Method for enhancing oxidation resistance of caramel color

Abstract

The invention discloses a method for enhancing oxidation resistance of caramel color, which comprises the following steps: (1) mixing an amino acid solution and a caramel color solution according to different volume ratios to obtain a mixed solution; (2) adjusting the pH value of the mixed solution; and (3) heating the mixed solution, carrying out condensation reflux, and cooling. By adjusting Maillard reaction conditions and controlling the UV-Vis absorbance and fluorescence intensity of a reaction system, the oxidation resistance of the caramel color food can be effectively improved, and the caramel color food is endowed with good oxidation resistance, so that oxidative deterioration of the food is prevented or delayed, and the shelf life of the food is more remarkably prolonged.

Description

Technical Field

[0001] The invention relates to the field of industrial reactions, in particular to a method for enhancing the antioxidant performance of caramel color. Background Art

[0002] Caramel color, also known as caramel, commonly known as sauce color, is a natural edible pigment formed by incomplete decomposition and dehydration of sugars such as maltose or sucrose at high temperatures. The aldehydes, ketones, acids, alcohols and unsaturated hydrocarbons contained in caramel color give it certain antioxidant activity. In the food industry, the application of caramel color is not only limited to improving the color of food, but also because its antioxidant activity helps maintain food quality and delay food deterioration caused by oxidation. Despite this, the antioxidant capacity of caramel color still needs to be further improved to meet a wider range of application needs.

[0003] Improving the antioxidant properties of caramel color can be achieved by finely controlling the preparation process, introducing antioxidants and catalysts, and using chemical cross-linking technology. Improving the antioxidant properties of caramel color by optimizing the preparation process of caramel color is a relatively common method at present. The patent CN113136113A proposes an improved preparation method of caramel color, which effectively improves the antioxidant properties of caramel color by first dehydrating and condensing sugars, then low-temperature polymerization, and finally high-temperature polymerization. The patent CN113397018A introduces a process for improving the antioxidant properties of caramel color, through the primary reaction of starch syrup and acid, followed by the addition of Ti-Mg catalyst for secondary reaction, promoting the formation of substituted furans, thereby enhancing the antioxidant capacity of caramel color. In addition, CN114196228A discloses a method for improving the antioxidant properties of caramel color, cross-linking polyphenol groups with sucrose molecules to obtain caramel color polymers, the molecular weight of the caramel color polymers is increased, and the antioxidant properties are improved. Although the proposed caramel color antioxidant improvement process is effective, there are problems such as complex operation, high cost, and possible impact on food taste and nutritional components. Therefore, there is an urgent need for a method for improving the antioxidant properties of liquid caramel color prepared by the ammonium sulfite method, which is low-cost, easy to operate, and does not affect food quality.

[0004] The Maillard reaction (MR) is a non-enzymatic interaction between reducing sugars and amino acids, peptides or proteins, which produces various byproducts, intermediates and brown products, which contribute significantly to the improvement of aroma, taste, color and antioxidant capacity. Since caramel color contains ketones, aldehydes and other molecules, which have a common functional group-carbonyl, they can react with amino-containing compounds (such as proteins, peptides or amino acids) to produce complex products when heated, which may have the ability to enhance antioxidant capacity. The antioxidant activity of Maillard reaction products (MRPs) is closely related to the intermediates, browning pigments and fluorescent compounds generated during the reaction. This complex process can be evaluated by monitoring the ultraviolet-visible (UV-Vis) absorbance and fluorescence intensity. Studies have shown that the antioxidant activity of Maillard reaction products is positively correlated with the increase of their UV-Vis absorbance and fluorescence intensity, that is, with the increase of reaction time, their UV-Vis absorbance and fluorescence intensity and antioxidant capacity are enhanced. At the same time, some studies have shown that when the Maillard reaction is under unsuitable conditions, excessive increases in UV-Vis absorbance and fluorescence intensity may reduce the antioxidant activity of the product. These research results show that there is a certain correlation between the absorbance and fluorescence intensity of the Maillard reaction system and its antioxidant activity.

