CN101574100A - Egg membrane powder serving as flour improver and enzymolysis modified egg membrane powder - Google Patents
Egg membrane powder serving as flour improver and enzymolysis modified egg membrane powder Download PDFInfo
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- CN101574100A CN101574100A CNA200910033059XA CN200910033059A CN101574100A CN 101574100 A CN101574100 A CN 101574100A CN A200910033059X A CNA200910033059X A CN A200910033059XA CN 200910033059 A CN200910033059 A CN 200910033059A CN 101574100 A CN101574100 A CN 101574100A
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Abstract
The invention discloses egg membrane powder serving as a flour improver and enzymolysis modified egg membrane powder. The egg membrane powder and the enzymolysis modified egg membrane powder are prepared through the following steps: rinsing fresh eggshells in a water bath at a temperature of 40 DEG C, and cooling the eggshells to the room temperature; adding deionized water into the eggshells according to a mass ratio of 1:1, crushing the eggshells intermittently at a rotating speed of 1,000 revolutions per minute until the grain size of the eggshells is between 1 and 10 millimeters, wherein the crushing time of 500 grams of the eggshells is between 3 and 5 minutes; putting the crushed eggshells into the deionized water according to the mass ratio being 1:5 of the eggshells to the water, and stirring the mixture so that egg membranes are separated from the eggshells; standing the mixed solution for 1 minute, filtering a suspension with a 60-mesh screen to obtain a cup product which is wet egg membrane coarse powder, and drying the wet egg membrane coarse powder at a temperature of 40 DEG C to obtain the egg membrane coarse powder; crushing the egg membrane coarse powder at a rotating speed of 2,400 revolutions per minute, and filtering the crushed egg membrane coarse powder through a 100-mesh screen to obtain a screen underflow which is the egg membrane powder; and performing enzymolysis on the egg membrane powder to obtain the enzymolysis modified egg membrane powder. The egg membrane powder is used in flour to improve the toughness, the strength and the anti-stirring property of dough gluten so that a flour product has excellent specific volume, good bulky taste, enduring soft texture and flour flesh with strong toughness.
Description
Technical field
The present invention relates to flour improver, be specifically related to egg membrane powder and enzymolysis modified egg membrane powder as flour improver.
Background technology
Wheat flour is according to solubility property, and protein can be divided into leucosin, wheat globulin, gliadin and glutenin in the wheat seed, mainly is gliadin and glutenin in the wheat gluten protein, claims storage protein (account for wheat gluten butt 80%).The formation of dough is the physics and the biochemical change procedure of a complexity.In this process, mucedin not only with water generation solvation, and under the effect of directed shearing force, between polypeptide chain because the fracture and the reorganization of disulfide bond and secondary key (hydrogen bond, hydrophobic bond, ionic bond), can form orderly space network structure, make dough have extensibility and elasticity, and wherein the disulfide bond in interchain and the chain play the crux effect to the network of dough densification.
China just cures illnesss such as bedsore, celostomia, scald, brothers' ringworm of the body with eggshell membrane (being commonly called as chorion ovi) very early.Nineteen ninety-five, Japanese Himyukl Kakoki etc. makes 1% egg film water solution (hydrolysis egg memebrane protein), mixes with tocopherol, can be used for eliminating the peroxide of skin lipid.U.S. a company makes E-3 type regeneration emulsifiable paste with glycolic acid, hydrolysis egg film, soft-shelled turtle alkane, tea mustard extract, Vitamin E linoleate etc., and every bottle 5500 yuan of China (30ml) prices.1997, Japanese Kawaguchi, Yoshihiro is used for egg membrane powder to remove the sebum agent, holds back the raw material of preparation such as finish.But at home and abroad food service industry does not especially have the application study of egg film as yet in Flour product.
Egg shell membrane is the fibrous film that is positioned between eggshell and egg white, form by inner layer film (ISM), outer membrane (OSM) and restriction film (LM), thick approximately 70um, account for greatly the egg weight in wet base 1.02% or dry weight 0.24%.Contain 90% the protein of having an appointment, 3% lipid and 2% carbohydrate in the egg film, knot is similar to memebrane protein in the cell.Major protein is keratin, collagen (most of is the 1.V.X type), compound protein etc. in the egg film.The macromolecular compound that also contains a lot of solubilities in the egg film is as acetylglucosamine galactolipin, glucuronic acid, hyaluronic acid, chondroitin sulfate.Keratin molecule interchain and chain include the disulfide bond of higher density in the egg film, thereby make molecular structure tight, and character is highly stable under field conditions (factors), water insoluble and multiple solvent.
Summary of the invention
The objective of the invention is to: egg membrane powder and enzymolysis modified egg membrane powder as flour improver are provided, use this reagent in flour, improve dough gluten toughness, elasticity, intensity and anti-stirring property, join in the middle of the Flour product, can make the bread produced and steamed bun have good specific volume, lasting tender texture and, make the dumpling wrapper of producing have better elasticity and sophistication than the face flesh of obdurability.
Technical solution of the present invention is: make according to following method as the egg membrane powder of flour improver: the fresh eggshell that will collect from life or bread, cake shop 40 ℃ of following water-baths flushings 5 minutes, is cooled to room temperature; Press mass ratio in the eggshell and add deionized water at 1: 1, pulverize with the 1000r/min high speed disintegrator, pulverized once every 10 seconds, the pulverizing time is 10 seconds at every turn, is crushed to the eggshell particle diameter between 1mm to 10mm, and the pulverizing time of pulverizing the 500g eggshell is 3～5 minutes; Put into deionized water than 1: 5 by eggshell and water quality after the pulverizing, egg film and eggshell are peeled off with the stirring rod stirring; Allow static 1 minute of mixed liquor, with 60 purposes sieve filtering suspension liquid, oversize is wet egg film meal, and 40 ℃ of dry wet egg film meal get egg film meal; Pulverize egg film meal with the omnipotent high speed disintegrator of 2400r/min, by 100 order molecular sieves, screenings is an egg membrane powder.
