MAİLLARD REAKSİYONU İLE ÜRETİLEN PROTEİN-KARBONHİDRAT KONJUGATLARININ FONKSİYONEL ÖZELLİKLERİ VE GIDA ENDÜSTRİSİNDEKİ ROLÜ

Öz

Proteinler, amfifilik bileşiklerdir ancak fonksiyonel özellikleri depolama sırasında asidik ve ya termal ko şullar altında kaybolabilmektedir. Karbonhidratlar ise geniş pH aralıklarına dayanıklıdır, fakat emülsiyon oluşturma yetenekleri zayıftır. Protein ve karbonhidratların bahsedilen bu kararsızlıklarını gidermek ve özelliklerini geliştirmek için çeşitli fiziksel, kimyasal ve enzimatik metotlar uygulanabilmektedir. Ancak, bu yöntemlerin bir bölümünün gıdaya uygun olmaması ve/veya ek maliyet gerektirmesi sorun oluşturabilmektedir. Proteinlerin karbonhidratlarla konjugasyonu, proteinlerin fonksiyonel kararlılığını artırmanın bir yoludur ve konjugasyon ile bu iki bileşen grubunun üstün özelliklerine sahip karbonhidrat-protein konjugatları (KPK) oluşmaktadır. KPK, gıdalarda doğal olarak meydana gelen Maillard reaksiyonunun kontrollü şartlarda (sıcaklık, bağıl nem, pH vb.) gerçekleştirilmesiyle elde edilebilmektedir. Yapılan çalışmalarda konjugatların geniş pH aralıklarında çözünebildiği, protein ve karbonhidratların bireysel niteliklerinden daha üstün emülgatör niteliklerine sahip oldukları görülmüştür. Ayrıca, zorlu çevresel şartlara dayanıklı olmaları sebebiyle KPK’lerin enkapsülasyondan, biyobozunur film üretimine kadar geniş bir uygulama alanına sahip olabileceğini düşündürmektedir. Bu çalışmada, KPK’lerin üretim parametreleri, analiz yöntemleri ve kullanım alanları derlenmiştir.

Anahtar Kelimeler

• Karbonhidrat-protein konjugatları
• Maillard reaksiyonu
• konjugat üretimi
• kullanım alanları
• fonksiyonel kararlılık

Destekleyen Kurum

TUBİTAK

Proje Numarası

120O763

Teşekkür

Yazarlar, 120O763 numaralı projeye mali desteklerinden dolayı TÜBİTAK'a teşekkür etmektedir.

FUNCTIONAL PROPERTIES OF PROTEIN-CARBOHYDRATE CONJUGATES PRODUCED BY MAILLARD REACTION AND THEIR ROLE IN THE FOOD INDUSTRY

Öz

Proteins are amphiphilic compounds; however, their functional properties may deteriorate during storage under acidic or thermal conditions. Carbohydrates, on the other hand, are stable over a wide pH range but have weak emulsifying abilities. To overcome these instabilities and improve their properties, various physical, chemical, and enzymatic methods can be applied. However, some of these methods may not be suitable for food applications and/or may require additional costs. The conjugation of proteins with carbohydrates is one approach to enhancing the functional stability of proteins, resulting in carbohydrate–protein conjugates (CPCs) that combine the advantageous properties of both groups. CPCs can be obtained through the controlled Maillard reaction, which naturally occurs in foods and involves factors such as temperature, relative humidity, and pH. Studies have shown that these conjugates are soluble over a broad pH range and possess superior emulsifying properties compared to proteins or carbohydrates alone. Furthermore, their resistance to harsh environmental conditions suggests that CPCs have potential for a wide range of applications, from encapsulation to biodegradable film production. This study reviews the production parameters, analytical methods, and application areas of CPCs.

Anahtar Kelimeler

• Carbohydrate-protein conjugates
• Maillard reaction
• conjugate production
• application areas
• functional stability

Proje Numarası

120O763

Teşekkür

Yazarlar, 120O763 numaralı projeye mali desteklerinden dolayı TÜBİTAK'a teşekkür etmektedir.

