CN105542195A - Preparation of protein-polysaccharide nano gel on basis of Maillard reaction in macromolecular crowding environment - Google Patents

Preparation of protein-polysaccharide nano gel on basis of Maillard reaction in macromolecular crowding environment Download PDF

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Publication number
CN105542195A
CN105542195A CN201610073381.5A CN201610073381A CN105542195A CN 105542195 A CN105542195 A CN 105542195A CN 201610073381 A CN201610073381 A CN 201610073381A CN 105542195 A CN105542195 A CN 105542195A
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protein
nanogel
maillard reaction
preparation
macromolecular crowding
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齐军茹
冯纪璐
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/02Dextran; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00Compositions of proteins; Compositions of derivatives thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/02Dextran; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00Characterised by the use of proteins; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Jellies, Jams, And Syrups (AREA)

Abstract

The invention belongs to the technical field of functional food processing, and discloses preparation of a protein-polysaccharide nano gel on the basis of Maillard reaction in a macromolecular crowding environment. The preparation method comprises the following steps: dissolving protein and polysaccharide in deionized water, stirring uniformly, regulating the pH value to 6.8-7, standing in a 4-DEG C refrigerator over night to perform hydration sufficiently, stirring at 60-95 DEG C to react for 6-48 hours, drying the reaction product to obtain powder, dissolving the powder in water to obtain a solution, regulating the pH value to the protein isoelectric point, carrying out heating treatment at 80-95 DEG C for 5-60 minutes, and cooling to obtain the protein-polysaccharide nano gel. The gel has the core-shell structure, has the advantages of small size and excellent stability, can be used for carrying biological active substances, and is hopeful to become the material for preparing new functional food.

