CN112167330A - Kiwi fruit preservative, preparation method thereof and kiwi fruit preservation method - Google Patents
Kiwi fruit preservative, preparation method thereof and kiwi fruit preservation method Download PDFInfo
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- CN112167330A CN112167330A CN202010949711.9A CN202010949711A CN112167330A CN 112167330 A CN112167330 A CN 112167330A CN 202010949711 A CN202010949711 A CN 202010949711A CN 112167330 A CN112167330 A CN 112167330A
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- chitosan
- kiwi fruit
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- kiwi
- preservative
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- 244000298697 Actinidia deliciosa Species 0.000 title claims abstract description 78
- 235000009436 Actinidia deliciosa Nutrition 0.000 title claims abstract description 78
- 230000002335 preservative effect Effects 0.000 title claims abstract description 44
- 239000003755 preservative agent Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000004321 preservation Methods 0.000 title abstract description 18
- 229920001661 Chitosan Polymers 0.000 claims abstract description 64
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 17
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000001110 calcium chloride Substances 0.000 claims abstract description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 10
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000661 sodium alginate Substances 0.000 claims abstract description 9
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 9
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 9
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims abstract description 5
- 235000010352 sodium erythorbate Nutrition 0.000 claims abstract description 4
- 239000004320 sodium erythorbate Substances 0.000 claims abstract description 4
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229960002713 calcium chloride Drugs 0.000 claims description 3
- 229940045110 chitosan Drugs 0.000 claims description 3
- 229960004106 citric acid Drugs 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 abstract description 14
- 239000012362 glacial acetic acid Substances 0.000 abstract description 10
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 7
- 229930003268 Vitamin C Natural products 0.000 description 7
- 235000019154 vitamin C Nutrition 0.000 description 7
- 239000011718 vitamin C Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 3
- 244000247812 Amorphophallus rivieri Species 0.000 description 3
- 235000001206 Amorphophallus rivieri Nutrition 0.000 description 3
- 229920002581 Glucomannan Polymers 0.000 description 3
- 229920002752 Konjac Polymers 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229940046240 glucomannan Drugs 0.000 description 3
- 239000000252 konjac Substances 0.000 description 3
- 235000010485 konjac Nutrition 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 241000219068 Actinidia Species 0.000 description 2
- 235000009434 Actinidia chinensis Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- CCBICDLNWJRFPO-UHFFFAOYSA-N 2,6-dichloroindophenol Chemical compound C1=CC(O)=CC=C1N=C1C=C(Cl)C(=O)C(Cl)=C1 CCBICDLNWJRFPO-UHFFFAOYSA-N 0.000 description 1
- 241000219066 Actinidiaceae Species 0.000 description 1
- 206010006458 Bronchitis chronic Diseases 0.000 description 1
- 206010051625 Conjunctival hyperaemia Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010015993 Eyelid oedema Diseases 0.000 description 1
- 241000282553 Macaca Species 0.000 description 1
- 201000007100 Pharyngitis Diseases 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 208000007451 chronic bronchitis Diseases 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000036387 respiratory rate Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/154—Organic compounds; Microorganisms; Enzymes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/157—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Food Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application relates to the field of fruit and vegetable preservation, and particularly discloses a kiwi fruit preservative which is prepared from the following raw materials in parts by weight, including 0.3-0.5 part of modified chitosan, 0.5-0.7 part of calcium chloride, 0.3-0.5 part of citric acid, 0.12-0.14 part of salicylic acid, 0.13-0.15 part of sodium alginate, 0.2-0.4 part of sodium isocyanate, 0.2-0.4 part of sodium erythorbate and 30-40 parts of water; wherein the modified chitosan is prepared by reacting iminodiacetonitrile, epichlorohydrin and chitosan. The preservative has the advantages that the chitosan is better in solubility under the condition that glacial acetic acid is not required to be added, so that the safety of the preservative is improved; in addition, a preparation method of the preservative and a preservation method of kiwi fruits are provided.
Description
Technical Field
The application relates to the technical field of fruit and vegetable preservation, in particular to a kiwi fruit preservative, a preparation method thereof and a kiwi fruit preservation method.
