http://dx.doi.org/10.4322/sc.2016.017

 

Transferência de métodos cromatográficos monodimensionais para cromatografia gasosa bidimensional abrangente e boas práticas para controle de qualidade experimental

Mühlen, Carin von; Marriott, Philip J.

Palavras-chave GCxGC, tutorial, padrões de referência, otimização de métodos.

Resumo Após vários anos de experiência em treinamentos de iniciantes em cromatografia gasosa bidimensional abrangente (GC×GC) detectamos que o passo mais demorado do processo de aprendizagem da técnica costuma ser a avaliação de desempenho do equipamento e princípios de transferência dos métodos monodimensionais para GC×GC. Mesmo para usuários experientes em cromatografia a gás monodimensional, a identificação dos sinais de uma má separação em um cromatograma bidimensional são muito diferentes daqueles observados na cromatografia monodimensional. Somado a isso, o número de variáveis a serem otimizadas aumenta pela presença de uma coluna extra que opera em suas próprias condições experimentais, e do modulador. Com base nessas observações, este artigo apresenta uma discussão sobre aspectos importantes a serem observados antes de mover um método GC para um GC×GC. Também são apresentados experimentos sistemáticos que podem ser realizados como aulas práticas ou análise de rotina para avaliar o desempenho do sistema e a qualidade de colunas cromatográficas. Um esquema resumindo passos sistemáticos para a transferência de métodos monodimensionais para o GC×GC é demonstrado como uma ferramenta de aprendizagem. O uso dessas rotinas permite uma avaliação consistente do desempenho dos equipamentos e a sistematização na transferência de métodos buscando-se a melhor eficiência de separação oferecida pela técnica.