[0005] Therefore, technicians in this field are committed to developing a method for effectively improving the antioxidant properties of caramel color by controlling the conditions for the Maillard reaction between caramel color and amino acids to control the UV-Vis absorbance and fluorescence intensity within a suitable range. Summary of the invention

[0006] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to provide a method for effectively improving the antioxidant property of caramel color with a simple process.

[0007] To achieve the above object, the present invention provides a method for enhancing the antioxidant performance of caramel color.

[0008] A method for enhancing the antioxidant properties of caramel color, comprising the following steps:

[0009] (1) mixing the amino acid solution and the caramel color solution in different volume ratios to obtain a mixed solution;

[0010] (2) adjusting the pH value of the mixed solution;

[0011] (3) The mixed solution is then heated, condensed, refluxed and cooled.

[0012] In the present invention, the caramel color can be prepared by an ammonium sulfite method to obtain liquid caramel color.

[0013] In the present invention, in step (1), the amino acid is one or two of glycine, lysine and arginine.

[0014] Preferably, the amino acid is one of glycine, lysine and arginine, or a mixed solution of glycine and arginine / lysine, or a mixed solution of lysine and arginine.

[0015] In the present invention, in step (1), the concentration of the amino acid solution is 0.01-0.04 mg / mL.

[0016] In the present invention, in step (1), the volume ratio of the amino acid solution to the caramel color solution is 1:1-1:4.

[0017] In the present invention, in step (2), the pH value of the mixed solution is adjusted using hydrochloric acid.

[0018] In the present invention, in step (2), the pH value of the mixed solution is 2.0-6.0.

[0019] More preferably, the pH value of the mixed solution is 2.0-4.0.

[0020] In the present invention, in step (3), the heating method is preferably water bath heating.

[0021] In the present invention, in step (3), the heating temperature is 70-100°C.

[0022] More preferably, the heating temperature is 80-100°C.

[0023] In the present invention, in step (3), the condensation reflux time is 10-30 min.

[0024] More preferably, the condensation reflux time is 10-20 min.

[0025] The UV-Vis absorbance of the Maillard reaction system was controlled within the range of 0.675-0.989, and the fluorescence intensity was controlled within the range of 29659.8-31721.2.

[0026] By adjusting the Maillard reaction conditions of liquid caramel color and amino acids and controlling the UV-Vis absorbance and fluorescence intensity of the reaction system, its antioxidant properties can be effectively improved, giving foods containing caramel color good antioxidant properties, thereby preventing or delaying the oxidative deterioration of foods and significantly extending the shelf life of foods.

[0027] Compared with the prior art, the present invention has at least the following beneficial effects:

[0028] 1. The present invention can improve the DPPH free radical scavenging ability, ABTS free radical scavenging ability and iron ion reducing ability of the caramel color through the Maillard reaction between the liquid caramel color and amino acids, thereby effectively improving the antioxidant property of the liquid caramel color.

[0029] 2. The present invention improves the antioxidant property of liquid caramel color through the Maillard reaction. The process is simple and safe, does not require the use of any chemical additives, is environmentally friendly and sustainable, and is easy to industrialize.

[0030] 3. The present invention can expand the application scope of liquid caramel color to a certain extent and enhance the comprehensive utilization value of liquid caramel color.

[0031] Technical Effects

[0032] The concept, specific structure and technical effects of the present invention will be further described below in conjunction with the attached table to fully understand the purpose, characteristics and effects of the present invention. DETAILED DESCRIPTION

[0033] The following describes several preferred embodiments of the present invention with reference to the attached tables of the specification, so that the technical contents are clearer and easier to understand. The present invention can be embodied in many different forms of embodiments, and the protection scope of the present invention is not limited to the embodiments mentioned in the text.

[0034] Embodiment 1:

[0035] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0036] (1) Prepare a 0.02 mg / mL glycine solution and mix it with the caramel color solution at a ratio of 1:1 (v / v);

[0037] (2) adjusting the pH value of the mixed solution to 2.0;

[0038] (3) The mixed solution was heated in a water bath at 80°C for 10 min to condense and reflux, and then cooled.

