Article pubs.acs.org/JAFC
Investigation of α‑Dicarbonyl Compounds in Baby Foods by HighPerformance Liquid Chromatography Coupled with Electrospray Ionization Mass Spectrometry Tolgahan Kocadağlı and Vural Gökmen* Department of Food Engineering, Hacettepe University, Ankara 06640, Turkey ABSTRACT: Baby foods are exposed to elevated temperatures during processing treatments such as sterilization or spray drying. These treatments decompose sugars leading to the formation of α-dicarbonyl compounds that are of importance since they have been associated with several metabolic disorders. In this study, an analytical method based on high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) was used to determine α-dicarbonyl compounds in baby foods. The method entailed aqueous extraction of α-dicarbonyl compounds from the samples and derivatization with o-phenylenediamine prior to chromatographic analysis. The results indicated that major degradation product was 3-deoxyglucosone in the samples including cereal-based infant formula, canned fruit and vegetable puree. Its concentration ranged between 3.9 and 827.1 mg/kg in infant formula and between 26.7 and 92.3 mg/kg in fruit puree samples. The concentrations of glucosone, 1-deoxyglucosone, 5-hydroxymethyl-2-furfural, furfural, glyoxal, methylglyoxal, and dimethylglyoxal levels were rather low. KEYWORDS: α-dicarbonyl compounds, 3-deoxyglucosone, sugar degradation products, baby foods
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INTRODUCTION Reactive carbonyl compounds form in Maillard reaction and caramelization reactions during thermal processing and storage of sugar rich foods.1,2 Reactive carbonyl species interact with cellular constituents yielding several age related diseases and metabolic disorders.3,4 α-Dicarbonyl compounds, in particular, are taking attention since they cause glycation of several biomolecules in vivo more than aldose or ketose sugars even though they are found in lower concentrations.3,5,6 Cytotoxicity of α-dicarbonyl compounds is another concern taking attention.7−9 However, α-dicarbonyl compounds play a major role in color and flavor formation during thermal processing of certain foods.10,11 Dehydration of hexose sugars leads to 3-deoxyglucosone, 1deoxyglucosone, and 3,4-dideoxyglucoson-3-ene bearing an αdicarbonyl moiety and consecutive dehydration yield to 5hydroxy-2-methylfurfural (HMF), all remaining C6 skeleton.12−14 Another C6 α-dicarbonyl compound, glucosone is formed by oxidation of hexoses.2,12 Common sugar fragments ( 0.05) in the total α-dicarbonyl 7717
dx.doi.org/10.1021/jf502418n | J. Agric. Food Chem. 2014, 62, 7714−7720
Journal of Agricultural and Food Chemistry
Article
Lower concentrations of short chain ( 0.05). Jarred vegetable purees were generally found to contain lesser amounts of α-dicarbonyl compounds and furfurals (Table 4). The results revealed that approximately 90% of the total αdicarbonyl compounds in baby foods were composed of 3deoxyglucosone. The average amount of dicarbonyls was estimated to be 8.3 mg per serving (50 g powder) for cerealbased infant formula. While average amounts for fruit and vegetable puree were estimated to be 7.3 and 4.3 mg per jar (125 g), respectively. Degen et al. (2012) reported the concentrations of α-dicarbonyl compounds and HMF in several foodstuffs.18 According to their results higher quantities per serving were reported to be 8.8, 7.3, and 7.7 mg for fruit juice, bread and cookies in staple foods (excluding vinegar, beer, honey and candies, some of which could contain up to 23.5 mg/serving). Studies about the bioavailability and intestinal absorption of α-dicarbonyl compounds are limited. However, recent studies demonstrated that certain detoxifying systems might be efficient in adults, such as glyoxalase, aldehyde reductase, and aldehyde dehydrogenase systems.25,26 3-Deoxyglucosone has shown to transform 3-deoxyfructose and 3-deoxy-2-ketogluconic acid, which are less reactive and secreted in urine.27−30 Degen et al. (2014) demonstrated that only 10− 15% of the dietary 3-deoxyglucosone recovered as metabolites in urine.26 However, the fate of the remaining is unknown. In the very low pH of the stomach, 3-deoxyglucosone is most probably dehydrated to HMF, which is another concern due to its metabolite 5-sulphoxymethyl-2-furfural. 3-Deoxyglucosone might also react with proteins and amino acids during gastrointestinal digestion. Since 3-deoxyglucosone in particular is very high in baby foods, its biological consequences should be
Notes
The authors declare no competing financial interest.