Enzymolysis modified egg membrane powder as flour improver of the present invention makes according to following method: A, preparation egg membrane powder: the fresh eggshell that will collect from life or bread, cake shop 40 ℃ of following water-baths flushings 5 minutes, is cooled to room temperature; Press mass ratio in the eggshell and add deionized water at 1: 1, pulverize with the 1000r/min high speed disintegrator, pulverized once every 10 seconds, the pulverizing time is 10 seconds at every turn, is crushed to the eggshell particle diameter between 1mm to 10mm, and the pulverizing time of pulverizing the 500g eggshell is 3～5 minutes; Put into deionized water than 1: 5 by eggshell and water quality after the pulverizing, egg film and eggshell are peeled off with the stirring rod stirring; Allow static 1 minute of mixed liquor, with 60 purposes sieve filtering suspension liquid, oversize is wet egg film meal, and 40 ℃ of dry wet egg film meal get egg film meal; Pulverize egg film meal with the omnipotent high speed disintegrator of 2400r/min, by 100 order molecular sieves, screenings is an egg membrane powder;
B, modified: add in the egg membrane powder water mix mixed liquor, the concentration of mixed liquor is 5.0g/200ml to 20.0g/200ml;
C, heat treatment: mixed liquor heat treatment 10 to 20 minutes in 100 ℃ of water-baths;
D, enzymolysis: add 2709 alkali proteases in the mixed liquor after heat treatment, the addition of 2709 alkali proteases is the 3-8% of egg membrane powder quality, transfer pH9.0～11.0,45～65 ℃ of enzyme reaction temperatures, constant temperature stirs 1.5h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, soluble protein (TCA-NSI) is 20%～40% in the egg film liquid, and degree of hydrolysis (DH) is 4.5%～15%; Or add trypsase (hydrolysising protease in the animal pancreas) in the mixed liquor after heat treatment, tryptic addition is the 2-3% of egg membrane powder quality, transfer pH7.5～9.8,35～55 ℃ of enzyme reaction temperatures, constant temperature stirs 2.5h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, soluble protein (TCA-NSI) is 15%～30% in the egg film liquid, and degree of hydrolysis (DH) is 5.5%～10%; Or add neutral proteinase (making) in the mixed liquor after heat treatment by fermentation of bacillus subtilis, the addition of neutral proteinase is the 3-5% of egg membrane powder quality, transfer pH6.0～8.0,35～50 ℃ of enzyme reaction temperatures, constant temperature stirs 3.0h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, soluble protein (TCA-NSI) is 10%～20% in the egg film liquid, and degree of hydrolysis (DH) is 3.5%～9%; Or add 537 acid proteases (enzyme preparation factory in Wuxi directly buys) in the mixed liquor after heat treatment, the addition of 537 acid proteases is the 3-6% of egg membrane powder quality, transfer pH2.8～3.2,35～50 ℃ of enzyme reaction temperatures, constant temperature stirs 1.5h, 4 ℃ static 12 hours, egg film liquid occurs faint yellow, soluble protein (TCA-NSI) is 20%～50% in the egg film liquid, and degree of hydrolysis (DH) is 9.8%～20%; Or add compound protease (bacillus protease complex) in the mixed liquor after heat treatment, the addition of compound protease is the 3-6% of egg membrane powder quality, transfer pH6.0～8.0,45～65 ℃ of enzyme reaction temperatures, constant temperature stirs 2.0h, 4 ℃ static 12 hours, egg film liquid occurs faint yellow, soluble protein (TCA-NSI) is 20%～40% in the egg film liquid, and degree of hydrolysis (DH) is 9.0%～18%;
E, accent pH: HCl or NaOH with 1mol/L regulate mmp reaction liquid, and making the pH value is 6.0～6.8;
F, enzyme goes out: 100 ℃ of water-baths 10 minutes make the thorough inactivation of enzyme;
G, the enzymolysis modified egg membrane powder that cools off liquidly, vacuum-packed 4～10 ℃ of refrigerations in back;
H, liquid enzymolysis modified egg membrane powder spraying or freeze drying get enzymolysis modified egg membrane powder.
Egg membrane powder of the present invention has the following advantages:
1, the initial raw material that uses is eggshell, should belong to the twice laid category, also helps the protection of environment, and used reaction raw materials is a chemical reagent cheap and easy to get, makes the cost of producing flour improver reduce greatly.
2, extensive mechanization operation is adopted in the preparation of egg membrane powder of the present invention, can make that the disulfide bond in the egg membrane powder is come out substantially, is added in the flour, and flour characteristic is had more fully effect.
3, of the present invention preparation is simple, need not complex device, and whole process of production does not have any poisonous and harmful substance adding simultaneously, does not have any disposal of pollutants yet.
4, egg membrane powder of the present invention is because of pulverizing through continuous, Jian's shear force and heat come out a large amount of disulfide bond groups, and a large amount of disulfide bond can form the interchain bond energy with mucedin, enlarge the gluten network structure, obviously increase the biceps of dough, even dough has better processing characteristics.
5, enzymolysis modified egg membrane powder of the present invention is in enzymolysis process, the peptide bond of the protein of egg film ruptures, form polypeptide different in size and a spot of free amino acid, the content of soluble protein and polypeptide increases gradually with enzymolysis, making has more between egg film peptide that the multikey base comes out, improve the physical characteristic such as water-soluble of egg film, special a large amount of disulfide bond group wherein comes out, and is very beneficial for the formation of the fine and close network structure of dough.
6, in bread dough, add egg membrane powder or enzymolysis modified egg membrane powder, do not need long fermentation, after baking, just can give significantly good fermentation taste of bread and lasting tender texture.
7, add egg membrane powder or enzymolysis modified egg membrane powder in flour, can improve gluten toughness, elasticity, intensity and the anti-stirring property of dough, the bread that generates can be preserved the longer time, promptly can prolong the ageing time of bread, and when in fried bread and Deep-fried doughnut, using this modifying agent, can prevent that bread from absorbing oil.
Description of drawings
Fig. 1 is the Electronic Speculum figure of egg membrane structure, and a is inwall * 5000, and b is outer surface * 5000, and c pulverizes the back and crosses 60 orders * 5000.
Fig. 2 is the farinogram of blank group.
Fig. 3 is for adding the farinogram of 0.5% egg membrane powder.
Fig. 4 is the rheological curve figure of blank group.
Fig. 5 is for adding the rheological curve figure of 0.5% egg membrane powder.
Fig. 6 is for adding the rheological curve figure of 0.5% enzymolysis modified egg membrane powder.
Fig. 7 is for adding the rheological curve figure of 0.5% existing market modifying agent.