Description

Based on the preparation of the protein-PS nanogel of Maillard reaction under macromolecular crowding environment
Technical field
The invention belongs to functional foodstuff processing technique field, be specifically related to a kind of preparation based on the protein-PS nanogel of Maillard reaction under macromolecular crowding environment.
Background technology
Maillard reaction, as a kind of green method of protein chemistry modification, is often used in foodstuffs industry to improve the functional performance of protein.Maillard reacts, and also known as carbonyl ammonia react, refers to, between the carbonyl of reducing sugar and the amino of protein, condensation and the reaction be polymerized occurs, belong to non-enzymatic browning.Hydrophilic polysaccharide and albumen generation covalent attachment can be made by spontaneous Maillard reaction, form amphipathic protein-polysaccharide covalent mixture, thus improve the functional performance such as emulsifying property, gel property, oxidation-resistance of albumen.Maillard reaction is divided into xeothermic reaction and damp and hot reaction two kinds, and both respectively have quality.At present substantially rested on to the research of Maillard reaction the graft effect good xeothermic stage, but be difficult to control due to the long reaction time (being generally several days to a few week) of xeothermic reaction, browning degree, therefore not attractive; The damp and hot reaction of the Maillard be employed subsequently then can better overcome the above problems, and its reaction times is shorter, browning degree is controlled, reaction controlling can be made to react the primary stage at Maillard, but graft(ing) degree is lower.
In recent years, the preparations and applicatio of protein nano particle receives the concern of scientific research personnel gradually, and the surface effects of its uniqueness and dimensional effect etc. have unrivaled advantage.But independent protein nano particle is easily assembled, and there is obvious pH susceptibility, be therefore unfavorable for actual production and application.Have research to be combined with other macromolecule organics by albumen and forms amphipathic nature block polymer, further self-assembly formation nanoparticle, but the nanoparticle of high molecular polymerization formation has higher cytotoxicity, is equally also unfavorable for industrial production and application.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method based on the protein-PS nanogel of Maillard reaction under macromolecular crowding environment.
Another object of the present invention is to provide a kind of protein-PS nanogel based on Maillard reaction under macromolecular crowding environment prepared by aforesaid method.
Another object of the present invention is to provide the above-mentioned application of protein-PS nanogel in functional food additives based on Maillard reaction under macromolecular crowding environment.
The object of the invention is achieved through the following technical solutions:
Based on a preparation method for the protein-PS nanogel of Maillard reaction under macromolecular crowding environment, comprise following preparation process:
(1) albumen and polysaccharide are dissolved in deionized water, stir, regulate pH6.8 ~ 7, in 4 DEG C of abundant aquations of refrigerator overnight;
(2) solution of step (1) is placed in stirring reaction 6 ~ 48h at 60 DEG C ~ 95 DEG C temperature, reaction product drying powdered, obtains Maillard reaction product;
(3) obtain solution by soluble in water for Maillard reaction product, regulate pH to albumen iso-electric point, heat treated 5 ~ 60min at 80 ~ 95 DEG C of temperature, obtains protein-PS nanogel after cooling.
Preferably, described albumen comprises at least one in soybean protein, Semen Pisi sativi protein, kidney bean albumen and whey-protein.
Preferably, described polysaccharide comprises at least one in soybean polysaccharide, dextran.
Preferably, the mass ratio of described albumen and polysaccharide is 1:(1 ~ 3); The described albumen concentration be dissolved in deionized water is 50 ~ 100g/L.
Preferably, the time of stirring described in step (1) is 2 ~ 6h.
Preferably, the drying described in step (2) refers to lyophilize or spraying dry.
Preferably, described in step (3), the concentration of solution is 0.1 ~ 10mg/mL.
Based on a protein-PS nanogel for Maillard reaction under macromolecular crowding environment, prepared by above method.
The above-mentioned vehicle of protein-PS nanogel as biologically active substance based on Maillard reaction under macromolecular crowding environment or the application of functional food ingredient.
Principle of the present invention is:
The present invention applies to " macromolecular crowding " effect in life science in the Maillard reaction of liquid-phase system, using polysaccharide as crowding agent, play its stereoeffect to reduce protein denaturation and aggregation extent, the reaction that reaction is combined towards albumen with polysaccharide covalent is carried out, thus the grafting degree both improving.
The present invention has amphipathic protein-polysaccharide covalent mixture by the damp and hot reaction preparation of Maillard under macromolecular crowding environment, and self-assembly forms stable protein-polysaccharide nanogel in aqueous further.Compared with the nanoparticle of Polymer Synthesizing, nanogel of the present invention not only has the stability of excellent dimensional effect and height, and has lower cytotoxicity, and is easily degraded.At present, have a small amount of research to prepare nanoparticle based on the xeothermic reaction of Maillard, but the research that under utilizing macromolecular crowding environment, the damp and hot reaction of Maillard and self-assembling reaction prepare nanoparticle not yet find.Protein-PS nanogel is prepared in the Maillard reaction that the present invention is based on liquid phase under macromolecular crowding environment, hydrophilic polysaccharide passes through Maillard reactive grafting on albumen, obtained have amphipathic protein-PS covalent complex, under the condition of heating, prepared covalent complex self-assembly formed with hydrophilic polysaccharide be shell, the hydrophobic albumen nanogel that is core.In heat-processed, albumen generation sex change, hydrophobic grouping is exposed to protein surface, under the driving of hydrophobic aggregation reactive force, albumen has the tendency of aggregate and precipitate, but stop albumen precipitation to the polysaccharide of albumen due to space steric effect by covalence graft, and form the nanogel with nucleocapsid structure further.In addition, in heat-processed, albumen generation gelation, makes nanogel inner casing have certain spacial framework, again due to the exposure of albumen hydrophobic grouping, makes nanogel kernel form multiple hydrophobic cavity.Therefore, lyophobic dust can be wrapped up by nanogel and transport under the driving of hydrophobic aggregation effect.
Preparation method of the present invention and the product tool obtained have the following advantages and beneficial effect:
(1) gel that the present invention utilizes the further self-assembly of the damp and hot reaction product of Maillard to obtain has nucleocapsid structure, and size is little, and stability is superior, not only can be used for the delivery of biologically active substance, and is expected to the batching becoming new functionalized food;
(2) the protein-PS nanogel good stability that reacts of the Maillard based on liquid-phase system under macromolecular crowding environment of the present invention, change at standing storage, pH, freeze-drying redissolve and dilution condition under change of size little;
(3) the present invention utilizes the macromole with biocompatibility to be prepared, do not add toxic reagent in process, method operation be simple and easy, cost is low, environmental friendliness, environmental protection.
Accompanying drawing explanation
Fig. 1 is the grain size distribution of soybean protein isolate-soybean polysaccharide nanogel that embodiment 1 prepares;
Fig. 2 is the transmission electron microscope picture of soybean protein isolate-soybean polysaccharide nanogel that embodiment 1 prepares;
Fig. 3 is the pH stability diagram of whey-protein-soybean polysaccharide nanogel that embodiment 2 prepares.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The soybean protein isolate and the soybean polysaccharide that by mass ratio are 1:1 are soluble in water, make its concentration be 50g/L, dispersed with stirring 6h, regulate pH to 6.8, spend the night in 4 DEG C of refrigerator aquations with dilute hydrochloric acid.Solution is placed in 60 DEG C of water-baths and reacts 30h, and lyophilize, gained powder is soybean protein isolate-soybean polysaccharide covalent complex.By soluble in water for above-mentioned powder, be made into the uniform solution that concentration is 1mg/mL, with the HCl solution regulator solution pH of 0.1mol/L to iso-electric point 4.8, in 80 DEG C of water-baths, heat 50min, after cooling, be soybean protein isolate-soybean polysaccharide nanogel.
The present embodiment gained soybean protein isolate-soybean polysaccharide nanogel adopts ZetasizerNano-ZS dynamic Laser granularity scanner to analyze known, and its particle diameter is between 59-459nm, and PDI value is 0.142, and its grain size distribution as shown in Figure 1.As shown in Figure 2, as seen from Figure 2, the nanogel that the present invention prepares has nucleocapsid structure to the transmission electron microscope picture of the present embodiment gained soybean protein isolate-soybean polysaccharide nanogel.
Embodiment 2
The whey-protein and the dextran that by mass ratio are 1:3 are soluble in water, make its concentration be respectively 50g/L and 150g/L, dispersed with stirring 2h, regulate pH to 7.0, spend the night in 4 DEG C of refrigerator aquations with dilute hydrochloric acid.Solution is placed in 95 DEG C of water-baths and reacts 6h, and carry out spraying dry and obtain powder.By soluble in water for above-mentioned powder, be made into the uniform solution that concentration is 0.1mg/mL, with the HCl solution regulator solution pH of 0.1mol/L to iso-electric point 5.2,5min is heated in 95 DEG C of water-baths, be whey-protein-dextran nanogel after cooling, the pH stability diagram of the whey-protein that the present embodiment prepares-soybean polysaccharide nanogel as shown in Figure 3, as seen from Figure 3, gained nanogel of the present invention does not have Second Aggregation phenomenon to occur in the scope of pH2 ~ 10, and its change of size is little.
Embodiment 3
The Semen Pisi sativi protein and the soybean polysaccharide that by mass ratio are 1:2 are soluble in water, make Semen Pisi sativi protein concentration be 100g/L, dispersed with stirring 5h, regulate pH to 6.9, spend the night in 4 DEG C of refrigerator aquations with dilute hydrochloric acid.Solution is placed in 65 DEG C of water-baths and reacts 48h, and lyophilize, gained powder is Semen Pisi sativi protein-soybean polysaccharide covalent complex.By soluble in water for above-mentioned powder, be made into the uniform solution that concentration is 10mg/mL, with the HCl solution regulator solution pH of 0.1mol/L to iso-electric point 5.2,30min is heated in 90 DEG C of water-baths, be Semen Pisi sativi protein-soybean polysaccharide nanogel after cooling, freeze-drying is redissolved little to the grain diameter influence of nanogel.
Embodiment 4
The kidney bean albumen and the soybean polysaccharide that by mass ratio are 1:1 are soluble in water, make kidney bean protein concentration be 50g/L, dispersed with stirring 3h, regulate pH to 7.0, spend the night in 4 DEG C of refrigerator aquations with dilute hydrochloric acid.Solution is placed in 60 DEG C of water-baths and reacts 24h, and lyophilize, gained powder is kidney bean albumen-soybean polysaccharide covalent complex.By soluble in water for above-mentioned powder, be made into the uniform solution that concentration is 3mg/mL, with the HCl solution regulator solution pH of 0.1mol/L to iso-electric point 4.7,35min is heated in 95 DEG C of water-baths, kidney bean albumen-soybean polysaccharide nanogel is after cooling, by nanogel solution dilution 10 times, its change of size is little.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (9)

