Water-soluble rosemary antioxidant as well as preparation method and application thereof

Abstract

The invention provides a water-soluble rosemary antioxidant. The antioxidant is prepared by mixing a rosemary extract, edible oil, a protein aqueous solution and a polysaccharide aqueous solution, wherein the mass volume concentration of the protein aqueous solution and the polysaccharide aqueous solution is 3%-4%, and the mass ratio of the protein aqueous solution to the polysaccharide aqueous solution is 1: (1-3); the ratio of the total mass of the rosemary extract and the edible oil to the total mass of the protein aqueous solution and the polysaccharide aqueous solution is 1: (1-4). The raw materials of the antioxidant prepared by the invention are all natural harmless raw materials, do not contain chemical reagents, and have a cleaning label; the water solubility and the stability are good, and meanwhile, the stability can still be kept under different pH conditions; the food preservative can obviously delay the occurrence time of lipid oxidation in food, and is suitable for preservation of various foods.

Description

Technical Field

[0001] The invention belongs to the technical field of food preservation, and particularly relates to a water-soluble rosemary antioxidant and a preparation method and application thereof. Background Art

[0002] With the continuous growth of the global population and the continuous expansion of the size of the middle-income population, human demand for high-quality protein foods has shown a continuous growth trend. Among them, meat food is one of the important sources of high-quality protein needed by humans. According to statistics, the total global meat production in 2023 will reach 371 million tons, an increase of 1.5% year-on-year. However, lipid oxidation is a common biochemical reaction that occurs during the processing and storage of meat and other foods. Lipid oxidation not only has an important impact on the sensory quality of food flavor, but also produces many harmful factors, which poses a potential threat to consumer health. According to statistics, the amount of meat lost due to lipid oxidation each year accounts for about 8%-12% of the total global meat production, causing a large amount of edible high-quality protein loss while also bringing huge socioeconomic losses and environmental damage risks. Therefore, the effective control of lipid oxidation during the processing and storage of meat foods is becoming an issue that is increasingly being concerned in the food processing industry.

[0003] In current industrial applications, due to the comprehensive consideration of cost and antioxidant effect, antioxidant products containing chemically synthesized ingredients are often used to control lipid oxidation in food. For example, tertiary butylhydroquinone (TBHQ), butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA) have been widely used in antioxidant applications in foods such as oils and meat. However, these chemically synthesized antioxidants have certain potential toxicity due to their synthetic raw materials and methods. For example, butylated hydroxytoluene (BHT) is produced by reaction with p-cresol and isobutyl alcohol, concentrated sulfuric acid as a catalyst, and alumina as a dehydrating agent. Therefore, local governments have strict restrictions on the use of such chemically synthesized antioxidants as food additives, and even the European Union and other regions are gradually banning the use of some chemically synthesized antioxidants. As consumers pay more and more attention to food safety and green processing of food, especially for clean labels in food, the promotion and application of green and natural food additives is becoming an emerging development trend in the food processing industry.

[0004] Among them, the rosemary antioxidant made from the extract from the plant rosemary is a natural food additive allowed by the national standard. Due to its green source and non-toxic and harmless to humans, there is no strict dosage limit for this antioxidant in many countries. Therefore, in the food industry, rosemary antioxidants are increasingly used in meat and other food processing. Among them, rosemary essential oil, carnosic acid, carnosol, rosmarinic acid and other main substances can be extracted from the leaves of rosemary, and carnosic acid, carnosol, rosmarinic acid and the like are molecules that play a key antioxidant effect. In addition, it has been found that the fat-soluble components such as carnosic acid and carnosol have the largest content in the effective ingredients of rosemary, and are also the components with the strongest antioxidant effect. However, the polarity of carnosic acid and carnosol is weak and difficult to dissolve in water, and this characteristic seriously limits their application in water-soluble environments.

