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Cross-linking of wheat gluten proteins during production of hard pretzels

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Abstract

The impact of the hot alkaline dip, prior to pretzel-baking, on the types and levels of cross-links between wheat proteins was studied. Protein extractability of pretzel dough in sodium dodecyl sulfate containing buffer decreased during alkaline dipping [45 s, 1.0% (w/v) NaOH, 90°C], and even more during baking (3 min at 250°C) and drying (10 min at 135°C). Reducing agent increased the extractability partly, indicating that both reducible (disulfide, SS) and non-reducible (non-SS) protein cross-links had been formed. The decrease in cystine levels suggested β-elimination of cystine releasing Cys and dehydroalanine (DHA). Subsequent reaction of DHA with Lys and Cys, induced the unusual and potentially cross-linking amino acids lysinoalanine (LAL) and lanthionine (LAN), respectively, in alkaline dipped dough (7 μmol LAN/g protein) and in the end product (9 μmol LAL and 50 μmol LAN/g protein). The baking/drying step increased sample redness, decreased Lys levels more than expected based on LAL formation (57 μmol/g protein), and induced a loss of reducing sugars (99 μmol/g protein), which suggested the potential contribution of Maillard-derived cross-links to the observed extractability loss. However, levels of Maillard products which possibly cross-link proteins, are small compared to DHA-derived cross-links. Higher dipping temperatures, longer dipping times, and higher NaOH concentrations increased protein extractability losses and redness, as well as LAL and LAN levels in the end product. No indications for Maillard-derived cross-links or LAL in pretzel dough immediately after dipping were found, even when severe dipping conditions were used.

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Abbreviations

DHA:

Dehydroalanine

HPAEC-IPAD:

High-performance anion-exchange chromatography with integrated pulsed amperometric detection

LAL:

Lysinoalanine

LAN:

Lanthionine

mc:

Moisture content

SDS:

Sodium dodecyl sulfate

SE-HPLC:

Size-exclusion high-performance liquid chromatography

SH:

Sulfhydryl

SS:

Disulfide

References

  • AACC (2000) Approved Methods of the American Association of Cereal Chemists, 10th edn edn. AACC International, St. Paul, MN

    Google Scholar 

  • Anese M, Nicoli MC, Massini R, Lerici CR (1999) Effects of drying processing on the Maillard reaction in pasta. Food Res Int 32(3):193–199

    Article  CAS  Google Scholar 

  • AOAC (1995) Official Methods of Analysis, 16th edn edn. Association of Official Analytical Chemists, Washington, DC

    Google Scholar 

  • Belitz HD, Grosch W, Schieberle P (2009a) Amino acids, peptides, proteins. In: Belitz HD, Grosch W, Schieberle P (eds) Food Chemistry, 4th edn edn. Springer-Verlag, Berlin, Heidelberg, pp 8–92

    Google Scholar 

  • Belitz HD, Grosch W, Schieberle P (2009b) Carbohydrates. In: Belitz HD, Grosch W, Schieberle P (eds) Food Chemistry, 4th edn edn. Springer-Verlag, Berlin, Heidelberg, pp 245–341

    Google Scholar 

  • Cleemput G, Roels SP, Oort Mv, Grobet PJ, Delcour JA (1993) Heterogeneity in the structure of water-soluble arabinoxylans in European wheat flours of variable bread-making quality. Cereal Chem 70:324–329

    CAS  Google Scholar 

  • Courtin CM, Van den Broeck H, Delcour JA (2000) Determination of reducing end sugar residues in oligo- and polysaccharides by gas-liquid chromatography. J Chromatogr A 866(1):97–104

    Article  PubMed  CAS  Google Scholar 

  • Cubadda RE, Carcea M, Marconi E, Trivisonno MC (2007) Influence of gluten proteins and drying temperature on the cooking quality of durum wheat pasta. Cereal Chem 84(1):48–55

    Article  CAS  Google Scholar 

  • Dai Z, Nemet I, Shen W, Monnier VM (2007) Isolation, purification and characterization of histidino-threosidine, a novel Maillard reaction protein crosslink from threose, lysine and histidine. Arch Biochem Biophys 463(1):78–88