The specific embodiment
Below according to specific embodiment technical solution of the present invention is specifically described, be interpreted as these embodiment and be not restriction to the technology of the present invention solution.
Example 1: produce egg membrane powder according to following method: the fresh eggshell that will collect from life or bread, cake shop 40 ℃ of following water-baths flushings 5 minutes, is cooled to room temperature; Press mass ratio in the eggshell and add deionized water at 1: 1, pulverize with the 1000r/min high speed disintegrator, pulverized once every 10 seconds, the pulverizing time is 10 seconds at every turn, is crushed to the eggshell particle diameter at 10mm, and the pulverizing time of pulverizing the 500g eggshell is 3 minutes; Put into deionized water than 1: 5 by eggshell and water quality after the pulverizing, egg film and eggshell are peeled off with the stirring rod stirring; Allow static 1 minute of mixed liquor, with 60 purposes sieve filtering suspension liquid, oversize is wet egg film meal, and 40 ℃ of dry wet egg film meal get egg film meal; Pulverize egg film meal with the omnipotent high speed disintegrator of 2400r/min, by 100 order molecular sieves, screenings is an egg membrane powder.
Example 2: produce egg membrane powder according to following method: the fresh eggshell that will collect from life or bread, cake shop 40 ℃ of following water-baths flushings 5 minutes, is cooled to room temperature; Press mass ratio in the eggshell and add deionized water at 1: 1, pulverize with the 1000r/min high speed disintegrator, pulverized once every 10 seconds, the pulverizing time is 10 seconds at every turn, is crushed to the eggshell particle diameter at 5mm, and the pulverizing time of pulverizing the 500g eggshell is 4 minutes; Put into deionized water than 1: 5 by eggshell and water quality after the pulverizing, egg film and eggshell are peeled off with the stirring rod stirring; Allow static 1 minute of mixed liquor, with 60 purposes sieve filtering suspension liquid, oversize is wet egg film meal, and 40 ℃ of dry wet egg film meal get egg film meal; Pulverize egg film meal with the omnipotent high speed disintegrator of 2400r/min, by 100 order molecular sieves, screenings is an egg membrane powder.
Example 3: produce egg membrane powder according to following method: the fresh eggshell that will collect from life or bread, cake shop 40 ℃ of following water-baths flushings 5 minutes, is cooled to room temperature; Press mass ratio in the eggshell and add deionized water at 1: 1, pulverize with the 1000r/min high speed disintegrator, pulverized once every 10 seconds, the pulverizing time is 10 seconds at every turn, is crushed to the eggshell particle diameter at 1mm, and the pulverizing time of pulverizing the 500g eggshell is 5 minutes; Put into deionized water than 1: 5 by eggshell and water quality after the pulverizing, egg film and eggshell are peeled off with the stirring rod stirring; Allow static 1 minute of mixed liquor, with 60 purposes sieve filtering suspension liquid, oversize is wet egg film meal, and 40 ℃ of dry wet egg film meal get egg film meal; Pulverize egg film meal with the omnipotent high speed disintegrator of 2400r/min, by 100 order molecular sieves, screenings is an egg membrane powder.
Example 4: produce enzymolysis modified egg membrane powder: A, preparation egg membrane powder according to following method: with embodiment 1;
B, modified: add in the egg membrane powder water mix mixed liquor, the concentration of mixed liquor is 5.0g/200ml;
C, heat treatment: mixed liquor heat treatment 10 minutes in 100 ℃ of water-baths;
D, enzymolysis: add 2709 alkali proteases in the mixed liquor after heat treatment, the addition of 2709 alkali proteases is 3% of an egg membrane powder quality, transfer pH9.0,45 ℃ of enzyme reaction temperatures, constant temperature stirs 1.5h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, soluble protein (TCA-NSI) is 20% in the egg film liquid, and degree of hydrolysis (DH) is 4.5%;
E, accent pH: the HCl with 1mol/L regulates mmp reaction liquid, and making the pH value is 6.0;
F, enzyme goes out: 100 ℃ of water-baths 10 minutes make the thorough inactivation of enzyme;
G, the enzymolysis modified egg membrane powder that cools off liquidly, vacuum-packed 4～10 ℃ of refrigerations in back;
H, liquid enzymolysis modified egg membrane powder spraying or freeze drying get enzymolysis modified egg membrane powder.
Example 5: produce enzymolysis modified egg membrane powder: A, preparation egg membrane powder according to following method: with embodiment 2;
B, modified: add in the egg membrane powder water mix mixed liquor, the concentration of mixed liquor is 12.5g/200ml;
C, heat treatment: mixed liquor heat treatment 15 minutes in 100 ℃ of water-baths;
D, enzymolysis: add 2709 alkali proteases in the mixed liquor after heat treatment, the addition of 2709 alkali proteases is 5.5% of an egg membrane powder quality, transfer pH10.0,55 ℃ of enzyme reaction temperatures, constant temperature stirs 1.5h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, soluble protein (TCA-NSI) is 30% in the egg film liquid, and degree of hydrolysis (DH) is 10%;
E, accent pH: the NaOH with 1mol/L regulates mmp reaction liquid, and making the pH value is 6.4;
F, enzyme goes out: 100 ℃ of water-baths 10 minutes make the thorough inactivation of enzyme;
G, the enzymolysis modified egg membrane powder that cools off liquidly, vacuum-packed 4～10 ℃ of refrigerations in back;
H, liquid enzymolysis modified egg membrane powder spraying or freeze drying get enzymolysis modified egg membrane powder.
Example 6: produce enzymolysis modified egg membrane powder: A, preparation egg membrane powder according to following method: with embodiment 3;
B, modified: add in the egg membrane powder water mix mixed liquor, the concentration of mixed liquor is 20.0g/200ml;
C, heat treatment: mixed liquor heat treatment 20 minutes in 100 ℃ of water-baths;
D, enzymolysis: add 2709 alkali proteases in the mixed liquor after heat treatment, the addition of 2709 alkali proteases is 8% of an egg membrane powder quality, transfer pH11.0,65 ℃ of enzyme reaction temperatures, constant temperature stirs 1.5h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, soluble protein (TCA-NSI) is 40% in the egg film liquid, and degree of hydrolysis (DH) is 15%;
E, accent pH: the HCl with 1mol/L regulates mmp reaction liquid, and making the pH value is 6.8;
F, enzyme goes out: 100 ℃ of water-baths 10 minutes make the thorough inactivation of enzyme;
G, the enzymolysis modified egg membrane powder that cools off liquidly, vacuum-packed 4～10 ℃ of refrigerations in back;
H, liquid enzymolysis modified egg membrane powder spraying or freeze drying get enzymolysis modified egg membrane powder.
