CN109265706A - A kind of modified corn alcohol soluble protein and preparation method thereof and antibacterial film preparation - Google Patents

A kind of modified corn alcohol soluble protein and preparation method thereof and antibacterial film preparation Download PDF

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Publication number
CN109265706A
CN109265706A CN201811097818.4A CN201811097818A CN109265706A CN 109265706 A CN109265706 A CN 109265706A CN 201811097818 A CN201811097818 A CN 201811097818A CN 109265706 A CN109265706 A CN 109265706A
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soluble protein
alcohol soluble
modified corn
fish
preparation
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张�浩
莫海珍
李红波
胡梁斌
周威
赵岩岩
崔震昆
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Henan Institute of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00Macromolecular products derived from proteins
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B4/00General methods for preserving meat, sausages, fish or fish products
    • A23B4/14Preserving with chemicals not covered by groups A23B4/02 or A23B4/12
    • A23B4/18Preserving with chemicals not covered by groups A23B4/02 or A23B4/12 in the form of liquids or solids
    • A23B4/20Organic compounds; Microorganisms; Enzymes
    • 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
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • 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
    • C08J2389/00Characterised by the use of proteins; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Biochemistry (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)

Abstract

A kind of modified corn alcohol soluble protein, including following components: zein powder, the sodium trimetaphosphate of purity 95%, dehydrated alcohol, sodium hydroxide, oleic acid, natural bactericidal agent, antioxidant and auxiliary agent.Corn (sorghum) alcohol soluble protein powder is modified by using crosslinking agent sodium trimetaphosphate (STMP), so as to improve the brittleness and other mechanical performances of film, optimizes best crosslinking condition.Using circular dichroism spectra, Fourier transform infrared spectroscopy characterizes the structure of protein films, and has detected its transparency, water solubility, extensibility, tensile strength, water penetration etc.;And show the zein solution dip-coating flesh of fish to form film, it cultivates at different temperature, the antibacterial and anti-oxidation characteristics of protein film is examined by measurement total plate count and peroxide value, food borne bacteria activity is inhibited to improve 50%~200%.