Background
The plant of Actinidia of Actinidiaceae of Actinidia is a high-grade fruit with high nutritive value, medicinal value and fresh food rate. In recent years, the kiwi industry has seen a geometric progression. The kiwi fruit belongs to a climacteric fruit, the after-ripening and softening process is accelerated along with the occurrence of an endogenous ethylene peak, and when the respiration peak and the ethylene peak of the kiwi fruit appear, the hardness of the kiwi fruit is quickly reduced to reach an edible state, so that the storage property is lost. Therefore, prolonging the fresh-keeping time and the storage quality of the kiwi fruits is the important importance of the development of the kiwi industry.
At present, the surface of kiwi fruit is coated with an antistaling agent to keep the kiwi fruit fresh, for example, the Chinese patent application with the publication number of CN104351331A discloses a natural kiwi fruit antistaling agent, which comprises the following components in percentage by weight: glacial acetic acid 0.5-1.0%, chitosan 0.5-2.5%, konjac glucomannan 0.5-3.5%, starch 0.5-2.5%, and water in balance; the preparation method comprises the following steps: 1) weighing raw materials: weighing chitosan, konjac glucomannan and starch according to mass percentage; 2) dissolving glacial acetic acid: weighing glacial acetic acid according to the mass ratio, and dissolving the glacial acetic acid by water to prepare glacial acetic acid solution; 3) dissolving and uniformly mixing: placing the glacial acetic acid solution in a water bath at 40-45 ℃, and adding chitosan, konjac glucomannan and starch in required mass percentage in sequence under continuous stirring to be fully mixed and dissolved into white homogeneous phase emulsion; 4) and (4) sealing and storing: and sealing and storing by using a glass bottle or a plastic bottle.
The preservative with a good preservation effect on the kiwi fruits can be prepared by the formula, but the chitosan has poor solubility in water, so that the preservative can be well dissolved in water only by adding glacial acetic acid; glacial acetic acid is an easily volatile substance, has irritation to nose, throat and respiratory tract after being inhaled into a human body, has strong irritation to eyes, can cause eyelid edema, conjunctival congestion, chronic pharyngitis, bronchitis and the like after being inhaled for a long time, and is not beneficial to the health of workers.
Disclosure of Invention
The first purpose of the application is to provide a kiwi fruit preservative which has the effect of enabling the solubility of chitosan to be better without adding glacial acetic acid, so that the safety of the preservative is improved.
The second purpose of the application is to provide a preparation method of the kiwi fruit preservative.
The third purpose of the application is to provide a fresh-keeping method of kiwi fruits.
The application provides a kiwi fruit preservative, adopts following technical scheme:
a kiwi fruit preservative is prepared from the following raw materials, by weight, 0.3-0.5 part of modified chitosan, 0.5-0.7 part of calcium chloride, 0.3-0.5 part of citric acid, 0.12-0.14 part of salicylic acid, 0.13-0.15 part of sodium alginate, 0.2-0.4 part of sodium isocyanate, 0.2-0.4 part of sodium erythorbate and 30-40 parts of water;
wherein the modified chitosan is prepared by reacting iminodiacetonitrile, epichlorohydrin and chitosan.
By adopting the technical scheme, the modified chitosan, the sodium alginate, the salicylic acid and the like can form a layer of protective film on the surface of the kiwi fruit, so that the invasion and growth of pathogenic bacteria can be effectively reduced, the respiratory rate of the kiwi fruit can be effectively inhibited, the softening of the kiwi fruit can be delayed, the modified chitosan has a good antibacterial effect, and the rotting rate of the kiwi fruit can be greatly reduced; the calcium chloride can effectively maintain the structure and the function of cell walls, enhance the hardness of fruits, reduce the activity of cell wall degrading enzymes and inhibit respiration, and the calcium chloride is mutually cooperated with salicylic acid to effectively inhibit the generation of ethylene in the kiwi fruits; therefore, the kiwi fruit can be kept fresh well by the preservative.
Preferably, the formula of the preservative is as follows: 0.40-0.45 part of modified chitosan, 0.55-0.60 part of calcium chloride, 0.45-0.50 part of citric acid, 0.13-0.14 part of salicylic acid, 0.14-0.15 part of sodium alginate, 0.2-0.3 part of sodium isocyanate, 0.2-0.3 part of sodium erythorbate and 35-38 parts of water.
By adopting the technical scheme, the fresh-keeping effect of the obtained fresh-keeping agent is better under the condition that the raw materials in the formula are in the range.