[0005] At present, there are some technologies that use fat-soluble rosemary antioxidant components to prepare related antioxidants, and have shown certain application effects. However, in order to increase its application in aqueous solution scenarios, most of them choose to add some chemically synthesized cosolvents to improve its stability in aqueous solution systems, such as Tween, propylene glycol, glycerides, etc. Therefore, this type of product does not have a clean label and is expensive, which greatly limits the use and further promotion of rosemary extract as a natural antioxidant. Therefore, there is an urgent need for a cost-controlled clean label carrier to dissolve and deliver natural water-insoluble antioxidant molecules such as carnosic acid and carnosol, so as to realize its antioxidant application in various application scenarios. Summary of the invention

[0006] In view of this, the present invention provides a water-soluble rosemary antioxidant with a clean label, which is produced by using completely natural raw materials and a simple production process and has controllable cost, stable state, excellent antioxidant effect.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions: A water-soluble rosemary antioxidant, which is prepared by mixing rosemary extract, edible oil, protein aqueous solution and polysaccharide aqueous solution; The mass volume concentration of the protein aqueous solution and the polysaccharide aqueous solution are both 3% to 4%, and the mass ratio of the protein aqueous solution to the polysaccharide aqueous solution is 1: (1 to 3); The ratio of the total mass of rosemary extract and edible oil to the total mass of protein aqueous solution and polysaccharide aqueous solution is 1: (1-4).

[0008] Furthermore, the mass ratio of the rosemary extract to the edible oil is 1:(3-5).

[0009] Furthermore, the protein in the protein aqueous solution includes whey protein, soy protein, pea protein, and myofibrillar protein.

[0010] Furthermore, the polysaccharides in the polysaccharide aqueous solution include beet pectin, apple pectin, citrus pectin, and sunflower pectin.

[0011] Furthermore, the edible oil includes rapeseed oil, sunflower oil, and soybean oil.

[0012] A method for preparing the above antioxidant comprises the following steps: S1. Preheating edible oil, adding rosemary extract, stirring, and filtering to obtain a rosemary oil-soluble antioxidant solution; S2. Preheat water, add polysaccharide powder, stir to dissolve, and stand at 4°C overnight until fully hydrated to obtain a polysaccharide aqueous solution; S3, preheat water, add protein powder, stir to dissolve, and let stand at 4°C overnight until completely hydrated to obtain a protein aqueous solution; S4. Stir and mix the polysaccharide aqueous solution and the protein aqueous solution, let stand at 4° C. overnight until they are completely hydrated, then add the rosemary oil-soluble antioxidant solution, and stir at high speed to obtain a water-soluble rosemary antioxidant.

[0013] Furthermore, in step S1, the edible oil preheating temperature is 40-45° C., and the stirring conditions are: rotation speed 800-1000 rpm, and time 20-30 min.

[0014] Furthermore, in step S2, the water preheating temperature is 75-85° C., and the stirring conditions are: rotation speed 1000-1500 rpm, and time 20-30 min.

[0015] Furthermore, in step S3, the water preheating temperature is 40-45° C., the stirring and mixing conditions are: a rotation speed of 800-1000 rpm, and a time of 25-35 min. The high-speed stirring conditions are: a rotation speed of 15000-17000 rpm, and a time of 2-4 min.

[0016] The use of the above-mentioned water-soluble rosemary antioxidant in food preservation.

[0017] Compared with the prior art, the present invention has the following beneficial effects: BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 This is a graph showing the stability results of the antioxidants prepared in Examples 1 and 2 of the present invention under different pH conditions. DETAILED DESCRIPTION

[0018] The present invention is further described in detail below in conjunction with specific embodiments so that those skilled in the art can understand the present invention more clearly.

[0019] Sources and physical and chemical parameters of key test materials: Rosemary extract powder (RMP) was purchased from Hunan Xianwei Sunshine Biotechnology Co., Ltd.

[0020] Sunflower pectin powder was purchased from Zhengzhou Chaofan Chemical Co., Ltd.

[0021] Apple pectin powder and citrus pectin powder were purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0022] Whey protein powder was purchased from Hilma Ingredients (a division of Hilma Corporation).

[0023] Soy protein powder was purchased from Henan Wanbang Industrial Co., Ltd.

[0024] Pea protein powder was purchased from Xinzheng Yulong Biotechnology Co., Ltd.

