阅读说明：本技术 一种油溶性万寿菊黄酮制剂及其制备方法和应用 (Oil-soluble marigold flavone preparation and preparation method and application thereof ) 是由 高伟 焦丽娟 徐建中 任婷婷 吴迪 于 2020-06-02 设计创作，主要内容包括：本发明涉及了一种油溶性抗氧化制剂,该油溶性抗氧化制剂包含：万寿菊黄酮,油溶性乳化剂,水溶性乳化剂。所述万寿菊黄酮提取自万寿菊,所述油溶性制剂可以完全溶解于油脂,代替EQ(乙氧基喹啉)使用,抗氧化能力强于EQ。(The invention relates to an oil-soluble antioxidant preparation, which comprises: marigold flavone, oil-soluble emulsifier and water-soluble emulsifier. The marigold flavone is extracted from marigold, the oil-soluble preparation can be completely dissolved in oil, and can replace EQ (ethoxyquinoline), and the antioxidant capacity is stronger than that of EQ.)

1. An oil-soluble antioxidant preparation characterized by:

comprises 1-30% of marigold flavone, 20-50% of oil-soluble emulsifier and 30-50% of water-soluble emulsifier.

2. The oil-soluble antioxidant preparation according to claim 1, characterized in that: comprises 1-20% of marigold flavone, 25-50% of oil-soluble emulsifier and 35-50% of water-soluble emulsifier.

3. The oil-soluble antioxidant preparation according to claim 1 or 2, wherein the marigold flavone is derived from marigold, wherein the content of quercetagetin is not less than 50%.

4. The oil-soluble antioxidant preparation as claimed in any one of claims 1 to 3, wherein the oil-soluble emulsifier is selected from any one or more of mono-and diglycerol fatty acid ester emulsifiers (HLB. ltoreq.6) and polyglyceryl fatty acid ester emulsifiers (HLB. ltoreq.6).

5. The oil-soluble antioxidant preparation according to claim 4, wherein the mono-diglycerol fatty acid ester emulsifier is preferably caprylic capric acid glyceride or glyceryl monooleate, and the polyglycerin fatty acid ester emulsifier is preferably polyglycerin ricinol ester.

6. The oil-soluble antioxidant preparation according to any one of claims 1 to 5, wherein the water-soluble emulsifier is one or more selected from the group consisting of mono-and diglycerol fatty acid ester emulsifiers (HLB. gtoreq.12), propylene glycol, glycerin, sorbitol, polyethylene glycol, and polyglycerin fatty acid ester emulsifiers (HLB. gtoreq.12), and preferably one or two selected from the group consisting of propylene glycol and polyethylene glycol.

7. The oil-soluble antioxidant preparation according to any one of claims 1 to 6, characterized in that it has a remarkable antioxidant property, with a small equivalent effective concentration, which is stronger than that of ethoxyquinoline.

8. The method for preparing an oil-soluble antioxidant preparation as set forth in any one of claims 1 to 7, characterized by comprising the steps of: mixing marigold flavone with water soluble emulsifier and oil soluble emulsifier, shearing, emulsifying, and homogenizing under high pressure.

9. The method according to claim 8, wherein the water-soluble emulsifier is added before the oil-soluble emulsifier, and the oil-soluble emulsifier emulsifies marigold flavone into a water-in-oil formulation after the water-soluble emulsifier melts it.

10. Use of an oil-soluble antioxidant preparation as claimed in any one of claims 1 to 9 in a fat-containing product.

Technical Field

The invention belongs to the technical field of natural product preparations, and particularly relates to an oil-soluble marigold flavone natural antioxidant.