■
REFERENCES
(1) Kroh, L. W. Caramelisation in food and beverages. Food Chem. 1994, 51, 373−379. (2) Thornalley, P. J.; Langborg, A.; Minhas, H. S. Formation of glyoxal, methylglyoxal and 3-deoxyglucosone in the glycation of proteins by glucose. Biochem. J. 1999, 344, 109−116. (3) Singh, R.; Barden, A.; Mori, T.; Beilin, L. Advanced glycation end-products: a review. Diabetologia 2001, 44, 129−146. (4) Abordo, E. A.; Minhas, H. S.; Thornalley, P. J. Accumulation of alpha-oxoaldehydes during oxidative stress: A role in cytotoxicity. Biochem. Pharmacol. 1999, 58, 641−648. (5) Igaki, N.; Sakai, M.; Hata, H.; Oimomi, M.; Baba, S.; Kato, H. Effects of 3-deoxyglucosone on the Maillard reaction. Clin. Chem. 1990, 36, 631−634. (6) Mera, K.; Takeo, K.; Izumi, M.; Maruyama, T.; Nagai, R.; Otagiri, M. Effect of reactive-aldehydes on the modification and dysfunction of human serum albumin. J. Pharm. Sci-Us. 2010, 99, 1614−1625. (7) Linden, T.; Cohen, A.; Deppisch, R.; Kjellstrand, P.; Wieslander, A. 3,4-Dideoxyglucosone-3-ene (3,4-DGE): A cytotoxic glucose degradation product in fluids for peritoneal dialysis. Kidney Int. 2002, 62, 697−703. (8) Amoroso, A.; Maga, G.; Daglia, M. Cytotoxicity of alphadicarbonyl compounds submitted to in vitro simulated digestion process. Food Chem. 2013, 140, 654−659. (9) Daglia, M.; Amoroso, A.; Rossi, D.; Mascherpa, D.; Maga, G. Identification and quantification of alpha-dicarbonyl compounds in balsamic and traditional balsamic vinegars and their cytotoxicity against human cells. J. Food Compos. Anal. 2013, 31, 67−74. (10) Cerny, C. The aroma side of the Maillard reaction. Ann. N.Y. Acad. Sci. 2008, 1126, 66−71. (11) Yaylayan, V. A. Recent advances in the chemistry of Strecker degradation and Amadori rearrangement: Implications to aroma and color formation. Food Sci. Technol. Res. 2003, 9, 1−6. (12) Gobert, J.; Glomb, M. A. Degradation of glucose: reinvestigation of reactive alpha-dicarbonyl compounds. J. Agric. Food Chem. 2009, 57, 8591−8597. (13) Locas, C. P.; Yaylayan, V. A. Isotope labeling studies on the formation of 5-(hydroxymethyl)-2-furaldehyde (HMF) from sucrose by pyrolysis-GC/MS. J. Agric. Food Chem. 2008, 56, 6717−6723. (14) Marceau, E.; Yaylayan, V. A. Profiling of alpha-dicarbonyl content of commercial honeys from different botanical origins: 7719
dx.doi.org/10.1021/jf502418n | J. Agric. Food Chem. 2014, 62, 7714−7720
Journal of Agricultural and Food Chemistry
Article
