CN107751357A - A kind of preparation method of food-grade fruit and vegetable fresh-keeping agent - Google Patents

A kind of preparation method of food-grade fruit and vegetable fresh-keeping agent Download PDF

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Publication number
CN107751357A
CN107751357A CN201711063939.2A CN201711063939A CN107751357A CN 107751357 A CN107751357 A CN 107751357A CN 201711063939 A CN201711063939 A CN 201711063939A CN 107751357 A CN107751357 A CN 107751357A
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Prior art keywords
chitosan
mass percent
food
hydrochloric acid
keeping agent
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CN201711063939.2A
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Inventor
王吉明
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Shanghai Rice Agriculture Science And Technology Co Ltd
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Shanghai Rice Agriculture Science And Technology Co Ltd
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Priority to CN201711063939.2A priority Critical patent/CN107751357A/en
Publication of CN107751357A publication Critical patent/CN107751357A/en
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/08Preserving with sugars
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154Organic compounds; Microorganisms; Enzymes
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/157Inorganic compounds
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Microbiology (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides a kind of preparation method of food-grade fruit and vegetable fresh-keeping agent, chitosan is dissolved in hydrochloric acid solution so that the concentration of volume percent of chitosan is 0.5~2%;After environmental balance, 1.2 times moles of Chitosan powder is added, is activated at 18~25 DEG C;It is 1~3 according to the mol ratio of chitosan and L cysteines:1 ratio weighs L cysteines, and L cysteines are added, and starting material is produced after being reacted 2~4 hours at 18~25 DEG C;Starting material is poured into absolute ethyl alcohol and filtered, load bag filter after obtaining sediment, dialysed 1 time with hydrochloric acid solution, then dialysed 1 time for the hydrochloric acid of 0.5~2% sodium chloride with containing mass percent concentration, dialysed 1 time for 0.5~2mM hydrochloric acid solutions of 0.2~1% sodium chloride with containing mass percent concentration again, freeze-drying obtains food-grade fruit and vegetable fresh-keeping agent.The fruit and vegetable fresh-keeping agent safety and sanitation of the present invention, fresh-keeping effect are excellent.

