CN106589402B - Natural products anthocyanin is improved in the method for acid heat condition stability inferior, its product and application - Google Patents

Natural products anthocyanin is improved in the method for acid heat condition stability inferior, its product and application Download PDF

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CN106589402B
CN106589402B CN201611064133.0A CN201611064133A CN106589402B CN 106589402 B CN106589402 B CN 106589402B CN 201611064133 A CN201611064133 A CN 201611064133A CN 106589402 B CN106589402 B CN 106589402B
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anthocyanin
protein isolate
solution
whey protein
natural products
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CN106589402A (en
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刘刚
胡中泽
秦新光
袁旦
梁征
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Wuhan Polytechnic University
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Wuhan Polytechnic University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00Macromolecular products derived from proteins

Abstract

The invention belongs to Food Science and Engineering technical fields, and in particular to a kind of raising natural products anthocyanin is in the method for acid heat condition stability inferior, its product and application.This method comprises: modified, combination and heat treatment and etc..It is provided by the present invention to improve natural products anthocyanin in the method for acid heat condition stability inferior, its acid heat stability is improved by carrying out glycosylation modification to whey protein isolate.On the one hand, whey protein isolate acid, thermal stability can be improved in glycosylation modification.On the other hand, anthocyanin is combined by glycated milk clear protein isolate, increases acid, the thermal stability of anthocyanin.This method compared with auxiliary toner and microencapsulation, that is, protects the bioactivity of small molecule in conjunction with this small-molecule active substance of anthocyanin using this natural wall material of whey protein isolate, and introduces this nutritional ingredient of whey protein isolate.

