CN1318510C - Edible membrane of cross-linking cereal gliadin and its preparation method - Google Patents
Edible membrane of cross-linking cereal gliadin and its preparation method Download PDFInfo
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- CN1318510C CN1318510C CNB2005100604799A CN200510060479A CN1318510C CN 1318510 C CN1318510 C CN 1318510C CN B2005100604799 A CNB2005100604799 A CN B2005100604799A CN 200510060479 A CN200510060479 A CN 200510060479A CN 1318510 C CN1318510 C CN 1318510C
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- cereal
- membrane
- gliadin
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- 239000004472 Lysine Substances 0.000 description 1
- 102000014171 Milk Proteins Human genes 0.000 description 1
- 108010011756 Milk Proteins Proteins 0.000 description 1
- 244000115721 Pennisetum typhoides Species 0.000 description 1
- 235000007195 Pennisetum typhoides Nutrition 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 235000008515 Setaria glauca Nutrition 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 108010046377 Whey Proteins Proteins 0.000 description 1
- 102000007544 Whey Proteins Human genes 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SHZGCJCMOBCMKK-SXUWKVJYSA-N alpha-L-fucose Chemical compound C[C@@H]1O[C@@H](O)[C@@H](O)[C@H](O)[C@@H]1O SHZGCJCMOBCMKK-SXUWKVJYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
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- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 108010050792 glutenin Proteins 0.000 description 1
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- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
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Landscapes
- Peptides Or Proteins (AREA)
Abstract
The present invention discloses an edible membrane of cross-linking cereal alcohol soluble protein and a preparation method of the membrane. The edible membrane of cross-linking cereal alcohol soluble protein comprises the following components according to the proportion by weight: 100 shares of alcohol soluble protein, 20 shares to 100 shares of plasticizing agent, 0.5 share to 1 share of hydrophobic modifier, 0.05 share to 0.1 shares of anti-oxidant, 0 share to 0.1 share of preservative and 1 share to 7 shares of cross linking agent. The membrane is made by a solution casting method or a plastic processing method through high-temperature cross-linking reaction. The membrane adopts cereal alcohol soluble protein as membrane forming matrix and adopts diglycol aldehyde as a new cross linking agent. Polyol plasticizer and hydrophobic modifier, antioxidant and preservative used as food additives are added in order to enhance the mechanical strength, the toughness, the hydrophobic property and the ageing resistance of the edible membrane of cross-linking cereal alcohol soluble protein.
Description
Technical field
The present invention relates to a kind of edible membrane of cross-linking cereal gliadin and preparation method thereof.
Background technology
A large amount of use plastic wrappings cause plastic garbage to spread unchecked, the serious harm ecotope.After the nineties in 20th century, " environment and development " becomes the focus of world attention problem.Pack the replacement conventional plastic with the edibility material and pack, develop so-called " environmentally friendly packing material ", become one of development trend of food product pack industry.In the research and development of numerous " environmentally friendly packing materials ", use the natural biological polymer and make edible packing membrane, be the important topic of food product pack development of new techniques.The edible packaging material has functions such as favorable mechanical performance and protection against the tide, oxygen barrier, fresh-keeping, antiultraviolet, can stop the food moisture absorption, dehydration, delays Food Oxidation, rotten.The main raw material of edible packaging material comprises polysaccharide, protein, lipid etc., and wherein protein comprises wheat-gluten, zein, soybean protein isolate and whey-protein etc.Gennadios etc. have commented based on the edible film of gluten powder, soybean protein, zein, milk proteins, Semen arachidis hypogaeae protein or collagen protein etc. or the preparation method and performance (the Gennadios A. of coated material, McHugh TH., WellerCL., Krochta JM., Edible coatings and films based on proteins.In Edible coatingsand films to improve food quality; Krochta JM., Baldwin EA., Nisperos-CarriedoMO., Eds., Technomic Publishing Co.:Lancaster, PA, 1994; 201-277).