[0039] Embodiment 2:

[0040] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0041] (1) Prepare a 0.01 mg / mL glycine solution and mix it with the caramel color solution at a ratio of 1:2 (v / v);

[0042] (2) adjusting the pH value of the mixed solution to 3.0;

[0043] (3) The mixed solution was heated in a 90°C water bath for 15 min to condense and reflux, and then cooled.

[0044] Embodiment 3:

[0045] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0046] (1) Prepare a 0.04 mg / mL glycine solution and mix it with the caramel color solution at a ratio of 1:4 (v / v);

[0047] (2) adjusting the pH value of the mixed solution to 4.0;

[0048] (3) The mixed solution was heated in a 100°C water bath for 20 min to condense and reflux, and then cooled.

[0049] Embodiment 4:

[0050] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0051] (1) Prepare a 0.02 mg / mL lysine solution and mix it with a caramel color solution at a ratio of 1:1 (v / v);

[0052] (2) adjusting the pH value of the mixed solution to 2.0;

[0053] (3) The mixed solution was heated in a 90°C water bath for condensation and reflux for 20 min, and then cooled.

[0054] Embodiment 5:

[0055] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0056] (1) Prepare a 0.01 mg / mL lysine solution and mix it with a caramel color solution at a ratio of 1:2 (v / v);

[0057] (2) adjusting the pH value of the mixed solution to 3.0;

[0058] (3) The mixed solution was heated in a 100°C water bath for 10 min under condensation reflux and then cooled.

[0059] Embodiment 6:

[0060] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0061] (1) Prepare a 0.04 mg / mL lysine solution and mix it with a caramel color solution at a ratio of 1:4 (v / v);

[0062] (2) adjusting the pH value of the mixed solution to 4.0;

[0063] (3) The mixed solution was heated in a water bath at 80°C for 15 min to condense and reflux, and then cooled.

[0064] Embodiment 7:

[0065] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0066] (1) Prepare a 0.02 mg / mL arginine solution and mix it with a caramel color solution at a ratio of 1:1 (v / v);

[0067] (2) adjusting the pH value of the mixed solution to 2.0;

[0068] (3) The mixed solution was heated in a 100°C water bath for 15 min to condense and reflux, and then cooled.

[0069] Embodiment 8:

[0070] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0071] (1) Prepare a 0.01 mg / mL arginine solution and mix it with a caramel color solution at a ratio of 1:2 (v / v);

[0072] (2) adjusting the pH value of the mixed solution to 3.0;

[0073] (3) The mixed solution was heated in a water bath at 80°C for 20 min to condense and reflux, and then cooled.

[0074] Embodiment 9:

[0075] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0076] (1) Prepare a 0.04 mg / mL arginine solution and mix it with a caramel color solution at a ratio of 1:4 (v / v);

[0077] (2) adjusting the pH value of the mixed solution to 4.0;

[0078] (3) The mixed solution was heated in a 90°C water bath for 10 min to condense and reflux, and then cooled.

[0079] Embodiment 10:

[0080] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0081] (1) preparing a 0.02 mg / mL solution of glycine and lysine mixed at a ratio of 1:1 (w / w), and then mixing it with a caramel color solution at a ratio of 1:1 (v / v);

[0082] (2) adjusting the pH value of the mixed solution to 2.0;

[0083] (3) The mixed solution was heated in a 90°C water bath for 10 min to condense and reflux, and then cooled.

[0084] Embodiment 11:

[0085] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0086] (1) preparing a 0.01 mg / mL solution of glycine and lysine in a ratio of 1:1 (w / w), and then mixing it with a caramel color solution in a ratio of 1:2 (v / v);

[0087] (2) adjusting the pH value of the mixed solution to 3.0;

[0088] (3) The mixed solution was heated in a water bath at 80°C for 15 min to condense and reflux, and then cooled.

[0089] Embodiment 12:

[0090] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0091] (1) preparing a 0.02 mg / mL solution of lysine and arginine mixed at a ratio of 1:1 (w / w), and then mixing it with a caramel color solution at a ratio of 1:1 (v / v);

[0092] (2) adjusting the pH value of the mixed solution to 2.0;

[0093] (3) The mixed solution was heated in a water bath at 80°C for 10 min to condense and reflux, and then cooled.

