Flavour characteristics of Spanish and Iranian saffron analysed by electronic tongue
Main Article Content
Keywords
electronic tongue, saffron, screen printed electrode, principal component analysis
Abstract
In this study, a portable electronic tongue was developed and successfully used to distinguish and to discriminate quality of saffron samples. The proposed system consisted of an array of voltammetric sensors based on screen-printed electrodes (SPE), where the working electrodes were of different chemical natures (e.g. carbon, gold and modified carbon electrode). Moreover, the carbon electrodes were chemically modified by electrocatalytic copper phthalocyanine derivatives. The electrodes were immersed in saffron infusions to produce complex voltammetric curves that were characterised for each saffron sample. The electrochemical signals provided by the array showed good correlations with the data obtained from traditional chemical analysis, in particular with the kaempferol, a flavonol with antioxidant activity. The calibration model was optimised using more meaningful description of factors. Finally, discriminant analysis showed that the proposed e-tongue based on SPEs modified with phthalocyanine is useful for discrimination of saffron samples with different qualities. All of these results reveal that proposed e-tongue has a high potential for saffron quality control due to its very simple sample preparation and also its fast response.
References
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Apetrei, C., Gutierrez, F., Rodriguez-Mendez, M.L. and Saja, J.A., 2007. Novel method based on carbon paste electrodes for the evaluation of the bitterness of virgin olive oils. Sensors and Actuators (B) 121: 567-575.
Apetrei, I.M. and Apetrei, C., 2013a. Voltammetric e-tongue for the quantification of total polyphenol content in olive oils. Food Research International54: 2075-2082.
Apetrei, M., Rodriguez-Mendez, M.L., Apetrei, C. and Saja, J.A., 2013b. Fish freshness monitoring using an e-tongue based on polypyrrole modified screen-printed electrode. IEEE, Journal of Sensors 13: 2548-2554.
Baldwin, E.A., Bai, J., Plotto, A. and Dea, S., 2011. Electronic noses and tongues: applications for the food and pharmaceutical industries. Sensors 11: 4744-4766.
Caballero-Ortega, H., Pereda-Miranda, R., Riveron-Negrete, L., Hernandez, J.M., Medecigo-Rios, M., Castillo-Villanueva, A. and Abdullaev, F.I., 2004. Chemical composition of saffron (Crocus sativus L.) from four countries. Acta Horticulture 650: 321-336.
Caballero-Ortega, H., Pereda-Miranda, R. and Abdullaev, F.I., 2007. HPLC quantification of major active components from 11 different saffron (Crocus sativus L.) sources. Food Chemistry 100: 1126-1131.
Campo, C.P., Garde-Cerdan, T., Sanchez, A.M., Maggi, L., Carmona, M. and Alonso, G.L., 2009. Determination of free amino acids and ammonium ion in saffron (Crocus sativus L.) from different geographical origins. Food Chemistry 114: 1542-1548.
Carmona, M., Martinez, J., Zalacain, A., Rodriguez-Mendez, M.L., Saja, J.A. and Alonso, G.L., 2006a. Analysis of saffron volatile fraction by TD-GC-MS and e-nose. European Food Research Technology 223: 96-101.
Carmona, M., Sanchez, A.M., Ferreres, F., Zalacain, A., Tomas-Barberan, F. and Alonso, G.L., 2007b. Identification of the flavonoid fraction in saffron spice by LC/DAD/MS/MS: comparative study of samples from different geographical origins. Food Chemistry 100: 445-450.
Carmona, M., Zalacain, A., Salinas, M.R. and Alonso, G.L., 2007a. A new approach to saffron aroma. Critical Reviews in Food Science and Nutrition 47: 145-159.
Carmona, M., Zalacain, A., Sanchez, A.M., Novella, J.L. and Alonso, G.L., 2006b. Crocetin esters, picrocrocin and its related compounds present in Crocus sativus stigmas and Gardenia jasminoides fruits. Tentative identification of seven new compounds by LC-ESI-MS. Journal of Agricultural and Food Chemistry 54: 973-979.
Dar, R.A., Brahman, P.K., Khurana, N., Wagay, J.A., Lone, Z.A., Ganaie, M.A. and Pitre, K.S., 2013. Evaluation of antioxidant activity of crocin, podophyllotoxin and kaempferol by chemical, biochemical and electrochemical assays. Arabian Journal of Chemistry, DOI: http://dx.doi.org/10.1016/j.arabjc.2013.02.004.