[0025] Example 1 This embodiment provides a water-soluble rosemary antioxidant, and the specific preparation method is as follows: S1. Take 80g of sunflower oil and preheat it to 40°C, add 20g of rosemary extract, stir at 1000rpm for 25min, filter, and obtain rosemary oil-soluble antioxidant solution (RO); at this time, the mass ratio of sunflower oil to rosemary extract is 4:1.

[0026] S2. Take 100 mL of water and preheat it to 80°C, add 3 g of sunflower pectin powder, stir and dissolve at 1200 rpm for 30 min, and let stand at 4°C overnight until completely hydrated to obtain sunflower pectin solution (SP); at this time, the mass volume concentration of the polysaccharide aqueous solution is 3%.

[0027] S3. Take 100 mL of water and preheat it to 45°C, add 3 g of whey protein powder, stir at 1000 rpm for 30 min, and let stand at 4°C overnight until completely hydrated to obtain whey protein solution (WPI); at this time, the mass volume concentration of the protein aqueous solution is 3%.

[0028] S4. SP and WPI were mixed in a mass ratio of 1:1, stirred at 1000 rpm for 30 min, and allowed to stand at 4°C overnight until completely hydrated to obtain a whey protein-sunflower pectin composite solution (WPI-SP). Then, WPI-SP and RO were mixed in a mass ratio of 4:1, 3:1, 2:1, and 1:1, respectively, and stirred and dissolved at 16000 rpm for 3 min to obtain four water-soluble rosemary antioxidants.

[0029] Example 2 This embodiment provides a water-soluble rosemary antioxidant, and the specific preparation method is basically the same as that of Example 1, except that: in step S4, SP and WPI are mixed in a mass ratio of 3:1, and the rest remain unchanged.

[0030] Example 3 This embodiment provides a water-soluble rosemary antioxidant, and the specific preparation method is basically the same as that of Example 1, except that: the mass volume concentration of SP in step S2 is 4%; the mass volume concentration of WPI in step S3 is 4%; and the rest remain unchanged.

[0031] Example 4 This embodiment provides a water-soluble rosemary antioxidant, and the specific preparation method is as follows: S1. The method is basically the same as Example 1, except that the mass ratio of sunflower seed oil to rosemary extract is 3:1, thereby obtaining a rosemary oil-soluble antioxidant solution (RO).

[0032] S2 is basically the same as Example 1, except that the sunflower pectin powder is replaced by an equal amount of apple pectin powder to obtain apple pectin solution (AP).

[0033] S3 is basically the same as Example 1, except that the whey protein powder is replaced by an equal amount of soy protein powder to obtain a soy protein solution (SF).

[0034] S4. The method is basically the same as Example 1, except that AP and SF are mixed in a mass ratio of 1:1, and then SF-AP and RO are mixed in a mass ratio of 4:1 to obtain a water-soluble rosemary antioxidant.

[0035] Example 5 This embodiment provides a water-soluble rosemary antioxidant, and the specific preparation method is as follows: S1. The method is basically the same as Example 1, except that rapeseed oil is used instead, and the mass ratio of rapeseed oil to rosemary extract is 5:1, so as to obtain a rosemary oil-soluble antioxidant solution (RO).

[0036] S2 is basically the same as Example 1, except that the sunflower pectin powder is replaced by an equal amount of citrus pectin powder to obtain a citrus pectin solution (CP).

[0037] S3, which is basically the same as Example 1, except that the whey protein powder is replaced by an equal amount of pea protein powder to obtain a pea protein solution (PP) S4. The method is basically the same as Example 1, except that CP and PP are mixed in a mass ratio of 2:1, and then PP-CP and RO are mixed in a mass ratio of 4:1 to obtain a water-soluble rosemary antioxidant.

[0038] Comparative Example 1 This comparative example provides a water-soluble rosemary antioxidant, and the specific preparation method is basically the same as that in Example 1, except that: the mass volume concentration of SP in step S2 is 2%; the mass volume concentration of WPI in step S3 is 2%; the mass ratio of WPI-SP to RO in step S4 is 4:1, and the rest remain unchanged.