The natural polymer that protein is made up of multiple amino acids, the interaction of hydrogen bond that intermolecular existence is stronger and intramolecularly/intermolecular disulfide bond.Usually solution or the suspension with protein, softening agent and other reagent is filming medium, adopt solution casting method to prepare protein film (Anker A., Foster GA., LoaderMA..Method of preparing gluten containing films and coatings. United States Patent (USP) 3.653,925,1972; Aydt TP., Weller CL., Testin RF., Mechanical and barrier properties of ediblecorn and wheat protein films.Trans.ASAE, 1991,34,207-211), improve protein solubility, improve membrane material characteristic (Gennadios A. by heat or acid-alkali treatment, Brandenburg AH., WellerCL., Testin RF., Effect of pH on properties of wheat gluten and soy protein isolatefilms.J.Agric.Food.Chem., 1993,41:1835-1839; Roy S., Gennadios A., WellerCL., Zeece MG., Testin RF., Physical and molecular properties of wheat gluten filmscast from heated film-forming solutions.J.Food Sci., 1999,64:57-60).
The a large amount of organic solvents of solution legal system film consumption.People begin to explore the conventional forming technique of polymer and prepare albuminous membranae in recent years, disclose " preparation method of water-proof and heat-resistant plastic soybean protein film " as Chinese patent 00116036.2.Intermolecular strong interaction makes the thermoforming processing of protein material be difficult for implementing, and high temperature process causes the protein thermolysis easily.Thereby, need add a large amount of softening agent during the protein material thermoforming, to reduce molecular interaction, improve the molecular chain snappiness.Spendable softening agent has water or polyvalent alcohol such as glycerine, monose, disaccharides or oligose etc.Discoveries such as Mangavel, the mechanical property of the gluten powder film of thermoforming is better than solution casting film (Mangavel C., Rossignol N., Perronnet A., Barbot J., Popineau Y., Gueguen J., Properties and microstructure of thermo-pressed wheatgluten films:a comparison with cast films.Biomacromolecules, 2004,5,1596-1601).
In preparation plasticising protein composition process, strong shearing can make the intermolecular disulfide bond fracture, reduces protein molecular weight.Under comparatively high temps, form chemically crosslinked between the protein molecule again.This provides theoretical foundation for adopting conventional device of plastic processing to prepare the cross-linked type protein in grain material.Employing mechanically mixing such as Domenek prepare the plasticising gluten powder, adopt mould pressing method to prepare crosslinked sample (Domenek S., Morel MH., Redl A., Guilbert S., Rheological investigation of swollen gluten polymer networks:effects of process parameters on cross-link density.Macrom.Symp., 2003,200:137-146), and investigate the plasticising gluten powder extrude complete processing (Pommet M., Redl A., MorelMH., Domenek S., Guilbert S., Thermoplastic processing of protein-based bioplastics:chemical engineering aspects of mixing, extrusion and hot molding.Macrom.Symp., 2003,197:207-218).
Over-all properties based on the material of grain protein is relatively poor, needs to handle or chemically crosslinked wait rigidity, barrier, thermotolerance and the hydrophobicity that improves material through uv irradiation, gamma-radiation irradiation, enzyme.Some can with the material of amino in the protein molecule, amide group, hydroxyl, thiol group generation chemical reaction, as halogenation acetic ester, diimine ester, two-n-hydroxyl-succinimide, dialdehyde or two ketone reagent, all can be used as proteinic chemical cross-linking agent, wherein the most frequently used is aldehydes reagent such as formaldehyde, oxalic dialdehyde or glutaraldehyde.
The present invention is a novel crosslinker to replace diglycol aldehyde, adopts solution casting method or plasticity-processing method to prepare the cross-linking cereal gliadin film.The present invention uses polyol plasticiser nontoxic or that toxicity is extremely low, improves the plasticity-processing characteristics of cereal gliadin; Use is as hydrophobically modified agent, oxidation inhibitor and the sanitas etc. of food safety auxiliary agent, with the hydrophobicity that improves the cross-linking cereal gliadin film and performance such as anti-aging.Based on the prepared cross-linking cereal gliadin film of the present invention, can be used for the edible packing membrane of food, sugar prod, medicine etc.
Summary of the invention
The purpose of this invention is to provide a kind of edible membrane of cross-linking cereal gliadin and preparation method thereof.