Esbensen, K., Schonkopf, S. and Midtgaard, T., 1994. Multi-variate analysis in practice (1st Ed.). CAMO AS, Trondheim, Norway.
Fanjul-Bolado, P., Hernandez-Santos, D., Lamas-Ardisana, P.J., Martin-Pernia, A. and Costa-Garcia, A., 2008. Electrochemical characterization of screen-printed and conventional carbon paste electrodes. Electrochimica Acta 53: 3635-3642.
Fanjul-Bolado, P., Queipo, P., Lamas-Ardisana, P.J. and Costa-Garcia, A., 2007. Manufacture and evaluation of carbon nanotube modified screen-printed electrodes as electrochemical tools. Talanta 74: 427-433.
Gay, M., Apetrei, C., Nevares, I., Alamo, M., Zurro, J., Prieto, N., Saja, J.A. and Rodriguez-Mendez, M.L., 2010. Application of an electronic tongue to study the effect of the use of pieces of wood and micro-oxygenation in the aging of red wine. Electrochim Acta 55: 6782-6788.
Ghasemi-Vamankhasti, M., Mohtasebi, S.S., Rodriguez-Mendez, M.L., Lozano, J., Razavi, S.H. and Ahmadi, H., 2011. Potential application of electronic nose technology in brewery. Trends in food Science and Technology 22: 165-174.
Haghighi, B., Feizy, J. and Hemati-Kakhki, A., 2007. LC determination of adulterated saffron prepared by adding styles colored with some natural colorants. Chromatographia 66: 325-332.
Heidarbeigi, K., Mohtasebi, S.S., Foroughirad, A., Ghasemi-Varnamkhasti, M., Rafiee, S. and Rezaei, K., 2015. Detection of adulteration in saffron samples using electronic nose. International Journal of Food Properties 18: 1391-1401.
Hoskuldsson, A., 1988. PLS regression methods. Journal of Chemometrics 2: 211-228.
International Organization for Standarization (ISO), 2011. ISO 3632 saffron (Crocus sativus L.). Part 1: specification. Part 2: test methods. ISO, Geneva, Switzerland.
Janczyk, M., Kutyla, A., Solohub, K., Wosicka, H., Cal, K. and Ciosek, P., 2011. Potentiometric electronic tongues for foodstuff and biosample recognition – an overview. Sensors 11: 4688-4701.
Kadara, R.O., Jenkinson, N. and Banks, C.E., 2009. Characterisation of commercially available electrochemical sensing platforms. Sensors and Actuators (B) 138: 556-562.
Labrador, R.H., Masot, R., Alcaniz, M., Baigts, D., Soto, J., Martinez-Manez, R., Garcia-Breijo, E., Gil, L. and Barat, J.M., 2010. Prediction of NaCl, nitrate and nitrite contents in minced meat by using a voltammetric electronic tongue and an impedimetric sensor. Food Chemistry 122: 864-870.
Matemadombo, F., Apetrei, C., Nyokong, T., Rodriguez-Mendez, M.L. and Saja, J.A., 2012. Comparison of carbon screen printed and disk electrodes in the detection of antioxidants using CoPc derivatives. Sensors and Actuators (B) 166-167: 457-466.
Medina-Plaza, C., Revilla, G., Munoz, R., Fernandez-Escudero, J.A., Barajas, E., Medrano, G., Saja, J.A. and Rodriguez-Mendez, M.L., 2014. Electronic tongue formed by sensors and biosensors containing phthalocyanines as electron mediators, Application to the analysis of red grapes. Journal of Porphyrins and Phthalocyanines 18: 76-86.
Ministerio de Economía y Hacienda (NCCEA), 1999. Normas de calidad del comercio exterior para el azafran. Ministerio de Economía y Hacienda, Madrid, Spain.
O’Halloran, M.P., Pravda, M. and Guilbault, G.G., 2001. Prussian blue bulk modified screen-printed electrodes for H2O2 detection and for biosensors. Talanta 55: 605-611.
Pedroza, M.A., Carmona, M., Pardo, F., Salinas, M.R. and Zalacain, A., 2012. Waste grape skins thermal dehydration: potential release of colour, phenolic and aroma compounds into wine. CyTA-Journal of Food 10: 225-234.