Background

The main raw material components in the feed are all susceptible to external influence to generate oxidation reaction to cause deterioration, so that the feed needs to be added with an antioxidant to prevent or delay oxidation. Ethoxyquin, EQ for short, was the most commonly used antioxidant additive in feed, and is generally sprayed on the surface of feed by spraying, which can effectively prevent rancidity of oil and fat and oxidation of protein in feed, and can prevent deterioration of vitamins. However, due to the physiological toxicity, the ethoxyquin is easy to accumulate in animal bodies and easily cause damage to human bodies through food chain layer accumulation, so that the ethoxyquin is prohibited from being applied to feeds in many countries. In the face of the prohibition of the use of ethoxyquinoline, a new antioxidant with excellent effect and safe use needs to be searched for as a substitute.

The marigold flavone is an extracted product of natural sources, contains various flavone components, and the quercetin marigold is the main component of the marigold, has the highest content, has various effects of oxidation resistance, cancer resistance, inflammation resistance, bacteria resistance, virus resistance and the like as a polyhydroxy flavonoid compound, and has remarkable oxidation resistance activity. As an antioxidant component from natural sources, marigold flavone has excellent effect, safe use and high development potential, but quercetin marigold is insoluble in water and oil, has low bioavailability and obviously limits the application of the quercetin in the fields of food and feed. Changing the solubility and expanding the application range are problems to be solved urgently.

At present, oil-soluble marigold flavone preparations are not reported in public, and oil-soluble preparations of other natural antioxidants mainly comprise:

CN201510394484 discloses a preparation method of fat-soluble tea polyphenol, which uses ethyl acetate and adopts microwave radiation-enzyme coupling catalysis technology to prepare the fat-soluble tea polyphenol, relates to chemical reaction and has certain safety problem.

CN201010601480 discloses a method for synthesizing and purifying fat-soluble rosmarinic acid ester, which comprises the steps of performing esterification reaction on rosmarinic acid and higher monohydric alcohol, wherein a solvent is 1, 4-dioxane, a catalyst is p-toluenesulfonic acid, a molecular sieve is used as a water absorbent, and the reaction time is 30-40 hours; after the reaction is finished, the fat-soluble rosmarinic acid ester product with the purity of more than 95 percent is prepared by purification. The process also involves chemical reactions, with certain safety concerns.

Disclosure of Invention

The invention provides a natural antioxidant preparation prepared by taking marigold flavone as a raw material, which has the characteristics of good oil solubility, remarkable antioxidant capacity, wide application range and the like.

The technical scheme of the oil-soluble antioxidant preparation is as follows:

the raw materials of the oil-soluble antioxidant preparation comprise marigold flavone, an oil-soluble emulsifier and a water-soluble emulsifier.

The marigold flavone is extracted from marigold flowers, and the main component of the marigold flavone is an extract of a flavonoid component.

The flavonoid component extracted from the flower meal after the lutein is extracted from the marigold is used, the raw material is economical, natural and environment-friendly, the obtained flavonoid component has strong antioxidant activity, and the content of quercetagetin is more than or equal to 50%.

The content of the quercetagetin in the oil-soluble antioxidant preparation is 1-30%.

The raw materials of the oil-soluble antioxidant preparation comprise 1-30% of marigold flavone, 20-50% of oil-soluble emulsifier and 30-50% of water-soluble emulsifier; preferably 1% -20% of marigold flavone, 25% -50% of oil-soluble emulsifier and 35% -50% of water-soluble emulsifier; more preferably 5% -15% of marigold flavone, 30% -50% of oil-soluble emulsifier and 40% -50% of water-soluble emulsifier; further preferably 5% -10% of marigold flavone, 40% -50% of oil-soluble emulsifier and 40% -45% of water-soluble emulsifier. The above percentages are mass percentages.

The oil-soluble emulsifier is selected from one or more of a mono-diglycerol fatty acid ester emulsifier (HLB is less than or equal to 6) and a polyglycerol fatty acid ester emulsifier (HLB is less than or equal to 6); the mono-diglycerol fatty acid ester emulsifier is preferably caprylic capric glyceride and monooleyl glyceride, and the polyglycerol fatty acid ester emulsifier is preferably polyglycerol ricinol ester. When two or more kinds of oil-soluble emulsifiers are selected for mixing, the mixing ratio thereof may be arbitrary, and it is preferable that the maximum amount of the components is not more than three times the minimum amount of the components; it is further preferred that the maximum amount of the ingredient is not more than twice the minimum amount of the ingredient.

