CN113412860A - Preservative for rice storage and preparation process thereof - Google Patents
Preservative for rice storage and preparation process thereof Download PDFInfo
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- CN113412860A CN113412860A CN202110791100.0A CN202110791100A CN113412860A CN 113412860 A CN113412860 A CN 113412860A CN 202110791100 A CN202110791100 A CN 202110791100A CN 113412860 A CN113412860 A CN 113412860A
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- 235000007164 Oryza sativa Nutrition 0.000 title claims abstract description 62
- 235000009566 rice Nutrition 0.000 title claims abstract description 62
- 239000003755 preservative agent Substances 0.000 title claims abstract description 33
- 230000002335 preservative effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 240000007594 Oryza sativa Species 0.000 title abstract 3
- 229920001218 Pullulan Polymers 0.000 claims abstract description 63
- 239000004373 Pullulan Substances 0.000 claims abstract description 63
- 235000019423 pullulan Nutrition 0.000 claims abstract description 63
- 229940094952 green tea extract Drugs 0.000 claims abstract description 23
- 235000020688 green tea extract Nutrition 0.000 claims abstract description 23
- 235000020708 ginger extract Nutrition 0.000 claims abstract description 19
- 229940002508 ginger extract Drugs 0.000 claims abstract description 19
- 150000004676 glycans Chemical class 0.000 claims abstract description 19
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 19
- 239000005017 polysaccharide Substances 0.000 claims abstract description 19
- 240000003183 Manihot esculenta Species 0.000 claims abstract description 16
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims abstract description 16
- 229920002472 Starch Polymers 0.000 claims abstract description 16
- 235000019698 starch Nutrition 0.000 claims abstract description 16
- 239000008107 starch Substances 0.000 claims abstract description 16
- 229940116257 pepper extract Drugs 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 241000209094 Oryza Species 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000543 intermediate Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000502 dialysis Methods 0.000 claims description 10
- 235000010384 tocopherol Nutrition 0.000 claims description 10
- 229960001295 tocopherol Drugs 0.000 claims description 10
- 229930003799 tocopherol Natural products 0.000 claims description 10
- 239000011732 tocopherol Substances 0.000 claims description 10
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- RZRQBRMLTFIIND-UHFFFAOYSA-N 1,4-dimethyl-2h-pyridine Chemical compound CN1CC=C(C)C=C1 RZRQBRMLTFIIND-UHFFFAOYSA-N 0.000 claims description 7
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 7
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 229940014800 succinic anhydride Drugs 0.000 claims description 7
- 239000008055 phosphate buffer solution Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- 238000009849 vacuum degassing Methods 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 244000269722 Thea sinensis Species 0.000 claims description 3
- 235000009569 green tea Nutrition 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229940032147 starch Drugs 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 235000002568 Capsicum frutescens Nutrition 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 241000234314 Zingiber Species 0.000 description 6
- 235000006886 Zingiber officinale Nutrition 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 235000008397 ginger Nutrition 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 229940007061 capsicum extract Drugs 0.000 description 4
- 239000001943 capsicum frutescens fruit extract Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 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
- A23B9/00—Preservation of edible seeds, e.g. cereals
- A23B9/14—Coating with a protective layer; Compositions or apparatus therefor
-
- 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
- A23B9/00—Preservation of edible seeds, e.g. cereals
- A23B9/16—Preserving with chemicals
- A23B9/24—Preserving with chemicals in the form of liquids or solids
- A23B9/26—Organic compounds; Microorganisms; Enzymes
-
- 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
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0018—Pullulan, i.e. (alpha-1,4)(alpha-1,6)-D-glucan; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Food Science & Technology (AREA)
- Wood Science & Technology (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
The invention discloses a preservative for rice storage and a preparation process thereof, and belongs to the technical field of rice storage. The preservative comprises the following raw materials in parts by weight: 40-80 parts of modified pullulan polysaccharide, 15-25 parts of cassava starch, 3.5-10.5 parts of ginger extract, 1.5-5.5 parts of pepper extract, 3-8 parts of film forming auxiliary agent and 0.3-1.2 parts of green tea extract. In addition, cassava starch is introduced into a pullulan film substrate, and is introduced into a film substrate by utilizing the branched chain structure characteristic of the cassava starch, so that the mechanical property and barrier property of a formed film can be improved, and the fresh-keeping capacity of the fresh-keeping agent under a humid condition is improved.