    Article  PubMed  CAS  Google Scholar 

  • Delcour JA, Hoseney RC (2010) Snack foods. In: Delcour JA, Hoseney RC. Principles of Cereal Science and Technology, 3rd edn edn. Association of Cereal Chemists, St. Paul, MN, pp 249–256

    Google Scholar 

  • Ding YS, Yu H, Mou SF (2002) Direct determination of free amino acids and sugars in green tea by anion-exchange chromatography with integrated pulsed amperometric detection. J Chromatogr A 982(2):237–244

    Article  PubMed  CAS  Google Scholar 

  • Friedman M (1999a) Chemistry, biochemistry, nutrition, and microbiology of lysinoalanine, lanthionine, and histidinoalanine in food and other proteins. J Agric Food Chem 47(4):1295–1319

    Article  PubMed  CAS  Google Scholar 

  • Friedman M (1999b) Lysinoalanine in food and in antimicrobial proteins. Adv Exp Med Biol 459:145–159

    Article  PubMed  CAS  Google Scholar 

  • Henle T, Schwarzenbolz U, Kostermeyer H (1997) Detection and quantification of pentosidine in foods. Z Lebensm Unters Forsch A: 204(2):95–98

    Article  CAS  Google Scholar 

  • Horn MJ, Jones DB, Ringel SJ (1941) Isolation of a new sulfur-containing amino acid (lanthionine) from sodium carbonate-treated wool. J Biol Chem 138(1):141–149

    CAS  Google Scholar 

  • Kieffer R, Schurer F, Kohler P, Wieser H (2007) Effect of hydrostatic pressure and temperature on the chemical and functional properties of wheat gluten: Studies on gluten, gliadin and glutenin. J Cereal Sci 45(3):285–292

    Article  CAS  Google Scholar 

  • Kuktaite R, Larsson H, Marttila S, Brismar K, Prieto-Linde M, Johansson E (2004) Gluten macropolymer in wheat flour doughs: Structure and function for wheat quality. In: Kuktaite R, Larsson H, Marttila S, Brismar K, Prieto-Linde M, Johansson E. Gluten Proteins. vol 295. Royal Soc Chemistry, Cambridge, pp 288–291

    Google Scholar 

  • Lagrain B, Brijs K, Veraverbeke WS, Delcour JA (2005) The impact of heating and cooling on the physico-chemical properties of wheat gluten-water suspensions. J Cereal Sci 42(3):327–333

    Article  CAS  Google Scholar 

  • Lagrain B, Thewissen BG, Brijs K, Delcour JA (2008) Mechanism of gliadin-glutenin cross-linking during hydrothermal treatment. Food Chem 107(2):753–760

    Article  CAS  Google Scholar 

  • Lagrain B, De Vleeschouwer K, Rombouts I, Brijs K, Hendrickx ME, Delcour JA (2010) The kinetics of beta-elimination of cystine and the formation of lanthionine in gliadin. J Agric Food Chem 58(19):10761–10767

    Article  PubMed  CAS  Google Scholar 

  • Lagrain B, Rombouts I, Brijs K, Delcour JA (2011) Kinetics of heat-induced polymerization of gliadin. J Agric Food Chem 59(5):2034–2039

    Article  PubMed  CAS  Google Scholar 

  • Lamberts L, Rombouts I, Brijs K, Gebruers K, Delcour JA (2008) Impact of parboiling conditions on Maillard precursors and indicators in long-grain rice cultivars. Food Chem 110(4):916–922

    Article  CAS  Google Scholar 

  • Lindsay MP, Skerritt JH (1999) The glutenin macropolymer of wheat flour doughs: structure-function perspectives. Trends Food Sci Tech 10(8):247–253

    Article  CAS  Google Scholar 

  • Linetsky M, Hill JMW, LeGrand RD, Hu F (2004) Dehydroalanine crosslinks in human lens. Exp Eye Res 79(4):499–512