Edible membrane of cross-linking cereal gliadin contains cereal gliadin 100 weight parts, softening agent 20~100 weight parts, hydrophobically modified agent 0.5~1 weight part, oxidation inhibitor 0.05~0.1 weight part, sanitas 0~0.1 weight part and linking agent 1~7 weight part.
Cereal gliadin is wheat gliadin, hordein, oat prolamine, secalin, rice prolamine, maize prolamine, zein or kafirin; Softening agent is 1,2-propylene glycol, 1, ammediol, glycol ether, triglycol, Tetraglycol 99, glycerine, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2,3-butyleneglycol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, glyceryl monoacetate or glyceryl diacetate; The hydrophobically modified agent is stearic acid, oxystearic acid, n-butyl stearate, single stearic acid glycerine lipoprotein, methyl hydroxystearate, soybean oil, peanut oil, Semen Maydis oil, Rice pollard oil, rapeseed oil, Oleum Gossypii semen, sunflower seed oil or camellia seed oil; Oxidation inhibitor is butylhydroxy anisole, tea-polyphenol, tocopherol, Progallin A, Tenox PG, Stabilizer GA 8, lauryl gallate, gallic acid octadecyl ester, xitix, Quicifal, D-saccharosonic acid, Sorbitol Powder or maltose alcohol; Sanitas is sthyl sorbate, Sorbic Acid butyl p-hydroxybenzoate, dehydroacetic acid (DHA), Tegosept M, propylparaben or ethyl p-hydroxybenzoate; Linking agent is D '-methoxyl group diglycol aldehyde, D '-methoxyl group-D-methylol diglycol aldehyde, L '-methoxyl group-L-methyl diglycol aldehyde or D '-methoxyl group-D ', D-dihydroxymethyl diglycol aldehyde.
Adopt the preparation method of the edible membrane of cross-linking cereal gliadin of solution casting method to be: the ethanol/water mixture with 60~90% is a solvent, add cereal gliadin 100 weight parts, 30~50 ℃ of following violent stirring, be configured to the solution that concentration is 50~100mg/ml, add softening agent 20~100 weight parts, hydrophobically modified agent 0.5~1 weight part, oxidation inhibitor 0.05~0.1 weight part, sanitas 0~0.1 weight part and linking agent 1~7 weight part, stir and obtain film-forming soln, be poured on the slick plastic plate, after treating that solvent evaporates finishes, at 50~120 ℃ of thermal treatment 0.5~1h, take off film, obtain edible membrane of cross-linking cereal gliadin.
Adopt the preparation method of the edible membrane of cross-linking cereal gliadin of rolling process to be: cereal gliadin 100 weight parts, softening agent 20~100 weight parts, hydrophobically modified agent 0.5~1 weight part, oxidation inhibitor 0.05~0.1 weight part and sanitas 0~0.1 weight part are carried out pre-mixing, then at 10~40 ℃ of mechanically milling 5~15min, and in mixing process, add linking agent 1~7 weight part, obtain the prolamine composition, send into rolling press calendering film forming, through 150~180 ℃ of thermal treatment 2~10min, obtain edible membrane of cross-linking cereal gliadin.
Advantage of the present invention is:
1) cereal gliadin does not need through chemistry or physically modified, and production cost is low;
2) utilize the replacement diglycol aldehyde to be novel crosslinker, adopt solution casting method or conventional plastic working method to prepare edible membrane of cross-linking cereal gliadin, production technique is simple;
3) edible membrane of cross-linking cereal gliadin contains softening agent, hydrophobically modified agent, sanitas and oxidation inhibitor, machine-shaping easily, and have higher hydrophobicity and ageing resistance;
4) edible membrane of cross-linking cereal gliadin or its degradation production are all nontoxic, safe to eat.
Embodiment
It is the prolamine of wheat, barley, oat, rye, rice, maize, corn or sorghum seed that the present invention uses cereal gliadin.Contain the prolamine of forming by nonpolar amino acid more than 40% in these cereal kernel protein.
The technology of extracting wheat gliadin from wheat gluten flour (also claiming vital wheat gluten) is known, as in following document, stating, the document is incorporated herein by reference: " sesame is learned by department; Li Jianwei; Wang Jinshui, girth intelligence, the research of gliadine and glutenin extraction conditions. Zhengzhou Engineering College's journal; 2004,25 (3): 33-39 ".