Kaynakça

1. Agustinisari, I., Mulia, K., Harimurti, N., Nasikin, M., Rienoviar, Herawati, H., Manalu, L. P. (2024). The Potency of Maillard Conjugates Containing Whey Protein as Natural Emulsifier. International Journal of Food Science, 2024(1): 3254132.
2. Augustin, M. A., Sanguansri, L., Bode, O. (2006). Maillard Reaction Products as Encapsulants for Fish Oil Powders. Journal of Food Science, 71(2): E25-E32.
3. Bianchi, F., Simonato, B. (2025). Pulses Protein Concentrates and Isolates as Stand-Alone Plant-Based Egg Replacers: An Explorative Study of Their Functional Properties and Technological Effect in Pancakes. Food and bioprocess technology: 1-16.
4. Boonlao, N., Ruktanonchai, U.R., Anal, A.K. (2023). Glycation of Soy Protein Isolate with Maltodextrin through Maillard Reaction Via Dry and Wet Treatments and Compare Their Techno-Functional Properties. Polymer Bulletin, 80(8): 8603-26.
5. Bork, L.V., Haase, P.T., Rohn, S., Kanzler, C. (2022). Formation of Melanoidins–Aldol Reactions of Heterocyclic and Short-Chain Maillard Intermediates. Food Chemistry, 380: 131852.
6. Cao, J., Yang, C., Zhang, J., Zhang, L., Tsao, R. (2025). Amadori Compounds: Analysis, Composition in Food and Potential Health Beneficial Functions. Critical Reviews in Food Science and Nutrition, 65(2): 406-28.
7. Capar, T. D., Yalcin, H. (2021). Protein/Polysaccharide Conjugation Via Maillard Reactions in an Aqueous Media: Impact of Protein Type, Reaction Time and Temperature. LWT, 152: 112252.
8. Cheng, J., Wang, J., Li, Z., Chen, B., Cui, L. (2023). Improving the Mechanical and Water-Resistance Properties of Pea Protein-Based Edible Film Via Wet-Heating Maillard Reaction: Insights into the Simultaneous Effect of Heating and Maillard Reaction. Food Packaging and Shelf Life, 35: 101024.