Example 7: produce enzymolysis modified egg membrane powder according to following method: with embodiment 4; Wherein during enzymolysis, add trypsase (hydrolysising protease in the animal pancreas) in the mixed liquor after heat treatment, tryptic addition is 2% of an egg membrane powder quality, transfer pH7.5,35 ℃ of enzyme reaction temperatures, constant temperature stirs 2.5h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, and soluble protein (TCA-NSI) is 15% in the egg film liquid, and degree of hydrolysis (DH) is 5.5%.
Example 8: produce enzymolysis modified egg membrane powder according to following method: with embodiment 5; Wherein during enzymolysis, add trypsase (hydrolysising protease in the animal pancreas) in the mixed liquor after heat treatment, tryptic addition is 2.5% of an egg membrane powder quality, transfer pH8.6,45 ℃ of enzyme reaction temperatures, constant temperature stirs 2.5h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, and soluble protein (TCA-NSI) is 22.5% in the egg film liquid, and degree of hydrolysis (DH) is 7.5%.
Example 9: produce enzymolysis modified egg membrane powder according to following method: with embodiment 6; Wherein during enzymolysis, add trypsase (hydrolysising protease in the animal pancreas) in the mixed liquor after heat treatment, tryptic addition is 3% of an egg membrane powder quality, transfer pH9.8,55 ℃ of enzyme reaction temperatures, constant temperature stirs 2.5h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, and soluble protein (TCA-NSI) is 30% in the egg film liquid, and degree of hydrolysis (DH) is 10%.
Example 10: produce enzymolysis modified egg membrane powder according to following method: with embodiment 4; Wherein during enzymolysis, add neutral proteinase (making) in the mixed liquor after heat treatment by fermentation of bacillus subtilis, the addition of neutral proteinase is 3% of an egg membrane powder quality, transfer pH6.0,35 ℃ of enzyme reaction temperatures, constant temperature stirs 3.0h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, and soluble protein (TCA-NSI) is 10% in the egg film liquid, and degree of hydrolysis (DH) is 3.5%.
Example 11: produce enzymolysis modified egg membrane powder according to following method: with embodiment 5; Wherein during enzymolysis, add neutral proteinase (making) in the mixed liquor after heat treatment by fermentation of bacillus subtilis, the addition of neutral proteinase is 4% of an egg membrane powder quality, transfer pH7.0,42 ℃ of enzyme reaction temperatures, constant temperature stirs 3.0h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, and soluble protein (TCA-NSI) is 15% in the egg film liquid, and degree of hydrolysis (DH) is 6.5%.
Example 12: produce enzymolysis modified egg membrane powder according to following method: with embodiment 6; Wherein during enzymolysis, add neutral proteinase (making) in the mixed liquor after heat treatment by fermentation of bacillus subtilis, the addition of neutral proteinase is 5% of an egg membrane powder quality, transfer pH8.0,50 ℃ of enzyme reaction temperatures, constant temperature stirs 3.0h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, and soluble protein (TCA-NSI) is 20% in the egg film liquid, and degree of hydrolysis (DH) is 9%.
Example 13: produce enzymolysis modified egg membrane powder according to following method: with embodiment 4; Wherein during enzymolysis, add 537 acid proteases (enzyme preparation factory in Wuxi directly buys) in the mixed liquor after heat treatment, the addition of 537 acid proteases is 3% of an egg membrane powder quality, transfer pH2.8,35 ℃ of enzyme reaction temperatures, constant temperature stirs 1.5h, 4 ℃ static 12 hours, egg film liquid occurs faint yellow, and soluble protein (TCA-NSI) is 20% in the egg film liquid, and degree of hydrolysis (DH) is 9.8%.
Example 14: produce enzymolysis modified egg membrane powder according to following method: with embodiment 5; Wherein during enzymolysis, add 537 acid proteases (enzyme preparation factory in Wuxi directly buys) in the mixed liquor after heat treatment, the addition of 537 acid proteases is 4.5% of an egg membrane powder quality, transfer pH3.0,42 ℃ of enzyme reaction temperatures, constant temperature stirs 1.5h, 4 ℃ static 12 hours, egg film liquid occurs faint yellow, and soluble protein (TCA-NSI) is 40% in the egg film liquid, and degree of hydrolysis (DH) is 10%.
Example 15: produce enzymolysis modified egg membrane powder according to following method: with embodiment 6; Wherein during enzymolysis, add 537 acid proteases (enzyme preparation factory in Wuxi directly buys) in the mixed liquor after heat treatment, the addition of 537 acid proteases is 6% of an egg membrane powder quality, transfer pH3.2,50 ℃ of enzyme reaction temperatures, constant temperature stirs 1.5h, 4 ℃ static 12 hours, egg film liquid occurs faint yellow, and soluble protein (TCA-NSI) is 50% in the egg film liquid, and degree of hydrolysis (DH) is 20%.
Example 16: produce enzymolysis modified egg membrane powder according to following method: with embodiment 4; Wherein during enzymolysis, add compound protease (bacillus protease complex) in the mixed liquor after heat treatment, the addition of compound protease is 3% of an egg membrane powder quality, transfer pH6.0,45 ℃ of enzyme reaction temperatures, constant temperature stirs 2.0h, 4 ℃ static 12 hours, egg film liquid occurs faint yellow, and soluble protein (TCA-NSI) is 20% in the egg film liquid, and degree of hydrolysis (DH) is 9.0%.
Example 17: produce enzymolysis modified egg membrane powder according to following method: with embodiment 5; Wherein during enzymolysis, add compound protease (bacillus protease complex) in the mixed liquor after heat treatment, the addition of compound protease is 4.5% of an egg membrane powder quality, transfer pH7.0,55 ℃ of enzyme reaction temperatures, constant temperature stirs 2.0h, 4 ℃ static 12 hours, egg film liquid occurs faint yellow, and soluble protein (TCA-NSI) is 30% in the egg film liquid, and degree of hydrolysis (DH) is 13%.