Pioggia, G., Francesco, F.D., Marchetti, A., Ferro, M. and Ahluwalia, A., 2007. A composite sensor array impedentiometric electronic tongue. Part I. Characterization. Biosensors and Bioelectronics 22: 2618-2623.
Prieto, N., Gay, M., Vidal, S., Aagaard, O., Saja, J.A. and Rodriguez-Mendez, M.L., 2011. Analysis of the influence of the type of closure in the organoleptic characteristics of a red wine by using an electronic panel. Food Chemistry 129: 589-594.
Procida, G., Pagliuca, G. and Cichelli, A., 2009. Geographical differentiation between Italian and Spanish saffron based on volatile fraction composition. A preliminary study. Agro Food Industry Hi-Tech 20: 48-53.
Psotova, J., Chlopcikova, S., Miketova, P., Hrbac, J. and Simanek, V., 2004. Chemoprotective effect of plant phenolics against anthracycline-induced toxicity on rat cardiomyocytes. Part III. Apigenin, baicalelin, kaempherol, luteolin and quercetin. Phytother Research 18: 516-521.
Rahaiee, S., Hashemi, M., Moini, S., Abbas Shojaosadati, S. and Razavi, S.H., 2015. Comparison of phytochemical constituents and antioxidant activities of aqueous and alcoholic extracts of saffron. Quality Assurance and Safety of Crops & Foods 7: 521-529.
Renedo, O.D., Alonso-Lomillo, M.A. and Arcos Martinez, M.J., 2007. Recent developments in the field of screen-printed electrodes and their related applications. Talanta 73: 202-219.
Riul, J.A., Dantas, C.A.R., Miyazaki, C.M. and Oliveira, J.O.N., 2010. Recent advances in electronic tongues. Analyst 135: 2481-2495.
Rodriguez-Mendez, M.L., Apetrei, C., Gay, M. and Saja, J.A., 2009. Biogenic amines and fish freshness assessment using a multisensor system based on voltammetric electrodes. Comparison between CPE and screen printed electrodes. Electrochimica Acta 54: 7033-7041.
Rodriguez-Mendez, M.L., Parra, V., Apetrei, C., Villanueva, S., Gay, M., Prieto, N., Martinez, J. and Saja, J.A., 2008. E-tongue based on voltammetric electrodes modified with electroactive materials. Applications. Microchimica Acta 163: 23-31.
Sanchez, A.M., Carmona, M., Zalacain, A., Carot, J.M., Jabaloyes, J.M. and Alonso, G.L., 2008. Rapid determination of crocetin esters and picrocrocin from saffron spice (Crocus sativus L.) using UV-visible spectrophotometry for quality control. Journal of Agricultural and Food Chemistry 56: 3167-3175.
Scampicchio, M., Benedetti, S., Brunetti, B. and Mannino, S., 2006. Amperometric electronic tongue for the evaluation of the tea astringency. Electroanalysis 18: 1643-1648.
Serrano-Diaz, J., Sanchez, A.M., Maggi, L., Carmona, M. and Alonso, G.L., 2011. Synergic effect of water soluble components on the coloring strength of saffron spice. Journal of Food Composition and Analysis24: 873-879.
Speranza, G., Dada, G., Manitto, P., Monti, D. and Grammatica, P., 1984. 13-cis crocin: a new crocinoid of saffron. Gazzetta Chimica Italiana 114: 189-192.
Verma, R.S., and Middha, D., 2010. Analysis of saffron (Crocus sativus L. stigma) components by LC-MS-MS. Chromatographia 71: 117-123.
Vlasov, Y.G., Ermolenko, Y.E., Legin, A.V., Rudnitskaya, A.M. and Kolodnikov, V., 2010. Chemical sensors and their systems. Journal of Analytical Chemistry 65: 890–898.
Wang, J. and Tian, B., 1992. Screen-printed stripping voltammetric/potentiometric electrodes for decentralized testing of trace lead. Analytical Chemistry 64: 1706-1709.
Wang, J., Tian, B., Nascimento, V.B. and Angnes, L., 1998. Performance of screen-printed carbon electrodes fabricated from different carbon inks. Electrochimica Acta 43: 3459-3465.
Winquist, F., 2008. Voltammetric electronic tongues – basic principles and applications. Microchimica Acta 163: 3-10.
Winterhalter, P. and Straubinger, R.M., 2000. Saffron. Renewed interest in an ancient spice. Food Review International 16: 39-59.