9. Choi, H.W., Kim, J.-H., Ham, S.H., Park, C., Kim, J.-W., & Choi, Y.J. (2025). Effect of Heating Time and Drying Method on the Functional Properties of Soy Protein Isolate–Maltodextrin Conjugates for Plant-Based Meringue Cookies. Future Foods, 11: 100587.
10. Choi, K.-O., Ryu, J., Kwak, H.-S., Ko, S. (2010). Spray-Dried Conjugated Linoleic Acid Encapsulated with Maillard Reaction Products of Whey Proteins and Maltodextrin. Food Science and Biotechnology, 19(4): 957-65.
11. Chutia, H., Mahanta, C. L. (2023). Clean Label Physical Conjugates of Protein-Based Bio-Emulsifiers for Food Applications. Food Chemistry Advances, 3: 100469.
12. Consoli, L., Dias, R.A.O., Rabelo, R.S., Furtado, G.F., Sussulini, A., Cunha, R.L., Hubinger, M.D. (2018). Sodium Caseinate-Corn Starch Hydrolysates Conjugates Obtained through the Maillard Reaction as Stabilizing Agents in Resveratrol-Loaded Emulsions. Food Hydrocolloids, 84: 458-72.
13. Cui, H., Yu, J., Zhai, Y., Feng, L., Chen, P., Hayat, K., &, Ho, C.-T. (2021). Formation and Fate of Amadori Rearrangement Products in Maillard Reaction. Trends in Food Science & Technology, 115: 391-408.
14. Dai, Q., Wang, H., Zhu, X., Hornung, P. S., Zhang, Y., Hu, W., &, Beta, T. (2025). Assessment of Ph-Induced Conformational Changes in Whey Protein Isolate–Dextran Conjugate Using Spectral Technology. Foods, 14(11): 1952.
15. Dıblan, S., Salum, P., Ulusal, F., Erbay, Z. (2024). Impact of Conjugation of Whey Protein Concentrate with Different Carbohydrates: Monitoring Structural and Technofunctional Variations. International Dairy Journal, 158: 106036.
16. Drozłowska, E., Starowicz, M., Śmietana, N., Krupa-Kozak, U., Łopusiewicz, Ł. (2023). Spray-Drying Impact the Physicochemical Properties and Formation of Maillard Reaction Products Contributing to Antioxidant Activity of Camelina Press Cake Extract. Antioxidants, 12(4): 919.
17. Dumitrașcu, L., Borda, D., Aprodu, I. (2023). Alternative Processing Options for Improving the Proteins Functionality by Maillard Conjugation. Foods, 12(19): 3588.
18. Dursun Capar, T., Yalcin, H. (2024). Conjugation Prepared by Wet-Maillard Reactions Improves the Stability and Properties of Lutein and Lycopene Loaded Nanoparticles. Journal of food science and technology, 61(10): 2008-2019.
19. El Hosry, L., Elias, V., Chamoun, V., Halawi, M., Cayot, P., Nehme, A., Bou-Maroun, E. (2025). Maillard Reaction: Mechanism, Influencing Parameters, Advantages, Disadvantages, and Food Industrial Applications: A Review. Foods, 14(11): 1881.
20. Erbay, Z., Çam, M., Aydemir, L. Y., Güven, O., Erkin, Ö. C., Dıblan, S., Salum, P., Çelik, Ö., Bolat-Gedik, E. B., Bilen-Çoban, A., Ulubaş, Ç. (2024). "Çift Katlı Emülsiyon/Püskürtmeli Kurutma Tekniği Ile Biyoaktif Gıda Katkı Maddesi Olarak Mikroenkapsüle Kazein Hidrolizatı Üretimi." Proje Numarası: TÜBİTAK 1001 Programı Proje Sonuç Raporu.
21. He, M., Li, L., Wu, C., Zheng, L., Jiang, L., Huang, Y., &, Li, Y. (2021). Effects of Glycation and Acylation on the Structural Characteristics and Physicochemical Properties of Soy Protein Isolate. Journal of food science, 86(5):1737-50.
22. Higa, F. A., Nickerson, M. T. (2023). Plant Protein-Carbohydrate Conjugates: A Review of Their Production, Functionality and Nutritional Attributes. Food Reviews International, 39(2): 750-71.
23. Hussain, A., Hussain, M., Ashraf, W., Karim, A., Aqeel, S. M., Khan, A., &, Lianfu, Z. (2024). Preparation, Characterization and Functional Evaluation of Soy Protein Isolate-Peach Gum Conjugates Prepared by Wet Heating Maillard Reaction. Food Research International, 192: 114681.