Preferably, the preparation steps of the modified chitosan are as follows according to parts by weight:
1) adding 0.10-0.13 part of iminodiacetonitrile into 4-6 parts of tetrahydrofuran, uniformly stirring, heating to 55-60 ℃, then adding 0.07-0.09 part of epoxy chloropropane, and stirring for reacting for 4-5 hours to obtain a mixed solution A; adding a sodium hydroxide aqueous solution into the mixed solution A, wherein the amount of the substance of the epichlorohydrin is 1.1-1.3 times of the amount of the substance of the sodium hydroxide, stirring for reacting for 1-2h, then adjusting the pH value to be neutral to obtain a mixed solution B, and concentrating the mixed solution B to obtain a solid C;
2) adding 0.5-1.0 part of chitosan into 5-7 parts of acetic acid solution with the concentration of 0.5-1.5mol/L, stirring until the chitosan is dissolved to obtain solution D, then adding the solid C into the solution D, and stirring for reacting for 2-3h to obtain solution E;
3) and adding ethanol with the volume same as that of the solution E into the solution E, standing for 1-2h, filtering to obtain a solid A, washing, and drying to obtain the modified chitosan.
By adopting the technical scheme, firstly, iminodiacetonitrile reacts with epichlorohydrin to obtain a compound which reacts with chitosan, and then the compound is hydrolyzed under alkaline conditions to obtain modified chitosan containing carboxyl, so that the water solubility of the chitosan is greatly improved.
Preferably, the epichlorohydrin obtained in the step 1) is added dropwise, 0.07-0.09 part of epichlorohydrin is added dropwise at a dropping speed of 1-2mL/min, and stirring is performed while the addition is changed.
By adopting the technical scheme, the reaction of the epoxy chloropropane and the iminodiacetonitrile is relatively quick, the epoxy chloropropane is dripped, and the reaction speed can be easily controlled by the dripping mode.
Preferably, the concentration of the sodium hydroxide solution in the step 1) is 35-40% by mass, and the pH is adjusted by adding 0.1-0.3mol/L hydrochloric acid.
By adopting the technical scheme, the concentration ranges of strong sodium oxide and hydrochloric acid are controlled, the ratio of the volume of the added aqueous solution to the volume of tetrahydrofuran is adaptive, and the concentration step is easy to implement.
Preferably, the drying temperature in the step 3) is 60-70 ℃, and the drying time is 1-2 h.
By adopting the technical scheme, the modified chitosan can be dried better and faster under the condition.
Preferably, the preparation steps of the preservative are as follows:
adding modified chitosan, calcium chloride, citric acid, salicylic acid, sodium alginate, iso-VC sodium, etc. into water, and stirring to dissolve.
By adopting the technical scheme, the modified chitosan has good water solubility, and can be added with other raw materials and stirred together to obtain the uniform preservative.
Preferably, the chitosan is chitosan oligosaccharide.
By adopting the technical scheme, the water solubility of the chitosan oligosaccharide is better.
Preferably, it comprises the following steps:
1) cleaning the kiwi fruits with clear water, blowing air on the surfaces of the kiwi fruits, drying water drops on the surfaces of the kiwi fruits by blowing, then uniformly spraying a preservative on the surfaces of the kiwi fruits, naturally airing, and storing the kiwi fruits in a warehouse;
2) an ethylene remover is arranged in the warehouse to reduce the ethylene content in the warehouse and keep ventilation.
By adopting the technical scheme, the preservative is sprayed, and then the ethylene in the warehouse is removed in time, so that the preservation effect of the kiwi fruits is better.
Preferably, the temperature of the warehouse in the step 2) is set to be 20-30 ℃.
By adopting the technical scheme, the fresh-keeping effect is better in the temperature range.
In summary, the present application has the following beneficial effects:
1. according to the method, a large number of carboxyl groups are introduced into chitosan molecules, so that the water solubility of chitosan is greatly improved, the film forming property of the preservative on the surface of kiwi fruits is good, and the preservation effect of the preservative is improved.
2. The kiwi fruit fresh-keeping agent is used for keeping the kiwi fruit fresh at 25-30 ℃, after the kiwi fruit is stored for 15 days, the minimum change rate of soluble total sugar of the kiwi fruit can reach 6.64%, the reduction rate of vitamin C is below 1.26Z%, the softening number is below 3, and the rotting number is almost 0.