The water-soluble emulsifier is one or more selected from mono-diglycerol fatty acid ester emulsifier (HLB is more than or equal to 12), propylene glycol, glycerol, sorbitol, polyethylene glycol and polyglycerol laurate emulsifier (HLB is more than or equal to 12), and preferably one or two selected from propylene glycol and polyethylene glycol. When two or more water-soluble emulsifiers are selected for mixing, the mixing ratio thereof may be arbitrary, and it is preferable that the maximum amount of the components is not more than three times the minimum amount of the components; it is further preferred that the maximum amount of the ingredient is not more than twice the minimum amount of the ingredient.

The oil-soluble emulsifier and the water-soluble emulsifier are both emulsifiers allowed to be used in feed additives or feed raw material catalogues.

The preparation method of the oil-soluble antioxidant preparation comprises the following steps: mixing marigold flavone with water soluble emulsifier and oil soluble emulsifier, shearing, emulsifying, and homogenizing under high pressure.

Furthermore, in the preparation method, the water-soluble emulsifier is added before the oil-soluble emulsifier, and the marigold flavone is melted by using the water-soluble emulsifier and then emulsified into a water-in-oil preparation by using the oil-soluble emulsifier.

The application also relates to the application of the oil-soluble antioxidant preparation in products containing fat. The product containing fat is preferably oil and feed. The oil is vegetable oil, animal oil, modified edible vegetable oil, modified edible animal oil or synthetic edible oil.

The invention has the beneficial effects that:

has remarkable oxidation resistance, can be completely dissolved in oil, and can replace ethoxyquinoline.

The product is an oil solution preparation, can be directly mixed with feed and the like, can also be sprayed on the surface of the feed by a spraying method, and is convenient to use.

The invention does not relate to chemical reaction and is more healthy and environment-friendly.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

Example 1

Mixing marigold flavone (containing 79.75% of quercetagetin) and propylene glycol in proportion, melting in 70 deg.C water bath, adding caprylic/capric glyceride (one of monoglyceride/diglyceride fatty acid esters, HLB being 4), shearing, emulsifying to obtain black uniform liquid, and detecting that the content of quercetagetin is 10.03%.

Tagetes flavone	Propylene glycol	Caprylic capric acid glyceride
			13g	54g	35g

Example 2

Mixing marigold flavone (containing 79.75% of quercetagetin) and polyethylene glycol in proportion, melting in 70 deg.C water bath, adding glycerol monooleate (one of monoglyceride and diglyceride fatty acid esters, HLB being 3.8), shearing, emulsifying to obtain black uniform liquid, and detecting that the content of marigold is 10.21%.

Tagetes flavone	Polyethylene glycol	Glyceryl monooleate
			13g	43.5g	43.5g

Example 3

Mixing marigold flavone (containing 79.75% of quercetagetin) and polyethylene glycol in proportion, melting in 70 deg.C water bath, adding polyglycerol polyricinoleate (one of polyglycerol fatty acid esters, HLB is 2), shearing, and emulsifying to obtain black uniform liquid, wherein the content of queretagetin in the oil soluble preparation is 13.61%.

Tagetes flavone	Polyethylene glycol	Polyglycerol polyricinoleate
			13g	26g	36g

Example 4

Mixing flos Tagetis Erectae flavone (containing quercetagetin 79.75%) with polyethylene glycol at a certain proportion, melting in 70 deg.C water bath, adding triglycerol monooleate (one of polyglyceryl fatty acid esters, HLB is 3), shearing and emulsifying caprylic/capric glyceride to obtain uniform liquid, and making into preparation with quercetagetis Elaeagnus content of 13.21%.