The technology of extracting hordein from barley grain or seed powder is known, as in following document, stating, these documents are incorporated herein by reference: " Yan Qichuan; yellow second place; Xu Yuan; the seeds prolamine electrophoresis method that ISTA on probation recommends is identified barley and wheat breed. Acta Agronomica Sinica, 1992,18 (1): 61-68; The Dong ox, Wang Lirong, Lan Lan, Zhang Deyi, the dissolution characteristics of high-lysine component research in the hordein. Botany Gazette, 1989,31:689-695 ".
The technology of extracting the oat prolamine from the oat grain powder is known, as in following document, stating, the document is incorporated herein by reference: " Li Lianchao; Lei Jianju, Wang Peihong, neat Accent; the rp-hplc analysis seeds prolamine characterizes the oat germplasm; chromatogram, 1991,9 (4): 253-256 ".
The technology of extracting secalin from rye seed powder is known, as in following document, stating, the document is incorporated herein by reference: " Charbonnier L, Terce-Laforgue T., Mosse J.; Ryeprolamins:extractability; separation, and characterization, J.Agric.Food Chem.; 1981,29:968-973 ".
The technology of extracting rice protein from rice meal, rice slag or rice are poor is known, as stating in following document, the document is incorporated herein by reference: " Wang Zhangcun, Yao Huiyuan: Extraction of Rice Protein from Rice Dregs research. grain and fodder industry; 2003, (8): 37-38 ".In addition, Chinese patent 03134973.0 discloses " extracting the method for rice protein from rice ", Chinese patent 03134972.2 discloses " alkaline process extracts the method for rice protein ", and Chinese patent 200410039303.0 discloses " being raw material extraction rice protein and the processing method of making Starch rice with the rice ".
The technology of extracting the maize prolamine from degreasing maize seed or degreasing maize seed powder is known; as in following document, stating; the document is incorporated herein by reference: " Okoh PN; Nwasike CC.; Ikediobi CO.; Studies on Seed Protein of Pearl Millets.1.Amino Acid Compositionof Protein Fractions of Early and Late Maturing Varieties.J.Agric.Food Chem.; 1985; 33,55-57 ".
The technology of extracting zein from Zein powder (also claiming corn gluten meal) is known, as in following document, stating, the document is incorporated herein by reference: " Zhang Zhong; Qi Aiyun; zein extraction process and Study on Functional; grain and fodder industry, 2004 (9): 21-23. " Chinese patent 00101222.3 discloses the technology of " using preparing alcohol-soluble corn protein membrane from corn gluten ", has wherein described the method for extracting zein from Zein powder.Highly purified zein can be selected from the commerical prod of content of prolamine 〉=80% (butt), can buy zein from Japan and the pure medicine of light company, U.S. Freeman Industries company.
The technology of extracting kafirin from sorghum seed or sorghum flour is known, as in following document, stating, these documents are incorporated herein by reference: " Emmambux MN.; Taylor JRN.; Sorghumkafirin interaction with various phenolic compounds.J.Sci.Food Agric.; 2003,83:402-407; Gao C., Taylor J., Wellner N., Byaruhanga YB., Parker ML., Mills ENC., Belton PS., Effect of preparation conditions on protein secondary structure andbiofilm formation of Kafirin.J.Agric.Food Chem., 2005,53:306-312; Huang CP., Hejlsoe-Kohsel E., Han XZ., Protelytic activity in sorghum flour and its interferencein protein analysis.Cereal Chem., 2000,77:343-344 ".
It is solvent that the present invention advises adopting 60~90% ethanol/water mixture, under 30~50 ℃, agitation condition, from wheat gluten flour, degreasing barley grain powder, degreasing oat grain powder, degreasing rye seed powder, rice protein powder, degreasing maize seed powder, Zein powder and degreasing sorghum seed powder, extract cereal gliadin, obtain extracting solution through centrifugal or filtering separation, be directly used in the preparation of edible membrane of cross-linking cereal gliadin.When adopting this method, can be according to the concentration of different solid than prolamine in the control extracting solution.After recording prolamine concentration, directly in extracting solution, add softening agent, hydrophobically modified agent, oxidation inhibitor, sanitas and the linking agent of defined amount of the present invention, obtain film-forming soln, be used for casting method and prepare edible membrane of cross-linking cereal gliadin.Certainly, also can extracting solution is concentrated, dry, obtain the prolamine solid, by defined concentration wiring solution-forming of the present invention, and softening agent, hydrophobically modified agent, oxidation inhibitor, sanitas and the linking agent of adding specified amount, obtain film-forming soln.
