Um procedimento de Microextração em Fase Sólida em Headspace (HS-SPME) para isolamento e determinação de alquilpirazinas em liquor de cacau, usando Cromatografia Gasosa com Detecção por Ionização em Chama (GC-FID) é apresentado aqui. As condições operacionais de HS-SPME foram otimizadas usando extrações de amostras fortificadas com quantidades conhecidas de alquilpirazinas tipicamente encontradas em derivados de cacau. A eficiência máxima de extração foi obtida com fibras de SPME recobertas com 65 µm de Carbowax/divinilbenzeno. Em adição, os melhores resultados foram obtidos usando 60 ºC como temperatura de extração, 15 min como tempo de equilíbrio amostra/headspace e 45 min como tempo de extração. Observou-se também que o uso de solução aquosa saturada de NaCl para suspender as amostras durante as extrações resultou em um incremento significativo nas áreas dos picos. Este procedimento se mostrou efetivo para a determinação das razões pirazínicas (quocientes entre as áreas dos picos de alquilpirazinas), que são úteis como parâmetros de qualidade para liquor de cacau.A Headspace Solid Phase Microextraction (HS-SPME) procedure for isolation and determination of alkylpyrazines in cocoa liquor, using Gas Chromatography with Flame Ionization Detection (GC-FID) for the separation and detection of the analytes, is presented here. The HS-SPME operational conditions were optimized using extractions of samples spiked with known amounts of alkylpyrazines typically found on cocoa products. The maximum extraction efficiency was obtained using SPME fibers coated with 65 µm Carbowax/divinylbenzene. Additionally, the best results were achieved with extraction temperature of 60 ºC, 15 min of sample/headspace equilibration time and 45 min extraction time. It was also observed that suspending the samples in saturated aqueous NaCl solution during extractions resulted in a significant increment on the peak areas. This procedure was found to be effective to determine the so-called pyrazinic ratios (quotient between peak areas of alkylpyrazines), which are useful as quality parameters for cocoa liquor.Keywords: cocoa liquor, alkylpyrazines, aroma, Maillard reaction products, SPME
IntroductionThe processing of cocoa seeds (Theobroma cacao, L.) 1 comprises their drying, fermentation of sugars contained in the pulp covering the seeds, roasting, separation and grounding of the roasted nibs. The resulting fatty solid product (known as cocoa liquor) is the base raw material for chocolate industry. The most significant flavor-impact substances on cocoa derivatives are N-and O-containing heterocyclic compounds generated during the roasting, which are products of the complex sequence of heatinduced chemical processes collectively known as Maillard reactions. 2 The substrates for the Maillard reactions are reducing sugars, small peptides, aminoacids and / or triglycerides contained in the raw, unroasted material. For cocoa, in terms of contribution to their sensorial characteristics (and, in consequence, to their commercial value), the most im...