24. Jiménez-Castaño, L., Villamiel, M., López-Fandiño, R. (2007). Glycosylation of Individual Whey Proteins by Maillard Reaction Using Dextran of Different Molecular Mass. Food Hydrocolloids, 21(3): 433-43.
25. Kato, A. (2002). Industrial Applications of Maillard-Type Protein-Polysaccharide Conjugates. Food Science and Technology Research, 8(3): 193-9.
26. Ke, C., Li, L. (2023). Influence Mechanism of Polysaccharides Induced Maillard Reaction on Plant Proteins Structure and Functional Properties: A Review. Carbohydrate Polymers, 302: 120430.
27. Khan, H., Mudgil, P., Alkaabi, S.A.S., AlRashdi, Y.H.S., Maqsood, S. (2024). Maillard Reaction-Based Conjugation of Pea Protein and Prebiotic (Polydextrose): Optimization, Characterization, and Functional Properties Enhancement. Frontiers in Sustainable Food Systems, 8: 1463058.
28. Kong, W., Sun, X., Zhang, X., Wang, Y., Zhao, Y., Gao, L., &, Zhang, R. (2025). Proteomic and Amino Acid Dynamics During Jujube Blackening: Structural Transformations and Maillard Reaction Linkages. Food Science & Nutrition, 13(7): e70644.
29. Kumar, S. M., Sabikhi, L., Lamba, H. (2021). Emulsification Properties of Sodium Caseinate‐Based Conjugates with Selected Polysaccharides. International Journal of Dairy Technology, 74(1): 44-51.
30. Kutzli, I., Weiss, J., Gibis, M. (2021). Glycation of Plant Proteins Via Maillard Reaction: Reaction Chemistry, Technofunctional Properties, and Potential Food Application. Foods, 10(2): 376.
31. Lee, S., Choi, E., Lee, K.-G. (2024). Kinetic Modelling of Maillard Reaction Products and Protein Content During Roasting of Coffee Beans. LWT, 211: 116950.
32. Lee, Y. Y., Tang, T. K., Phuah, E. T., Alitheen, N. B., Tan, C. P., Lai, O. M. (2017). New Functionalities of Maillard Reaction Products as Emulsifiers and Encapsulating Agents, and the Processing Parameters: A Brief Review. J Sci Food Agric, 97(5): 1379-85.
33. Lesmes, U., McClements, D. J. (2012). Controlling Lipid Digestibility: Response of Lipid Droplets Coated by Β-Lactoglobulin-Dextran Maillard Conjugates to Simulated Gastrointestinal Conditions. Food Hydrocolloids, 26(1): 221-30.
34. Li, Z., Jiang, H., Guo, M., Zhang, Z., You, X., Wang, X., &, Wang, C. (2024). Modification of Casein with Oligosaccharides Via the Maillard Reaction: As Natural Emulsifiers. Food Research International, 191: 114648.
35. Liu, S., Sun, H., Ma, G., Zhang, T., Wang, L., Pei, H., &, Gao, L.(2022). Insights into Flavor and Key Influencing Factors of Maillard Reaction Products: A Recent Update. Frontiers in Nutrition, 9: 973677.
36. Luo, Y., Zhu, S., Peng, J., Cui, H., Huang, Q., Xu, B., Ho, C.-T. (2023). Feasibility Study of Amadori Rearrangement Products of Glycine, Diglycine, Triglycine, and Glucose as Potential Food Additives for Production, Stability, and Flavor Formation. Journal of Agricultural and Food Chemistry, 72(1): 657-69.
37. Meng, Y., Zhao, X., Jiang, Y., Ban, Q., Wang, X. (2023). Effect of Maillard Reaction Conditions on the Gelation and Thermal Stability of Whey Protein Isolate/D-Tagatose Conjugates. Food Chemistry, 405: 134928.
38. Nooshkam, M., Varidi, M., Zareie, Z., Alkobeisi, F. (2023). Behavior of Protein-Polysaccharide Conjugate-Stabilized Food Emulsions under Various Destabilization Conditions. Food Chemistry: X, 18: 100725.
