CN1543819A - Method for manufacturing carboxymethyl glycosaminoglycan film-forming agent for fresh-keeping of winter jujube - Google Patents

Method for manufacturing carboxymethyl glycosaminoglycan film-forming agent for fresh-keeping of winter jujube Download PDF

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CN1543819A
CN1543819A CNA2004100388526A CN200410038852A CN1543819A CN 1543819 A CN1543819 A CN 1543819A CN A2004100388526 A CNA2004100388526 A CN A2004100388526A CN 200410038852 A CN200410038852 A CN 200410038852A CN 1543819 A CN1543819 A CN 1543819A
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carboxymethylamino
polyose
solution
glycosaminoglycan
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CN100502670C (en
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陈西广
刘成圣
孟祥红
李刚
韩明修
张维学
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Abstract

The invention discloses a process for manufacturing hydroxyethyl glycosaminoglycan film-forming agent for fresh-keeping of winter jujube. The specific execution mode is as follows: soaking novel codfish crab shells into 20 times hydrochloric acid of 1N for 12h, cleaning them to neutral with clear water, adding a sodium hydrate solution of 1.5 N therein and boiling for 3 h; cleaning with clear water until the pH value indicates neutral. Said alternation processing is executed for 2 times, then they are soaked in hydrochloric acid of 3N for 36 h, and are washed to neutral. A sodium hydrate solution with a concentration of 55% with the amount of 20 times thereof is added to the obtained chitinous polysaccharide to execute a deacetylation reaction at a heating temperature of 110 DEG C for 4 h, and then the de-acetamino-polysaccharide is obtained after washing and drying treatment. The hydroxyethyl group aminopolysaccharides is obtained by adding alcohol isopropylicum being 50 times thereof, solid body sodium hydrate being 1.5 times thereof, water being 0.5 time thereof and chlorethanol being 4 times thereof into the aminopolysaccharides for a reaction for 2 h, washing and drying the product with acetone. The hydroxyethyl group aminopolysaccharides is dissolved in an aqueous solution according to a concentration of 1%, and the solution is diluted to a concentration of 800 ppm after a centrifugation treatment. 0.01% Toween60 and 0.1% span60 are added into the solution which is then mixed homogeneously. Then 0.15% hard corn embryo oil and 0.15% glycerol are added in turns into the solution which is then stirred homogeneously for each addition. The raw materials adopted in accordance with the invention mainly come from dermaskeletons of crustaceans and insect, are very abundant in content; the preparation method is simple and easy to handle; the process used for winter jujube fresh-keeping exhibits excellent effects and is easy to use, with a long storage periodic time.