Description
Technical Field
The invention belongs to the technical field of rice storage, and particularly relates to a preservative for rice storage and a preparation process thereof.
Background
The preservation of rice has been a difficult problem in the preservation of grains, especially in high-temperature and high-humidity seasons, mold is easy to grow, mildew and quality deterioration occur, and the main causes are that the rice nutrient is exposed in high-temperature and high-humidity air for a long time, and is polluted by mold and the like and fatty acid contained in the rice nutrient is oxidized. And the changes reduce the color, aroma, taste, nutritive value and edible quality of the rice, and the rice is aged. In addition, some microorganisms, especially mold, are liable to grow in the rice, decomposing the nutritional components in the rice; many intermediates and even toxins are also produced. Therefore, the fresh-keeping and storage problems of rice are receiving much attention.
Chinese patent CN201810116903.4 discloses a preparation method of a pullulan-based rice preservative, which discloses that pullulan is used as a film-forming substrate, and the good film-forming property and oxygen resistance of the pullulan and the oxidation resistance of ascorbic acid are utilized to achieve the effect of preserving rice. However, pullulan films are brittle, hydrophilic and lacking in antibacterial property, and when a pullulan film is coated on the surface of rice, the pullulan film absorbs water easily in a humid environment, so that the dryness of the pullulan film is difficult to maintain, ascorbic acid is oxidized and decomposed in water, and the antioxidant property of the preservative after moisture absorption is greatly reduced. Therefore, the rice preservative provided by the invention hardly plays a role in keeping rice fresh in a humid environment, such as rainy seasons in high-temperature and high-humidity areas in south China or in eastern areas.
Therefore, the invention provides the rice storage preservative and the preparation process thereof.
Disclosure of Invention
The invention aims to provide a rice storage preservative and a preparation process thereof.
The technical problems to be solved by the invention are as follows: the common pullulan-based rice preservative has the technical problems that the common pullulan-based rice preservative is easy to absorb water, wet and mildew in a humid environment.
The purpose of the invention can be realized by the following technical scheme:
an antistaling agent for rice storage comprises the following raw materials in parts by weight: 40-80 parts of modified pullulan polysaccharide, 15-25 parts of cassava starch, 3.5-10.5 parts of ginger extract, 1.5-5.5 parts of pepper extract, 3-8 parts of film forming auxiliary agent and 0.3-1.2 parts of green tea extract.
Further, the film forming auxiliary agent is one of glycerol and butanediol.
Further, the modified pullulan polysaccharide is prepared by the following steps:
step A, dissolving tocopherol and succinic anhydride in anhydrous pyridine, reacting for 48 hours at room temperature, dripping reaction liquid into hydrochloric acid solution with the pH value of 12, separating out white flocculent precipitate, refrigerating at 0 ℃ overnight, performing suction filtration, washing with deionized water for 3 times, recrystallizing with ethanol, and performing vacuum drying to obtain an intermediate 1, wherein the phenolic hydroxyl group and the anhydride are used for reaction, wherein the dosage ratio of the tocopherol to the succinic anhydride to the anhydrous pyridine is 0.005 mol: 0.02-0.03 mol: 20-50mL, the reaction formula is shown as follows;
and step B, dissolving the pullulan in deionized water, adding a sodium periodate solution under the condition of keeping out of the sun at room temperature, stirring for reaction for 6 hours, putting a reaction product into a dialysis bag, dialyzing for 3 days with the deionized water, intercepting a product with the molecular weight of 10000-12000 to obtain oxidized pullulan, and oxidizing hydroxyl groups on the pullulan molecules by using the sodium periodate, wherein the dosage ratio of the pullulan to the deionized water to the sodium periodate solution is 10 g: 50-100 mL: 10g, wherein the concentration of the sodium periodate in the sodium periodate solution is 0.05mol/L, and the reaction formula is shown as follows;