Description

A kind of preparation method of food-grade fruit and vegetable fresh-keeping agent
Technical field
The invention belongs to Food Chemistry field, is related to a kind of antistaling agent, specifically a kind of food-grade fruit and vegetable fresh-keeping agent Preparation method.
Background technology
Chitosan:A large amount of existing natural alkaline polysaccharides in nature, harmless, degradable, bio-compatibility is good, it is cheap and There is excellent scattered a, moisturizing, film forming, many advantages, such as antibiotic property.When carrying out coating-film fresh-keeping using it, film layer has penetrating, resistance It is water-based, micro- controlled atmosphere environment is formed to various gas molecules increase penetration resistance, increases carbon dioxide content in fruits and vegetables, oxygen drop It is low, suppress fruits and vegetables respiratory metabolism moisture loss, slow down institutional framework aging.Transport loss is effectively reduced, extends the time.
Right chitosan film itself inherent defect such as machinery removes intensity difference, and scope of restraining fungi is partially narrow, therefore this is modified, to Obtain more preferably effect.
Cys:The material is also the material with physiological function that nature is widely present, and can be had in animals and plants Effect defence harmful substance increase activity, while be also the amino of unique active sulfydryl in the amino acids of constitutive protein matter Acid, its reproducibility sulfydryl can suppress the enzymatic browning of fruit, while have bacteriostasis, but Cys are amino acids Small-molecule substance, the aqueous solution, which is coated in fruit surface, can not form diaphragm, can not directly use.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of preparation side of food-grade fruit and vegetable fresh-keeping agent Method, the preparation method of described this food-grade fruit and vegetable fresh-keeping agent will solve in the prior art that antistaling agent machinery removes intensity difference, suppression The partially narrow technical problem of bacterium scope.
The invention provides a kind of preparation method of food-grade fruit and vegetable fresh-keeping agent, it is characterised in that including following step Suddenly:
1) chitosan is dissolved in mass percent concentration in 0.05~0.5% hydrochloric acid solution so that the body of chitosan Product percent concentration is 0.5~2%;After 18~25 DEG C of environmental balances, 1.2 times moles of Chitosan powder is added, 18 Activated 0.5~2 hour at~25 DEG C;
2) it is 1~3 according to the mol ratio of chitosan and Cys:1 ratio weighs Cys, by the Guangs of L- half Propylhomoserin adds, and stirs, starting material is produced after being reacted 2~4 hours at 18~25 DEG C;
3) starting material is poured into absolute ethyl alcohol and filtered, load bag filter after obtaining sediment, with PH=4 0.5~2mM Hydrochloric acid solution dialyses 1 time, then with 0.5~2mM hydrochloric acids dialysis 1 containing mass percent concentration for 0.5~2% sodium chloride It is secondary, then dialysed 1 time for 0.5~2mM hydrochloric acid solutions of 0.2~1% sodium chloride with containing mass percent concentration, finally freezing is dry It is dry to obtain food-grade fruit and vegetable fresh-keeping agent.Further, the preparation method of above-mentioned a kind of food-grade fruit and vegetable fresh-keeping agent, including it is as follows Step:
1) chitosan is dissolved in mass percent concentration to obtain Solute mass and liquor capacity in 0.1% hydrochloric acid solution Than the chitosan solution for 1.0%, after 18~25 DEG C of environmental balances, in molar ratio 1:1.2 add Chitosan powder again, 18 Activated 1 hour at~25 DEG C;
2) it is and then according to the mol ratio of chitosan and Cys 2:1 ratio weighs Cys, by L- half It is slowly added to after cystine dissolving, stirs, starting material is produced after being reacted 3 hours at 18~25 DEG C;
3) starting material is poured into ethanol and filtered, load bag filter after obtaining sediment, with 1mM hydrochloric acid solutions dialysis 1 It is secondary, then dialysed 1 time for the 1mM hydrochloric acids of 1% sodium chloride with containing mass percent concentration, then be with containing mass percent concentration The 1mM hydrochloric acid solutions of 0.5% sodium chloride dialyse 1 time, and finally freeze-drying obtains food-grade fruit and vegetable fresh-keeping agent.
Further, the mass percent of the raw material used in preparation process is as follows:
Chitosan 43%;
Cys 21.5%;
Mass percent concentration is 1% hydrochloric acid 35.5%.
Chitosan is easy to dissolve in weak acid solvent, especially it is worthy of note that dissolving after solution in contain amino (NH2 +), these amino suppress bacterium by combining negatron.Meanwhile chitosan has extremely strong adsorption capacity, effectively prevents gold Belong to the infringement to caused by vegetables and fruits such as ion, bacterium.The present invention, which also uses Cys, can accelerate the formation of glutelin, prevent The only effect of aging;VC oxidation and brown stain can be prevented;Prevent radiation damage effect.So that the present invention have inoxidizability and The feature of stability.