3. The method can effectively prolong the fresh-keeping time of the kiwi fruits by timely removing the ethylene in the warehouse.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation examples of raw materials and/or intermediates chitosan: the chitosan oligosaccharide is adopted, the raw tea manufacturer is a source biological technology company Limited of Hebei Chuang, the content is 99 percent, and the average molecular weight is 15000.
Preparation example 1
The raw materials of the modified chitosan are shown in table 1, and the preparation steps are as follows:
1) adding iminodiacetonitrile into tetrahydrofuran of 4kg, stirring uniformly, heating to 55 ℃, then dripping epichlorohydrin at the dripping speed of 1mL/min, stirring while changing dripping, and after finishing dripping, stirring and reacting for 4 hours to obtain a mixed solution A; adding a 35% sodium hydroxide aqueous solution in percentage by mass into the mixed solution A, wherein the amount of the substance of the epichlorohydrin is 1.1 times of the amount of the substance of the sodium hydroxide, stirring for reaction for 1 hour, then adjusting the pH to be neutral by using a hydrochloric acid solution with the concentration of 0.1mol/L to obtain a mixed solution B, and carrying out rotary evaporation on the mixed solution B to obtain a solid C;
2) adding chitosan into 5kg of 0.5mol/L acetic acid solution, stirring until the chitosan is dissolved to obtain solution D, then dividing the solid C into three equal parts, adding the three equal parts into the solution D, wherein the interval time between every two adjacent times is 1h, and after the addition is finished, continuing stirring and reacting for 2h to obtain solution E;
3) and adding ethanol with the volume same as that of the solution E into the solution E, standing for 1h, filtering to obtain a solid A, washing the solid with ethanol for 3 times, and drying at 60 ℃ for 2h to obtain the modified chitosan.
TABLE 1 preparation example 1 raw materials and amounts (kg) of raw materials
Preparation example 1 | Preparation example 2 | Preparation example 3 | |
Iminodiacetonitrile | 0.10 | 0.11 | 0.13 |
Epoxy chloropropane | 0.07 | 0.08 | 0.09 |
Chitosan | 0.5 | 0.7 | 1.0 |
Preparation example 2
The raw materials of the modified chitosan are shown in table 1, and the preparation steps are as follows:
1) adding iminodiacetonitrile into 5kg tetrahydrofuran, stirring uniformly, heating to 57 ℃, then dripping epichlorohydrin, wherein the dripping speed is 1.5mL/min, stirring while changing the dripping speed, and after the dripping is finished, stirring and reacting for 4.5h to obtain a mixed solution A; adding a sodium hydroxide aqueous solution with the mass percentage concentration of 37% into the mixed solution A, wherein the amount of the substance of the epichlorohydrin is 1.2 times of the amount of the substance of the sodium hydroxide, stirring for reacting for 1.5h, then adjusting the pH to be neutral by using a hydrochloric acid solution with the concentration of 0.2mol/L to obtain a mixed solution B, and carrying out rotary evaporation on the mixed solution B to obtain a solid C;
2) adding chitosan into 6kg of acetic acid solution with the concentration of 1.0mol/L, stirring until the chitosan is dissolved to obtain solution D, then dividing the solid C into three equal parts, adding the three equal parts into the solution D, wherein the interval time between every two adjacent times is 1.5 hours, and after the addition is finished, continuing stirring and reacting for 2.5 hours to obtain solution E;
3) and adding ethanol with the volume same as that of the solution E into the solution E, standing for 1h, filtering to obtain a solid A, washing the solid with ethanol for 3 times, and drying at 65 ℃ for 1.5h to obtain the modified chitosan.