Example 18: produce enzymolysis modified egg membrane powder according to following method: with embodiment 6; Wherein during enzymolysis, add compound protease (bacillus protease complex) in the mixed liquor after heat treatment, the addition of compound protease is 6% of an egg membrane powder quality, transfer pH8.0,65 ℃ of enzyme reaction temperatures, constant temperature stirs 2.0h, 4 ℃ static 12 hours, egg film liquid occurs faint yellow, and soluble protein (TCA-NSI) is 40% in the egg film liquid, and degree of hydrolysis (DH) is 18%.
The main component of egg film is a protein, exists with the form of glycoprotein, is similar to the formation of cell membrane protein.Contain 90% the protein of having an appointment, 3% liposome and 2% carbohydrate in the egg film.Protein wherein has keratin, collagen (most of is the I.V.X type), compound protein etc., as OC17 (ovocleidin), sialoglycoprotein (siatoprotein), OPN (osteo-pontin), ovalbumin (ovalburfin), lysozyme (lysozyme), leaf beautiful jade albumen (porphyrin), ovot-ransterrin, β-N-acetylglucosaminidase.The macromolecular compound that also contains a lot of solubilities in the egg film is as N-second phthalein Glucosamine galactolipin, glucuronic acid, hyaluronic acid, chondroitin sulfate, amino acid etc.Inorganic matter in the egg film has calcium, magnesium, chromium, and leaded hardly, aluminium, cadmium, mercury, iodine.In addition, the egg film also contains the sticking carbohydrate of class of warding off more, and the amino acid in the egg film is formed can see Table 1.
The amino acid of table 1 egg film is formed (%)
Proline (Pro) during egg film amino acid is formed, (Cys) is in the majority for cysteine, contains distinctive desmosine of elastin laminin and the distinctive hydroxyproline of collagen (Hyp) simultaneously, hydroxylysine (Hyly).Contain 10.38% cystine (Cys) and 3.05% methionine (Met) in the egg film approximately, as flour-dough improver, on the one hand, cystine is by changing between the protein molecule and the disulfide bond of protein molecule inside, weaken the structure of protein, promoted the formation of gluten.On the other hand, has high healthy nutritive value in the egg film again, easy soluble substance in the egg film such as N-diethylstilbestrol Glucosamine, galactolipin, glucuronic acid, hyaluronic acid, chondroitin sulfate etc., having multiple medicinal efficacies such as reducing blood lipid, anticoagulation, anti-inflammatory is one of characteristics of this reagent.
The egg memebrane protein is through after enzymolysis modified, peptide bond ruptures, make a large amount of hydrophilic bond, hydrophobic bonds etc. come out, can and gluten protein or starch between interact to form compound, combine with hydrophilic bond as gliadin, glutenin and oleophylic bond are closed etc., the gluten protein molecule is coupled to each other, form finer and closely woven more firm gluten network, promptly can improve gluten toughness, elasticity, intensity and anti-stirring property allow flour have the better processability energy, according to amino acid composition as can be known, the egg memebrane protein has high healthy nutritive value, can improve the trophic level of dough bread.
The specific composition of egg film and structures shape the particularity of egg film.At first, shell membrane is guaranteeing to play an important role the metabolism gas (O in the embryo development procedure aspect embryo's normal development
2And CO
2), moisture content and build the material of bone all by shell membrane infiltration transhipment by the chorion supply.From chorion under current potential or concentration gradient effect, through shell membrane be penetrated into the contacted arterial blood of shell membrane inner surface in, form blood calcium, thereby build the bone of nestling.These substance transportation speed depend on the thickness and the density of membrane fiber, as table 2.
Thickness, the density of table 2 membrana putaminis fiber
The disulfide bond that keratin molecule interchain in the egg film and chain include higher density, thus make molecular structure tight, and character is highly stable under field conditions (factors), Electronic Speculum figure such as Fig. 1.Protein in the wheat flour can be divided into gliadin (alcohol soluble protein), glutenin, wheat globulin, leucosin and sour molten albumen etc. according to its dissolution properties difference.Wherein back three kinds only account for about 10% of total protein, and all the other all are glutenin and gliadin.According to their operational characteristic, it can be divided into gluten protein and non-gluten protein two big classes.Non-gluten protein comprises wheat globulin, leucosin and sour molten albumen.In their water solubles or the rare salting liquid, dough is formed no correlation.Gluten protein comprises gliadin, accounts for 40～50% of total protein, and glutenin accounts for 30～40% of total protein, and they are main components of gluten, accounts for about 80% of flour protein total amount, dough is formed play an important role.Wherein gliadin has favorable extensibility based on intramolecular disulfide bond, but lacks flexibility and toughness.Glutenin is owing to can form in the molecule and intermolecular disulfide bond and springiness and toughness, but extensibility is relatively poor.Both combine with water when forming gluten, have remedied defective separately, make gluten high resilience and extensibility, and the effect of the carbon dioxide that produces when keeping the flour fermentation is arranged, and make the bread porous of baking soft.Therefore, the quality and quantity of gluten has material impact to Bread Quality.Gluten is a kind of protein complex of height aquation.When flour mixes with water when stirring, flour begins suction and changes, wherein, and the most importantly effect of being cross-linked with each other of gluten protein.The key of effect has disulfide bond, ionic bond, hydrogen bond, and what want most is disulfide bond.The molecule that forms gluten in the wheat flour contains a hundreds of amino acid residue, and 10% sulfur-containing amino acid (i.e. half deamination acid) is wherein arranged approximately, and it plays a part very important being cross-linked with each other of protein on.