The present invention compares with prior art, and its technological progress is significant.The present invention using chitosan it is distinctive well into The film antibiotic property antibacterial inoxidizability good with Cys, the micromoles per gram of sulfhydryl content 300 is produced using chemic modified method (mmol/g) Cys modification of chitosan.The fruit and vegetable fresh-keeping agent safety and sanitation of the present invention, fresh-keeping effect are excellent.
Brief description of the drawings
Fig. 1 shows the ultraviolet spectral analysis result of the food-grade fruit and vegetable fresh-keeping agent of the present invention.
Fig. 2 shows the results of IR of the food-grade fruit and vegetable fresh-keeping agent of the present invention.
Fig. 3 shows the content of sulfydryl in food-grade fruit and vegetable fresh-keeping agent of the invention.
Fig. 4 shows that the prevent-browning that different solutions are carried out to apple stripping and slicing is tested (in file:A. b.1-mcp distilled water is protected The food-grade fruit and vegetable fresh-keeping agent of the fresh dose of c. present invention).
Fig. 5 shows the food-grade fruit and vegetable fresh-keeping agent of the present invention to Escherichia coli inhibition.
Fig. 6 shows the food-grade fruit and vegetable fresh-keeping agent of the present invention to staphylococcus aureus inhibition.
Fig. 7 shows the food-grade fruit and vegetable fresh-keeping agent of the present invention to bacillus cereus inhibition.
Embodiment
The raw material that following embodiments use:
Chitosan, Cys, 1- ethyls (3- dimethylamino-propyls) carbodiimide hydrochloride, sodium chloride, hydroxide Sodium, iodine, KI, sodium thiosulfate are that analysis is pure.Soluble starch, nutrient agar are food-grade.Antibacterial test bacterial strain is removed from office Lan Shi negative bacteriums, Gram-positive S grape ball, bacillus cereus are conventional commercial product.
The equipment of use:Aseptic working platform, constant incubator, pressure steam sterilizer, Fourier transformation infrared spectrometer, Ultraviolet-uisible spectrophotometer, freeze drier are conventional commercial product.
Embodiment 1
The preparation method of food-grade fruit and vegetable fresh-keeping agent is described below:
Chitosan is dissolved in mass percent concentration to obtain Solute mass and liquor capacity ratio in 0.1% hydrochloric acid solution For 1.0% chitosan solution, after 18~25 DEG C of environmental balances, in molar ratio 1:1.2 add Chitosan powder again, 18~ Activated at 25 DEG C 1 hour, be then 2 according to the mol ratio of chitosan and Cys:1 ratio weighs the Guang ammonia of L- half Acid, it is slowly added to, stirs after Cys are dissolved, starting material is produced after being reacted 3 hours at 18~25 DEG C.
Starting material is poured into ethanol and filtered, loads bag filter after obtaining sediment, with 1mM hydrochloric acids (PH=4) solution Dialysis 1 time, then dialysed 1 time for the 1mM hydrochloric acids of 1% sodium chloride with containing mass percent concentration, then with containing mass percent Concentration is dialysed 1 time for the 1mM hydrochloric acid solutions of 0.5% sodium chloride, and finally freeze-drying obtains food-grade fruit and vegetable fresh-keeping agent.
More than dialysis interval be not less than 24 hours, dialysis procedure can not strong light direct beam, temperature must not be higher than 15 DEG C, gained become Property chitosan storage temperature must not be higher than 3 DEG C.
Embodiment 2
The preparation method of food-grade fruit and vegetable fresh-keeping agent is described below:
The mass percent of the raw material of use is as follows:
Chitosan 43%;
Cys 21.5%;
Mass percent concentration is 1% hydrochloric acid 35.5%.
Above-mentioned chitosan is divided into 2.2 parts;
1 part of chitosan is dissolved in hydrochloric acid solution and obtains chitosan solution, after 18~25 DEG C of environmental balances, is added again 1.2 parts of Chitosan powders, activate 1 hour at 18~25 DEG C, be slowly added to after then Cys are dissolved, stirring is equal It is even, produce starting material after being reacted 3 hours at 18~25 DEG C.
Starting material is poured into ethanol and filtered, loads bag filter after obtaining sediment, with 1mM hydrochloric acids (PH=4) solution Dialysis 1 time, then dialysed 1 time for the 1mM hydrochloric acids of 1% sodium chloride with containing mass percent concentration, then with containing mass percent Concentration is dialysed 1 time for the 1mM hydrochloric acid solutions of 0.5% sodium chloride, and finally freeze-drying obtains food-grade fruit and vegetable fresh-keeping agent.
More than dialysis interval be not less than 24 hours, dialysis procedure can not strong light direct beam, temperature must not be higher than 15 DEG C, gained become Property chitosan storage temperature must not be higher than 3 DEG C.
3 antibacterial test of embodiment
The food-grade fruit and vegetable fresh-keeping agent (turning property chitosan) that embodiment 1 obtains is dissolved in distilled water, mass percent concentration Respectively 0.2%, 0.5%, 1%, 1.5%.By Escherichia coli, staphylococcus aureus, bacillus streak inoculation to flat board, Cultivated 24 hours in constant incubator, temperature is human body temperature (37 DEG C).Antibacterial ring size after sterilization is dipped into above-mentioned solution, Antibacterial ring size is transferred on germy culture medium after 15 minutes, each one antibacterial ring size of concentration, and ginseng is used as using blank ring According to being positioned in constant incubator 24 hours, temperature is human body temperature (37 DEG C).Bacteriostasis rate calculation formula:
To Escherichia coli inhibition as shown in figure 5, to staphylococcus aureus inhibition as shown in fig. 6, to waxy Bacillus inhibition is as shown in Figure 7.Show that fungistatic effect is notable.
Embodiment 4
The food-grade fruit and vegetable fresh-keeping agent ultraviolet spectral analysis result that embodiment 1 obtains is as shown in figure 1, chitosan spectrogram Gao Bo Several sections of 3680~2950cm-1For the association peak of hydroxyl, while hand over and cover with the stretching vibration peak of amino, this is that there is hydroxyl in molecule Hydrogen bond association between base and between hydroxyl amino causes, and association peak in this part substantially narrows after chitin modified, 1024cm-1The alcoholic extract hydroxyl group C-O stretching vibration absworption peak degree intensity at place becomes strong, and explanation-OH reacts in conjunction with 1726cm-1Place There are C=O characteristic absorption peaks, and intensity is remarkably reinforced, and illustrates to generate esters in course of reaction, in 1631cm-1There is acid amides I at place Absworption peak, in 1517cm-1There is the peak position at acid amides II peaks at place, illustrates to form amido link in derivative, in 2490cm-1Locate small peak It is sulfydryl absworption peak.In summary, the carboxyl on the amino and Cys of chitosan produces reaction and with the shape of amido link Formula combines, while the sulfydryl on Cys has been connected on chitosan.
Embodiment 5
Fourier turn infrared is described below:
The chitosan that mass fraction is 1.000%, Cys are taken, turning property chitosan aqueous solution is applied to glass Piece, remove after drying and forming-film, reference scanning is carried out using air as background, infrared flash ranging is carried out with FFIR It is fixed.Part chitosan, Cys are taken, turning property chitosan aqueous solution prepares the aqueous solution that mass fraction is 1.001%, It is that reference is established baseline and is scanned using UP water (resistivity is 18M Ω * cm at 25 DEG C), observes the absorption maximum peak position of derivative Put and obtain related group information in structure, scanning wavelength is 200~800nm.
As shown in Fig. 2 chitosan is similar to the absorption spectrum of Cys, have in 200~400nm wave-length coverages bright Aobvious absworption peak, illustrates that chitosan has similar chromophoric group with Cys, chitosan has maximum absorption band in 210nm, is shell Glycan maximum absorption wavelength, equally there is absworption peak in 309nm.Cys have the maximum absorption band of carboxylic group in 210nm Also auxochrome amino, turning property chitosan has two absworption peaks simultaneously, illustrates only two chromophoric groups, the absorption maximum of ester group Wavelength value is 210nm, a length of 209nm of maximum absorption wave of turning property chitosan, herein because the absorption maximum of amide groups, surface shell Being reacted between glycan and Cys, the carboxyl of amino and Cys for chitosan forms amido link, It is coincide with the results of FT-IR.
The sulfhydryl content of embodiment 6 detects
Appropriate turning property chitosan is taken with 3:1000 ratios are dissolved in UP water, are adjusted with 1mM hydrochloric acids to the section of PH=2~3, 1% starch solution of drop of intervention 4, is changed into sapphirine, and stablize 30 seconds and calculate as follows with the solution of 1mM iodine solution titration
Turning property chitosan sulfhydryl content
The iodine solution that concentration is 0.001mol/L is taken to titrate 5 groups of samples similar in quality after weighing, each group result is close, mercapto For base content in 325 μm of above and below ol/g, content range is 316.27 ± 6.70 to 332.10 ± 3.06 μm of ol/g.
At reactant (i.e. pure fruit antistaling agent), the time, condition, under the premise of post processing is identical, using demarcate concentration as Five groups of reactant control groups (a group-e groups) similar in quality after 0.001mol/L iodine solutions weigh surely, each group measurement result is close, Thiol concentration stability range fluctuates in 300 μm of ol/g, and content range is 316.27 ± 6.70 to 332.10 ± 3.06 μm of ol/ G (, n=3) and (as shown in Figure 3).
Embodiment 7
Prevent-browning experiment is carried out to apple stripping and slicing with different solutions and sees Fig. 4, does not occur within 5 days obvious brown stain, single antistaling agent Solution or the obvious brown stain of stripping and slicing of distilled water processing.
Modification of chitosan is to Vc contents in fruit:Concentration is that 1.0~1.5%wt carries out coating problems to jujube class, after four days It is 324.51mg/100g to measure Vc contents, declines 13.89%, general antistaling agent (1-mcc antistaling agents) group then have dropped 34.77%, similarly to apple film, Vc contents are 2.25mg/100g after four days, have dropped 43.75%, general antistaling agent group is then It has dropped 53.75%.