and step C, dissolving pullulan oxide in deionized water, dropwise adding ethylenediamine under the stirring state, reacting for 4 hours at room temperature, adding a sodium cyanoborohydride solution, reacting for 24 hours at room temperature, putting a reaction product into a dialysis bag, dialyzing for 2 days with the deionized water, intercepting a product with the molecular weight of 11000-14000 to obtain an intermediate 2, reacting amino in the ethylenediamine with aldehyde group in the pullulan oxide, and aminating in the presence of the sodium cyanoborohydride, wherein the dosage ratio of the pullulan oxide to the deionized water to the ethylenediamine to the sodium cyanoborohydride solution is 0.001 mol: 10-50 mL: 0.001 mol: 2g, wherein the dosage ratio of the sodium cyanoborohydride to the deionized water in the sodium cyanoborohydride solution is 0.03-0.05 g: 2mL, the reaction formula is shown below;
step C, dissolving the intermediate 2 in anhydrous dimethyl sulfoxide to obtain a solution a, dissolving the intermediates 1, 4-dimethylpyridine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in the anhydrous dimethyl sulfoxide, and stirring at room temperature for reaction for 1h to obtain a solution b; and then, dripping the solution b into the solution a at a dripping speed of 1 drop/second, reacting for 48 hours, precipitating with absolute ethyl alcohol, filtering, and drying to obtain modified pullulan, wherein the hydrophobic modification of the pullulan is realized by utilizing the reaction of carboxyl in the intermediate 1 and amino in the intermediate 1, wherein the dosage ratio of the intermediate 2 to anhydrous dimethyl sulfoxide in the solution a is 0.001 mol: 10-30mL, wherein the dosage ratio of the intermediate 1, 4-dimethylpyridine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and anhydrous dimethyl sulfoxide in the solution b is 0.001 mol: 0.0012 mol: 0.0012 mol: 10-30mL, the molar ratio of intermediate 2 to intermediate 1 is 1: 1-1.2, the reaction formula is shown as follows.
Further, the ginger extract is prepared by the following steps:
cleaning ginger, drying, slicing, and crushing the dried ginger slices by using a crusher to obtain dried ginger powder; then, according to the feed-liquid ratio of 1: 20-30 adding 80% ethanol, extracting under 57 deg.C water bath, stirring for 3 hr, cooling to room temperature, centrifuging, filtering, and concentrating to obtain rhizoma Zingiberis recens extract.
Further, the capsicum extract is prepared by the following steps:
screening chili powder by a 50-mesh sieve, and then mixing the chili powder and the chili powder according to a material-liquid ratio of 1: 6 adding 80% ethanol, extracting in water bath at 55 deg.C under stirring for 4 hr, centrifuging, filtering, concentrating, and drying to constant weight to obtain Capsici fructus extract.
Further, the green tea extract is prepared by the following steps:
pulverizing dried green tea into powder, sieving with 50 mesh sieve, adding into 60-80% ethanol solution by mass, performing ultrasonic treatment at 75 deg.C for 60min, leaching for 2 hr, cooling to room temperature, centrifuging, filtering, and concentrating to obtain green tea extract.
A preparation process of a preservative for rice storage comprises the following steps:
adding modified pullulan polysaccharide and cassava starch into a phosphate buffer solution, swelling for 20-40min at room temperature when the solid concentration is 15-18 wt%, adding a ginger extract, a pepper extract, a film forming aid and a green tea extract under a stirring state, adding ethanol to enable the solid concentration to be 7-12 wt%, stirring at room temperature until the solid concentration is completely dissolved, enabling the solution to be clear and transparent, and finally performing vacuum degassing for 15-25min to obtain the rice storage preservative.
The invention has the beneficial effects that:
according to the invention, the reaction of amino and carboxyl is utilized to graft the tocopherol onto the molecular chain of the pullulan, so that the hydrophobic structure of the tocopherol is utilized to reduce the hygroscopicity of the pullulan and the hygroscopicity of the preservative under a humid condition, and the tocopherol has certain inoxidizability, so that the modified pullulan has certain inoxidizability, and the mildew of the preservative under the humid condition is avoided;
the fresh-keeping agent of the invention is introduced with ginger extract, pepper extract and green tea extract, and biological source extract is used as additive to increase the antibacterial, antioxidant and fresh-keeping capability of the fresh-keeping agent.
