessile cells. Journal of Basic Microbiology 2010; 50(Suppl 1):S89- S97. PMid:20473968. http://dx.doi.org/10.1002/ jobm.200900442

35. M.artins M, Henriques M, Azeredo J, Rocha SM, Coimbra MA, Oliveira R. Morphogenesis Control in Candida albicans and Candida dubliniensis through Signaling Molecules Produced by Planktonic and Biofilm Cells. Eukaryotic Cell 2007; 6(12):2429-2436. PMid:17981993 PMCid:PMC2168255. http://dx.doi. org/10.1128/EC.00252-07

36. C.aldeira M, Barros AS, Bilelo MJ, Parada A, Câmara JS, Rocha SM. Profiling allergic asthma volatile metabolic patterns using a headspacesolid phase microextraction/gas chromatography based methodology. Journal of Chromatography A 2011; 1218(24):3771-3780. PMid:21546028. http:// dx.doi.org/10.1016/j.chroma.2011.04.026

37. R.ocha SM, Caldeira M, Carrola J, Santos M, Cruz N, Duarte IF. Exploring the human urine metabolomic potentialities by comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry. Journal of Chromatography A 2012; 1252: 155-163. PMid:22776727. http://dx.doi. org/10.1016/j.chroma.2012.06.067

38. C.aldeira M, Perestrelo R, Barros A.S, Bilelo MJ, Morête A, Câmara JS, et al. Allergic asthma exhaled breath metabolome: A challenge for comprehensive two-dimensional gas chromatography. Journal of Chromatography A 2012; 1254:87-97. PMid:22835687. http://dx.doi.org/10.1016/j.chroma.2012.07.023

39. P.ereira ARF. Estudo da biodiversidade de estirpes vínicas de S. cerevisiae [tese]. Aveiro: Universidade de Aveiro; 2012.