Identification of 3,4-dideoxyglucoson-3-ene (3,4-DGE) and related compounds. J. Agric. Food Chem. 2009, 57, 10837−10844. (15) Weenen, H. Reactive intermediates and carbohydrate fragmentation in Maillard chemistry. Food Chem. 1998, 62, 393−401. (16) Belitz, H. D.; Grosch, W.; Schieberle, P. Food Chemistry, 4th ed.; Springer-Verlag: Berlin, Germany, 2009. (17) Weigel, K. U.; Opitz, T.; Henle, T. Studies on the occurrence and formation of 1,2-dicarbonyls in honey. Eur. Food Res. Technol. 2004, 218, 147−151. (18) Degen, J.; Hellwig, M.; Henle, T. 1,2-Dicarbonyl compounds in commonly consumed foods. J. Agric. Food Chem. 2012, 60, 7071− 7079. (19) Gensberger, S.; Mittelmaier, S.; Glomb, M. A.; Pischetsrieder, M. Identification and quantification of six major alpha-dicarbonyl process contaminants in high-fructose corn syrup. Anal. Bioanal. Chem. 2012, 403, 2923−31. (20) Arribas-Lorenzo, G.; Morales, F. J. Analysis, distribution, and dietary exposure of glyoxal and methylglyoxal in cookies and their relationship with other heat-induced contaminants. J. Agric. Food Chem. 2010, 58, 2966−2972. (21) Gensberger, S.; Glomb, M. A.; Pischetsrieder, M. Analysis of sugar degradation products with alpha-dicarbonyl structure in carbonated soft drinks by UHPLC-DAD-MS/MS. J. Agric. Food Chem. 2013, 61, 10238−10245. (22) Glomb, M. A.; Tschirnich, R. Detection of alpha-dicarbonyl compounds in Maillard reaction systems and in vivo. J. Agric. Food Chem. 2001, 49, 5543−5550. (23) Gökmen, V.; Açar, Ö . Ç .; Serpen, A.; Morales, F. J. Effect of leavening agents and sugars on the formation of hydroxymethylfurfural in cookies during baking. Eur. Food Res. Technol. 2008, 226, 1031− 1037. (24) Gökmen, V.; Şenyuva, H. Z. Improved method for the determination of hydroxymethylfurfural in baby foods using liquid chromatography-mass spectrometry. J. Agric. Food Chem. 2006, 54, 2845−2849. (25) Degen, J.; Vogel, M.; Richter, D.; Hellwig, M.; Henle, T. Metabolic transit of dietary methylglyoxal. J. Agric. Food Chem. 2013, 61, 10253−60. (26) Degen, J.; Beyer, H.; Heymann, B.; Hellwig, M.; Henle, T. Dietary influence on urinary excretion of 3-deoxyglucosone and its metabolite 3-deoxyfructose. J. Agric. Food Chem. 2014, 62, 2449−56. (27) Kato, H.; van Chuyen, N.; Shinoda, T.; Sekiya, F.; Hayase, F. Metabolism of 3-deoxyglucosone, an intermediate compound in the Maillard reaction, administered orally or intravenously to rats. Biochim. Biophys. Acta 1990, 1035, 71−76. (28) Collard, F.; Vertommen, D.; Fortpied, J.; Duester, G.; Van Schaftingen, E. Identification of 3-deoxyglucosone dehydrogenase as aldehyde dehydrogenase 1A1 (retinaldehyde dehydrogenase 1). Biochimie 2007, 89, 369−373. (29) Kanazu, T.; Shinoda, M.; Nakayama, T.; Deyashiki, Y.; Hara, A.; Sawada, H. Aldehyde reductase is a major protein associated with 3deoxyglucosone reductase-activity in rat, pig and human livers. Biochem. J. 1991, 279, 903−906. (30) Vander Jagt, D. L.; Hunsaker, L. A. Methylglyoxal metabolism and diabetic complications: Roles of aldose reductase, glyoxalase-1, betaine aldehyde dehydrogenase, and 2-oxoaldehyde dehydrogenase. Chem-Biol. Interact. 2003, 143, 341−351.