Description

A kind of modified corn alcohol soluble protein and preparation method thereof and antibacterial film preparation
Technical field
The invention belongs to bioprotein technical field of modification, in particular to arrive a kind of modified corn alcohol soluble protein and Preparation method and antibacterial membrane preparation method.
Background technique
Plastics are applied very wide in food packaging, it has light-weight, convenient for molding and packaging operation, has good Barrier, can also meet fresh food controlled atmosphere fresh-keeping packing certain air permeability require the advantages that.But the easy band of plastic products Electrostatic and cause material surface pollute and heat-sealing etc. operating difficulties;The monomer molecule of certain plastic resins has certain toxicity, When remaining monomer molecule in plastic resin, there is safe and healthy problem for food packaging.Phthalic acid in recent years The discovery of the plasticisers such as ester is even more to cause people to the worry of its foodsafety.In addition, Plastics Packaging Wastes are difficult to degrade, It is easy to cause problem of environmental pollution.
Protein material is from a wealth of sources, and because of its natural reproducible, biodegradable, the film raw material based on protein is close It is gradually taken seriously over year.Amino acid profile and the space structure variation of protein very greatly, also result in corresponding biomembrane and add The difference of the physics and chemical property of work method and formation film.And degradable films can as the barrier of solute and gas, It keeps food quality and extends Food Shelf-life, so degradable package material causes the very big concern of food-processing industry.
Zein is a kind of natural edible plants macromolecular, has degradability, non-toxic, biocompatibility, Hydrophobicity.Zein matrix membrane can have anti-oxidation function in the case where not adding antioxidant.In addition to packaging material Outside, zein film biocompatibility with higher and adaptability, can be used for biological support, such as be implanted into the adsorbing base of cell And as the physical support and molding guiding for forming neologism.Kafirin is one of sorghum prolamin, Content in sorghum is 7-8%, is a kind of edible cheap protein resource of rich content, is a kind of hydrophobic proteins, is not easy It is hydrolyzed by protease and carbohydrate-splitting enzyme, is suitable for the packaging of food.
But since corn (sorghum) alcohol soluble protein film brittleness is larger, and stickiness, extensibility and tensile strength are poor, Mechanical performance is not met by needs of production.The research of currently available technology is mainly the operation of simple laboratory scale With the application in food, such as film or the manual film that immerses form liquid by hand, it is difficult to large-scale production.Therefore egg is advanced optimized White matter membrane preparation technology, it is necessary for improving the physico-chemical property of film.
Summary of the invention
In order to overcome the shortcomings in the background art, the purpose of the present invention is to provide a kind of modified corn alcohol soluble protein and its Preparation method and antibacterial membrane preparation method.Using corn (sorghum) alcohol soluble protein as research object, by addition sodium trimetaphosphate and Oleic acid is modified corn (sorghum) alcohol soluble protein, so as to improve the brittleness and other mechanical performances of protein films.Exist simultaneously It wherein adds natural bactericidal agent, antioxidant and other auxiliary agents and produces food anti-bacterial packaging film, obtain its performance and fresh-keeping effect To improving, to improve the shelf stability and safety of food product, there is preferable economic benefit and social value.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of modified corn alcohol soluble protein, including following components:
Zein powder
The sodium trimetaphosphate of purity 95%
Dehydrated alcohol
Sodium hydroxide
Oleic acid
Natural bactericidal agent
Antioxidant
Auxiliary agent.
Zein powder, is dissolved in 80% ethanol solution, matched by a kind of preparation method of modified corn alcohol soluble protein The zein powder solution of 2% (m/V) is made;0.1mol/LNaOH solution adjusting corn alcohol soluble protein powder pH value of solution is used again The sodium trimetaphosphate of purity 95% is added in value, and oleic acid, natural bactericidal agent, antioxidant and other auxiliary agents after reaction, then are spent Ionized water dialysis 12h, obtains modified corn alcohol soluble protein (Z-SP) product after pellet frozen is dry.
In order to be further improved technical solution, 0.1mol/LNaOH solution of the present invention is substituted with 0.1mol/LHCL.
A kind of application of modified corn alcohol soluble protein in fresh-keeping, applying step are as follows:
S1: flesh of fish pretreatment: after fresh fish is lethal, decaptitating truncates, removes fish scale, removes internal organ, with after scalding, uses Distilled water rinsing, sloughs moisture;
S2: the preparation of coating liquid: the optimum proportioning of modified corn alcohol soluble protein is obtained by Responds Surface Methodology, by step It is put into 10s in coating liquid by the pretreated flesh of fish in S1, taking-up is put into the pallet through ultraviolet-sterilization, to be filmed after dry;
S3: treated in the step S2 flesh of fish packaging: is added into the different sulphur of benzyl of 90 μ L/g by zeins amount Cyanate is put into packaging bag.
Due to the adoption of the technical scheme as described above, the invention has the following beneficial effects: the present invention with corn (sorghum) Alcohol soluble protein is research object, is modified by addition sodium trimetaphosphate and oleic acid to corn (sorghum) alcohol soluble protein, thus Improve the brittleness and other mechanical performances of protein films.Protein antibacterial film is made of natural edible plants macromolecular, tool There is degradability, non-toxic, preferable biocompatibility and hydrophobicity.This research is with zeins and kafirin For research object, the membrance casting condition of zeins and kafirin has been inquired into.By using three metaphosphoric acid of crosslinking agent Sodium (STMP) is modified corn (sorghum) alcohol soluble protein powder, and so as to improve the brittleness and other mechanical performances of film, optimization is most Good crosslinking condition.Using circular dichroism spectra, Fourier transform infrared spectroscopy characterizes the structure of protein films, and it is transparent to have detected its Degree, water solubility, extensibility, tensile strength, water penetration etc.;And show the zein solution dip-coating flesh of fish to form film, It cultivates at different temperature, the antibacterial and anti-oxidation characteristics of protein film is examined by measurement total plate count and peroxide value, inhibit Food borne bacteria activity improves 50%~200%.This has researched and developed novel packaging material for food, improves degradable compound The properties of protein films are able to extend the shelf life of food.Research achievement is for promoting protein film to have in the food industry Have wide practical use and use value is preserved the ecological environment more importantly reducing white pollution, there is important meaning Justice.