Dried prolamine solid can be used for as the described thermoplasticity processing of claim 9 of the present invention film forming, i.e. rolling process film forming.The first step is carried out pre-mixing with grain protein, softening agent, hydrophobically modified agent, oxidation inhibitor and sanitas.The present invention is not very strict to premixed requirement, can adopt the mixing instrument of high-speed mixer or Haake, mixed at room temperature 2~10min under 50~3000r/min rotating speed; Also can the material elementary mixing evenly be got final product by the manual 10~30min that stirs of instrument.Second step was adopted further mixing above-mentioned pre-mixing material of mechanical mixing method, can adopt mill at 10~40 ℃ of following mechanically milling 5~15min, and add linking agent in mixing process, obtained the cereal gliadin composition.The 3rd step was sent the cereal gliadin composition into rolling press calendering film forming, and film is carried out 2~10min heat cross-linking at 150~180 ℃, obtained edible membrane of cross-linking cereal gliadin.
One of key of the present invention is that employing replacement diglycol aldehyde is D '-methoxyl group diglycol aldehyde, D '-methoxyl group-D-methylol diglycol aldehyde, L '-methoxyl group-L-methyl diglycol aldehyde or D '-methoxyl group-D ', D-dihydroxymethyl diglycol aldehyde is a novel crosslinker, and albuminous membranae is carried out chemically crosslinked.The molecular structure that replaces diglycol aldehyde is
R in the formula
1=R
2=H, R
1=H and R
2=CH
2OH, R
1=H and R
2=CH
3, or R
1=R
2=CH
2OH.Replacing diglycol aldehyde can the D-erythrose, D-threose, D-pectinose, D-wood sugar, D-allose, D-glucose, D-Ganluo sugar, D-gulose, D-semi-lactosi, D-fructose, D-sorbose, L-Fucose or L-rhamnosyl are raw material, makes through methyl glucosideization, periodate oxidation two-step reaction.
The method of monose methyl glucoside is known, as in following document, stating, the document is incorporated herein by reference: " Hockett RC.; Phelps FP.; Hudson CS; Relations between rotatory powerand structure in the sugar group.XXXIII.The alpha and beta methyl pyranos ides ofL-fucose (L-galactomethylose) and their triacetates.J.Am.Chem.Soc.; 1939,61:1658-1660 ".The present invention's suggestion prepares the methyl glucoside as follows:
In container, add methyl alcohol, feed dried hydrogen chloride gas, making the hydrogenchloride mass concentration is 1%, add the dry monose of crossing then, be made into the monose mass content and be 10% suspension, under refluxad react 8h, the cooling back is neutralized to pH=7.0~8.0 with saturated sodium hydroxide solution, methyl alcohol is removed in underpressure distillation, with the acetic acid ethyl dissolution solid and carry out recrystallization, filters and obtains methylglycoside.
It is known preparing the method that replaces diglycol aldehyde by the methyl glucoside, as in following document, stating, the document is incorporated herein by reference: " Maclay WD.; Hann RM.Hudson CS.; The cleavage of thecarbon chains of some methyl aldohexomethylo-pyranosides by oxidation withperiodic acid.J.Am.Chem.Soc.; 1939,61:1660-1666 ".The present invention's suggestion preparation as follows replaces diglycol aldehyde:
It is 3~10% the aqueous solution that the methyl glucoside is made into mass concentration, and adding mole number is the Periodic acid of 2.1 times of methyl glucosides, reacts 12~24h under room temperature, lucifuge condition, be neutralized to neutrality with 10% hot strontium hydroxide solution, remove by filter precipitation, filtrate is vacuumized at 50~60 ℃ be concentrated into drying, use alcohol extraction solid 4 times, filtrate is merged, be concentrated into syrupy shape, use ether dissolution, add sherwood oil, room temperature is placed 16h, filters to obtain the dialdehyde crystal.