In conclusion, the rice preservative provided by the invention has small hygroscopicity under a humid condition and excellent antibacterial and antioxidant capabilities.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the modified pullulan polysaccharide is prepared by the following steps:
step A, dissolving tocopherol and succinic anhydride in anhydrous pyridine, reacting for 48 hours at room temperature, dripping reaction liquid into hydrochloric acid solution with the pH value of 12, separating out white flocculent precipitate, refrigerating at 0 ℃ overnight, performing suction filtration, washing with deionized water for 3 times, recrystallizing with ethanol, and performing vacuum drying to obtain an intermediate 1, wherein the phenolic hydroxyl group and the anhydride are used for reaction, wherein the dosage ratio of the tocopherol to the succinic anhydride to the anhydrous pyridine is 0.005 mol: 0.02 mol: 20 mL;
and step B, dissolving the pullulan in deionized water, adding a sodium periodate solution under the condition of keeping out of the sun at room temperature, stirring for reaction for 6 hours, putting a reaction product into a dialysis bag, dialyzing for 3 days with the deionized water, intercepting a product with the molecular weight of 10000 to obtain oxidized pullulan, and oxidizing hydroxyl groups on the pullulan molecules by using the sodium periodate, wherein the dosage ratio of the pullulan to the deionized water to the sodium periodate solution is 10 g: 50mL of: 10g, wherein the concentration of the sodium periodate in the sodium periodate solution is 0.05 mol/L;
and step C, dissolving pullulan oxide in deionized water, dropwise adding ethylenediamine under a stirring state, reacting for 4 hours at room temperature, adding a sodium cyanoborohydride solution, reacting for 24 hours at room temperature, putting a reaction product into a dialysis bag, dialyzing for 2 days with deionized water, intercepting a product with a molecular weight of 11000 to obtain an intermediate 2, reacting amino in ethylenediamine with aldehyde groups in the pullulan oxide, and aminating in the presence of sodium cyanoborohydride, wherein the dosage ratio of the pullulan oxide, the deionized water, the ethylenediamine and the sodium cyanoborohydride solution is 0.001 mol: 10mL of: 0.001 mol: 2g, wherein the dosage ratio of the sodium cyanoborohydride to the deionized water in the sodium cyanoborohydride solution is 0.03 g: 2 mL;
step C, dissolving the intermediate 2 in anhydrous dimethyl sulfoxide to obtain a solution a, dissolving the intermediates 1, 4-dimethylpyridine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in the anhydrous dimethyl sulfoxide, and stirring at room temperature for reaction for 1h to obtain a solution b; and then, dripping the solution b into the solution a at a dripping speed of 1 drop/second, reacting for 48 hours, precipitating with absolute ethyl alcohol, filtering, and drying to obtain modified pullulan, wherein the hydrophobic modification of the pullulan is realized by utilizing the reaction of carboxyl in the intermediate 1 and amino in the intermediate 1, wherein the dosage ratio of the intermediate 2 to anhydrous dimethyl sulfoxide in the solution a is 0.001 mol: 10mL, the dosage ratio of the intermediate 1, 4-dimethylpyridine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and anhydrous dimethyl sulfoxide in the solution b is 0.001 mol: 0.0012 mol: 0.0012 mol: 10mL, molar ratio of intermediate 2 to intermediate 1 was 1: 1.