Referências Bibliográficas

[1] Ong RCY, Marriott PJ. A Review of Basic Concepts in Comprehensive Two-dimensional Gas Chromatography. J Chromatogr Sci. 2002;40(5):276–91.
[2] Marriott PJ, Shellie R. Principles and applications of comprehensive two-dimensional gas chromatography. TrAC, Trends Anal Chem. 2002;21(9-10):573–83.
[3] Adahchour M, Beens J, Vreuls RJJ, Brinkman UATh. Recent developments in comprehensive two-dimensional gas chromatography (GC×GC) I. Introduction and instrumental set-up. TrAC Trends Anal Chem. 2006;25(5):438–54.
[4] Adahchour M, Beens J, Vreuls RJJ, Brinkman UATh. Recent developments in comprehensive two-dimensional gas chromatography (GC×GC) II. Modulation and detection. TrAC Trends Anal Chem. 2006;25(6):540–53.
[5] Vreuls RJJ, Brinkman UATh. Recent developments in comprehensive two-dimensional gas chromatography (GC×GC) III. Applications for petrochemicals and organohalogens. TrAC Trends Anal Chem. 2006;25(7):726–41.
[6] Adahchour M, Beens J, Vreuls RJJ, Brinkman UATh. Recent developments in comprehensive two-dimensional gas chromatography (GC×GC): IV. Further applications, conclusions and perspectives. TrAC Trends Anal Chem. 2006;25(8):438–54.
[7] Adahchour M, Beens J, Brinkman UATh. Recent developments in the application of comprehensive two-dimensional gas chromatography. J Chromatogr A. 2008;1186(1-2):67–108.
[8] Poppi RJ, Ferreira EC, Fidélis CH de V, Godoy LAF de, Pedroso MP, Augusto F. Comprehensive two-dimensional gas chromatography (GC × GC). Quím Nova. 2009;32(2):422–30.
[9] Zini, CA. Cromatografia gasosa bidimensional. Sci Chromatogr. 2009;1:31–49.
[10] von Mühlen C, Zini CA, Caramão EB, Marriott PJ. Nomenclatura na língua portuguesa em Cromatografia Multidimensional Abrangente. Quím Nova. 2007;30(3):682–7.
[11] von Mühlen C. Índices de retenção em cromatografia gasosa bidimensional abrangente. Sci Chromatogr. 2009;1(3):21-8.
[12] Pedroso MP. Detecção em cromatografia gasosa rápida e cromatografia gasosa bidimensional abrangente. Sci Chromatogr. 2011; 3(2):145-54.
[13] von Mühlen C, Zini CA, Caramão EB, Marriott PJ. Caracterização de amostras petroquímicas e derivados utilizando a Cromatografia Gasosa Bidimensional Abrangente (GC×GC). Quím Nova. 2006;29(4):765–75.
[14] Moraes MSA, Bortoluzzi JH, Migliorini MV, Zini CA, Caramão EB. Cromatografia gasosa bidimensional abrangente aplicada à análise qualitativa dos componentes majoritários do bio-óleo da pirólise de bagaço de laranja. Sci Chromatogr. 2011;3(4):301–14. Available from: http://dx.doi.org/10.4322/sc.2011.018
[15] Mateus EP, Zrostlíková J, Ribeiro AB, Marriott PJ, da Silva MDR. Análise de resíduos contaminados com creosoto por cromatografia gasosa bidimensional abrangente (GCxGC). Uma ferramenta analítica para amostras ambientais complexas. Sci Chromatogr. 2010;2(2):57–68.
[16] Silva JM; Zini CA, Caramão EB. Aplicação da cromatografia gasosa bidimensional abrangente com microdetector de captura de elétrons para determinação de agrotóxicos em sedimentos. Quím Nova. 2011;34(6):962-7. http://dx.doi.org/10.1590/S0100-40422011000600009
[17] Migliorini MV, Moraes, MSA, Machado ME, Caramão EB. Caracterização de fenóis no bio-óleo da pirólise de caroço de pêssego por GC/MS e GC×GC/TOFMS. Scientia Chromatographica 2013; 5(1):47-65 http://dx.doi.org/10.4322/sc.2013.006
[18] von Mühlen C, Oliveira EC, Morrison PD, Zini CA, Caramão EB, Marriott PJ. Qualitative and Quantitative Study of Nitrogen-containing Compounds in Heavy Gas Oil using Comprehensive Two-Dimensional Gas Chromatography with Nitrogen Phosphorus Detection. J Sep Sci. 2007;30(18):3223-32.
[19] von Mühlen C, Khummueng W, Zini CA, Caramão EB, Marriott PJ. Detector technologies for comprehensive two-dimensional gas chromatography. J Sep Sci. 2006;29:1909–21. Available from: http://dx.doi.org/10.1002/jssc.200500443
[20] Schoenmakers PJ, Marriott PJ, Beens J. Nomenclature and Conventions in Comprehensive Multidimensional Chromatography. LCGC Eur. 2003;16(6):335–9.
[21] Marriott PJ, Wu Z-y, Schoenmakers PJ. Nomenclature and Conventions in Comprehensive Multidimensional Chromatography – An Update. LCGC Eur. 2012;25(5). Available from: http://www.chromatographyonline.com/nomenclature-and-conventions-comprehensive-multidimensional-chromatography-update
[22] Grob K. Split and Splitless Injection for Quantitative Gas Chromatography: Concepts, Processes, Practical Guidelines, Sources of Error. Weinheim: Wiley-VCH; 2001.
[23] Krupčík J, Májek P, Gorovenko R, Blaško J, Kubinec R, Sandra P. Considerations on the determination of the limit of detection and the limit of quantification in one-dimensional and comprehensive two-dimensional gas chromatography. J Chromatogr A. 2015;1396:117–30. Available from: http://www.sciencedirect.com/science/article/pii/S0021967315005233
[24] Khummueng W, Trenerry C, Rose G, Marriott PJ. Application of comprehensive two-dimensional gas chromatography with nitrogen-selective detection for the analysis of fungicide residues in vegetable samples. J Chromatogr A. 2006;1131(1-2):203–14.
[25] Fernandes DR, Pereira VB, Stelzer KT, Gomes AO, Neto FRA, Azevedo DA. Quantification of trace O-containing compounds in GTL process samples via Fischer–Tropsch reaction by comprehensive two-dimensional gas chromatography/mass spectrometry. Talanta. 2015;144:627–35.
[26] von Mühlen C, de Oliveira EC, Zini CA, Caramão EB, Marriott PJ. Characterization of Nitrogen-Containing Compounds in Heavy Gas Oil Petroleum Fractions Using Comprehensive Two-Dimensional Gas Chromatography Coupled to Time-of-Flight Mass Spectrometry. Energy & Fuels.2010;24(6):3572–80. Available from: http://pubs.acs.org/doi/abs/10.1021/ef1002364