Specific embodiment
By the following examples can the detailed explanation present invention, the open purpose of the present invention is intended to protect model of the present invention Enclose all interior technological improvements.
Zein powder, is dissolved in 80% ethanol solution, matched by a kind of preparation method of modified corn alcohol soluble protein The zein powder solution of 2% (m/V) is made;0.1mol/LNaOH solution adjusting corn alcohol soluble protein powder pH value of solution is used again The sodium trimetaphosphate of purity 95% is added in value, and oleic acid, natural bactericidal agent, antioxidant and other auxiliary agents after reaction, then are spent Ionized water dialysis 12h, obtains modified corn alcohol soluble protein (Z-SP) product after pellet frozen is dry.
It is as follows for the rheology measurement process of above embodiments:
Polymer (zein and Z-SP) solution to be measured that mass fraction is 2.0% is prepared by solvent of 80% ethyl alcohol, wherein The pH value of solution is adjusted with 0.1mol/LHCl and NaOH solution.
Using the rheological curve, shear stress and viscoplasticity of rheometer measurement solution.In rheological curve measurement, taper plate Using C60/1TIL, shear rate (D) range used is 0.1~1000s-1, testing time 1min.Viscoplasticity (but small oscillations Shearing) measurement in, frequency (f) scanning range be 0.1~100Hz, shear stress (τ) be 0.1Pa (in linear viscoelastic region).Except examining Examining temperature influences outside test, and test temperature is (25.0 ± 0.2) DEG C.
The response phase method of the preparation condition of Z-SP optimizes
According to the preparation method of protein solution, with the mass ratio (R of sodium trimetaphosphate and the molten egg of corn alcoholS/Z), reaction pH, Reaction time is investigation condition, determines center combination test level according to single factor experiment result, using shear stress as response, is led to It crosses data analysis and obtains optimum organization[13]
Each factor of 1 center combination design of table and its level
Table 1 Each factor and its level of central composite design
Circular dichroism spectra measurement
Near ultraviolet sample liquid preparation process: claiming 0.2gZein and Z-SP to be dissolved in 80% ethanol solution respectively, and 2mg/mL egg is made White solution;
Far ultraviolet sample liquid preparation process: 80% ethanol solution for taking two kinds of near ultraviolet protein solutions to be dissolved in respectively is made 0.2mg/mL protein solution.It is centrifuged after completely dissolution, the circular dichroism of the protein liquid is measured using circular dichroism spectrometer.
Measure wave-length coverage: 250~320nm of near ultraviolet, 190~260nm of far ultraviolet[14]
Fourier transform infrared spectroscopy measurement
Zein the and Z-SP powder being freeze-dried in right amount is weighed, is allowed to the ratio of potassium bromide be 1:75, potassium bromide need to shift to an earlier date Dry (105 DEG C, 4h or more) in an oven.The two is uniformly mixed in agate Yan Portland and is ground into fine powder, and suitable sample is taken to exist It is measured after being pressed into transparent sheet in clean compression mold, and background single channel spectrum is surveyed with the tabletting of potassium bromide production, then Sample channel spectrum, to obtain comparison spectrogram.
The above result of study shows: zeins is modified by phosphorylation, the enhancing of solution viscoplasticity, protein secondary Apparent variation also has occurred in structure.Zein process is appropriate modified, can expand its application range in the market.
Modified corn alcohol soluble protein obtained in above-described embodiment is subjected to the fresh-keeping application of the flesh of fish, detailed process is as follows:
S1: fish pretreatment
After fresh and alive grass carp is lethal, decaptitating truncates, removes fish scale, removes internal organ, is split fish with by the tool of scalding Meat is divided into consistent sample uniform in size (weight is depending on the fish index measured), is then rinsed, sloughed with distilled water Moisture, grouping.(being divided into tri- groups of a, b, c, film, b, c as coating group, c do not add Benzy to a control group).
S2: coating method
Coating liquid is made in the optimal combination of the Zein film obtained by response surface[38], the flesh of fish cut is put into film 10s in liquid, taking-up are put into through drying in drying box, temperature 70 C or so in the ultraviolet pallet for killing bacterium.A few minutes stir one Under, after being evaporated completely to solvent, sample surfaces will form the film of layer of transparent[39]
S3: packaging and storage
Packaging bag and superclean bench are subjected to ultraviolet-sterilization 2h in advance, then packaging bag is wiped with alcohol, so After packed.By the flesh of fish handled well (every piece weighs about 10g size), it is divided into tri- groups of a, b, c, a group not film as a control group, For b group as coating group, c group is as coating group and adds benzyl isothiocyanate (additive amount is by the addition of zeins amount, 90 μ L/g), three groups of samples respectively under the conditions of 4,15,25,37 DEG C storage 0,1,2,3,4,5,6, take out after 7d, measurement bacterium colony is total Number.The flesh of fish handled well (every piece weighs about 300g) is divided into two groups of a, b, a group not film as a control group, b group as coating group, Store 0 under the conditions of 4,15,25,37 DEG C to it, 1,3,5,7, take out after 9d, measure peroxide value, and under 4 DEG C of holding conditions The flesh of fish quality carry out subjective appreciation[17,40]
Maize alcohol-soluble protein film is fresh-keeping in the flesh of fish
(1) measurement of total plate count is the scissors after the fillet sample sterilizing after culture, fish in aseptic operating platform Meat strand is diluted.It draws 10 μ L dilutions with liquid-transfering gun under each dilution to be added dropwise on agar plate, each processing parallel 3 Secondary test cultivates in 37 DEG C of constant incubators for 24 hours, carries out plate count.The foundation GB489.1- of total plate count measurement 2016[41]
(2) measurement of peroxide value is operated according to GB5009.227-2016, calculation formula are as follows:
X1=(V-V0)×c×0.1269×100/m。
X1: peroxide value, unit are gram every hectogram (g/100g);
V: the sodium thiosulfate standard solution volume of sample consumption, unit are milliliter (mL);
V0: the sodium thiosulfate standard solution volume of blank test consumption, unit are milliliter (mL);
C: the concentration of sodium thiosulfate standard solution, unit are mole every liter (mol/L);
M: sample mass, unit are gram (g).
(3) subjective appreciation takes out grass carp of a, b, c group Jing Guo different disposal, carries out subjective appreciation from 4 DEG C of refrigerators.Its Index is the color, smell, quality of the flesh of fish respectively.Score value is divided into 4 grades under each index, and specific standards are shown in Table 12.Scoring Personnel be by professional training, the comprehensive scores of grass carp meat at 15~20 points be it is fresh, 10~15 points be that quality is good, 5- 10 points be quality it is general, 1~5 point be inferior quality.Each sample is in parallel three times.
12 subjective appreciation standard of table
Table 12 The sensory evaluation standards