Description

Improve natural products anthocyanin the method for acid heat condition stability inferior, its product and Using
Technical field
The invention belongs to Food Science and Engineering technical fields, and in particular to a kind of raising natural products anthocyanin is in acid heat The method of condition stability inferior, its product and application.
Background technique
Anthocyanin is a kind of biologically active flavonoid substance, is largely present in water-soluble in water fruits and vegetables and flowers Property pigment.Its as water-soluble plant natural pigment, with high security, it is without side-effects the advantages that;Have simultaneously anti-oxidant, anti- A variety of physiological hygiene functions such as inflammatory reaction, anti-aging;Therefore, it can be widely applied in food, drug and cosmetics.
But the physical and chemical factors such as processing and the pH in storage, temperature, illumination, enzyme, metal ion can all lead to its generation Degradation, largely limits its extensive use in the fields such as agricultural product and food processing.Its stability is improved at present Method mainly include by auxiliary color effect and microencapsulation physical method, chemical modification and applied bioengineering technology come Improve its stability.However the effect of auxiliary color is more demanding to the condition of processed and applied process, limits its reality to a certain extent Using.Although microencapsulation can improve the stability and dispersibility of anthocyanin to a certain extent, its colouring effect will affect. Its molecular structure can be changed by the methods of chemical modification, and organic reagent can be introduced and lead to the generation of by-product, influenced Application of the anthocyanin as natural pigment.Biotechnology correlative study report is few, and from application, this technology realizes high stable Property anthocyanin there are also very long distance.
Documents and materials are shown in protein and sugar occurs in Maillard reaction, due to introducing polyhydroxy in protein groups Sugar chain, thermal stability of the entire product under weak electrostatic interaction can be improved in the steric effect of glycan molecule.And anthocyanin can be with It can be interacted by active force with whey protein isolate maillard reaction product, active force includes Van der Waals force, electrostatic Power, hydrogen bond and hydrophobicity etc., so as to reach thermal stability and colour stable of the stable anthocyanin molecule in acidic pH environment The effect of property.
Chinese patent application 201610267232.2 provides a kind of stable high anthocyanin blueberry buccal tablets and its preparation side Method, but the purpose is to provide a kind of lozenge pure natural, without side-effects.
Summary of the invention
To solve the deficiencies in the prior art, it is steady under the conditions of acid heat that the present invention provides a kind of raising natural products anthocyanin Qualitative method, that is, protect the bioactivity of this small molecule of anthocyanin, but introduce this nutrition of whey protein isolate at Divide this, provides a kind of new thinking to improve anthocyanin stability.
Technical solution provided by the invention is as follows:
A method of natural products anthocyanin is improved in acid heat condition stability inferior, comprising the following steps:
1) modified: whey protein isolate and small molecular sugar being modified by Maillard reaction, obtain glycosylation whey Protein isolate.
Specifically, the method for modifying in step 1) are as follows: by whey protein isolate solid powder and small molecular sugar solid powder Mixing, is dissolved in distilled water, and agitating solution is uniformly mixed, and adjusts pH value of solution to neutrality, freeze-drying obtain whey protein isolate with The uniform mixed-powder of small molecular sugar, then reacted under conditions of constant temperature and humidity, obtain the clear protein isolate of glycated milk.
Preferably, in step 1), the mass ratio of whey protein isolate solid powder and small molecular sugar solid powder be 1:1~ 2, it is 5~10wt% that whey protein isolate, which is dissolved in solid content in the solution that water is configured to small molecular sugar,.
Preferably, in step 1), mixing time be 12~for 24 hours, adjust the pH to 7.0 of solution.
Preferably, in step 1), the condition of constant temperature and humidity are as follows: 60~70 DEG C of temperature, relative humidity is 78~80%, reaction Time be 12~for 24 hours.
2) it combines: the clear protein isolate of glycated milk that step 1) obtains being configured to solution, then is mixed with anthocyanin solution.
Specifically, it is 1~5mg/mL that the clear protein isolate of glycated milk that step 1) obtains, which is configured to concentration, in step 2) Solution, then mixed with anthocyanin solution, make ultimate density 0.05~0.1wt% of the anthocyanin in system.With anthocyanin When solution mixes the clear protein isolate of glycated milk that is added with mix after system total weight weight percent for 0.1%~ 0.5%.
3) it is heat-treated: the mixed solution in step 2) being heated into certain time, combines the two sufficiently.
In step 3), heat treatment temperature is 80~100 DEG C, and heat treatment time is 5~10min.
Specifically, the small molecular sugar is reductive monosaccharide or reducing disaccharides.
Preferably, the small molecule is glucose, fructose or lactose.
Specifically, the anthocyanin is the anthocyanin that extract by solvents obtains.
Raising natural products anthocyanin provided by the present invention can be applicable in various in the method for acid heat condition stability inferior Reductive monosaccharide or disaccharides.And it is possible to be applicable in the anthocyanin extracted with various solvent extraction methodes.
The present invention also provides the methods according to above-mentioned raising natural products anthocyanin in acid heat condition stability inferior to prepare Obtained stabilization anthocyanin copolymer.
The present invention also provides the applications of stable anthocyanin copolymer provided by the present invention, as natural pigment additive Or nutritional additive.