[0039] Comparative Example 2 This comparative example provides a water-soluble rosemary antioxidant, and the specific preparation method is basically the same as that in Example 1, except that: the mass volume concentration of SP in step S2 is 5%; the mass volume concentration of WPI in step S3 is 5%; the mass ratio of WPI-SP to RO in step S4 is 4:1, and the rest remain unchanged.

[0040] Comparative Example 3 This comparative example provides a water-soluble rosemary antioxidant, and the specific preparation method is basically the same as that of Example 1, except that: in step S4, SP and WPI are mixed in a mass ratio of 1:3, the mass ratio of WPI-SP to RO is 4:1, and the rest remain unchanged.

[0041] Comparative Example 4 This comparative example provides a water-soluble rosemary antioxidant, and the specific preparation method is basically the same as that of Example 1, except that: in step S4, the mass ratio of WPI-SP to RO is 1:2, and the rest remains unchanged.

[0042] Comparative Example 5 The comparative example provides a water-soluble rosemary antioxidant, and the specific preparation method is as follows: add 15 grams of rosemary extract powder to 70 milliliters of Tween 80, stir evenly at 50° C., then add 15 milliliters of propylene glycol, stir evenly, and obtain the water-soluble rosemary antioxidant.

[0043] Comparative Example 6 This comparative example provides a conventional commercially available fat-soluble antioxidant (item number 41.19.25, Kalsec, USA), the main formula of which is as follows: 80-90% rapeseed oil and 10-20% rosemary extract.

[0044] Comparative Example 7 This comparative example provides a conventional commercially available water-soluble antioxidant (item number 41.19.133, Kalsec, USA), the main formula of which is as follows: 45-55% Tween 80, 15-25% diacetyl tartaric acid mono- and diglycerides (DATEM), 10-20% propylene glycol, and 10-20% rosemary extract.

[0045] Furthermore, in order to understand the stability of each antioxidant prepared above, the prepared products were left to stand and stored for a long time to observe whether stratification occurred, and then they were diluted with 20 times water to observe the solubility. The specific results are shown in Table 1.

[0046] Table 1 Stability of the prepared antioxidants

[0047] As can be seen from the table above, the water-soluble antioxidants prepared in Examples 1-5 have uniform appearance, good fluidity, and are easy to use in the production process. In addition, dilution with 20 times water still shows good compatibility, and no stratification occurs. When used, it can be diluted accordingly according to needs, and is flexible to use. After 60 days of storage, the overall solution is also uniform, and no stratification occurs, which can ensure a good shelf life when prepared into a product.

[0048] Although the appearance and long-term storage performance of Comparative Example 1 are acceptable, the stability after dilution with water is poor. Although the solubility in water and storage performance of Comparative Example 2 are good, the stock solution is too viscous and has poor fluidity, which is not conducive to production and use, and the loss is large. Comparative Examples 3 and 4 are not only unstable in long-term storage, but also have poor stability after dilution with water. Although the solubility and storage stability of Comparative Examples 5 and 7 meet the standards, they contain chemical reagents and do not have clean label characteristics; and Comparative Example 6 is a fat-soluble antioxidant. Although the storage stability meets the standards, it has poor solubility in water and does not meet the water solubility requirements.

[0049] Further, in order to understand the stability of each antioxidant prepared above under different pH conditions, samples of Examples 1 and 2 were selected for testing. The specific results are shown in Figure 1 (In Figure A, pH=3, and in Figure B, pH=7).

[0050] Depend on Figure 1 It can be seen that the antioxidant prepared in this application still has good stability under different pH (3-7) conditions, further broadening the use environment scenarios. Overall, as the mass ratio of WPI-SP and RO increases, its particle size tends to decrease, but it does not affect the stability, and no stratification occurs, which can meet the use requirements.

[0051] Furthermore, in order to understand the antioxidant properties of the antioxidants prepared above, the antioxidant effects of fish and pork during low-temperature storage at 4°C were evaluated, and the specific results are shown in Table 2 below.