    Article  PubMed  CAS  Google Scholar 

  • Maga JA (1984) Lysinoalanine in foods. J Agric Food Chem 32(5):955–964

    Article  CAS  Google Scholar 

  • Martins SIFS, Jongen WMF, van Boekel MAJS (2000) A review of Maillard reaction in food and implications to kinetic modelling. Trends Food Sci Tech 11(9–10):364–373

    Article  CAS  Google Scholar 

  • Mestdagh F, De Wilde T, Castelein P, Németh O, Van Peteghem C, De Meulenaer B (2008) Impact of the reducing sugars on the relationship between acrylamide and Maillard browning in French fries. Eur Food Res Technol 227(1):69–76

    Article  CAS  Google Scholar 

  • Payne PI, Nightingale MA, Krattiger AF, Holt LM (1987) The relationship between HMW glutenin subunit composition and the bread-making quality of british-grown wheat-varieties. J Sci Food Agric 40(1):51–65

    Article  CAS  Google Scholar 

  • Rombouts I, Lamberts L, Celus I, Lagrain B, Brijs K, Delcour JA (2009) Wheat gluten amino acid composition analysis by high-performance anion-exchange chromatography with integrated pulsed amperometric detection. J Chromatogr A 1216(29):5557–5562

    Article  PubMed  CAS  Google Scholar 

  • Rombouts I, Lagrain B, Brijs K, Delcour JA (2010) [beta]-Elimination reactions and formation of covalent cross-links in gliadin during heating at alkaline pH. J Cereal Sci 52(3):362–367

    Article  CAS  Google Scholar 

  • Rombouts I, Lagrain B, Brijs K, Delcour JA (2011) Colorimetric determination of dehydroalanine in wheat gluten. J Cereal Sci 54(1):148–150

    Google Scholar 

  • Schofield JD, Bottomley RC, Timms MF, Booth MR (1983) The effect of heat on wheat gluten and the involvement of sulfhydryl-disulfide interchange reactions. J Cereal Sci 1(4):241–253

    Article  CAS  Google Scholar 

  • Seetharaman K, Yao N, Rout MK (2004) Role of water in pretzel dough development and final product quality. Cereal Chem 81(3):336–340

    Article  CAS  Google Scholar 

  • Sternberg M, Kim CY, Schwende FJ (1975) Lysinoalanine-presence in foods and food ingredients. Science 190(4218):992–994

    Article  PubMed  CAS  Google Scholar 

  • Vaclavik VA, Christian EW (2008) Essentials of Food Science, 3rd edn edn. Springer, New York, NY

    Google Scholar 

  • Visschers RW, de Jongh HHJ (2005) Disulphide bond formation in food protein aggregation and gelation. Biotechnol Adv 23(1):75–80

    Article  PubMed  CAS  Google Scholar 

  • Walsh LP (1993) Method for making hard pretzels. US Patent 005238693, 09/29/1992

  • Whitaker JR, Feeney RE (1983) Chemical and physical modification of proteins by the hydroxide ion. Crit Rev Food Sci Nutr 19(3):173–212

    Article  PubMed  CAS  Google Scholar 

  • Yao N, Owusu-Apenten R, Zhu L, Seetharaman K (2006) Effect of alkali dipping on dough and final product quality. J Food Sci 71(3):C209–C215

    Article  CAS  Google Scholar 

  • Zimmermann N, Freund S, Fredenhagen A, Jung G (1993) Solution structures of the lantibiotics duramycin-B and duramycin-C. Eur J Biochem 216(2):419–428

    Article  PubMed  CAS  Google Scholar 

Download references

Acknowledgments

This work is part of the Methusalem programme “Food for the Future” at the K.U.Leuven. B. Lagrain and K. Brijs wish to acknowledge the Research Foundation—Flanders (FWO, Brussels, Belgium) and the Industrial Research Fund (K.U.Leuven, Leuven, Belgium), respectively, for financial support.

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Correspondence to Ine Rombouts.

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Rombouts, I., Lagrain, B., Brijs, K. et al. Cross-linking of wheat gluten proteins during production of hard pretzels. Amino Acids 42, 2429–2438 (2012). https://doi.org/10.1007/s00726-011-1048-2

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