Preparation example 3
The raw materials of the modified chitosan are shown in table 1, and the preparation steps are as follows:
1) adding iminodiacetonitrile into 6kg tetrahydrofuran, stirring uniformly, heating to 60 ℃, then dripping epichlorohydrin at the dripping speed of 2mL/min, stirring while changing dripping, and after finishing dripping, stirring and reacting for 5h to obtain a mixed solution A; adding a sodium hydroxide aqueous solution with the mass percentage concentration of 40% into the mixed solution A, wherein the amount of the substance of the epichlorohydrin is 1.3 times of the amount of the substance of the sodium hydroxide, stirring for reacting for 2 hours, then adjusting the pH to be neutral by using a hydrochloric acid solution with the concentration of 0.3mol/L to obtain a mixed solution B, and performing rotary evaporation on the mixed solution B to obtain a solid C;
2) adding chitosan into 7kg of acetic acid solution with the concentration of 1.5mol/L, stirring until the chitosan is dissolved to obtain solution D, then dividing the solid C into three equal parts, adding the three equal parts into the solution D, wherein the interval time between every two adjacent times is 2 hours, and after the addition is finished, continuously stirring and reacting for 3 hours to obtain solution E;
3) and adding ethanol with the volume same as that of the solution E into the solution E, standing for 2h, filtering to obtain a solid A, washing the solid with ethanol for 3 times, and drying at 70 ℃ for 1h to obtain the modified chitosan.
Examples
Examples 1 to 5
The raw materials and the amounts of the raw materials of the antistaling agents of the examples 1-5 are shown in the table 1, and the preparation steps are as follows:
adding modified chitosan, calcium chloride, citric acid, salicylic acid, sodium alginate, iso-VC sodium, etc. into water, and stirring to dissolve.
Wherein the modified chitosan was obtained from preparation example 1.
TABLE 2 antistaling agents of examples 1-9 and the amounts (kg) of the raw materials
Examples 6 to 9
The respective raw materials and the amounts of the raw materials of the antistaling agents of examples 6 to 9 are shown in Table 2, and the other preparation steps are the same as those of example 4. Wherein the modified chitosan was obtained from preparation example 1.
Example 10
The preservative of example 10 was different from that of example 4 in that the modified chitosan was obtained from preparation example 2, and the rest of the procedure was the same as that of example 4.
Example 11
The preservative of example 11 was different from that of example 4 in that modified chitosan was obtained from preparation example 3, and the rest of the procedure was the same as that of example 4.
Comparative example
Comparative example 1
The preservative of comparative example 1 is different from that of example 4 in that the modified chitosan was replaced with chitosan of the same mass, and the remaining steps were the same as those of example 4.
Comparative example 2
The preservative obtained in example 2 of the Chinese invention patent application with the publication number of CN 104351331A.
Application example 1
A preservation method of macaque fruits comprises the following specific steps:
1) cleaning the kiwi fruits with clear water, blowing air on the surfaces of the kiwi fruits, drying water drops on the surfaces of the kiwi fruits by blowing, then uniformly spraying a preservative on the surfaces of the kiwi fruits, naturally airing, and storing the kiwi fruits in a warehouse;
2) the temperature of the warehouse is set to be 20 ℃, and an ethylene remover is arranged in the warehouse to reduce the ethylene content in the warehouse and keep ventilation.
The preservative was obtained from example 1.
Application examples 2 to 13
The difference between the kiwi fruit preservation method of application examples 2-13 and application example 1 is that the preservative is sequentially from examples 2-11 and comparative examples 1-2, and the rest steps are the same as application example 1.
Application example 14
The difference between the kiwi fruit preservation method of application example 14 and application example 1 is that the temperature of the warehouse in step 2) is set to 35 ℃, and the rest steps are the same as application example 1.
Performance test
Detection method/test method
Randomly grouping picked kiwi fruits into 15 groups, wherein each group comprises 25 kiwi fruits, and sequentially storing the kiwi fruits by using the preservation method of application examples 1-14; and the rest group is a blank control group, the kiwi fruits in the blank control group are not sprayed with the preservative, the preservation temperature is 25 ℃, and then the softening number of the kiwi fruits is counted after 15 days.
The fruit quality determination method comprises the following steps: the content of soluble total sugar is measured by anthrone colorimetry, wherein the change rate of the content of soluble total sugar is (changed amount/original content) × 100%;
the vitamin C content was measured by the 2, 6-dichloroindophenol method, in which the vitamin C reduction rate (amount of change/original content) × 100%.