1., based on a preparation method for the protein-PS nanogel of Maillard reaction under macromolecular crowding environment, it is characterized in that comprising following preparation process:
(1) albumen and polysaccharide are dissolved in deionized water, stir, regulate pH6.8 ~ 7, in 4 DEG C of abundant aquations of refrigerator overnight;
(2) solution of step (1) is placed in stirring reaction 6 ~ 48h at 60 DEG C ~ 95 DEG C temperature, reaction product drying powdered, obtains Maillard reaction product;
(3) obtain solution by soluble in water for Maillard reaction product, regulate pH to albumen iso-electric point, heat treated 5 ~ 60min at 80 ~ 95 DEG C of temperature, obtains protein-PS nanogel after cooling.
2. a kind of preparation method based on the protein-PS nanogel of Maillard reaction under macromolecular crowding environment according to claim 1, is characterized in that: described albumen comprises at least one in soybean protein, Semen Pisi sativi protein, kidney bean albumen and whey-protein.
3. a kind of preparation method based on the protein-PS nanogel of Maillard reaction under macromolecular crowding environment according to claim 1, is characterized in that: described polysaccharide comprises at least one in soybean polysaccharide, dextran.
4. a kind of preparation method based on the protein-PS nanogel of Maillard reaction under macromolecular crowding environment according to claim 1, is characterized in that: the mass ratio of described albumen and polysaccharide is 1:(1 ~ 3); The described albumen concentration be dissolved in deionized water is 50 ~ 100g/L.
5. a kind of preparation method based on the protein-PS nanogel of Maillard reaction under macromolecular crowding environment according to claim 1, is characterized in that: the time of stirring described in step (1) is 2 ~ 6h.
6. a kind of preparation method based on the protein-PS nanogel of Maillard reaction under macromolecular crowding environment according to claim 1, is characterized in that: the drying described in step (2) refers to lyophilize or spraying dry.
7. a kind of preparation method based on the protein-PS nanogel of Maillard reaction under macromolecular crowding environment according to claim 1, is characterized in that: described in step (3), the concentration of solution is 0.1 ~ 10mg/mL.
8., based on a protein-PS nanogel for Maillard reaction under macromolecular crowding environment, it is characterized in that: prepared by the method described in any one of claim 1 ~ 7.
9. the vehicle of protein-PS nanogel as biologically active substance based on Maillard reaction under macromolecular crowding environment according to claim 8 or the application of functional food ingredient.
CN201610073381.5A 2016-02-01 2016-02-01 Preparation of protein-polysaccharide nano gel on basis of Maillard reaction in macromolecular crowding environment Pending CN105542195A (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN107118360A (en) * 2017-06-10 2017-09-01 复旦大学 A kind of soybean protein isolate base natural polymer hydrogel and preparation method thereof
WO2020133653A1 (en) * 2018-12-26 2020-07-02 淮阴工学院 Protein/polysaccharide/essential oil nanometer edible film and preparation method therefor
CN113068808A (en) * 2021-05-06 2021-07-06 福建农林大学 Processing method for improving quality of fried fish cake
WO2021136785A1 (en) 2019-12-30 2021-07-08 Arla Foods Amba Method of producing dense whey protein nanogels, the resulting whey protein nanogels or nanogel compositions, and food products containing such whey protein nanogels or nanogel compositions
CN113892624A (en) * 2021-09-15 2022-01-07 华南理工大学 Soybean high-definition flavor-developing base material and preparation method and application thereof