Replace diglycol aldehyde and contain two active aldehydes, can be in wide temperature range with the prolamine molecule on amido following reaction takes place,
Thereby two or more prolamines are crosslinked, form cross-linked network.Gliadin represents the prolamine molecule in the formula.
Film forming properties, hydrophobic performance and the ageing resistance of giving the edible membrane of cross-linking cereal gliadin excellence are one of keys of the present invention.Being used of softening agent and hydrophobically modified agent makes the cereal gliadin composition except can adopting the solution casting method film forming, also can adopt macromolecular material thermoplasticity processing units and method film forming.The intermolecular crosslinked action of the use of hydrophobically modified agent and prolamine is greatly improved the hydrophobicity of cross-linking cereal gliadin film.Simultaneously, the present invention adopts oxidation inhibitor and the sanitas that uses as foodstuff additive, improves the storage time and the ageing-resistant performance of cross-linking cereal gliadin film.
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
The preparation method who with the wheat gliadin is the feedstock production edible membrane of cross-linking cereal gliadin is: take by weighing the 100g gluten powder, add in the ethanol/water mixed solvent of 500ml60%, extract wheat gliadin at 30 ℃ of induction stirring 2h, centrifugation obtains supernatant liquor, replenishing suitable 60% ethanol/water mixed solvent, to make prolamine concentration be 50mg/ml, get prolamine solution 100ml, add 1g 1, the 2-propylene glycol, the 25mg stearic acid, 2.5mg butylhydroxy anisole and 50mg D '-methoxyl group diglycol aldehyde, stir and obtain film-forming soln, be poured on the slick plastic plate, after treating that solvent evaporates finishes, at 50 ℃ of thermal treatment 1h, take off film, obtain edible membrane of cross-linking cereal gliadin.
Embodiment 2:
The preparation method who with the hordein is the feedstock production edible membrane of cross-linking cereal gliadin is: take by weighing 100g barley grain powder, add in the ethanol/water mixed solvent of 500ml90%, extract wheat gliadin at 50 ℃ of induction stirring 2h, centrifugation obtains supernatant liquor, replenishing suitable 90% ethanol/water mixed solvent, to make prolamine concentration be 100mg/ml, get prolamine solution 100ml, add 10g 1, ammediol, the 100mg oxystearic acid, the 10mg tea-polyphenol, 10mg sthyl sorbate and 700mg D '-methoxyl group-D-methylol diglycol aldehyde, stir and obtain film-forming soln, be poured on the slick plastic plate, after treating that solvent evaporates finishes, at 120 ℃ of thermal treatment 30min, take off film, obtain edible membrane of cross-linking cereal gliadin.
Embodiment 3:
With the oat prolamine is that the preparation method of feedstock production edible membrane of cross-linking cereal gliadin is: take by weighing 10g oat prolamine, in the ethanol/water mixed solvent of adding 70%, be made into the solution that mass concentration is 80mg/ml, add the 5g glycol ether, the 80mg n-butyl stearate, the 8mg tocopherol, 80mg Sorbic Acid butyl p-hydroxybenzoate and 300mgL '-methoxyl group-L-methyl diglycol aldehyde, stir and obtain film-forming soln, be poured on the slick plastic plate, after treating that solvent evaporates finishes, at 100 ℃ of thermal treatment 45min, take off film, obtain edible membrane of cross-linking cereal gliadin.
Embodiment 4:
The preparation method who with the secalin is the feedstock production edible membrane of cross-linking cereal gliadin is: take by weighing the 100g secalin, the 40g triglycol, the 1g single stearic acid glycerine lipoprotein, 100mg Progallin A and 80mg dehydroacetic acid (DHA), place in the mixing instrument of Haake, mixed at room temperature 5min under the 50r/min rotating speed, the mixture material is placed in the mill, in 10 ℃ of mixing 15min, and in mixing process, add 300mgD '-methoxyl group-D ', D-dihydroxymethyl diglycol aldehyde, obtain the grain protein composition, through four-roll calender calendering film forming, at 150 ℃ of crosslinked 10min of warm air, obtain edible membrane of cross-linking cereal gliadin.
