Şirin OBA, Ömer Said TOKER, Haniyeh RASOULİ PİROUZİAN, İbrahim PALABIYIK, Nevzat KONAR, Nevzat ARTIK, Osman SAĞDIÇ

SÜTLÜ ÇİKOLATA İÇİN KATI FAZ MİKROEKSTRAKSIYON YÖNTEMİNİN OPTİMİZASYONU

Bu çalışmada, isomalt içeren sütlü çikolatalarda 2,3,5,6 tetra metal pirazin tayini için HS-SPME ekstraksiyonunun optimizasyonunda merkezi kompozit tasarım uygulanmıştır. SPME verimliliği etkileyen dengeleme süresi, ekstraksiyon süresi ve ekstraksiyon sıcaklığı için optimum koşullar olarak sırasıyla 10 dk, 40 dk ve 57 °C olarak belirlenmiştir. Çalışmada StableFlex fibere uygulanmış 100 µm polidimetilsiloksan, 65 µm polidimetilsiloksan/divinilbenzen, 75 µm karboksen/polidimetilsiloksan ve 50/30 µm divinilbenzen/karboksen/polidimetilsiloksan kaplamalar SPME fiberler olarak incelenmiştir. Çikolata örneklerinin hazırlama koşulları ayrıca tepe boşluğunun kaplama bileşimi üzerindeki etkileri ölçülerek de değerlendirilmiştir. Özellikle örneklerin kuru koşullarda 60 °C’de 30 dk örnek ekstraksiyonunda 50/30 µm divinilbenzen/karboksen/polidimetilsiloksan kaplı SPME fiber en yüksek ekstraksiyon verimliliğini sağlamıştır.

Anahtar Kelimeler:

çikolata, isomalt, merkezi kompozit tasarım, optimizasyon, SPME

OPTIMIZATION OF SOLID-PHASE MICROEXTRACTION CONDITIONS OF MILK CHOCOLATE

In the current study, the Central Composite Design was applied to optimize HS-SPME extraction in order to detect 2,3,5,6 tetramethyl pyrazine in isomalt contaning milk chocolate. The optimal conditions for the three experimental responses influencing SPME efficiency were 10 min, 40 min and 57 °C for equilibration time, extraction time and extraction temperature, respectively. SPME fibers coated with 100 m polydimethylsiloxane coating, 65 µm polydimethylsiloxane/divinylbenzene coating, 75 µm carboxen/polydimethylsiloxane coating and 50/30 µm divinylbenzene/carboxen/polydimethylsiloxane on a StableFlex fiber were investigated. The preparation conditions of the chocolate samples were also evaluated by measuring their effects on the coating composition of the head space. The SPME fiber coated with 50/30 µm divinylbenzene/carboxen-polydimethylsiloxane provided the highest extraction efficiency, especially when the samples were extracted at 60 °C for 30 min under dry conditions. Eighty-one blends were extracted and experimentally detected most of which have been formerly stated as odor-active components.

Keywords:

Chocolate, isomalt, central composite design, optimization, SPME,

PDF

___

Afoakwa, E.O. (2010). Chocolate Science and Technology. Wiley-Blackwell, Oxford, UK.
Afoakwa, E.O., Paterson, A., Fowler, M., Vieira, J. (2008). Particle size distribution and compositional effects on textural properties and appearance of dark chocolates. J Food Eng, 87(2): 181–190.
Beckett, S.T. (2008). The Science of Chocolate. Royal Society of Chemistry, London.
Braga, S.C.G.N., Oliveira, L.F., Hashimoto, J.C., Gama, M.R., Efraim, P., Joppi, R.J., Augusto, F. (2018). Study of volatile profile in cocoa nibs, cocoa liqour and chocolate on production process using GC X GX-QMS. Microchem J, 141: 353–361.
Brito, E.S., Narain, N. (2003). Effect of pH and distillate volume on monitoring aroma quality of bittersweet chocolate. Food Qual Prefer, 14: 219–226.
Brunetto, M.R., Cayama, Y.D., Gutierrez, L., Roa, S.C., Mendez, Y.C., Gallignani, M., Zambrano, A., Gomez, A., Ramos, G. (2009). Headspace gas chromatography-mass spectrometry determination of alkylpyrazines in cocoa liquor samples. Food Chem, 112: 253–257.
Burbank, H.M., Qian, M.C. (2005). Volatile sulfur compounds in cheddar cheese determined by headspace solid-phase microextraction and gas chromatograph-pulsed flame photometric detection. J Chromatogr A, 1066(1-2): 149–57.
Da Veiga Moreira, I.M., Vilela, L.D.F., Santos, C., Lima, N., Schwan, R.F. (2018). Volatile compounds and protein profiles analyses of fermented cocoa beans and chocolates from different hybrids cultivated in Brazil. Food Res Int, 109: 196–203.
De Brito, E.S., Garcia, N.H.P., Amancio, A.C., Valente, A.L.P., Pini, G.F., Augusto, F. (2001). Effect of autoclaving cocoa nibs before roasting on the precursors of the Maillard reaction and pyrazines. Int J Food Sci Technol, 36: 625–630.
Di Carro., M., Ardini, F., Magi, E. (2015). Multivariate optimization of headspace solid-phase microextraction followed by gas chromatography-mass spectrometry fort he determination of methylpyrazines in cocoa liquors. Microchem J, 121: 172–177.
Ducki, S., Miralles-Garcia, J., Zumbe, A., Tornero, A., Storey, D.M. (2008). Evaluation of solid-phase microextraction coupled to gas chromatography-mass spectrometry for the headspace analysis of volatile compounds in cocoa products. Talanta, 74: 1166–1174.
Engeseth, N.J., Pangan, M.F.A. (2018). Current context on chocolate flavor development – a review. Curr Opin Food Sci, 21: 84–91.
Hue, C., Gunata, Z., Bergounhou, A., Assemat, S., Boulanger, R., Sauvage, F.X., Davrieux, F. (2014). Near infrared spectroscopy as a new tool to determine cocoa fermentation levels through ammonia nitrogen quantification. Food Chem, 148: 240–245.
Kataoka, H., Lord, H.L., Pawliszyn, J. (2000). Applications of solid-phase microextraction in food analysis. J Chromatogr A, 880: 35–62.
Khairy, H.L., Saadon, A.F., Zzaman, W., Yang, T.A., Easa, A.M. (2018). Identification of flavor compounds in rambutan seed fat and its mixture with cocoa butter determined by SPME-GCMS. J King Saud Univ Sci, 30: 316–323.
Kone, K.M., Guchi, S.T., Durand, N., Ban-Koffi, L., Berthiot, L., Tachan, A.F., Brou, K., Boulanger, R., Montet, D. (2016). Contribution of predominant yeasts to the occuruence of aroma compounds during cocoa bean fermentation. Food Res Int, 89(2): 910–917.
Kumari, N., Grimbs, A., D’Souza, R.N., Verma, S.K., Corno, M., Kuhnert, N., Ullrich, M.S. (2018). Origin and varietal based proteomic and peptidomic fingrprinting of Theobroma cacao in non-fermented and fermented cocoa beans. Food Res Int, 111: 137–147.
Little, T.M., Hills, F.J. (1978). Agricultural Experimentation Design and Analysis. John Wiley, New York.
Mani, V. (1999). Properties of commercial SPME coatings. In: Aplication of solid phase microextraction, Pawliszyn, J. (chief ed.), RSC Chromatography Monographs, The UK, pp. 5–96.
Matich, A.J. (1999). Anaylsis of food and plant volatiles. In: Applications of solid phase microextraction, Pawliszyn, J. (chief eds.), Royal Society of Chemistry, Cambridge, pp. 343–363.
Mexis, S.F., Badeka, A.V., Riganakos, K.A., Kontominas, M.G. (2010). Effect of active and modified atmosphere packaging on quality retention of dark chocolate with hazelnuts. Innov Food Sci Emerg Technol, 11: 177–186.
Nagelkerke, N.J.D. (1991). A note on a general definition of the coefficient of determination. Biometrika, 78(3): 691–692.
Nicolotti, L., Cordero, C., Cagliero, C., Liberto, E., Sgorbini, B., Rubiolo, P., Bicchi, C. (2013). Quantitative fingerprinting by headspace-two-dimensional comprehensive gas chromatography–mass spectrometry of solid matrices: some challenging aspects of the exhaustive assessment of food volatiles. Anal Chim Acta, 798: 115–125.
Owusu, M. (2010). Influence of raw material and processing on aroma in chocolate. Ph.D. Dissertation, University of Copenhagen, Denmark, 98 p.
Perego, P., Fabiano, B., Cavicchioli, M., Del Borghi, M. (2004). Cocoa quality and processing: A study by solid-phase microextraction and gas chromatography analysis of methylpyrazines. Food Bioprod Process, 82(4): 291–297.
Pini, G.F., De Brito, E.S., García, N.H.P., Valente, A.L.P., Augusto, F. (2004). A headspace solid phase microextraction (HS-SPME) method for the chromatographic determination of alkylpyrazines in cocoa samples. J Braz Chem Soc, 15: 267–271.
Rodriguez-Campos, J., Escolana-Buendia, H.B., Conteras-Ramos, S.M., Orozco-Avila, I., Jaramillo-Flores, E., Lugo-Cervantes, E. (2012). Effects of fermentation time and drying temperature on volatile compounds in cocoa. Food Chem, 132(1): 277–288.
Rodriguez-Campos, J., Escolana-Buendia, H.B., Conteras-Ramos, S.M., Orozco-Avila, I., Lugo-Cervantes, E., Jaramillo-Flores, M.E. (2011). Dynamics of volatile and non-volatile compounds in cocoa (Theobroma cacao L.) during fermentation and drying processes using principal component analysis. Food Res Technol, 44: 250–258.
Toker, O.S., Sagdic, O., Şener, D., Konar, N., Zorlucan, T., Dağlıoğlu, O. (2016). The influence of particle size on some physicochemical, rheological and melting properties and volatile compound profile of compound chocolate and cocolin samples. European Food Res Technol, 242(8): 1253–1266.
Tran, P.D., De Walle, D.V., De Clerq, N., De Winne, A., Kadow, D., Lieberei, R., Messens, K., Tran, D.N., Dewettinck, K., Van Durme, J. (2015). Assesing cocoa aroma quality by multiple analytical approaches. Food Res Int, 77: 657–669.
Van Durme, J., Ingels, I., De Winne, A. (2016). Inline roasting hyphenated with gas chromatography-mass spectrometry as an innovative approach for assessment of cocoa fermentation quality and aroma formation potential. Food Chem, 205: 66–72.
Yang, X., Perpard, T. (1994). Solid phase microextraction for flavor analysis. J Agr Food Chem, 42: 1925–1930.