Tagetes flavone	Polyethylene glycol	Tripolyglycerol monooleate	Caprylic capric acid glyceride
				13g	26g	26g	13g

Example 5

Mixing marigold flavone (containing 79.75% of quercetagetin) and water-soluble monoglyceride (one of mono-diglycerol fatty acid esters, HLB is 16) in proportion, melting in 70 deg.C water bath, adding polyglycerol polyricinoleate (HLB is 2), shearing, and emulsifying to obtain uniform liquid, which can be used as the preparation with quercetagetin content of 11.36%.

Tagetes flavone	Water-soluble monoglyceride	Polyglycerol polyricinoleate
			13g	52g	26g

Example 6

Marigold flavone (quercetin marigold content 79.75%), polyglycerol-10 laurate (one of polyglycerol fatty acid esters, HLB being 16) were mixed in proportion, melted in a 70 ℃ water bath, and then added with glycerol monooleate (one of mono-diglycerol fatty acid esters, HLB being 3.8) and sheared and emulsified to obtain a homogeneous liquid (viscous compared with other examples), and the prepared preparation had a quercetin content of 11.31%.

Tagetes flavone	Polyglycerol-10 laurate	Glyceryl monooleate
			13g	52g	26g

Comparative example 1:

mixing marigold flavone (the content of quercetagetin is 79.75%) and propylene glycol according to a certain proportion, mixing and melting at 70 deg.C water bath, adding span 80(HLB is 4.3), shearing and emulsifying to obtain green dispersion liquid, standing to obtain separated marigold flavone, and detecting that the content of quercetagetin is 9.67%.

Tagetes flavone	Propylene glycol	Span 80
			13g	54g	35g

Comparative example 2:

mixing marigold flavone (containing 79.75% of quercetagetin) and tween 80(HLB is 15) at a certain proportion, melting in 70 deg.C water bath, adding glycerol monooleate (one of monoglyceride and diglyceride, HLB is 3.8), shearing, emulsifying to obtain oily liquid with precipitate, and detecting marigold content to be 8.76%.

Tagetes flavone	Tween 80	Glyceryl monooleate
			13g	43.5g	43.5g

Comparative example 3

Mixing flos Tagetis Erectae flavone (content of quercetagetin 79.75%) and polyethylene glycol at a certain proportion, melting in 70 deg.C water bath, adding span 60(HLB is 4.7), shearing, emulsifying to obtain oily liquid, but precipitating, and detecting content of quercetagetin at 9.16% in the prepared oil soluble preparation.

Tagetes flavone	Polyethylene glycol	Span 60
			13g	26g	36g

Comparative example 4

Mixing marigold flavone (containing 79.75% of quercetagetin) and sucrose ester (HLB ═ 16) at a certain proportion, melting in 70 deg.C water bath, adding triglycerol monooleate (one of polyglyceryl fatty acid esters, HLB ═ 3) and caprylic/capric glyceride, shearing and emulsifying to obtain viscous liquid, precipitating, and detecting the content of quercetagetin at 7.13%.

Tagetes flavone	Sucrose esters	Tripolyglycerol monooleate	Caprylic capric acid glyceride
				13g	26g	26g	13g

Comparative example 5

Mixing marigold flavone (content of quercetagetin 79.75%) and sucrose ester (HLB ═ 16) at a certain proportion, melting in 70 deg.C water bath, adding polyglycerol polyricinoleate (HLB ═ 2), shearing, emulsifying to obtain viscous paste, and precipitating, wherein the content of quercetagetin detected by the prepared preparation is 6.79%.

Tagetes flavone	Sucrose esters	Polyglycerol polyricinoleate
			13g	52g	26g

Comparative example 6

Mixing marigold flavone (containing 79.75% of quercetagetin), polyglycerol-10 laurate (one of polyglycerol fatty acid esters, HLB is 16) according to a certain proportion, melting in water bath at 70 deg.C, adding span 60(HLB is 4.7), shearing, emulsifying to obtain viscous paste, and separating out precipitate, wherein the content of quercetagetin in the prepared preparation is 7.47%.