Embodiment 5:
With the rice prolamine is that the preparation method of feedstock production edible membrane of cross-linking cereal gliadin is: take by weighing 100g rice prolamine, the 40g Tetraglycol 99, the 1g methyl hydroxystearate, 100mg Tenox PG and 80mg Tegosept M, place in the high-speed mixer, mixed at room temperature 2min under the 3000r/min rotating speed, the mixture material is placed in the mill, in 40 ℃ of mixing 5min, and in mixing process, add 300mg D '-methoxyl group-D ', D-dihydroxymethyl diglycol aldehyde, obtain the grain protein composition, through tri-roll press machine calendering film forming, at 180 ℃ of crosslinked 2min of warm air, obtain edible membrane of cross-linking cereal gliadin.
Embodiment 6:
With the maize prolamine is that the preparation method of feedstock production edible membrane of cross-linking cereal gliadin is: respectively with the maize prolamine replace the oat prolamine, with glycerine replace glycol ether, with the positive butyl ester of soybean oil place of magnesium stearate, replace tocopherol, replace the Sorbic Acid butyl p-hydroxybenzoate with propylparaben with Stabilizer GA 8, all the other conditions are with embodiment 3.
Embodiment 7:
The preparation method who with the zein is the feedstock production edible membrane of cross-linking cereal gliadin is: respectively with zein replace secalin, with 1, the 2-butyleneglycol replaces triglycol, replaces single stearic acid glycerine lipoprotein, replaces Progallin A, replaces dehydroacetic acid (DHA) with ethyl p-hydroxybenzoate with lauryl gallate with peanut oil, and all the other conditions are with embodiment 4.
Embodiment 8:
The preparation method who with the kafirin is the feedstock production edible membrane of cross-linking cereal gliadin is: respectively with kafirin replace the rice prolamine, with 1, the 3-butyleneglycol replaces Tetraglycol 99, replaces methyl hydroxystearate, replaces Tenox PG with the gallic acid octadecyl ester with Semen Maydis oil, and all the other conditions are with embodiment 5.
Embodiment 9~14:
The preparation method who with the wheat gliadin is the feedstock production edible membrane of cross-linking cereal gliadin is: respectively with 1,4-butyleneglycol, 2,3-butyleneglycol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, glyceryl monoacetate or glyceryl diacetate replace 1, the 2-propylene glycol, all the other conditions are with embodiment 1.
Embodiment 15~19:
The preparation method who with the hordein is the feedstock production edible membrane of cross-linking cereal gliadin is: with Rice pollard oil, rapeseed oil, Oleum Gossypii semen, sunflower seed oil or camellia seed oil place of magnesium stearate, all the other conditions are with embodiment 2 respectively.
Embodiment 20~24:
With the oat prolamine is that the preparation method of feedstock production edible membrane of cross-linking cereal gliadin is: replace tocopherol with xitix, Quicifal, D-saccharosonic acid, Sorbitol Powder or maltose alcohol respectively, all the other conditions are with embodiment 3.
The invention provides a kind of edible membrane of cross-linking cereal gliadin and preparation method thereof.Main raw material grain protein involved in the present invention belongs to renewable agricultural resource, wide material sources; The preparation method and the technical process of cereal gliadin edible film involved in the present invention are simple, are easy to promotion and implementation.The edible membrane of cross-linking cereal gliadin that makes based on the present invention has excellent mechanical property, hydrophobicity and ageing resistance, does not contain harmful additive, can be used for the edible packing membrane of food, sugar prod and medicine etc.
Claims (7)
1. edible membrane of cross-linking cereal gliadin, it is characterized in that, it comprises cereal gliadin 100 weight parts, softening agent 20~100 weight parts, hydrophobically modified agent 0.5~1 weight part, oxidation inhibitor 0.05~0.1 weight part, sanitas 0~0.1 weight part and linking agent 1~7 weight part, the hydrophobically modified agent is a stearic acid, oxystearic acid, n-butyl stearate, single stearic acid glycerine lipoprotein, methyl hydroxystearate, soybean oil, peanut oil, Semen Maydis oil, Rice pollard oil, rapeseed oil, Oleum Gossypii semen, sunflower seed oil or camellia seed oil, linking agent is D '-methoxyl group diglycol aldehyde, D '-methoxyl group-D-methylol diglycol aldehyde, L '-methoxyl group-L-methyl diglycol aldehyde or D '-methoxyl group-D ', D-dihydroxymethyl diglycol aldehyde.