39. Ono, W., Oka, D., Tsujii, Y., Noguchi, T. (2021). Dry-Heat Treatment of Skim Milk Powder Improves Acid-Induced Gelation Due to Protein Glycation and Cross-Linking of Caseins. Food Science and Technology Research, 27(6): 923-31.
40. Pirestani, S., Nasirpour, A., Keramat, J., Desobry, S., Jasniewski, J. (2017). Effect of Glycosylation with Gum Arabic by Maillard Reaction in a Liquid System on the Emulsifying Properties of Canola Protein Isolate. Carbohydrate Polymers, 157: 1620-7.
41. Qiu, C., Meng, Y., Zhang, Z., Li, X., McClements, D. J., Li, G., &, Ji, H. (2025). Enhancement of Soy Protein Functionality by Conjugation or Complexation with Polysaccharides or Polyphenols: A Review. Comprehensive Reviews in Food Science and Food Safety, 24(1): e70095.
42. Qu, B., Zhong, Q. (2017). Casein-Maltodextrin Conjugate as an Emulsifier for Fabrication of Structured Calcium Carbonate Particles as Dispersible Fat Globule Mimetics. Food Hydrocolloids, 66: 61-70.
43. Salum, P. 2023. "Çift Katlı Emülsiyon/Püskürtmeli Kurutma Tekniği Ile Biyoaktif Gıda Katkı Maddesi Olarak Mikroenkapsüle Kazein Hidrolizatı Üretimi." Doktora Tezi, Fen Bilimleri Enstitüsü, Adana Alparslan Türkeş Bilim ve Teknoloji Üniversitesi.
44. Salum, P., Ulubaş, Ç., Güven, O., Cam, M., Aydemir, L. Y., Erbay, Z. (2024). Design and Process Optimisation of Double Emulsions Loaded with Casein Hydrolysate. International Dairy Journal, 157: 106026.
45. Shahnaz, T., Fawole, A. O., Adeyanju, A. A., Onuh, J. O. (2024). Food Proteins as Functional Ingredients in the Management of Chronic Diseases: A Concise Review. Nutrients, 16(14): 2323.
46. Shakoor, A., Zhang, C., Xie, J., Yang, X. (2022). Maillard Reaction Chemistry in Formation of Critical Intermediates and FlavourCompounds and Their Antioxidant Properties. Food Chemistry, 393: 133416.
47. Shepherd, R., Robertson, A., Ofman, D. (2000). Dairy Glycoconjugate Emulsifiers: Casein–Maltodextrins. Food Hydrocolloids, 14(4): 281-6.
48. Silva, T. J., Barrera‐Arellano, D., Ribeiro, A. P. B. (2021). Oleogel‐Based Emulsions: Concepts, Structuring Agents, and Applications in Food. Journal of food science, 86(7): 2785-801.
49. Song, Y., Jia, Z., Yan, L., Liu, Y., Cui, Z., Wang, Y., Zhang, C. (2025). Exploring the Material Basis and Formation Pathways of the Burnt Aroma During the Stir-Frying Process of Gardeniae Fructus Using Sensomics and Chemical Components Approach. Food Chemistry: X: 102690.
50. Spotti, M. J., Martinez, M. J., Pilosof, A. M. R., Candioti, M., Rubiolo, A. C., Carrara, C. R. (2014). Influence of Maillard Conjugation on Structural Characteristics and Rheological Properties of Whey Protein/Dextran Systems. Food Hydrocolloids, 39: 223-30.
51. Su, Y., Lu, C., Chang, C., Li, J., Sun, Y., Zhang, W., &, Yang, Y. (2022). Preparation and Characterization of W1/O/W2 Emulsions Stabilized by Glycated and Heat‐Modified Egg White Proteins. Journal of the Science of Food and Agriculture, 102(13): 5795-807.
52. Teixé-Roig, J., Oms-Oliu, G., Odriozola-Serrano, I., Martín-Belloso, O. (2023). Emulsion-Based Delivery Systems to Enhance the Functionality of Bioactive Compounds: Towards the Use of Ingredients from Natural, Sustainable Sources. Foods, 12(7): 1502.
53. Uceda, A. B., Mariño, L., Casasnovas, R., Adrover, M. (2024). An Overview on Glycation: Molecular Mechanisms, Impact on Proteins, Pathogenesis, and Inhibition. Biophysical Reviews, 16(2): 189-218.