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107118360A (en) * 2017-06-10 2017-09-01 复旦大学 A kind of soybean protein isolate base natural polymer hydrogel and preparation method thereof
WO2020133653A1 (en) * 2018-12-26 2020-07-02 淮阴工学院 Protein/polysaccharide/essential oil nanometer edible film and preparation method therefor
US11760852B2 (en) 2018-12-26 2023-09-19 Huaiyin Institute Of Technology Protein/polysaccharide/essential oil nanometer edible film and preparation method therefor
WO2021136785A1 (en) 2019-12-30 2021-07-08 Arla Foods Amba Method of producing dense whey protein nanogels, the resulting whey protein nanogels or nanogel compositions, and food products containing such whey protein nanogels or nanogel compositions
CN115103599A (en) * 2019-12-30 2022-09-23 阿拉食品公司 Method for producing a dense whey protein nanogel, whey protein nanogel or nanogel composition produced thereby and food products containing such whey protein nanogel or nanogel composition
EP4385337A2 (en) 2019-12-30 2024-06-19 Arla Foods amba Method of producing dense whey protein nanogels, the resulting whey protein nanogels or nanogel compositions, and use of such whey protein nanogels or nanogel compositions
EP4385337A3 (en) * 2019-12-30 2024-07-10 Arla Foods amba Method of producing dense whey protein nanogels, the resulting whey protein nanogels or nanogel compositions, and use of such whey protein nanogels or nanogel compositions
CN113068808A (en) * 2021-05-06 2021-07-06 福建农林大学 Processing method for improving quality of fried fish cake
CN113892624A (en) * 2021-09-15 2022-01-07 华南理工大学 Soybean high-definition flavor-developing base material and preparation method and application thereof

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Application publication date: 20160504