Egg membrane powder among the present invention and enzymolysis modified egg membrane powder all contain a large amount of sulfur-containing amino acid (i.e. half deamination acid), be that a large amount of disulfide bond (S-S-) exist, make gluten protein combination better mutually, this combination both can be between protein main chain, also can carry out in protein molecule, it can make original unrelated gluten protein be cross-linked with each other into a macromolecular space network.And various disulfide bond is coupled to bigger cubic network mutually with protein main chain in the aleuronat molecule, other composition then is filled in the network, produce certain airtight effect and filling effect, and the egg film plays more important role to mutually combining between protein main chain, thereby elasticity, toughness, the better dough of extensibility have been formed, even bread and other Flour product have better quality and mouthfeel.Their big or small quality depends on quality and quantity, egg film addition and the kind of gluten, and has determined the quality of quality, volume, biceps, elasticity, intensity and other Flour product of bread.Therefore, when add egg membrane powder in dough after, it just can make the intermolecular disulfide group of gluten protein increase, and particularly to combining between protein molecule, increases the muscle effect thereby play.It is similar that this and oxidant improve principle to flour and dough characters.As glucose oxidase is the high-purity enzyme preparation that is made by fermentation of Aspergillus niger, it can become glucose oxidase gluconic acid, water and oxygen in flour, make the sulphur hydrogen bond in the gluten protein oxidized, form the disulfide bond of better network structure, thereby improved the institutional framework of gluten greatly, and make dough have good anti-mechanical agitation characteristic, and reach other operating characteristics, finally improved the quality of flour product.When the effect addition of modifying agent is identical with the glucose oxidase amount among the present invention, they are close to the improved effect of flour dough and bread, even be higher than the improving effect of glucose oxidase, and the modifying agent among the present invention has cheap, safe and reliable, also have alimentary health-care function etc., so the present invention has good application future.
Among the present invention, egg membrane powder is directly to extract from egg shell membrane.Egg membrane powder is directly used in dough, the Flour product as bread.Can obviously improve elasticity, the extensibility of dough, can reduce the dough fermentation time, improve the dough fermentation height, can improve the bulking value of bread, make the bread quality become soft, mouthfeel is better.Blank dough is through after the chilled storage, bread color and luster variation, and epidermis is thick and hard, and the epidermis drying has tangible vesicle to occur, bread crumb jaundice, obfuscation, during with hand tearing bread crumb, fracture does not have elasticity easily, falls assortedly during section easily, and mouthfeel is poor.But the crust that adds egg membrane powder or enzymolysis modified egg membrane powder is thin and epidermis is very soft, and vesicle does not appear in epidermis, and the outward appearance and the new sweet dough bread of this modifying agent difference of not adding are less, the crumb color is whiter, the internal structure homogeneous has certain elasticity with hand tearing bread crumb, and bread does not have peculiar smell.Along with the increase of addition, the toughness of bread crumb is become better and better.
Among the present invention, obviously increase of dough maximum swelling height behind the interpolation egg membrane powder (fermentation height) illustrates that the gas of holding of dough improves, and the dough gas retaining is good.Prolongation dough network with the chilled storage time has been subjected to heavy damage and the decline of yeast gas deliverability, and egg membrane powder can be strengthened the network structure of dough Flour product, can slow down the damaged condition of chilled storage, make dough have good final proof height dough.
Among the present invention, in the process of making wheaten food, add the operability that egg membrane powder can improve dough, increase the wheaten food volume, improve tissue, improve the product mouthfeel, effectively delay wearing out of wheaten food etc., but expanded application is in wheaten foods such as steamed bun.
Among the present invention, the egg membrane powder of flour improver and enzymolysis modified egg membrane powder can the liquid condition supplies, also can provide according to spraying dry powder or freeze-dried powder state.
Among the present invention, the egg membrane powder of flour improver and enzymolysis modified egg membrane powder can directly add in the dough, or it is added in the dough, as cooperating interpolation with other modifying agent as other form.
Among the present invention, can make the dough Flour product that better effect be arranged egg membrane powder and other modifying agent combination, for example can combine, to reach the improvement effect of bigger enhancing flour with emulsifying agent, oxidant, enzyme preparation, food colloid etc. according to operating position.
Emulsifying agent such as diacetyl tartarate list (two) glyceride (DATEM), stearoyl lactate (SSL), CSL (CSL) etc.Emulsifying agent can interact with gluten protein and form compound, hydrophilic radical is in conjunction with gliadin, lipophilic group is connected with each other the gluten protein molecule and becomes big molecule by little molecule in conjunction with glutenin, and then forms the fine and closely woven gluten network of sound construction.
Oxidant such as ascorbic acid etc., sulfydryl in its oxidable mucedin (SH), (S-S-) couple together by disulfide bond, thereby strengthened gluten network, and by eliminating the stability that glutathione that yeast itself contains improves protein, the freezing flour-dough biceps is improved, and baking quality is improved.
Food colloid such as sodium carboxymethylcellulose (CMC), kappa-carrageenan, Arabic gum and locust bean gum etc., colloid can reduce the injury that freezing flour-dough is freezing, thaw and cause, add the biceps that xanthans can increase dough in the freezing flour-dough prescription, increase the water absorption rate of dough and hold gas, improve freezing flour-dough bread specific volume and crumb water activity.
Enzyme preparation such as glucose oxidase, glutamine transaminage, AMS, pentosanase, lipoxygenase, lipase, phytase etc., can be gluconic acid as glucose oxidase with conversion of glucose under the condition that oxygen exists, produce hydrogen peroxide simultaneously, hydrogen peroxide is a kind of very strong oxidant, can with the sulfydryl in the protein molecular (SH) be oxidized to disulfide bond (thereby-S-S-) strengthen the intensity of gluten.
Embodiment 19: the application experiment of egg membrane powder of the present invention in producing bread
One, test objective
With egg membrane powder dough is improved test, detect the rheological characteristic effect of egg membrane powder dough by farinograph, flow graph, and by curing the effect of modifying agent to loaf volume, matter structure that detect.
Two, raw material and instrument
Flour (the safe limited company of face industry roc of China Oil and Food Import and Export Corporation), yeast (Angel Yeast Co., Ltd), egg membrane powder of the present invention, existing a kind of bread improver in the market, dough batch, proofing box, BRABENDER farinograph, flow graph, volume measuring instrument etc.
Three, test method
1) dough: the flour of getting 293 grams adds a kind of bread improver in egg membrane powder or the market, and addition is as shown in table 3, is that radix calculates with flour 100%, adds water 60%, salt 1%, yeast 1%, sugar 16% respectively.
2) flow process: play face → cut apart → leave standstill → moulding → ferment → cure → cool off → measure.
3) method: the face of beating is 3 minutes at a slow speed, refuels after quick 1 minute 3 minutes at a slow speed, to dough maturity again; Be divided into dough is divided into 80 gram doughs; Leave standstill is 5 minutes; Be shaped to and be twisted into circle; Fermentation is temperature 36-38 ℃, humidity 80-85%, 120 minutes time; Bake and bank up with earth and be 150 ℃, down fiery 220 ℃, the time 25min of getting angry; Cooling; Measure.