[0052] Table 2 Antioxidant effects of various antioxidants in fish and pork

[0053] It can be seen from the above table that the water-soluble antioxidants prepared in Examples 1-5 have good antioxidant effects in the storage of fish and pork. When RO accounts for one-half of the weight of the antioxidant, the amount used is only 0.13%, which can delay the lipid oxidation of fish for more than two weeks and the lipid oxidation of pork for more than one week; when RO accounts for one-third of the weight of the antioxidant, the amount used is only 0.2%, which can delay the lipid oxidation of fish for more than two weeks and the lipid oxidation of pork for more than one week; when RO accounts for one-quarter of the weight of the antioxidant, the amount used is only 0.27%, which can delay the lipid oxidation of fish for more than two weeks and the lipid oxidation of pork for more than one week; when RO accounts for one-fifth of the weight of the antioxidant, the amount used is only 0.33%, which can delay the lipid oxidation of fish for more than two weeks and the lipid oxidation of pork for more than one week.

[0054] Compared with the water-soluble antioxidant prepared by conventional chemical reagents (Comparative Example 5) and commercial antioxidants (Comparative Examples 6 and 7), the antioxidant performance is superior; especially in terms of antioxidant properties for fish meat, the antioxidant of the present application can further delay lipid oxidation in fish meat, and the anti-oxidation effect is twice that of Comparative Examples 5-7.

[0055] The specific raw materials not described in the present invention are all existing materials and can be directly purchased from the market.

[0056] The above are only preferred embodiments of the present invention and are not intended to limit the protection scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A water-soluble rosemary antioxidant, characterized in that The antioxidant is prepared by mixing rosemary extract, edible oil, protein aqueous solution and polysaccharide aqueous solution; The mass volume concentration of the protein aqueous solution and the polysaccharide aqueous solution are both 3% to 4%, and the mass ratio of the protein aqueous solution to the polysaccharide aqueous solution is 1: (1 to 3); The ratio of the total mass of rosemary extract and edible oil to the total mass of protein aqueous solution and polysaccharide aqueous solution is 1: (1-4).

2. The antioxidant according to claim 1, characterized in that The mass ratio of the rosemary extract to the edible oil is 1:(3-5).

3. The antioxidant according to claim 1, characterized in that The protein in the protein aqueous solution includes whey protein, soy protein, pea protein and myofibrillar protein.

4. The antioxidant according to claim 1, characterized in that The polysaccharides in the polysaccharide aqueous solution include beet pectin, apple pectin, citrus pectin and sunflower pectin.

5. The antioxidant according to claim 1, characterized in that The edible oil includes rapeseed oil, sunflower oil and soybean oil.

6. A method for preparing the antioxidant according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1. Preheating edible oil, adding rosemary extract, stirring, and filtering to obtain a rosemary oil-soluble antioxidant solution; S2. Preheat water, add polysaccharide powder, stir to dissolve, and stand at 4°C overnight until fully hydrated to obtain a polysaccharide aqueous solution; S3, preheat water, add protein powder, stir to dissolve, and let stand at 4°C overnight until completely hydrated to obtain a protein aqueous solution; S4. Stir and mix the polysaccharide aqueous solution and the protein aqueous solution, let stand at 4° C. overnight until they are completely hydrated, then add the rosemary oil-soluble antioxidant solution, and stir at high speed to obtain a water-soluble rosemary antioxidant.

7. The preparation method according to claim 6, characterized in that: In step S1, the edible oil preheating temperature is 40-45° C., and the stirring conditions are: rotation speed 800-1000 rpm, and time 20-30 min.

8. The preparation method according to claim 6, characterized in that: In step S2, the water preheating temperature is 75-85° C., and the stirring conditions are: rotation speed 1000-1500 rpm, and time 20-30 min.

9. The preparation method according to claim 6, characterized in that: In step S3, the water preheating temperature is 40-45° C., the stirring and mixing conditions are: a rotation speed of 800-1000 rpm, and a time of 25-35 min. The high-speed stirring conditions are: a rotation speed of 15000-17000 rpm, and a time of 2-4 min.

10. Use of the water-soluble rosemary antioxidant according to any one of claims 1 to 5 in food preservation.

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