Zagal, J.H., Griveau, S., Santander-Nelli, M., Gutierrez-Granados, S. and Bedioui, F., 2012. Carbon nanotubes and metalloporphyrins and metallophthalocynines-based materials for electroanalysis. Journal of Porphyrins and Phthalocyanines 16: 713-740.
Zalacain, A., Ordoudi, S.A., Diaaz-Plaza, E.M., Carmona, M., M. Zquez, I.B., Tsimidou, Z. and Alonso, G.L., 2005. Near-infrared spectroscopy in saffron quality control: determination of chemical composition and geographical origin. Journal of Agriculture and Food Chemistry 53: 9337-9341.
Apetrei, C., Gutierrez, F., Rodriguez-Mendez, M.L. and Saja, J.A., 2007. Novel method based on carbon paste electrodes for the evaluation of the bitterness of virgin olive oils. Sensors and Actuators (B) 121: 567-575.
Apetrei, I.M. and Apetrei, C., 2013a. Voltammetric e-tongue for the quantification of total polyphenol content in olive oils. Food Research International54: 2075-2082.
Apetrei, M., Rodriguez-Mendez, M.L., Apetrei, C. and Saja, J.A., 2013b. Fish freshness monitoring using an e-tongue based on polypyrrole modified screen-printed electrode. IEEE, Journal of Sensors 13: 2548-2554.
Baldwin, E.A., Bai, J., Plotto, A. and Dea, S., 2011. Electronic noses and tongues: applications for the food and pharmaceutical industries. Sensors 11: 4744-4766.
Caballero-Ortega, H., Pereda-Miranda, R., Riveron-Negrete, L., Hernandez, J.M., Medecigo-Rios, M., Castillo-Villanueva, A. and Abdullaev, F.I., 2004. Chemical composition of saffron (Crocus sativus L.) from four countries. Acta Horticulture 650: 321-336.
Caballero-Ortega, H., Pereda-Miranda, R. and Abdullaev, F.I., 2007. HPLC quantification of major active components from 11 different saffron (Crocus sativus L.) sources. Food Chemistry 100: 1126-1131.
Campo, C.P., Garde-Cerdan, T., Sanchez, A.M., Maggi, L., Carmona, M. and Alonso, G.L., 2009. Determination of free amino acids and ammonium ion in saffron (Crocus sativus L.) from different geographical origins. Food Chemistry 114: 1542-1548.
Carmona, M., Martinez, J., Zalacain, A., Rodriguez-Mendez, M.L., Saja, J.A. and Alonso, G.L., 2006a. Analysis of saffron volatile fraction by TD-GC-MS and e-nose. European Food Research Technology 223: 96-101.
Carmona, M., Sanchez, A.M., Ferreres, F., Zalacain, A., Tomas-Barberan, F. and Alonso, G.L., 2007b. Identification of the flavonoid fraction in saffron spice by LC/DAD/MS/MS: comparative study of samples from different geographical origins. Food Chemistry 100: 445-450.
Carmona, M., Zalacain, A., Salinas, M.R. and Alonso, G.L., 2007a. A new approach to saffron aroma. Critical Reviews in Food Science and Nutrition 47: 145-159.
Carmona, M., Zalacain, A., Sanchez, A.M., Novella, J.L. and Alonso, G.L., 2006b. Crocetin esters, picrocrocin and its related compounds present in Crocus sativus stigmas and Gardenia jasminoides fruits. Tentative identification of seven new compounds by LC-ESI-MS. Journal of Agricultural and Food Chemistry 54: 973-979.
Dar, R.A., Brahman, P.K., Khurana, N., Wagay, J.A., Lone, Z.A., Ganaie, M.A. and Pitre, K.S., 2013. Evaluation of antioxidant activity of crocin, podophyllotoxin and kaempferol by chemical, biochemical and electrochemical assays. Arabian Journal of Chemistry, DOI: http://dx.doi.org/10.1016/j.arabjc.2013.02.004.
Esbensen, K., Schonkopf, S. and Midtgaard, T., 1994. Multi-variate analysis in practice (1st Ed.). CAMO AS, Trondheim, Norway.
Fanjul-Bolado, P., Hernandez-Santos, D., Lamas-Ardisana, P.J., Martin-Pernia, A. and Costa-Garcia, A., 2008. Electrochemical characterization of screen-printed and conventional carbon paste electrodes. Electrochimica Acta 53: 3635-3642.