Specifically, being used as natural pigment additive or nutrition in the system that temperature is 20~90 DEG C and/or pH is 2~6 Additive.
Beneficial effect
Based on technical solution provided by the present invention, on the one hand, whey protein isolate acid, heat can be improved in glycosylation modification Stability can be used as a kind of stabilizer, can also be used as a kind of nutritional additive.On the other hand, by utilizing glycosylation Whey protein isolate is combined anthocyanin, increases the stability of anthocyanin.This method using whey protein isolate this Natural wall material protects the bioactivity of small molecule in conjunction with this small-molecule active substance of anthocyanin, and introduce cream This nutritional ingredient of clear protein isolate.And stable anthocyanin copolymer provided by the present invention may act as multiple functions addition Agent carry out using, and the big process conditions of variation degree can be resistant to, can be wide to be applied to various relevant techniques raw In production.
Specific embodiment
The principles and features of the present invention are described below, and illustrated embodiment is served only for explaining the present invention, is not intended to It limits the scope of the invention.
Embodiment main material and instrument
Whey protein isolate, glucose, lactose (analysis is pure) purchase are in Shanghai Aladdin biochemical technology limited liability company; Cyanidin -3-O- glucoside (Cyanidin-3-O-Glucoside, C3G);Electronics pH meter, constant temperature and humidity incubator etc..
Embodiment 1
Whey protein isolate and glucose 1:1 in mass ratio are dissolved in deionized water, the solid content of its solution is contained Amount is 5%.It adjusts solution ph and to 7.0 and continuously stirs 12h, be then freeze-dried.Powder after freeze-drying is placed in phase To humidity 79%, temperature is to cultivate for 24 hours in 70 DEG C of constant temperature and humidity incubators.Obtained maillard reaction product is placed in -20 DEG C It is frozen in environment.
The maillard reaction product of whey protein isolate and glucose is total to Cyanidin -3-O- glucoside (C3G's) Polymers: the maillard reaction product 500mg of whey protein isolate and glucose is taken, 100mL is settled to.It is configured to 0.5wt%'s Solution.Then the pH of solution is adjusted to 5.8, after C3G solution slowly is added dropwise into solution, keeps C3G final dense in system Degree is 0.1%.Mixture is protected from light to heating 5min in 90 DEG C of water-baths, makes the Maillard reaction of whey protein isolate and glucose Product occurs thermal denaturation and sufficiently reacts with C3G.After the water bath is over, regulation system pH to 3.0 and room temperature are protected from light stirring 12h.It will Obtained copolymer is placed in stored refrigerated in refrigerator.
Embodiment 2
Whey protein isolate and lactose 1:1 in mass ratio are dissolved in deionized water, the solid content of its solution is made 10%.It adjusts solution ph to 7.0 and to continuously stir for 24 hours, be then freeze-dried.Powder after freeze-drying is placed in relatively Humidity 79%, temperature are to cultivate for 24 hours in 70 DEG C of constant temperature and humidity incubators.Obtained maillard reaction product is placed in -20 DEG C of rings It is frozen in border.
The copolymerization of the maillard reaction product of whey protein isolate and lactose and Cyanidin -3-O- glucoside (C3G) Object: the maillard reaction product 100mg of whey protein isolate and glucose is taken, 100mL is settled to.It is configured to the molten of 0.1wt% Liquid.Then the pH of solution is adjusted to 5.8, after C3G solution slowly is added dropwise into solution, makes ultimate density of the C3G in system It is 0.1%.Mixture is protected from light to heating 6min in 90 DEG C of water-baths, makes the maillard reaction product of whey protein isolate and lactose Thermal denaturation occurs and is sufficiently reacted with C3G.After the water bath is over, regulation system pH to 3.0 and room temperature are protected from light stirring 6h.By what is obtained Copolymer is placed in stored refrigerated in refrigerator.
Embodiment 3
Whey protein isolate and glucose 1:2 in mass ratio are dissolved in deionized water, the solid content of its solution is contained Amount is 5%.It adjusts solution ph and to 7.0 and continuously stirs 12h, be then freeze-dried.Powder after freeze-drying is placed in phase To humidity 80%, temperature is to cultivate for 24 hours in 60 DEG C of constant temperature and humidity incubators.Obtained maillard reaction product is placed in -20 DEG C It is frozen in environment.
The maillard reaction product of whey protein isolate and glucose is total to Cyanidin -3-O- glucoside (C3G's) Polymers: the maillard reaction product 500mg of whey protein isolate and glucose is taken, 100mL is settled to.It is configured to 0.2wt%'s Solution.Then the pH of solution is adjusted to 5.8, after C3G solution slowly is added dropwise into solution, keeps C3G final dense in system Degree is 0.05%.Mixture is protected from light to heating 5min in 95 DEG C of water-baths, keeps the Mei Lade of whey protein isolate and glucose anti- It answers product that thermal denaturation occurs and is sufficiently reacted with C3G.After the water bath is over, regulation system pH to 5.0 and room temperature are protected from light stirring 12h. Obtained copolymer is placed in stored refrigerated in refrigerator.
Embodiment 4
Whey protein isolate and glucose 1:1.5 in mass ratio are dissolved in deionized water, the solid content of its solution is made Content is 8%.It adjusts solution ph and to 7.0 and continuously stirs 18h, be then freeze-dried.Powder after freeze-drying is placed in Relative humidity 78%, temperature are to cultivate 18h in 65 DEG C of constant temperature and humidity incubators.Obtained maillard reaction product is placed in -20 It is frozen in DEG C environment.