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dx.doi.org/10.1021/jf502418n | J. Agric. Food Chem. 2014, 62, 7714−7720
Investigation of α‑Dicarbonyl Compounds in Baby Foods by HighPerformance Liquid Chromatography Coupled with Electrospray Ionization Mass Spectrometry Tolgahan Kocadağlı and Vural Gökmen* Department of Food Engineering, Hacettepe University, Ankara 06640, Turkey ABSTRACT: Baby foods are exposed to elevated temperatures during processing treatments such as sterilization or spray drying. These treatments decompose sugars leading to the formation of α-dicarbonyl compounds that are of importance since they have been associated with several metabolic disorders. In this study, an analytical method based on high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) was used to determine α-dicarbonyl compounds in baby foods. The method entailed aqueous extraction of α-dicarbonyl compounds from the samples and derivatization with o-phenylenediamine prior to chromatographic analysis. The results indicated that major degradation product was 3-deoxyglucosone in the samples including cereal-based infant formula, canned fruit and vegetable puree. Its concentration ranged between 3.9 and 827.1 mg/kg in infant formula and between 26.7 and 92.3 mg/kg in fruit puree samples. The concentrations of glucosone, 1-deoxyglucosone, 5-hydroxymethyl-2-furfural, furfural, glyoxal, methylglyoxal, and dimethylglyoxal levels were rather low. KEYWORDS: α-dicarbonyl compounds, 3-deoxyglucosone, sugar degradation products, baby foods
■
INTRODUCTION Reactive carbonyl compounds form in Maillard reaction and caramelization reactions during thermal processing and storage of sugar rich foods.1,2 Reactive carbonyl species interact with cellular constituents yielding several age related diseases and metabolic disorders.3,4 α-Dicarbonyl compounds, in particular, are taking attention since they cause glycation of several biomolecules in vivo more than aldose or ketose sugars even though they are found in lower concentrations.3,5,6 Cytotoxicity of α-dicarbonyl compounds is another concern taking attention.7−9 However, α-dicarbonyl compounds play a major role in color and flavor formation during thermal processing of certain foods.10,11 Dehydration of hexose sugars leads to 3-deoxyglucosone, 1deoxyglucosone, and 3,4-dideoxyglucoson-3-ene bearing an αdicarbonyl moiety and consecutive dehydration yield to 5hydroxy-2-methylfurfural (HMF), all remaining C6 skeleton.12−14 Another C6 α-dicarbonyl compound, glucosone is formed by oxidation of hexoses.2,12 Common sugar fragments ( 0.05) in the total α-dicarbonyl 7717
dx.doi.org/10.1021/jf502418n | J. Agric. Food Chem. 2014, 62, 7714−7720
Journal of Agricultural and Food Chemistry
Article
Lower concentrations of short chain ( 0.05). Jarred vegetable purees were generally found to contain lesser amounts of α-dicarbonyl compounds and furfurals (Table 4). The results revealed that approximately 90% of the total αdicarbonyl compounds in baby foods were composed of 3deoxyglucosone. The average amount of dicarbonyls was estimated to be 8.3 mg per serving (50 g powder) for cerealbased infant formula. While average amounts for fruit and vegetable puree were estimated to be 7.3 and 4.3 mg per jar (125 g), respectively. Degen et al. (2012) reported the concentrations of α-dicarbonyl compounds and HMF in several foodstuffs.18 According to their results higher quantities per serving were reported to be 8.8, 7.3, and 7.7 mg for fruit juice, bread and cookies in staple foods (excluding vinegar, beer, honey and candies, some of which could contain up to 23.5 mg/serving). Studies about the bioavailability and intestinal absorption of α-dicarbonyl compounds are limited. However, recent studies demonstrated that certain detoxifying systems might be efficient in adults, such as glyoxalase, aldehyde reductase, and aldehyde dehydrogenase systems.25,26 3-Deoxyglucosone has shown to transform 3-deoxyfructose and 3-deoxy-2-ketogluconic acid, which are less reactive and secreted in urine.27−30 Degen et al. (2014) demonstrated that only 10− 15% of the dietary 3-deoxyglucosone recovered as metabolites in urine.26 However, the fate of the remaining is unknown. In the very low pH of the stomach, 3-deoxyglucosone is most probably dehydrated to HMF, which is another concern due to its metabolite 5-sulphoxymethyl-2-furfural. 3-Deoxyglucosone might also react with proteins and amino acids during gastrointestinal digestion. Since 3-deoxyglucosone in particular is very high in baby foods, its biological consequences should be
Notes
The authors declare no competing financial interest.