2. edible membrane of cross-linking cereal gliadin according to claim 1, it is characterized in that described cereal gliadin is wheat gliadin, hordein, oat prolamine, secalin, rice prolamine, maize prolamine, zein or kafirin.
3. edible membrane of cross-linking cereal gliadin according to claim 1 is characterized in that described softening agent is 1,2-propylene glycol, 1, ammediol, glycol ether, triglycol, Tetraglycol 99, glycerine, 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 2,3-butyleneglycol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, glyceryl monoacetate or glyceryl diacetate.
4. edible membrane of cross-linking cereal gliadin according to claim 1, it is characterized in that described oxidation inhibitor is butylhydroxy anisole, tea-polyphenol, tocopherol, Progallin A, Tenox PG, Stabilizer GA 8, lauryl gallate, gallic acid octadecyl ester, xitix, Quicifal, D-saccharosonic acid, Sorbitol Powder or maltose alcohol.
5. edible membrane of cross-linking cereal gliadin according to claim 1, it is characterized in that described sanitas is sthyl sorbate, Sorbic Acid butyl p-hydroxybenzoate, dehydroacetic acid (DHA), Tegosept M, propylparaben or ethyl p-hydroxybenzoate.
6. the preparation method of an edible membrane of cross-linking cereal gliadin as claimed in claim 1, it is characterized in that, ethanol/water mixture with 60~90% is a solvent, add cereal gliadin 100 weight parts, 30~50 ℃ of following violent stirring, be configured to the solution that concentration is 50~100mg/ml, add softening agent 20~100 weight parts, hydrophobically modified agent 0.5~1 weight part, oxidation inhibitor 0.05~0.1 weight part, sanitas 0~0.1 weight part and linking agent 1~7 weight part, stir and obtain film-forming soln, be poured on the slick plastic plate, after treating that solvent evaporates finishes, at 50~120 ℃ of thermal treatment 0.5~1h, take off film, obtain edible membrane of cross-linking cereal gliadin.
7. the preparation method of an edible membrane of cross-linking cereal gliadin as claimed in claim 1, it is characterized in that, with cereal gliadin 100 weight parts, softening agent 20~100 weight parts, hydrophobically modified agent 0.5~1 weight part, oxidation inhibitor 0.05~0.1 weight part and sanitas 0~0.1 weight part carry out pre-mixing, then at 10~40 ℃ of mechanically milling 5~15min, and in mixing process, add linking agent 1~7 weight part, obtain the prolamine composition, send into rolling press calendering film forming, through 150~180 ℃ of thermal treatment 2~10min, obtain edible membrane of cross-linking cereal gliadin.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1232368A (en) * | 1996-10-07 | 1999-10-20 | 沃尼尔·朗伯公司 | Process for formation of plasticized proteinaceous materials, and composition contg. same |
CN1302550A (en) * | 2000-01-01 | 2001-07-11 | 天津商学院 | Process for preparing alcohol-soluble corn protein membrane from corn gluten |
CN1463611A (en) * | 2002-06-06 | 2003-12-31 | 华中农业大学 | Process for production of biological degradable chewing gum |
-
2005
- 2005-08-25 CN CNB2005100604799A patent/CN1318510C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1232368A (en) * | 1996-10-07 | 1999-10-20 | 沃尼尔·朗伯公司 | Process for formation of plasticized proteinaceous materials, and composition contg. same |
CN1302550A (en) * | 2000-01-01 | 2001-07-11 | 天津商学院 | Process for preparing alcohol-soluble corn protein membrane from corn gluten |
CN1463611A (en) * | 2002-06-06 | 2003-12-31 | 华中农业大学 | Process for production of biological degradable chewing gum |
Non-Patent Citations (1)
Title |
---|
Properties and micros-tructure of thermo-pressed wheat glutenf-ilm:a comparison with cast films Mangavel C.et al,Biomacromolecules,No.5 2004 * |
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