The maillard reaction product of whey protein isolate and glucose is total to Cyanidin -3-O- glucoside (C3G's) Polymers: the maillard reaction product 500mg of whey protein isolate and glucose is taken, 100mL is settled to.It is configured to 0.4wt%'s Solution.Then the pH of solution is adjusted to 5.8, after C3G solution slowly is added dropwise into solution, keeps C3G final dense in system Degree is 0.08%.Mixture is protected from light to heating 5min in 85 DEG C of water-baths, keeps the Mei Lade of whey protein isolate and glucose anti- It answers product that thermal denaturation occurs and is sufficiently reacted with C3G.After the water bath is over, regulation system pH to 4.0 and room temperature are protected from light stirring 12h. Obtained copolymer is placed in stored refrigerated in refrigerator.
Effect example
As shown in Figure 1, being the THERMAL STABILITY of different compositional systems at various ph values, specific difference compositional system exists The data comparative diagram of Thermal Degradation Experiments under different pH value.In figure: C3G is anthocyanin;WPI-Lac is whey protein isolate and cream The maillard reaction product of sugar;WPI-Glu is the maillard reaction product of whey protein isolate and glucose;Sample bath temperature It is 80 DEG C.
The thermal degradation fit curve equations of different compositional systems, related coefficient and thermal degradation half-life period are as shown in table 1.Table 1, Thermal degradation fit curve equation, related coefficient and the thermal degradation half-life period of C3G at different conditions
Fig. 1 and table 1 reflect the thermal degradation situation of C3G at different conditions.In pH=6.0, since C3G is in partial neutral Environment in structure it is extremely unstable, cause thermal stability poor, thermal degradation half-life period be 109.2min;Egg is separated with whey The C3G thermal degradation half-life period that white-grape sugar copolymer mixes is 731.6min and whey protein isolate-lactose copolymerization The C3G thermal degradation half-life period that object mixes is 1010.8min, illustrates whey protein isolate-glucose/lactose copolymer With protecting ability of the C3G not by heat damage in environment.Likewise, C3G is shown in slant acidity environment in pH=3.0 Stable anthocyanin structure, thermal degradation half-life period are 386.3min;One is blended in whey protein isolate-grape sugar copolymer The C3G thermal degradation half-life period risen is the C3G thermal degradation that 1446.6min and whey protein isolate-lactose copolymer mix Half-life period is 1916.7min.From the above, it can be seen that under the conditions of acidity to slant acidity, anthocyanin and whey protein isolate-sugar The thermal stability of the mixed system of copolymer is obviously improved compared with the thermal stability of the unitary system of anthocyanin.Pass through difference THERMAL STABILITY discovery under the different pH value of sample temperature, whey protein isolate-sugar copolymer can significantly improve C3G and exist Thermal stability under 20~90 DEG C of acidity and neutral environment.Especially in 70~90 DEG C of system, it is the most prominent to promote effect.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of improve natural products anthocyanin in the method for acid heat condition stability inferior, which comprises the following steps:
1) modified: whey protein isolate and small molecular sugar are modified by Maillard reaction, obtain glycated milk sorting from Albumen, the small molecular sugar are reductive monosaccharide or reducing disaccharides;
2) it combines: the clear protein isolate of glycated milk that step 1) obtains being configured to solution, then is mixed with anthocyanin solution;
3) it is heat-treated: the mixed solution in step 2) being heated, obtains stablizing anthocyanin copolymer.
2. according to claim 1 improve natural products anthocyanin in the method for acid heat condition stability inferior, feature exists In: the anthocyanin is the anthocyanin that extract by solvents obtains.
3. the method according to claim 1 or 2 for improving natural products anthocyanin in acid heat condition stability inferior, feature It is, the method for modifying in step 1) are as follows: whey protein isolate solid powder is mixed with small molecular sugar solid powder, is dissolved in In distilled water, agitating solution is uniformly mixed, and adjusts pH value of solution to neutrality, and freeze-drying obtains the equal of whey protein isolate and small molecular sugar Even mixed-powder, then reacted under conditions of constant temperature and humidity, obtain the clear protein isolate of glycated milk.
4. according to claim 3 improve natural products anthocyanin in the method for acid heat condition stability inferior, feature exists In:
In step 1), the mass ratio of whey protein isolate solid powder and small molecular sugar solid powder is 1:1~2, whey separation It is 5~10wt% that albumen and small molecular sugar, which are dissolved in solid content in the solution that water is configured to,;
In step 1), mixing time be 12~for 24 hours, adjust the pH to 7.0 of solution;
In step 1), the condition of constant temperature and humidity are as follows: 60~70 DEG C of temperature, relative humidity be 78~80%, the reaction time be 12~ 24h。
5. the method according to claim 1 or 2 for improving natural products anthocyanin in acid heat condition stability inferior, feature It is: in step 2), the clear protein isolate of glycated milk that step 1) obtains is configured to the solution that concentration is 1~5mg/mL, then It is mixed with anthocyanin solution, makes ultimate density 0.05~0.1wt% of the anthocyanin in system.
6. the method according to claim 1 or 2 for improving natural products anthocyanin in acid heat condition stability inferior, feature Be: in step 3), heat treatment temperature is 80~100 DEG C, and heat treatment time is 5~10min.
7. a kind of raising natural products anthocyanin according to any one of claims 1 to 6 is in the side of acid heat condition stability inferior The stabilization anthocyanin copolymer that method is prepared.
8. a kind of application of stable anthocyanin copolymer according to claim 7, it is characterised in that: add as natural pigment Add agent or nutritional additive.
9. the application of stable anthocyanin copolymer according to claim 8, it is characterised in that: temperature be 20~90 DEG C And/or pH be 2~6 system in be used as natural pigment additive or nutritional additive.
CN201611064133.0A 2016-11-28 2016-11-28 Natural products anthocyanin is improved in the method for acid heat condition stability inferior, its product and application Active CN106589402B (en)