■
REFERENCES
(1) Kroh, L. W. Caramelisation in food and beverages. Food Chem. 1994, 51, 373−379. (2) Thornalley, P. J.; Langborg, A.; Minhas, H. S. Formation of glyoxal, methylglyoxal and 3-deoxyglucosone in the glycation of proteins by glucose. Biochem. J. 1999, 344, 109−116. (3) Singh, R.; Barden, A.; Mori, T.; Beilin, L. Advanced glycation end-products: a review. Diabetologia 2001, 44, 129−146. (4) Abordo, E. A.; Minhas, H. S.; Thornalley, P. J. Accumulation of alpha-oxoaldehydes during oxidative stress: A role in cytotoxicity. Biochem. Pharmacol. 1999, 58, 641−648. (5) Igaki, N.; Sakai, M.; Hata, H.; Oimomi, M.; Baba, S.; Kato, H. Effects of 3-deoxyglucosone on the Maillard reaction. Clin. Chem. 1990, 36, 631−634. (6) Mera, K.; Takeo, K.; Izumi, M.; Maruyama, T.; Nagai, R.; Otagiri, M. Effect of reactive-aldehydes on the modification and dysfunction of human serum albumin. J. Pharm. Sci-Us. 2010, 99, 1614−1625. (7) Linden, T.; Cohen, A.; Deppisch, R.; Kjellstrand, P.; Wieslander, A. 3,4-Dideoxyglucosone-3-ene (3,4-DGE): A cytotoxic glucose degradation product in fluids for peritoneal dialysis. Kidney Int. 2002, 62, 697−703. (8) Amoroso, A.; Maga, G.; Daglia, M. Cytotoxicity of alphadicarbonyl compounds submitted to in vitro simulated digestion process. Food Chem. 2013, 140, 654−659. (9) Daglia, M.; Amoroso, A.; Rossi, D.; Mascherpa, D.; Maga, G. Identification and quantification of alpha-dicarbonyl compounds in balsamic and traditional balsamic vinegars and their cytotoxicity against human cells. J. Food Compos. Anal. 2013, 31, 67−74. (10) Cerny, C. The aroma side of the Maillard reaction. Ann. N.Y. Acad. Sci. 2008, 1126, 66−71. (11) Yaylayan, V. A. Recent advances in the chemistry of Strecker degradation and Amadori rearrangement: Implications to aroma and color formation. Food Sci. Technol. Res. 2003, 9, 1−6. (12) Gobert, J.; Glomb, M. A. Degradation of glucose: reinvestigation of reactive alpha-dicarbonyl compounds. J. Agric. Food Chem. 2009, 57, 8591−8597. (13) Locas, C. P.; Yaylayan, V. A. Isotope labeling studies on the formation of 5-(hydroxymethyl)-2-furaldehyde (HMF) from sucrose by pyrolysis-GC/MS. J. Agric. Food Chem. 2008, 56, 6717−6723. (14) Marceau, E.; Yaylayan, V. A. Profiling of alpha-dicarbonyl content of commercial honeys from different botanical origins: 7719
dx.doi.org/10.1021/jf502418n | J. Agric. Food Chem. 2014, 62, 7714−7720
Journal of Agricultural and Food Chemistry
Article