example 2:
the modified pullulan polysaccharide is prepared by the following steps:
step A, dissolving tocopherol and succinic anhydride in anhydrous pyridine, reacting for 48 hours at room temperature, dripping reaction liquid into hydrochloric acid solution with the pH value of 12, separating out white flocculent precipitate, refrigerating at 0 ℃ overnight, performing suction filtration, washing with deionized water for 3 times, recrystallizing with ethanol, and performing vacuum drying to obtain an intermediate 1, wherein the phenolic hydroxyl group and the anhydride are used for reaction, wherein the dosage ratio of the tocopherol to the succinic anhydride to the anhydrous pyridine is 0.005 mol: 0.03 mol: 50 mL;
and step B, dissolving the pullulan in deionized water, adding a sodium periodate solution under the condition of keeping out of the sun at room temperature, stirring for reaction for 6 hours, putting a reaction product into a dialysis bag, dialyzing for 3 days with the deionized water, intercepting a product with the molecular weight of 12000 to obtain pullulan oxide, and oxidizing hydroxyl groups on the pullulan molecules by using the sodium periodate, wherein the dosage ratio of the pullulan to the deionized water to the sodium periodate solution is 10 g: 100mL of: 10g, wherein the concentration of the sodium periodate in the sodium periodate solution is 0.05 mol/L;
and step C, dissolving pullulan oxide in deionized water, dropwise adding ethylenediamine under a stirring state, reacting for 4 hours at room temperature, adding a sodium cyanoborohydride solution, reacting for 24 hours at room temperature, putting a reaction product into a dialysis bag, dialyzing for 2 days with deionized water, intercepting a product with a molecular weight of 14000 to obtain an intermediate 2, reacting amino in ethylenediamine with aldehyde groups in the pullulan oxide, and aminating in the presence of sodium cyanoborohydride, wherein the dosage ratio of the pullulan oxide, the deionized water, the ethylenediamine and the sodium cyanoborohydride solution is 0.001 mol: 50mL of: 0.001 mol: 2g, wherein the dosage ratio of the sodium cyanoborohydride to the deionized water in the sodium cyanoborohydride solution is 0.05 g: 2 mL;
step C, dissolving the intermediate 2 in anhydrous dimethyl sulfoxide to obtain a solution a, dissolving the intermediates 1, 4-dimethylpyridine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in the anhydrous dimethyl sulfoxide, and stirring at room temperature for reaction for 1h to obtain a solution b; and then, dripping the solution b into the solution a at a dripping speed of 1 drop/second, reacting for 48 hours, precipitating with absolute ethyl alcohol, filtering, and drying to obtain modified pullulan, wherein the hydrophobic modification of the pullulan is realized by utilizing the reaction of carboxyl in the intermediate 1 and amino in the intermediate 1, wherein the dosage ratio of the intermediate 2 to anhydrous dimethyl sulfoxide in the solution a is 0.001 mol: 30mL, the dosage ratio of the intermediate 1, 4-dimethylpyridine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and anhydrous dimethyl sulfoxide in the solution b is 0.001 mol: 0.0012 mol: 0.0012 mol: 30mL, and the molar ratio of intermediate 2 to intermediate 1 is 1.2.
Example 3:
an antistaling agent for rice storage comprises the following raw materials in parts by weight: 40 parts of the modified pullulan prepared in example 1, 15 parts of tapioca starch, 3.5 parts of ginger extract, 1.5 parts of pepper extract, 3 parts of film forming aid and 0.3 part of green tea extract; the film-forming aid is glycerol.
The ginger extract is prepared by the following steps:
cleaning ginger, drying, slicing, and crushing the dried ginger slices by using a crusher to obtain dried ginger powder; then, according to the feed-liquid ratio of 1: 20 adding 80% ethanol by weight for leaching, stirring and extracting for 3h in water bath at 57 ℃, cooling to room temperature for centrifuging, filtering, and concentrating to obtain rhizoma Zingiberis recens extract.
The capsicum extract is prepared by the following steps:
screening chili powder by a 50-mesh sieve, and then mixing the chili powder and the chili powder according to a material-liquid ratio of 1: 6 adding 80% ethanol, extracting in water bath at 55 deg.C under stirring for 4 hr, centrifuging, filtering, concentrating, and drying to constant weight to obtain Capsici fructus extract.
The green tea extract is prepared by the following steps:
pulverizing dried green tea into powder, sieving with 50 mesh sieve, adding into 60% ethanol solution, performing ultrasonic treatment at 75 deg.C for 60min, leaching for 2 hr, cooling to room temperature, centrifuging, filtering, and concentrating to obtain green tea extract.
The rice storage preservative is prepared by the following steps:
adding modified pullulan polysaccharide and cassava starch into a phosphate buffer solution, swelling for 40min at room temperature, adding a ginger extract, a pepper extract, a film forming aid and a green tea extract under a stirring state, adding ethanol to enable the solid concentration to be 7 wt%, stirring at room temperature until the solid concentration is completely dissolved, enabling the solution to be clear and transparent, and finally vacuum degassing for 25min to obtain the rice storage preservative.