Claims (4)

1. a kind of modified corn alcohol soluble protein, it is characterized in that: including following components:
Zein powder
The sodium trimetaphosphate of purity 95%
Dehydrated alcohol
Sodium hydroxide
Oleic acid
Natural bactericidal agent
Antioxidant
Auxiliary agent.
2. a kind of preparation method of modified corn alcohol soluble protein as described in claim 1, it is characterized in that: by zein powder It is dissolved in 80% ethanol solution, is configured to the zein powder solution of 2% (m/V);It is adjusted again with 0.1mol/LNaOH solution Zein powder solution ph, be added purity 95% sodium trimetaphosphate, oleic acid, natural bactericidal agent, antioxidant and other Auxiliary agent, after reaction, then with deionized water dialysis 12h, after pellet frozen is dry modified corn alcohol soluble protein (Z-SP) product.
3. the preparation method of modified corn alcohol soluble protein as claimed in claim 2, it is characterized in that: the 0.1mol/LNaOH Solution is substituted with 0.1 mol/LHCL.
4. application of a kind of modified corn alcohol soluble protein as described in claim 1 in fresh-keeping, it is characterized in that: its applying step Are as follows:
S1: flesh of fish pretreatment: after fresh fish is lethal, decaptitating truncates, removes fish scale, removes internal organ, with after scalding, with distillation Water rinsing, sloughs moisture;
S2: the preparation of coating liquid: obtaining the optimum proportioning of modified corn alcohol soluble protein by Responds Surface Methodology, will be in step S1 It is put into 10s in coating liquid by the pretreated flesh of fish, taking-up is put into the pallet through ultraviolet-sterilization, to be filmed after dry;
S3: treated in the step S2 flesh of fish packaging: is added into the benzyl isothiocyanic acid of 90 μ L/g by zeins amount Ester is put into packaging bag.
CN201811097818.4A 2018-09-20 2018-09-20 A kind of modified corn alcohol soluble protein and preparation method thereof and antibacterial film preparation Pending CN109265706A (en)

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CN112773885A (en) * 2021-03-19 2021-05-11 东北农业大学 Zein disinfectant and preparation method thereof
CN113789100A (en) * 2021-07-19 2021-12-14 河南省路嘉路桥股份有限公司 Waterproof material for concrete matrix and preparation method thereof

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CN111286038A (en) * 2020-04-09 2020-06-16 武汉轻工大学 Preparation method and application of polyglycerol-modified zein
CN112773885A (en) * 2021-03-19 2021-05-11 东北农业大学 Zein disinfectant and preparation method thereof
CN113789100A (en) * 2021-07-19 2021-12-14 河南省路嘉路桥股份有限公司 Waterproof material for concrete matrix and preparation method thereof

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Application publication date: 20190125