[0094] Embodiment 13:

[0095] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0096] (1) preparing a 0.01 mg / mL solution of lysine and arginine in a ratio of 1:1 (w / w), and then mixing it with a caramel color solution in a ratio of 1:4 (v / v);

[0097] (2) adjusting the pH value of the mixed solution to 3.0;

[0098] (3) The mixed solution was heated in a 90°C water bath for 15 min to condense and reflux, and then cooled.

[0099] Embodiment 14:

[0100] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0101] (1) preparing a 0.02 mg / mL solution of glycine and arginine mixed at a ratio of 1:1 (w / w), and then mixing it with a caramel color solution at a ratio of 1:1 (v / v);

[0102] (2) adjusting the pH value of the mixed solution to 2.0;

[0103] (3) The mixed solution was heated in a water bath at 80°C for 15 min to condense and reflux, and then cooled.

[0104] Embodiment 15:

[0105] The present invention provides a method for enhancing the antioxidant performance of caramel color, which is prepared by the following steps:

[0106] (1) preparing a 0.02 mg / mL solution of glycine and arginine mixed at a ratio of 1:1 (w / w), and then mixing it with a caramel color solution at a ratio of 1:2 (v / v);

[0107] (2) adjusting the pH value of the mixed solution to 3.0;

[0108] (3) The mixed solution was heated in a 90°C water bath for 10 min to condense and reflux, and then cooled.

[0109] Comparative Example 1:

[0110] This comparative example is based on Example 1-15, and the difference from Example 1-15 is:

[0111] Liquid caramel color is directly dissolved in deionized water without pH adjustment and heating.

[0112] Comparative Example 2:

[0113] (1) preparing a 0.05 mg / mL solution of glycine-lysine mixed at a ratio of 1:1 (w / w), and then mixing it with a caramel color solution at a ratio of 1:2 (v / v);

[0114] (2) adjusting the pH value of the mixed solution to 3.0;

[0115] (3) The mixed solution was heated in a 90°C water bath for 60 min to condense and reflux, and then cooled.

[0116] Comparative Example 3:

[0117] (1) preparing a 0.02 mg / mL solution of glycine and arginine in a ratio of 1:1 (w / w), and then mixing it with a caramel color solution in a ratio of 1:5 (v / v);

[0118] (2) adjusting the pH value of the mixed solution to 5.0;

[0119] (3) The mixed solution was heated in a 90°C water bath for 30 min to condense and reflux, and then cooled.

[0120] Test samples: caramel color samples prepared in Examples 1-15 and Comparative Examples 1-3.

[0121] Performance test: For the above Maillard reaction system, a UV-visible spectrophotometer and a fluorescence spectrometer were used to monitor the absorbance and fluorescence intensity of the system after the reaction was completed, and the antioxidant activity was determined as follows:

[0122] 1. UV-visible absorption spectrum measurement

[0123] The Maillard reaction system after the reaction was completed was scanned spectrally in the range of 200-600 nm using an ultraviolet-visible spectrophotometer.

[0124] 2. Fluorescence spectroscopy

[0125] The Maillard reaction system was scanned by fluorescence spectrometer after the reaction was completed, with the excitation wavelength set to 280 nm, the emission spectrum to 300-600 nm, and the slit width to 5 nm.

[0126] 3. Antioxidant properties

[0127] (1) Determination of DPPH free radical scavenging ability

[0128] Take 2 mL of the caramel solution after the above treatment in a test tube, add 2 mL of 0.1 mmol / L DPPH ethanol solution, mix well, and react at room temperature in the dark for 30 minutes. The absorbance value is measured at a wavelength of 517 nm. i Measure 2mL of anhydrous ethanol + 2mL of caramel solution, and the absorbance value at 517nm is A j ; Mix 2mL deionized water and 2mL DPPH ethanol solution and react at room temperature in the dark for 30 minutes. The absorbance value at a wavelength of 517nm is A 0 The DPPH free radical scavenging rate was calculated according to the following formula:

[0129]