Example 4:
an antistaling agent for rice storage comprises the following raw materials in parts by weight: 60 parts of the modified pullulan prepared in example 2, 17 parts of tapioca starch, 7 parts of ginger extract, 3 parts of pepper extract, 6 parts of a film forming aid, and 0.7 part of green tea extract; the film-forming aid is butanediol.
The ginger extract is prepared by the following steps: prepared according to the procedure of example 3.
The capsicum extract is prepared by the following steps: prepared according to the procedure of example 3.
The green tea extract is prepared by the following steps: prepared according to the procedure of example 3.
The rice storage preservative is prepared by the following steps:
adding the modified pullulan polysaccharide and the cassava starch into a phosphate buffer solution, swelling for 30min at room temperature when the solid concentration is 16 wt%, adding the ginger extract, the pepper extract, the film forming aid and the green tea extract under stirring, adding ethanol to make the solid concentration be 10 wt%, stirring at room temperature until the solid concentration is completely dissolved, and obtaining a clear and transparent solution, and finally vacuum degassing for 25min to obtain the rice storage preservative.
Example 5:
an antistaling agent for rice storage comprises the following raw materials in parts by weight: 80 parts of modified pullulan polysaccharide prepared in the step 1, 25 parts of cassava starch, 10.5 parts of ginger extract, 5.5 parts of pepper extract, 8 parts of film forming aid and 1.2 parts of green tea extract; the film-forming aid is glycerol.
The ginger extract is prepared by the following steps: prepared according to the procedure of example 3.
The capsicum extract is prepared by the following steps: prepared according to the procedure of example 3.
The green tea extract is prepared by the following steps: prepared according to the procedure of example 3.
The rice storage preservative is prepared by the following steps:
adding the modified pullulan polysaccharide and the cassava starch into a phosphate buffer solution, swelling for 40min at room temperature, adding the ginger extract, the pepper extract, the film forming aid and the green tea extract under a stirring state, adding ethanol to enable the solid concentration to be 12 wt%, stirring at room temperature until the solid concentration is completely dissolved, enabling the solution to be clear and transparent, and finally vacuum degassing for 25min to obtain the rice storage preservative.
Comparative example 1:
an antistaling agent for rice storage comprises the following raw materials in parts by weight: 40 parts of pullulan polysaccharide, 15 parts of cassava starch, 3.5 parts of ginger extract, 1.5 parts of pepper extract, 3 parts of film forming auxiliary agent and 0.3 part of green tea extract; the film-forming aid is glycerol.
The remainder was the same as for example 3.
Comparative example 2:
an antistaling agent for rice storage comprises the following raw materials in parts by weight: 60 parts of the modified pullulan prepared in example 2, 7 parts of ginger extract, 3 parts of pepper extract, 6 parts of a film forming aid, and 0.7 part of green tea extract; the film-forming aid is butanediol.
The remainder was the same as in example 4.
Comparative example 3:
an antistaling agent for rice storage comprises the following raw materials in parts by weight: 80 parts of the modified pullulan polysaccharide prepared in the step 1 and 25 parts of cassava starch; the film-forming aid is glycerol.
The remainder was the same as in example 5.
Example 6:
the rice antistaling agent obtained in the examples 3-5 and the comparative examples 1-3 is sprayed on the rice under the stirring state, then the rice is stirred at 30 ℃ and dried to constant weight, the obtained treated rice and the blank rice are placed at the temperature of 30 ℃ and the humidity of 50 percent for 90 days, then the fatty acid content in the rice is sampled and measured, and the rice is placed at the temperature of 30 ℃ and the humidity of 80 percent for 40 days, then the rice is sampled and measured for mildew rate and odor, wherein, the mildew rate treats the weight of the sampled rice according to the weight of the mildewed rice, and the test data are shown as follows.