The rheological behavior measuring method: the parallel-plate spacing is 1mm, dough is placed between two flat boards leaves standstill 5min, so that residual pressure is lax, redundance is wiped off, and the lid that will scribble mineral oil then at once covers to prevent that water from dividing evaporation; Frequency scanning: strain: 1%; Temperature: 25 ℃; Frequency: 0.1～50Hz.
Four, experimental result
1, the farinograph measurement result sees Table 3; The crumpling resistance of length reflection stabilization time dough or to supporting the shear degradation performance.Stabilization time is long more, and the toughness of dough is good more, and the intensity of gluten is big more, and the processing of the process of dough is good more.As known from Table 3, add 0.5% egg membrane powder, the formation time of dough is obviously increased, illustrate that the interpolation of egg memebrane protein has influenced the forming process of gluten network structure, this may be because under external directed shearing force, and two in the dough between the mucedin polypeptide chain dredged key and secondary key (hydrogen bond, hydrophobic bond, Gao Zijian) fracture, and the egg membrane powder peptide chain reassembles into network by the key group of self with mucedin, form new spacial framework, promptly can the court of a feudal ruler have grown the formation time of its gluten.The reduction degree is the destroyed speed of dough in whipping process, promptly to churned mechanically ability to bear size, has reflected gluten strength.Its numerical value is big more, illustrates that gluten strength is more little, and dough easily because of subsiding or rheology loses original shape, makes its dough add the formula poor performance.Evaluation of estimate is to adopt the supporting specific ruler of farinograph to measure, and combines formation time, stabilization time, reduction degree and the rupture time etc. of dough, has weighed dough character comprehensively, and evaluation of estimate is high more, and flower characters is good more.As shown in Table 3, the interpolation of 0.5% egg membrane powder significantly reduces dough reduction degree, the also bigger raising of evaluation of estimate, this explanation adds a certain amount of egg membrane powder can make the flour farinograph property obtain bigger improvement, by table 3 and Fig. 2,3 as can be seen, the opaque performance figure of egg membrane powder of the present invention obviously will be higher than blank and market bread improver.
Table 3 farinograph experimental result
Annotate: contrast and be blank, do not add any modifying agent
2, the flow graph measurement result sees Table 4; As table 4 and Fig. 4,5,7 as can be known, in the frequency scanning process, add G ' and the G of egg membrane powder dough and " all obviously increase a lot; this is owing to contain a large amount of disulfide bond in the egg film (S-S-); the exchange reaction of dough glutenin subunit generation sulfydryl (being positioned at cysteine residues) and disulfide group (being positioned at cystine residue) under the orientation of mixer stirs; it is crosslinked that egg memebrane protein and glutenin subunit pass through intermolecular disulfide bond then, forms the orderly fibrous condensate of big molecule.The hydrogen bond that forms between mucedin and other albumen, also extremely important to stablizing structure of dough.The increase gradually that these all show as dough elasticity on the macroscopic view promptly causes G ' increase, frequency add during for 0.1Hz the increase of 0.5% egg memebrane protein G ' and remarkable positive correlation stabilization time of dough (p=0.028, r=0.918); Egg film DDGS has reasonable stickiness, " amplification maximum; this may intert in network skeleton because gliadin by the effect formation chondritic of disulfide bond, hydrogen bond and hydrophobic bond in peptide chain and the egg memebrane protein, combines with glutenin by non-covalent bond that but the egg film is the G of molten thing not.The slipping property and the stickiness that show as dough from macroscopic view improve, even G " increases.By table 4 and Fig. 4,5,7 as can be seen, the rheological behavior of egg membrane powder modifying agent of the present invention obviously will be higher than the bread improver in blank and market.
Table 4 flow graph experimental result
3, cure experimental result and see Table 5; As can be seen from Table 5, egg membrane powder can improve loaf volume effectively, makes quality become soft, improves the baking quality of bread, and effect is far superior to the market modifying agent.
Table 5 cures experimental result
Embodiment 20: enzymolysis modified egg membrane powder adds the test (method is with the test of above-mentioned egg membrane powder) of dough and bread to
1, the flow graph measurement result sees Table 6; The character of the class solid of storage modulus G ' reflection viscoelastic materials is elasticity, " character of class I liquid I of reflection viscoelastic materials is stickiness to loss modulus G; as table 6 and Fig. 4,6,7 as can be known; " be lower than interpolation egg membrane powder dough slightly, but be higher than the effect of market modifying agent in the frequency scanning process; add the G ' and the G of egg film modification product dough.
Table 6 flow graph experimental result
Annotate: blank and market modifying agent data and last same
2, cure experimental result and see Table 7; As can be seen from Table 7, more effectively increased bread specific volume, improved the baking quality of bread, illustrated after the modification more favourable the bread characteristic through curing the enzymolysis modified as can be known egg membrane powder of test.
Table 7 cures experimental result
The above only is the preferred embodiments of the present invention; be not limited to the present invention; for a person skilled in the art; the present invention can have various changes and variation; within the spirit and principles in the present invention all; any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (2)
1, as the egg membrane powder of flour improver, it is characterized in that egg membrane powder complies with following method and make: the fresh eggshell that will collect from life or bread, cake shop 40 ℃ of following water-baths flushings 5 minutes, is cooled to room temperature; Press mass ratio in the eggshell and add deionized water at 1: 1, pulverize with the 1000r/min high speed disintegrator, pulverized once every 10 seconds, the pulverizing time is 10 seconds at every turn, is crushed to the eggshell particle diameter between 1mm to 10mm, and the pulverizing time of pulverizing the 500g eggshell is 3～5 minutes; Put into deionized water than 1: 5 by eggshell and water quality after the pulverizing, egg film and eggshell are peeled off with the stirring rod stirring; Allow static 1 minute of mixed liquor, with 60 purposes sieve filtering suspension liquid, oversize is wet egg film meal, and 40 ℃ of dry wet egg film meal get egg film meal; Pulverize egg film meal with the omnipotent high speed disintegrator of 2400r/min, by 100 order molecular sieves, screenings is an egg membrane powder.