[0130] (2) Determination of ABTS free radical scavenging ability

[0131] 7.4mmol / L ABTS and 2.6mmol / L potassium persulfate solution were mixed at a ratio of 1:1 (v / v) and allowed to stand at room temperature in the dark for 16 hours to prepare ABTS stock solution; ABTS stock solution was diluted with PBS solution (0.1mol / L, pH 7.4) to obtain ABTS working solution when its absorbance at 734nm was 0.70±0.05. 0.03mL caramel solution (0.5mg / mL) and 3mL ABTS working solution were mixed and shaken, allowed to stand at room temperature in the dark for 10 minutes, and the absorbance at 734nm was measured as A a ; Use 3mL of deionized water instead of ABTS working solution to determine the absorbance value of A b ; Use deionized water instead of caramel color sample solution to determine the absorbance value of A c , the ABTS free radical scavenging rate was calculated according to the following formula:

[0132]

[0133] (3) Determination of iron ion reducing power

[0134] Take 1 mL of the caramel color solution after the above treatment in a test tube, add phosphate buffer solution (0.2 mol / mL, pH 6.6), 2.5 mL of 1% (w / v) potassium ferrocyanide, mix well, heat in a water bath (50°C, 20 min), cool quickly, add 2.5 mL of 10% (w / v) trichloroacetic acid, mix well, take out 2.5 mL, add 2.5 mL of deionized water and 0.5 mL of FeCl 3 (0.1%, w / v), and the absorbance was measured at a wavelength of 700 nm after sufficient reaction for 20 min.

[0135] The results of the UV-visible absorbance and fluorescence intensity of the caramel color prepared by the present invention and the antioxidant activity are shown in Table 1.

[0136] Table 1

[0137]

[0138] As shown in Table 1 above, the present invention controls the Maillard reaction conditions of caramel color and amino acids, controls the UV-Vis absorbance of the Maillard reaction system at 294nm within the range of 0.675-0.989, and controls the fluorescence intensity at 420nm within the range of 29659.8-31721.2. The liquid caramel color obtained has improved scavenging rates for DPPH and ABTS free radicals, and iron ion reducing ability, and can improve the antioxidant capacity of caramel color food, prevent food from oxidative deterioration, and thus extend the shelf life. The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to allow people familiar with this technology to understand the content of the present invention and implement it accordingly, rather than for limiting the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

[0139] The preferred specific embodiments of the present invention are described in detail above. It should be understood that ordinary technicians in the field can make many modifications and changes based on the concept of the present invention without creative work. Therefore, all technical solutions that can be obtained by technicians in the technical field based on the concept of the present invention through logical analysis, reasoning or limited experiments on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A method for enhancing the antioxidant properties of caramel color, characterized in that: The following steps are involved: (1) mixing the amino acid solution and the caramel color solution in different volume ratios to obtain a mixed solution; (2) adjusting the pH value of the mixed solution; (3) The mixed solution is then heated, condensed, refluxed and cooled.

2. The method for enhancing the antioxidant properties of caramel color according to claim 1, characterized in that: In step (1), the amino acid is one or two of glycine, lysine and arginine.

3. The method for enhancing the antioxidant properties of caramel color according to claim 1, characterized in that: In step (1), the concentration of the amino acid solution is 0.01-0.04 mg / mL.

4. The method for enhancing the antioxidant properties of caramel color according to claim 1, characterized in that: In step (1), the volume ratio of the amino acid solution to the caramel color solution is 1:1-1:

4.

5. The method for enhancing the antioxidant properties of caramel color according to claim 1, characterized in that: In step (2), the pH value of the mixed solution is 2.0-6.

0.

6. The method for enhancing the antioxidant properties of caramel color according to claim 5, characterized in that: The pH value of the mixed solution is 2.0-4.

0.

7. The method for enhancing the antioxidant properties of caramel color according to claim 1, characterized in that: In step (3), the heating temperature is 70-100°C.

8. The method for enhancing the antioxidant properties of caramel color according to claim 7, characterized in that: In step (3), the heating temperature is 80-100°C.

9. The method for enhancing the antioxidant properties of caramel color according to claim 1, characterized in that: In step (3), the condensation reflux time is 10-30 min.

10. The method for enhancing the antioxidant performance of caramel color according to claim 9, characterized in that: The condensation reflux time is 10-20 minutes.

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