[27] Grob K, Biedermann M, Li Z. Checking the capacity of a splitless injector — a simple test. J Chromatogr. 1988;448:387–90.
[28] Grob Jr. K. Band broadening in space in splitless injection. J Chromatogr A. 1985;324:251–9.
[29] Sabin GP, Prestes OD, Martins ML, Adaime, MB, Zanella R. Aumento da resposta analítica por meio da otimização do sistema de injeção sem divisão de fluxo em cromatografia gasosa empregando a lei dos gases ideais. Quim. Nova. 2011;34(3):414-418.
[30] Grob K, Biedermann M. Vaporising systems for large volume injection or on-line transfer into gas chromatography: Classification, critical remarks and suggestions. J Chromatogr A. 1996;750(1–2):11–23.
[31] Grob K, Biedermann M. Video-taped sample evaporation in hot chambers simulating gas chromatography split/splitless injectors: I. Thermospray injection. J Chromatogr A. 2000;897(1–2):237–46.
[32] Grob Jr. K, Neukom HP. Dependence of the splitting ratio on column temperature in split injection capillary gas chromatography. J Chromatogr A.1982;236(2):297–306. Available from: http://www.sciencedirect.com/science/article/pii/S0021967300848785
[33] van Es AJ, Rijks JA, Cramers CA, Golay MJE. Turbulent flow in capillary gas chromatography—evaluation of a theoretical concept by Golay. J Chromatogr A. 1990;517:143–59.
[34] Collins CH, Braga GL, Bonato PS. Fundamentos de Cromatografia. Campinas, Brasil: Editora Unicamp; 2006.
[35] Golay MJE. A problem of optimization in capillary gas chromatography. J Chromatogr A. 1985;348:416–20.
[36] Moretti P, Vezzani S, Castello G. A calculation method for the prediction of effective plate height in capillary gas chromatography. J Chromatogr A. 2009;1216(51):8986–91. Available from: http://www.sciencedirect.com/science/article/pii/S0021967309015891
[37] Frysinger GS, Gaines RB. Forensic Analysis of Ignitable Liquids in Fire Debris by Comprehensive Two-Dimensional Gas Chromatography. J Forensic Sci. 2002;47(3):471–82.
[38] Frysinger GS, Gaines RB, Xu L, Reddy CM. Resolving the Unresolved Complex Mixture in Petroleum-Contaminated Sediments. Environ Sci & Technol. 2003;37(8):1653–62.
[39] Beens J, Tijssen R, Blomberg J. Comprehensive two-dimensional gas chromatography (GC x GC) as a diagnostic tool. J High Resolut Chromatogr. 1998;21(1):63–4.
[40] Beens J, Dallüge J, Adahchour M, Vreuls RJJ, Brinkman UATh. Moving cryogenic modulator for the comprehensive two-dimensional gas chromatography (GC x GC) for surface water contaminants. J Microcolumn Sep. 2001;13(3):134–40.
[41] Marriott PJ, Kinghorn RM. Longitudinally Modulated Cryogenic System. A Generally Applicable Aproach to Solute Trapping and Mobilization in Gas Chromatography. Anal Chem. 1997;69:2582–8.
[42] Phillips JB, Luu D, Pawliszyn J. Multiplex gas chromatography by thermal modulation of a fused silica capillary column. Anal Chem. 1985;57:2779–87.
[43] Poliak M, Fialkov AB, Amirav A. Pulsed flow modulation two-dimensional comprehensive gas chromatography – tandem mass spectrometry with supersonic molecular beams. J Chromatogr A. 2008;1210(1):108-14.
[44] Tranchida PQ, Franchina FA, Dugo P, Mondello L. Flow-modulation low-pressure comprehensive two-dimensional gas chromatography. J Chromatogr A. 2014;1372:236–44.
[45] Klee MS, Cochran J, Merrick M, Blumberg LM. Evaluation of conditions of comprehensive two-dimensional gas chromatography that yield a near-theoretical maximum in peak capacity gain. J Chromatogr A. 2015;1383:151–9. Available from: http://www.sciencedirect.com/science/article/pii/S0021967315000771
[46] Mostafa A, Edwards M, Górecki T. Optimization aspects of comprehensive two-dimensional gas chromatography. J Chromatogr A. 2012;1255:38–55. Available from: http://www.sciencedirect.com/science/article/pii/S0021967312003706
[47] Tran TC, Logan GA, Grosjean E, Harynuk J, Ryan D, Marriott P. Comparison of column phase configurations for comprehensive two dimensional gas chromatographic analysis of crude oil and bitumen. Org Geochem. 2006;37(9):1190–4. Available from: http://www.sciencedirect.com/science/article/pii/S0146638006001057
[48] Grob K, Grob G, Grob K. Testing capillary gas chromatographic columns. J Chromatogr A. 1981;219(1):13-20. Available from: http://dx.doi.org/10.1016/S0021-9673(00)80568-3
[49] Grob Jr. K, Grob G, Grob K. Comprehensive, standardized quality test for glass capillary columns. J Chromatogr A. 1978;156(1):1–20. Available from: http://www.sciencedirect.com/science/article/pii/S0021967300831209
[50] Dimandja J-MD, Clouden GC, Colón I, Focant J-F, Cabey WV, Parry RC. Standardized test mixture for the characterization of comprehensive two-dimensional gas chromatography columns: the Phillips mix. J Chromatogr A. 2003;1019(1–2):261–72. Available from: http://www.sciencedirect.com/science/article/B6TG8-49RCGR9-4/2/47bdd023011f9ea6052858b6cbf580ab
[51] Dorman FL, Schettler PD, Vogt LA, Cochran JW. Using computer modeling to predict and optimize separations for comprehensive two-dimensional gas chromatography. J Chromatogr A. 2008;1186(1–2):196–201.
[52] Khummueng W, Harynuk J, Marriott PJ. Modulation ratio in comprehensive two-dimensional gas chromatography. Anal Chem. 2006;78(13):4578–87.
[53] Marriott P, von Mühlen C. Studies on Modulation Ratio in Comprehensive Two-Dimensional Gas Chromatography. Sci Chromatogr. 2016;(no prelo).
[54] Collins CH, de Aquino Neto FR, da Silva JRP. Terminologia Em Cromatografia. Parte II. Símbolos Para Cromatografia. Quím Nova. 1989;12(1):92–4.