2,, it is characterized in that enzymolysis modified egg membrane powder makes according to following method as the enzymolysis modified egg membrane powder of flour improver:
A, preparation egg membrane powder: the fresh eggshell that will collect from life or bread, cake shop 40 ℃ of following water-baths flushings 5 minutes, is cooled to room temperature; Press mass ratio in the eggshell and add deionized water at 1: 1, pulverize with the 1000r/min high speed disintegrator, pulverized once every 10 seconds, the pulverizing time is 10 seconds at every turn, is crushed to the eggshell particle diameter between 1mm to 10mm, and the pulverizing time of pulverizing the 500g eggshell is 3～5 minutes; Put into deionized water than 1: 5 by eggshell and water quality after the pulverizing, egg film and eggshell are peeled off with the stirring rod stirring; Allow static 1 minute of mixed liquor, with 60 purposes sieve filtering suspension liquid, oversize is wet egg film meal, and 40 ℃ of dry wet egg film meal get egg film meal; Pulverize egg film meal with the omnipotent high speed disintegrator of 2400r/min, by 100 order molecular sieves, screenings is an egg membrane powder;
B, modified: add in the egg membrane powder water mix mixed liquor, the concentration of mixed liquor is 5.0g/200ml to 20.0g/200ml;
C, heat treatment: mixed liquor heat treatment 10 to 20 minutes in 100 ℃ of water-baths;
D, enzymolysis: add 2709 alkali proteases in the mixed liquor after heat treatment, the addition of 2709 alkali proteases is the 3-8% of egg membrane powder quality, transfer pH9.0～11.0,45～65 ℃ of enzyme reaction temperatures, constant temperature stirs 1.5h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, soluble protein (TCA-NSI) is 20%～40% in the egg film liquid, and degree of hydrolysis (DH) is 4.5%～15%; Or add trypsase (hydrolysising protease in the animal pancreas) in the mixed liquor after heat treatment, tryptic addition is the 2-3% of egg membrane powder quality, transfer pH7.5～9.8,35～55 ℃ of enzyme reaction temperatures, constant temperature stirs 2.5h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, soluble protein (TCA-NSI) is 15%～30% in the egg film liquid, and degree of hydrolysis (DH) is 5.5%～10%; Or add neutral proteinase (making) in the mixed liquor after heat treatment by fermentation of bacillus subtilis, the addition of neutral proteinase is the 3-5% of egg membrane powder quality, transfer pH6.0～8.0,35～50 ℃ of enzyme reaction temperatures, constant temperature stirs 3.0h, 4 ℃ static 12 hours, little light yellow appears in egg film liquid, soluble protein (TCA-NSI) is 10%～20% in the egg film liquid, and degree of hydrolysis (DH) is 3.5%～9%; Or add 537 acid proteases (enzyme preparation factory in Wuxi directly buys) in the mixed liquor after heat treatment, the addition of 537 acid proteases is the 3-6% of egg membrane powder quality, transfer pH2.8～3.2,35～50 ℃ of enzyme reaction temperatures, constant temperature stirs 1.5h, 4 ℃ static 12 hours, egg film liquid occurs faint yellow, soluble protein (TCA-NSI) is 20%～50% in the egg film liquid, and degree of hydrolysis (DH) is 9.8%～20%; Or add compound protease (bacillus protease complex) in the mixed liquor after heat treatment, the addition of compound protease is the 3-6% of egg membrane powder quality, transfer pH6.0～8.0,45～65 ℃ of enzyme reaction temperatures, constant temperature stirs 2.0h, 4 ℃ static 12 hours, egg film liquid occurs faint yellow, soluble protein (TCA-NSI) is 20%～40% in the egg film liquid, and degree of hydrolysis (DH) is 9.0%～18%;
E, accent pH: HCl or NaOH with 1mol/L regulate mmp reaction liquid, and making the pH value is 6.0～6.8;
F, enzyme goes out: 100 ℃ of water-baths 10 minutes make the thorough inactivation of enzyme;
G, the enzymolysis modified egg membrane powder that cools off liquidly, vacuum-packed 4～10 ℃ of refrigerations in back;
H, liquid enzymolysis modified egg membrane powder spraying or freeze drying get enzymolysis modified egg membrane powder.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101805773A (en) * | 2010-03-25 | 2010-08-18 | 淮安鸿玛生物科技有限公司 | Method for producing egg membrane protein |
| CN103238643A (en) * | 2012-09-24 | 2013-08-14 | 河北同和生物制品有限公司 | Biological calcium supplement special for flour |
| CN103483710A (en) * | 2013-09-25 | 2014-01-01 | 镇江市华银仪表电器有限公司 | Oil-proof and water-proof insulating cable material and preparation method thereof |
| CN108336362A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | The preparation method of alloy-coated material |
| CN111808215A (en) * | 2020-07-10 | 2020-10-23 | 上海林清轩生物科技有限公司 | Method for preparing bioactive substances from eggshell membrane by complex enzyme hydrolysis method |
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2009
- 2009-06-11 CN CNA200910033059XA patent/CN101574100A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805773A (en) * | 2010-03-25 | 2010-08-18 | 淮安鸿玛生物科技有限公司 | Method for producing egg membrane protein |
| CN101805773B (en) * | 2010-03-25 | 2012-07-18 | 淮安鸿玛生物科技有限公司 | Method for producing egg membrane protein |
| CN103238643A (en) * | 2012-09-24 | 2013-08-14 | 河北同和生物制品有限公司 | Biological calcium supplement special for flour |
| CN103238643B (en) * | 2012-09-24 | 2014-09-24 | 河北同和生物制品有限公司 | Biological calcium supplement special for flour |
| CN103483710A (en) * | 2013-09-25 | 2014-01-01 | 镇江市华银仪表电器有限公司 | Oil-proof and water-proof insulating cable material and preparation method thereof |
| CN108336362A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | The preparation method of alloy-coated material |
| CN111808215A (en) * | 2020-07-10 | 2020-10-23 | 上海林清轩生物科技有限公司 | Method for preparing bioactive substances from eggshell membrane by complex enzyme hydrolysis method |
| CN111808215B (en) * | 2020-07-10 | 2022-05-27 | 上海林清轩生物科技有限公司 | Method for preparing bioactive substances from eggshell membrane by complex enzyme hydrolysis method |
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