Identification of 3,4-dideoxyglucoson-3-ene (3,4-DGE) and related compounds. J. Agric. Food Chem. 2009, 57, 10837−10844. (15) Weenen, H. Reactive intermediates and carbohydrate fragmentation in Maillard chemistry. Food Chem. 1998, 62, 393−401. (16) Belitz, H. D.; Grosch, W.; Schieberle, P. Food Chemistry, 4th ed.; Springer-Verlag: Berlin, Germany, 2009. (17) Weigel, K. U.; Opitz, T.; Henle, T. Studies on the occurrence and formation of 1,2-dicarbonyls in honey. Eur. Food Res. Technol. 2004, 218, 147−151. (18) Degen, J.; Hellwig, M.; Henle, T. 1,2-Dicarbonyl compounds in commonly consumed foods. J. Agric. Food Chem. 2012, 60, 7071− 7079. (19) Gensberger, S.; Mittelmaier, S.; Glomb, M. A.; Pischetsrieder, M. Identification and quantification of six major alpha-dicarbonyl process contaminants in high-fructose corn syrup. Anal. Bioanal. Chem. 2012, 403, 2923−31. (20) Arribas-Lorenzo, G.; Morales, F. J. Analysis, distribution, and dietary exposure of glyoxal and methylglyoxal in cookies and their relationship with other heat-induced contaminants. J. Agric. Food Chem. 2010, 58, 2966−2972. (21) Gensberger, S.; Glomb, M. A.; Pischetsrieder, M. Analysis of sugar degradation products with alpha-dicarbonyl structure in carbonated soft drinks by UHPLC-DAD-MS/MS. J. Agric. Food Chem. 2013, 61, 10238−10245. (22) Glomb, M. A.; Tschirnich, R. Detection of alpha-dicarbonyl compounds in Maillard reaction systems and in vivo. J. Agric. Food Chem. 2001, 49, 5543−5550. (23) Gökmen, V.; Açar, Ö . Ç .; Serpen, A.; Morales, F. J. Effect of leavening agents and sugars on the formation of hydroxymethylfurfural in cookies during baking. Eur. Food Res. Technol. 2008, 226, 1031− 1037. (24) Gökmen, V.; Şenyuva, H. Z. Improved method for the determination of hydroxymethylfurfural in baby foods using liquid chromatography-mass spectrometry. J. Agric. Food Chem. 2006, 54, 2845−2849. (25) Degen, J.; Vogel, M.; Richter, D.; Hellwig, M.; Henle, T. Metabolic transit of dietary methylglyoxal. J. Agric. Food Chem. 2013, 61, 10253−60. (26) Degen, J.; Beyer, H.; Heymann, B.; Hellwig, M.; Henle, T. Dietary influence on urinary excretion of 3-deoxyglucosone and its metabolite 3-deoxyfructose. J. Agric. Food Chem. 2014, 62, 2449−56. (27) Kato, H.; van Chuyen, N.; Shinoda, T.; Sekiya, F.; Hayase, F. Metabolism of 3-deoxyglucosone, an intermediate compound in the Maillard reaction, administered orally or intravenously to rats. Biochim. Biophys. Acta 1990, 1035, 71−76. (28) Collard, F.; Vertommen, D.; Fortpied, J.; Duester, G.; Van Schaftingen, E. Identification of 3-deoxyglucosone dehydrogenase as aldehyde dehydrogenase 1A1 (retinaldehyde dehydrogenase 1). Biochimie 2007, 89, 369−373. (29) Kanazu, T.; Shinoda, M.; Nakayama, T.; Deyashiki, Y.; Hara, A.; Sawada, H. Aldehyde reductase is a major protein associated with 3deoxyglucosone reductase-activity in rat, pig and human livers. Biochem. J. 1991, 279, 903−906. (30) Vander Jagt, D. L.; Hunsaker, L. A. Methylglyoxal metabolism and diabetic complications: Roles of aldose reductase, glyoxalase-1, betaine aldehyde dehydrogenase, and 2-oxoaldehyde dehydrogenase. Chem-Biol. Interact. 2003, 143, 341−351.
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dx.doi.org/10.1021/jf502418n | J. Agric. Food Chem. 2014, 62, 7714−7720