Fanjul-Bolado, P., Queipo, P., Lamas-Ardisana, P.J. and Costa-Garcia, A., 2007. Manufacture and evaluation of carbon nanotube modified screen-printed electrodes as electrochemical tools. Talanta 74: 427-433.
Gay, M., Apetrei, C., Nevares, I., Alamo, M., Zurro, J., Prieto, N., Saja, J.A. and Rodriguez-Mendez, M.L., 2010. Application of an electronic tongue to study the effect of the use of pieces of wood and micro-oxygenation in the aging of red wine. Electrochim Acta 55: 6782-6788.
Ghasemi-Vamankhasti, M., Mohtasebi, S.S., Rodriguez-Mendez, M.L., Lozano, J., Razavi, S.H. and Ahmadi, H., 2011. Potential application of electronic nose technology in brewery. Trends in food Science and Technology 22: 165-174.
Haghighi, B., Feizy, J. and Hemati-Kakhki, A., 2007. LC determination of adulterated saffron prepared by adding styles colored with some natural colorants. Chromatographia 66: 325-332.
Heidarbeigi, K., Mohtasebi, S.S., Foroughirad, A., Ghasemi-Varnamkhasti, M., Rafiee, S. and Rezaei, K., 2015. Detection of adulteration in saffron samples using electronic nose. International Journal of Food Properties 18: 1391-1401.
Hoskuldsson, A., 1988. PLS regression methods. Journal of Chemometrics 2: 211-228.
International Organization for Standarization (ISO), 2011. ISO 3632 saffron (Crocus sativus L.). Part 1: specification. Part 2: test methods. ISO, Geneva, Switzerland.
Janczyk, M., Kutyla, A., Solohub, K., Wosicka, H., Cal, K. and Ciosek, P., 2011. Potentiometric electronic tongues for foodstuff and biosample recognition – an overview. Sensors 11: 4688-4701.
Kadara, R.O., Jenkinson, N. and Banks, C.E., 2009. Characterisation of commercially available electrochemical sensing platforms. Sensors and Actuators (B) 138: 556-562.
Labrador, R.H., Masot, R., Alcaniz, M., Baigts, D., Soto, J., Martinez-Manez, R., Garcia-Breijo, E., Gil, L. and Barat, J.M., 2010. Prediction of NaCl, nitrate and nitrite contents in minced meat by using a voltammetric electronic tongue and an impedimetric sensor. Food Chemistry 122: 864-870.
Matemadombo, F., Apetrei, C., Nyokong, T., Rodriguez-Mendez, M.L. and Saja, J.A., 2012. Comparison of carbon screen printed and disk electrodes in the detection of antioxidants using CoPc derivatives. Sensors and Actuators (B) 166-167: 457-466.
Medina-Plaza, C., Revilla, G., Munoz, R., Fernandez-Escudero, J.A., Barajas, E., Medrano, G., Saja, J.A. and Rodriguez-Mendez, M.L., 2014. Electronic tongue formed by sensors and biosensors containing phthalocyanines as electron mediators, Application to the analysis of red grapes. Journal of Porphyrins and Phthalocyanines 18: 76-86.
Ministerio de Economía y Hacienda (NCCEA), 1999. Normas de calidad del comercio exterior para el azafran. Ministerio de Economía y Hacienda, Madrid, Spain.
O’Halloran, M.P., Pravda, M. and Guilbault, G.G., 2001. Prussian blue bulk modified screen-printed electrodes for H2O2 detection and for biosensors. Talanta 55: 605-611.
Pedroza, M.A., Carmona, M., Pardo, F., Salinas, M.R. and Zalacain, A., 2012. Waste grape skins thermal dehydration: potential release of colour, phenolic and aroma compounds into wine. CyTA-Journal of Food 10: 225-234.
Pioggia, G., Francesco, F.D., Marchetti, A., Ferro, M. and Ahluwalia, A., 2007. A composite sensor array impedentiometric electronic tongue. Part I. Characterization. Biosensors and Bioelectronics 22: 2618-2623.
Prieto, N., Gay, M., Vidal, S., Aagaard, O., Saja, J.A. and Rodriguez-Mendez, M.L., 2011. Analysis of the influence of the type of closure in the organoleptic characteristics of a red wine by using an electronic panel. Food Chemistry 129: 589-594.
Procida, G., Pagliuca, G. and Cichelli, A., 2009. Geographical differentiation between Italian and Spanish saffron based on volatile fraction composition. A preliminary study. Agro Food Industry Hi-Tech 20: 48-53.