Fatty acid content | Surface mildew condition | Smell(s) | |
Example 3 | 31.78mgKOH/100g | The mildew rate is 1.02 percent | Without musty smell |
Example 4 | 30.29mgKOH/100g | Mildew rate is 0.89% | Without musty smell |
Example 5 | 32.17mgKOH/100g | Mildew rate is 0.81% | Without musty smell |
Comparative example 1 | 22.32mgKOH/100g | The mildew rate is 42.56 percent | Has a musty taste |
Comparative example 2 | 26.86mgKOH/100g | The mildew rate is 8.89 percent | Without musty smell |
Comparative example 3 | 27.26mgKOH/100g | The mildew rate is 22.67 percent | Has a musty taste |
Rice without rice husk | 17.67mgKOH/100g | Mildew rate is 73.13% | Has strong moldy taste |
As can be seen from the above table, the anti-aging ability of the antistaling agents obtained in examples 3-5 to rice is superior to the corresponding performance of the antistaling agents obtained in comparative examples 1-3; the fresh-keeping abilities of the fresh-keeping agents obtained in examples 3 to 5 under humid conditions were superior to those of the fresh-keeping agents obtained in comparative examples 1 to 3.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. A preservative for rice storage is characterized in that: the method comprises the following raw materials: modified pullulan polysaccharide, cassava starch, ginger extract, pepper extract, film forming aid and green tea extract;
the modified pullulan polysaccharide is prepared by the following steps:
step A, dissolving tocopherol and succinic anhydride in anhydrous pyridine, reacting for 48 hours at room temperature, precipitating, filtering, washing with water, recrystallizing, and drying in vacuum to obtain an intermediate 1;
step B, dissolving pullulan polysaccharide in deionized water, adding sodium periodate solution at room temperature under the condition of keeping out of the sun, stirring for reaction for 6 hours, and dialyzing by a dialysis bag to obtain oxidized pullulan polysaccharide;
step C, dissolving pullulan oxide polysaccharide in deionized water, dropwise adding ethylenediamine under the stirring state, reacting for 4 hours at room temperature, adding a sodium cyanoborohydride solution, reacting for 24 hours at room temperature, dialyzing by a dialysis bag to obtain an intermediate 2;
step D, dissolving the intermediate 2 in anhydrous dimethyl sulfoxide to obtain a solution a, dissolving the intermediates 1, 4-dimethylpyridine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in the anhydrous dimethyl sulfoxide, and stirring at room temperature for reaction for 1h to obtain a solution b; and (3) dripping the solution b into the solution a, reacting for 48h, precipitating, filtering and drying to obtain the modified pullulan.
2. The rice storage preservative according to claim 1, characterized in that: the preservative for rice storage comprises the following raw materials in parts by weight: 40-80 parts of modified pullulan polysaccharide, 15-25 parts of cassava starch, 3.5-10.5 parts of ginger extract, 1.5-5.5 parts of pepper extract, 3-8 parts of film forming auxiliary agent and 0.3-1.2 parts of green tea extract.
3. The rice storage preservative according to claim 1, characterized in that: the molecular weight cut off in the dialysis bag in step B was 10000-12000.
4. The rice storage preservative according to claim 1, characterized in that: the molecular weight cut off of the dialysis bag in step C was 11000-14000.
5. The rice storage preservative according to claim 1, characterized in that: the green tea extract is prepared by the following steps:
pulverizing dried green tea into powder, sieving with 50 mesh sieve, adding into 60-80% ethanol solution by mass, performing ultrasonic treatment at 75 deg.C for 60min, leaching for 2 hr, centrifuging at room temperature, vacuum filtering, and concentrating to obtain green tea extract.
6. The preparation process of the rice storage preservative according to claim 1, wherein the preparation process comprises the following steps: the method comprises the following steps:
adding modified pullulan polysaccharide and cassava starch into a phosphate buffer solution to form a solution c, swelling for 20-40min at room temperature, adding ginger extract, pepper extract, film-forming aid and green tea extract under stirring, adding ethanol to form a solution d, stirring at room temperature to be clear and transparent, and finally vacuum degassing for 15-25min to obtain the rice storage preservative.
7. The preparation process of the rice storage preservative according to claim 6, wherein the preparation process comprises the following steps: the concentration of the solid in the solution c is 15-18 wt%.
8. The preparation process of the rice storage preservative according to claim 6, wherein the preparation process comprises the following steps: the concentration of the solid in the solution d is 7-12 wt%.
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