Tagetes flavone	Polyglycerol-10 laurate	Span 60
			13g	52g	26g

The oxidation resistance and stability of different samples were compared:

(1) evaluation of antioxidant ability

500g of safflower seed oil is respectively taken and put into a 100mL beaker by adopting a Schaal oven enhanced storage method. Adding a certain amount of sample into oil, mixing well, placing in an oven with an open mouth at 60 + -0.5 deg.C for strengthening storage, stirring once every 24h, changing the position of the beaker, and measuring its peroxide value (POV). Each group was replicated 2 times and the results averaged.

The samples were the products described in the examples, and the EQ and marigold flavone materials used as controls, and the amount of the samples added to the oil was such that the active ingredient content was consistent.

The antioxidant effect of the different samples in safflower seed oil is shown in table 1 below:

TABLE 1 peroxide number measurement results

As can be seen from the data in Table 1, the peroxide values of the samples of the raw material group, the example group and the comparative example group, to which marigold flavone was added, increased slowly compared to EQ, and the antioxidant ability was stronger than EQ. Compared with marigold flavone raw material group and comparative example group, the peroxide value of the sample of the example group is increased slowly, and the oxidation resistance of the grease is stronger than that of the raw material and the comparative example.

(2) Evaluation of oil-soluble Effect

Evaluating the dissolving effect of oil-soluble marigold flavone in oil by adopting a turbidity method and an observation method, respectively taking 100g of safflower seed oil, taking a certain amount of sample to add into the safflower seed oil, uniformly mixing, standing at room temperature to observe the stability of the safflower seed oil, and regularly monitoring the turbidity value and the stability condition of the safflower seed oil. Each group was replicated 2 times and the results averaged.

The samples are the products of examples and comparative examples, and the EQ and white marigold flavone raw materials of a control group, and the addition amount of the samples in the oil is required to ensure the consistent content of the active ingredients.

The dissolution effect of the different samples in safflower seed oil is shown in the following tables 2 and 3:

TABLE 2 haze value measurement results

Table 3 stability observations

Sample (I)	Dissolution behavior
		Raw material group	Can not be dissolved
Adding EQ group	Can be uniformly dispersed in safflower seed oil, and can be left for 7 days without layering and precipitation
		EXAMPLE 1 group	Uniformly dispersing in safflower seed oil, standing for 7 days without demixing and precipitation
EXAMPLE 2 group	Uniformly dispersing in safflower seed oil, standing for 7 days without demixing and precipitation
		EXAMPLE 3 group	Uniformly dispersing in safflower seed oil, standing for 7 days without demixing and precipitation
EXAMPLE 4 group	Uniformly dispersing in safflower seed oil, standing for 7 days without demixing and precipitation
		EXAMPLE 5 group	Uniformly dispersing in safflower seed oil, standing for 7 days without demixing and precipitation
EXAMPLE 6 group	Uniformly dispersing in safflower seed oil, standing for 7 days without demixing and precipitation
		Comparative example 1	A small part is dissolved, and a green substance is separated out.
Comparative example 2	A small part is dissolved, and a green substance is separated out.
		Comparative example 3	A small part is dissolved, and a green substance is separated out.
Comparative example 4	Very little part is dissolved and green substances are separated out.
		Comparative example 5	Very little part is dissolved and green substances are separated out.
Comparative example 6	Very little part is dissolved and green substances are separated out.

As can be seen from the data in tables 2 and 3, the results of comparing the turbidity and dissolution effect of each sample in oil show that: the samples of the example group have better dissolution effect in safflower seed oil, the turbidity value is slowly increased, no obvious layering and precipitation exist, and the effect is shown in the comparative example group, so that the oil-soluble marigold flavone preparation has better stability in oil, and can be applied to oil products.

The two groups of experimental results show that the oil-soluble marigold flavone can be well dissolved in oil products, keeps good stability and oxidation resistance, and is an antioxidant with excellent effect.