TABLE 3 preservation of Kiwi fruits by the preservation method of application examples 1-14
From the detection results in table 3, it can be seen that with the adoption of the preservative and the kiwi fruit preservation method, kiwi fruits with low change rate of soluble total sugar, low reduction of vitamin C, and few softening number and rotting number can be obtained at the storage temperature of 25-30 ℃, which are superior to the kiwi fruit storage method in application example 13, wherein in the kiwi fruit preservation method, the rotting number is almost 0, and a good preservative effect is achieved.
From the test data of application example 4 and application examples 6-9, it can be seen that when the amount of the added modified chitosan is gradually increased, the change of the soluble total sugar of the kiwi fruits is not obviously influenced, the decrease rate of the vitamin C is gradually reduced, but the rising trend of the vitamin C is gradually reduced after the addition amount of the modified chitosan is 0.45 kg.
As can be seen from the test data of application example 4 and application examples 10 to 11, the modified chitosans obtained in preparation examples 1 to 3 were not significantly different in properties.
As can be seen from the detection data of application example 4 and application example 12, the change rate of soluble total sugar, the reduction rate of vitamin C, the softening number and the rotting number of the kiwi fruits are better than those of the kiwi fruits by adding the modified chitosan, and the modified chitosan has better solubility in water, so that the preservative can form a film on the surfaces of the kiwi fruits better, and the preservative has better effect.
From the test data of example 1 and application 14, it can be seen that at the warehouse temperature of 20 ℃ or 30 ℃, relatively fresh kiwi fruits can be obtained.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. An antistaling agent for kiwi fruit is characterized in that the antistaling agent is prepared from the following raw materials, by weight, 0.3-0.5 part of modified chitosan, 0.5-0.7 part of calcium chloride, 0.3-0.5 part of citric acid, 0.12-0.14 part of salicylic acid, 0.13-0.15 part of sodium alginate, 0.2-0.4 part of sodium isocyanate, 0.2-0.4 part of sodium iso-VC and 30-40 parts of water;
wherein the modified chitosan is prepared by reacting iminodiacetonitrile, epichlorohydrin and chitosan.
2. The kiwi fruit preservative according to claim 1, characterized in that: the formula of the preservative is as follows: 0.40-0.45 part of modified chitosan, 0.55-0.60 part of calcium chloride, 0.45-0.50 part of citric acid, 0.13-0.14 part of salicylic acid, 0.14-0.15 part of sodium alginate, 0.2-0.3 part of sodium isocyanate, 0.2-0.3 part of sodium erythorbate and 35-38 parts of water.
3. The kiwi fruit preservative according to claim 1, characterized in that: the preparation method of the modified chitosan comprises the following steps of:
1) adding 0.10-0.13 part of iminodiacetonitrile into 4-6 parts of tetrahydrofuran, uniformly stirring, heating to 55-60 ℃, then adding 0.07-0.09 part of epoxy chloropropane, and stirring for reacting for 4-5 hours to obtain a mixed solution A; adding a sodium hydroxide aqueous solution into the mixed solution A, wherein the amount of the substance of the epichlorohydrin is 1.1-1.3 times of the amount of the substance of the sodium hydroxide, stirring for reacting for 1-2h, then adjusting the pH value to be neutral to obtain a mixed solution B, and concentrating the mixed solution B to obtain a solid C;
2) adding 0.5-1.0 part of chitosan into 5-7 parts of acetic acid solution with the concentration of 0.5-1.5mol/L, stirring until the chitosan is dissolved to obtain solution D, then adding the solid C into the solution D, and stirring for reacting for 2-3h to obtain solution E;
3) and adding ethanol with the volume same as that of the solution E into the solution E, standing for 1-2h, filtering to obtain a solid A, washing, and drying to obtain the modified chitosan.
4. The kiwi fruit preservative according to claim 3, characterized in that: and (2) dropwise adding the epoxy chloropropane in the step 1), and dropwise adding 0.07-0.09 part of epoxy chloropropane at the dropwise adding speed of 1-2mL/min while stirring.
5. The kiwi fruit preservative according to claim 3, characterized in that: the mass percentage concentration of the sodium hydroxide solution in the step 1) is 35-40%, and the pH is adjusted by adding 0.1-0.3mol/L hydrochloric acid.
6. The kiwi fruit preservative according to claim 3, characterized in that: the drying temperature in the step 3) is 60-70 ℃, and the drying time is 1-2 h.