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CN110013034A (en) * 2019-04-17 2019-07-16 武汉轻工大学 Improve Microencapsulation Method of anthocyanin stability and products thereof, purposes
CN110547393A (en) * 2019-08-29 2019-12-10 中国农业大学 Method for improving stability of anthocyanin by regulating interaction between protein and anthocyanin through ultrahigh pressure treatment

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Publication number Priority date Publication date Assignee Title
CN101161610A (en) * 2006-10-12 2008-04-16 欧阳杰 Etherification molecule decorating method for increasing anthocyanin class pigment stability
CN103160141A (en) * 2013-03-26 2013-06-19 华南师范大学 Application of tannic acid in improvement of stability of purple-fleshed sweet potato pigment
CN103304657A (en) * 2012-03-16 2013-09-18 东北林业大学 Glycosylated modifying method for improving antioxidant activity of whey protein
CN105876792A (en) * 2016-04-19 2016-08-24 东北农业大学 Preparation method of novel beta-carotene microcapsules
CN105942324A (en) * 2016-05-18 2016-09-21 湖南农业大学 Production method of DioscoreaalataL. instant powder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101161610A (en) * 2006-10-12 2008-04-16 欧阳杰 Etherification molecule decorating method for increasing anthocyanin class pigment stability
CN103304657A (en) * 2012-03-16 2013-09-18 东北林业大学 Glycosylated modifying method for improving antioxidant activity of whey protein
CN103160141A (en) * 2013-03-26 2013-06-19 华南师范大学 Application of tannic acid in improvement of stability of purple-fleshed sweet potato pigment
CN105876792A (en) * 2016-04-19 2016-08-24 东北农业大学 Preparation method of novel beta-carotene microcapsules
CN105942324A (en) * 2016-05-18 2016-09-21 湖南农业大学 Production method of DioscoreaalataL. instant powder

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