Claims (3)

1. a kind of preparation method of food-grade fruit and vegetable fresh-keeping agent, it is characterised in that comprise the following steps:
1) chitosan is dissolved in mass percent concentration in 0.05~0.5% hydrochloric acid solution so that the volume hundred of chitosan It is 0.5~2% to divide specific concentration;After 18~25 DEG C of environmental balances, 1.2 times moles of Chitosan powder is added, 18~25 Activated 0.5~2 hour at DEG C;
2) it is 1~3 according to the mol ratio of chitosan and Cys:1 ratio weighs Cys, by Cys Add, stir, starting material is produced after being reacted 2~4 hours at 18~25 DEG C;
3) starting material is poured into absolute ethyl alcohol and filtered, load bag filter after obtaining sediment, with PH=4 0.5~2mM hydrogen chlorine Acid solution is dialysed 1 time, is then dialysed 1 time for 0.5~2mM hydrochloric acids of 0.5~2% sodium chloride with containing mass percent concentration, Dialysed 1 time for 0.5~2mM hydrochloric acid solutions of 0.2~1% sodium chloride with containing mass percent concentration, be finally freeze-dried again Obtain food-grade fruit and vegetable fresh-keeping agent.
2. a kind of preparation method of food-grade fruit and vegetable fresh-keeping agent as claimed in claim 1, it is characterised in that comprise the following steps:
1) it is to obtain Solute mass in 0.1% hydrochloric acid solution to be with liquor capacity ratio chitosan to be dissolved in into mass percent concentration 1.0% chitosan solution, after 18~25 DEG C of environmental balances, in molar ratio 1:1.2 add Chitosan powder again, 18~25 Activated 1 hour at DEG C;
2) it is and then according to the mol ratio of chitosan and Cys 2:1 ratio weighs Cys, by the Guang ammonia of L- half It is slowly added to after acid dissolving, stirs, starting material is produced after being reacted 3 hours at 18~25 DEG C;
3) starting material is poured into ethanol and filtered, load bag filter after obtaining sediment, dialysed 1 time with 1mM hydrochloric acid solutions, so It is afterwards 0.5% with containing the 1mM hydrochloric acids dialysis that mass percent concentration is 1% sodium chloride 1 time, then with containing mass percent concentration The 1mM hydrochloric acid solutions of sodium chloride dialyse 1 time, and finally freeze-drying obtains food-grade fruit and vegetable fresh-keeping agent.
A kind of 3. preparation method of food-grade fruit and vegetable fresh-keeping agent as claimed in claim 1, it is characterised in that:Adopted in preparation process The mass percent of raw material is as follows:
Chitosan 43%;
Cys 21.5%;
Mass percent concentration is 1% hydrochloric acid 35.5%.
CN201711063939.2A 2017-11-02 2017-11-02 A kind of preparation method of food-grade fruit and vegetable fresh-keeping agent Pending CN107751357A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3646729A3 (en) * 2018-10-29 2020-07-29 Freshgard Ltd. Compositions and methods for extending shelf life of harvested crop
CN112029127A (en) * 2020-08-19 2020-12-04 天津盛天利材料科技有限公司 Special preservative film for pomegranate with high air permeability and moisture permeability and processing method thereof
CN114931164A (en) * 2022-06-10 2022-08-23 安徽省农业科学院农产品加工研究所 Fresh-cut turmeric fresh-keeping film forming solution and preparation method thereof

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CN105053172A (en) * 2015-08-17 2015-11-18 北京市农林科学院 Fresh keeping agent, preparation method thereof, and application of fresh keeping agent in fresh keeping treatment of dishcloth gourds
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Patent Citations (3)

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CN101112208A (en) * 2007-08-28 2008-01-30 福建省农业科学院农业工程技术研究所 Antistaling agent for preventing the browning of the fresh fruit having been cut and the using method thereof
CN105053172A (en) * 2015-08-17 2015-11-18 北京市农林科学院 Fresh keeping agent, preparation method thereof, and application of fresh keeping agent in fresh keeping treatment of dishcloth gourds
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3646729A3 (en) * 2018-10-29 2020-07-29 Freshgard Ltd. Compositions and methods for extending shelf life of harvested crop
CN112029127A (en) * 2020-08-19 2020-12-04 天津盛天利材料科技有限公司 Special preservative film for pomegranate with high air permeability and moisture permeability and processing method thereof
CN114931164A (en) * 2022-06-10 2022-08-23 安徽省农业科学院农产品加工研究所 Fresh-cut turmeric fresh-keeping film forming solution and preparation method thereof
CN114931164B (en) * 2022-06-10 2023-09-12 安徽省农业科学院农产品加工研究所 Fresh-cut yellow ginger fresh-keeping film-forming liquid and preparation method thereof

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