7. The kiwi fruit preservative according to claims 1-6, characterized in that: the preparation steps of the preservative are as follows:
adding modified chitosan, calcium chloride, citric acid, salicylic acid, sodium alginate, iso-VC sodium, etc. into water, and stirring to dissolve.
8. The kiwi fruit preservative according to claims 1-6, characterized in that: the chitosan is chitosan oligosaccharide.
9. A method of preserving kiwi fruit according to any one of claims 1 to 6, wherein: which comprises the following steps:
1) cleaning the kiwi fruits with clear water, blowing air on the surfaces of the kiwi fruits, drying water drops on the surfaces of the kiwi fruits by blowing, then uniformly spraying a preservative on the surfaces of the kiwi fruits, naturally airing, and storing the kiwi fruits in a warehouse;
2) an ethylene remover is arranged in the warehouse to reduce the ethylene content in the warehouse and keep ventilation.
10. The method for preserving kiwi fruit according to claim 9, wherein: the temperature of the warehouse in the step 2) is set to be 20-30 ℃.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112167336A (en) * | 2020-09-10 | 2021-01-05 | 长沙沃霖农副产品开发有限公司 | Chinese chestnut storage method |
CN114532397A (en) * | 2022-02-25 | 2022-05-27 | 贵州省现代农业发展研究所(贵州省现代农村发展研究中心、贵州省农村经济与社会发展科学研究所、贵州省农产品加工研究所) | Preparation method of kiwi fruit preservative |
CN114794223A (en) * | 2022-04-15 | 2022-07-29 | 广西东鸣现代农业发展有限公司 | Kiwi fruit normal-temperature storage and preservation method |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102492071A (en) * | 2011-12-09 | 2012-06-13 | 湖南科技大学 | Macromolecule chelating agent and preparation method thereof |
CN104351332A (en) * | 2014-12-08 | 2015-02-18 | 贵州大学 | Kiwi fruit compound preservative, preparation method thereof and kiwi fruit preservation method |
CN112063842A (en) * | 2020-08-18 | 2020-12-11 | 温州科锐环境资源利用有限公司 | Deplating recovery process for electroplating ABS (acrylonitrile butadiene styrene) plastic |
CN112244151A (en) * | 2020-10-19 | 2021-01-22 | 北京华阜康生物科技股份有限公司 | Immunodeficiency mouse feed and preparation process thereof |
CN113638249A (en) * | 2021-08-17 | 2021-11-12 | 新昌县高纤纺织有限公司 | Printing and dyeing auxiliary for textile fabric finishing and preparation method thereof |
-
2020
- 2020-09-10 CN CN202010949711.9A patent/CN112167330A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102492071A (en) * | 2011-12-09 | 2012-06-13 | 湖南科技大学 | Macromolecule chelating agent and preparation method thereof |
CN104351332A (en) * | 2014-12-08 | 2015-02-18 | 贵州大学 | Kiwi fruit compound preservative, preparation method thereof and kiwi fruit preservation method |
CN112063842A (en) * | 2020-08-18 | 2020-12-11 | 温州科锐环境资源利用有限公司 | Deplating recovery process for electroplating ABS (acrylonitrile butadiene styrene) plastic |
CN112244151A (en) * | 2020-10-19 | 2021-01-22 | 北京华阜康生物科技股份有限公司 | Immunodeficiency mouse feed and preparation process thereof |
CN113638249A (en) * | 2021-08-17 | 2021-11-12 | 新昌县高纤纺织有限公司 | Printing and dyeing auxiliary for textile fabric finishing and preparation method thereof |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112167336A (en) * | 2020-09-10 | 2021-01-05 | 长沙沃霖农副产品开发有限公司 | Chinese chestnut storage method |
CN114532397A (en) * | 2022-02-25 | 2022-05-27 | 贵州省现代农业发展研究所(贵州省现代农村发展研究中心、贵州省农村经济与社会发展科学研究所、贵州省农产品加工研究所) | Preparation method of kiwi fruit preservative |
CN114794223A (en) * | 2022-04-15 | 2022-07-29 | 广西东鸣现代农业发展有限公司 | Kiwi fruit normal-temperature storage and preservation method |
CN115005387A (en) * | 2022-06-15 | 2022-09-06 | 安徽王家坝生态农业有限公司 | Fresh-keeping and easy-to-store pressed salted duck and preparation method thereof |
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