54. Wang, Q., Ismail, B. (2012). Effect of Maillard-Induced Glycosylation on the Nutritional Quality, Solubility, Thermal Stability and Molecular Configuration of Whey Proteinv. International Dairy Journal, 25(2): 112-22.
55. Xiao, T., Ma, X., Hu, H., Xiang, F., Zhang, X., Zheng, Y., &, Shi, A. (2025). Advances in Emulsion Stability: A Review on Mechanisms, Role of Emulsifiers, and Applications in Food. Food Chemistry: X: 102792.
56. Xu, D., Yuan, F., Wang, X., Li, X., Hou, Z., Gao, Y. (2010). The Effect of Whey Protein Isolate-Dextran Conjugates on the Freeze-Thaw Stability of Oil-in-Water Emulsions. Journal of Dispersion Science and Technology, 32(1): 77-83.
57. Xue, F., Li, C., Zhu, X., Wang, L., Pan, S. (2013). Comparative Studies on the Physicochemical Properties of Soy Protein Isolate-Maltodextrin and Soy Protein Isolate-Gum Acacia Conjugate Prepared through Maillard Reaction. Food Research International, 51(2): 490-5.
58. Xue, F., Gu, Y., Wang, Y., Li, C., Adhikari, B. (2019). Encapsulation of Essential Oil in Emulsion Based Edible Films Prepared by Soy Protein Isolate-Gum Acacia Conjugates. Food Hydrocolloids, 96: 178-89.
59. Yan, Y., Zhu, Q., Diao, C., Wang, J., Wu, Z., Wang, H. (2020). Enhanced Physicochemical Stability of Lutein-Enriched Emulsions by Polyphenol-Protein-Polysaccharide Conjugates and Fat-Soluble Antioxidant. Food Hydrocolloids, 101: 105447.
60. Yang, T. C., Hiramatsu, H. (2024). Spectroscopic Analysis of the Initial Step of the Maillard Reaction of D‐Fructose and Nα‐Acetyl‐L‐Lysine. Journal of Raman Spectroscopy, 55(11): 1156-64.
61. Yuan, M., Cao, Y., Zheng, H., Chen, K., Lu, Y., Wang, J., &, Shen, Y. (2024). Structural and Functional Properties of Maillard-Reacted Casein Phosphopeptides with Different Carbohydrates. Food Science and Biotechnology, 33(7): 1603-14.
62. Zhang, J., Wu, N., Lan, T., Yang, X. (2014). Improvement in Emulsifying Properties of Soy Protein Isolate by Conjugation with Maltodextrin Using High-Temperature, Short-Time Dry-Heating Maillard Reaction. International Journal of Food Science and Technology, 49(2): 460-7.
63. Zhang, M., Hutchinson, R. A. (2022). Innovative Process for Facile Dextran-Bovine Serum Albumin Conjugate Synthesis: Mechanism, Kinetics, and Characterization. Carbohydrate Polymers, 295: 119850.
64. Zhang, Q., Li, L., Lan, Q., Dong, H., Wu, D., Chen, H., &, Qin, W. (2021). Glycinin-Carbohydrate Conjugates: Preparation, Characterization, and Application in Processing of Whole Soybean Curd. Food Hydrocolloids, 111: 106383.
65. Zhang, Z., Holden, G., Wang, B., Adhikari, B. (2023). Maillard Reaction-Based Conjugation of Spirulina Protein with Maltodextrin Using Wet-Heating Route and Characterisation of Conjugates. Food Chemistry, 406: 134931.
66. Zhang, Z., Wang, B., Chen, J., Adhikari, B. (2024). Modification of Plant and Algal Proteins through the Maillard Reaction and Complex Coacervation: Mechanisms, Characteristics, and Applications in Encapsulating Oxygen-Sensitive Oils. Sustainable Food Technology, 2(3): 567-93.
67. Zhao, C., Yin, H., Yan, J., Niu, X., Qi, B., Liu, J. (2021). Structure and Acid-Induced Gelation Properties of Soy Protein Isolate–Maltodextrin Glycation Conjugates with Ultrasonic Pretreatment. Food Hydrocolloids, 112: 106278.
68. Zhao, L., Lu, X., Luo, H., Wang, Q., Gao, Q., Zhang, X., &, Wang, S. (2025). Structural Diversity of Monosaccharides Dictates Emulsification Functionality: Role of Casein-Glycation Conjugates Fabricated Via Wet-Heating Maillard Reaction. Food and Bioproducts Processing.