Psotova, J., Chlopcikova, S., Miketova, P., Hrbac, J. and Simanek, V., 2004. Chemoprotective effect of plant phenolics against anthracycline-induced toxicity on rat cardiomyocytes. Part III. Apigenin, baicalelin, kaempherol, luteolin and quercetin. Phytother Research 18: 516-521.
Rahaiee, S., Hashemi, M., Moini, S., Abbas Shojaosadati, S. and Razavi, S.H., 2015. Comparison of phytochemical constituents and antioxidant activities of aqueous and alcoholic extracts of saffron. Quality Assurance and Safety of Crops & Foods 7: 521-529.
Renedo, O.D., Alonso-Lomillo, M.A. and Arcos Martinez, M.J., 2007. Recent developments in the field of screen-printed electrodes and their related applications. Talanta 73: 202-219.
Riul, J.A., Dantas, C.A.R., Miyazaki, C.M. and Oliveira, J.O.N., 2010. Recent advances in electronic tongues. Analyst 135: 2481-2495.
Rodriguez-Mendez, M.L., Apetrei, C., Gay, M. and Saja, J.A., 2009. Biogenic amines and fish freshness assessment using a multisensor system based on voltammetric electrodes. Comparison between CPE and screen printed electrodes. Electrochimica Acta 54: 7033-7041.
Rodriguez-Mendez, M.L., Parra, V., Apetrei, C., Villanueva, S., Gay, M., Prieto, N., Martinez, J. and Saja, J.A., 2008. E-tongue based on voltammetric electrodes modified with electroactive materials. Applications. Microchimica Acta 163: 23-31.
Sanchez, A.M., Carmona, M., Zalacain, A., Carot, J.M., Jabaloyes, J.M. and Alonso, G.L., 2008. Rapid determination of crocetin esters and picrocrocin from saffron spice (Crocus sativus L.) using UV-visible spectrophotometry for quality control. Journal of Agricultural and Food Chemistry 56: 3167-3175.
Scampicchio, M., Benedetti, S., Brunetti, B. and Mannino, S., 2006. Amperometric electronic tongue for the evaluation of the tea astringency. Electroanalysis 18: 1643-1648.
Serrano-Diaz, J., Sanchez, A.M., Maggi, L., Carmona, M. and Alonso, G.L., 2011. Synergic effect of water soluble components on the coloring strength of saffron spice. Journal of Food Composition and Analysis24: 873-879.
Speranza, G., Dada, G., Manitto, P., Monti, D. and Grammatica, P., 1984. 13-cis crocin: a new crocinoid of saffron. Gazzetta Chimica Italiana 114: 189-192.
Verma, R.S., and Middha, D., 2010. Analysis of saffron (Crocus sativus L. stigma) components by LC-MS-MS. Chromatographia 71: 117-123.
Vlasov, Y.G., Ermolenko, Y.E., Legin, A.V., Rudnitskaya, A.M. and Kolodnikov, V., 2010. Chemical sensors and their systems. Journal of Analytical Chemistry 65: 890–898.
Wang, J. and Tian, B., 1992. Screen-printed stripping voltammetric/potentiometric electrodes for decentralized testing of trace lead. Analytical Chemistry 64: 1706-1709.
Wang, J., Tian, B., Nascimento, V.B. and Angnes, L., 1998. Performance of screen-printed carbon electrodes fabricated from different carbon inks. Electrochimica Acta 43: 3459-3465.
Winquist, F., 2008. Voltammetric electronic tongues – basic principles and applications. Microchimica Acta 163: 3-10.
Winterhalter, P. and Straubinger, R.M., 2000. Saffron. Renewed interest in an ancient spice. Food Review International 16: 39-59.
Zagal, J.H., Griveau, S., Santander-Nelli, M., Gutierrez-Granados, S. and Bedioui, F., 2012. Carbon nanotubes and metalloporphyrins and metallophthalocynines-based materials for electroanalysis. Journal of Porphyrins and Phthalocyanines 16: 713-740.
Zalacain, A., Ordoudi, S.A., Diaaz-Plaza, E.M., Carmona, M., M. Zquez, I.B., Tsimidou, Z. and Alonso, G.L., 2005. Near-infrared spectroscopy in saffron quality control: determination of chemical composition and geographical origin. Journal of Agriculture and Food Chemistry 53: 9337-9341.
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