Description

A kind of manufacture method of carboxymethylamino polyose fresh-keeping of dong jujube film forming agent
One, technical field: the invention discloses a kind of manufacture method of glycosaminoglycan film forming agent, particularly a kind of carboxymethylamino polyose film forming agent manufacture method that is used for fresh-keeping of dong jujube.
Two, background technology: the winter jujube is nutritious, and sugar content reaches 37.1%, except containing several amino acids, protein, general flavone, nicotinic acid, Cobastab 1, B 2Outward, Vit C contents is abundant especially, can reach 3038 milligrams/1000 grams, is apple V C70 times of content, 100 times of pears.In three maturity periods, white ripe phase soluble solid content is 23.2%, increases to 37.1% to the crisp ripe phase, to full ripe stage up to 43.9%.Because the winter jujube is the typical late-maturing kind of eating raw, so the crisp ripe phase is the best period that the winter jujube is gathered, fruity the best when changeing red fully with pericarp.The winter jujube that is used for Long-term Storage, should crisp ripe be that fruit has just begun paintedly to gather when painted and be the best to being no more than 1/4 area in early days.Maturity is low excessively, and storage back local flavor is bad, and duration of storage is easily dehydration shrinkage also, the soft silk floss of pulp, not crisp; Maturity is too high, and duration of storage easily reddens, deliquescing, and the mildew that rots obviously shortens storage period.
Glycosaminoglycan claims shitosan, chitin, glycosaminoglycan, aminoglycan, crust amine again, is the product that chitin partly or entirely takes off acetyl, and formal name used at school is 1, the amino 2-deoxidation-β of 4-2--D glucose.The glycosaminoglycan glycan is mainly derived from the ectoskeleton of crustacean and insect, and content is very abundant on earth.As a kind of natural polycation compound, because it has characteristics such as good film forming, biological degradability, Bc, avirulence and broad spectrum antibacterial, more and more be subject to people's attention in the exploitation aspect inhibition bacterium and the fruit freshness preserving in recent years.The fungistatic effect of low-molecular-weight CMC is better, and the fungistatic effect of the CMC of variable concentrations is different.There are carboxyl and amino after the chitin carboxy methylation in the molecule, have good water-solubility, help shitosan and dissociate a large amount of NH +Ion deposits to the surface of somatic cells, thereby reaches antibacterial purpose.The effect of glycosaminoglycan aspect biological preservation also shows the film forming that it is good; has stronger mechanical strength; fruit surface had protective effect; the film that forms is the semi permeability film; can control the evaporation of moisture; therefore the ratio and the respiration rate of control oxygen and carbon dioxide, have the fruit freshness preserving effect.
Three, summary of the invention: purpose of the present invention be exactly at existing stored under refrigeration mode to picking time of winter jujube in advance, cause winter jujube active ingredient to descend, memory time is short simultaneously, defective such as perishable, a kind of manufacture method of glycosaminoglycan fresh-keeping of dong jujube film forming agent is provided, improves the fresh-keeping quality of winter jujube with this.
Technical matters route of the present invention is as follows:
1. with the shell of crab shell, dried small shrimp, shell-fish insect or the chitin of larva shell extraction preparations such as cicada slough and maggot, or the chitin for preparing with cell membranes such as microbial fermentation, fungi fermentation, culture plant cell; Partly or entirely take off the acetylamino polysaccharide through what chemical method, physics method or biological enzyme technology method carried out that part or all of deacetylation obtains; Also comprise with above raw material and monose through the macromolecule of chemistry and the preparation of biology enzyme method, hang down the aminosugars of molecule and oligomer.
2. above chitin obtains being dissolvable in water the carboxymethyl chitin derivative of water through carboxymethylation reaction.It also can be the carboxymethylamino polyose derivative that above glycosaminoglycan obtains through carboxymethylation reaction.
3. the carboxymethyl chitin derivative of different molecular weight or carboxymethylamino polyose derivative can also can be the hydrolysates with carboxymethyl chitin product or carboxymethylamino polyose product from different molecular weight raw material chitins or the direct carboxymethylation reaction preparation of raw material glycosaminoglycan.
4. add emulsifying agent in the carboxymethylamino polyose solution in the technology path 3, this emulsifying agent can be Toween10~80, span20~60, sucrose fatty ester, monoglyceride, odium stearate, quaternary ammonium salt etc.
5. add plant seed extract and fully emulsified even in the mixed liquor in the technology path 4, this extract can be wheat germ oil, maize germ, grape seed extract, cherry seed extract.
6. the emulsion in the technology path 5 is adjusted the pH value with acid or alkali, and the acid of use can be inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, also can be organic acid such as acetic acid, lactic acid, ascorbic acid, citric acid; Alkali can be NaOH, potassium hydroxide.
7. add the little molecular regulation osmotic pressure of organic matter in the solution in the technology path 6, the little molecule of the organic matter of adding can be sorbierite, sweet mellow wine, glucose, mannose, maltose, glycine, glycerine.
8. the solution-treated winter jujube in the technology path 7, processing mode can be to spray before plucking or pluck the back and soak.The winter jujube of selecting for use can be first red phase, half red phase and intact red phase.
9. the winter jujube after handling in the technology path 8 carries out the dry tack free film forming.The drying and forming-film mode can be that nature dries also can be to dry in the shade or cool breeze dries up.
10. the winter jujube of dry tack free film forming is deposited with the polybag packing of semi-transparent gas.Storage temperature can be-5~15 ℃, and ambient humidity can be 75~98%, has preservation.
The technical scheme of working out according to above-mentioned technology path is as follows:
1. fresh cod crab shell soaks with watery hydrochloric acid, and the hydrochloric acid consumption can be 10~100 times on a raw material cod crab shell, and concentration of hydrochloric acid can be 0.1~4N, and soak time can be 10~48 hours, and soaking number of times can be 1~3 time.After washing neutrality with clear water, add caustic soda and boil, add caustic soda amount and can be 10~100 times of raw material crab shell, caustic soda concentration can be 1~4N, and can be 2~20 hours heat time heating time, and the alkali treatment number of times can be 1~3 time.Above process also can be the soda acid alternate treatment.Finally wash pH value neutrality with clear water, drying obtains chitosan.
2. add concentrated base in the chitosan that obtains in the summary of the invention 1 and carry out deacetylation; the alkali consumption can be 10~100 times of chitosan; the concentration of alkali can be 25%~60%; heating-up temperature can be-5~25 ℃ also can be 80~120 ℃; processing time can be 2~8 hours, and the washing drying obtains taking off the acetyl chitosan and also is glycosaminoglycan.
3. the chitosan raw material in the summary of the invention 1 also can be shell or the larva shells such as cicada slough and maggot of general crab shell, dried small shrimp, shell-fish insect.Product in the summary of the invention 1 also can be the chitin of cell membrane preparations such as microbial fermentation, fungi fermentation, culture plant cell.
4. the deacetylation of the amino sugar that obtains through alkali deacetylated processing of the chitosan in the summary of the invention 2 can be 45%~55% also can be 75%~100%.
5. the process of the glycosaminoglycan in the summary of the invention 4 acid hydrolysis, oxidative degradation, enzyme degraded or irradiation-induced degradation obtain the basic glycosaminoglycan of certain molecular weight, also can be the mixtures of sized molecules amount shitosan.The molecular weight of small-molecular weight shitosan can be 2000Da~300,000 Da, and the molecular weight of macromolecule shitosan can be 40Da~2,000,000 Da.Wherein the ratio of macromolecule carboxymethylamino polyose in mixture can be 0-30%.
6. the chitosan in the summary of the invention 1,3 reacts with chloroacetic acid in organic solvent, obtains the carboxymethyl chitin derivative, and reaction condition can be at neutral or alkaline water and chloroacetate reaction; Also can be in alkali organic solvent with chloroacetate reaction, reaction dissolvent also can be the mixture of organic solvent and water.But require to react the carboxylation degree of the product that obtains in 0.7~1.4 scope.
7. the alkali of the indication in the summary of the invention 6 can be NaOH, potassium hydroxide, and consumption can be 0.5~1.2 times of chitin raw material; The organic solvent of the indication in the summary of the invention 6 can be methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isobutanol, methyl-sulfoxide, pyridine etc., and consumption can be chitinous 0~100 times an of raw material.Also can use the mixture of organic solvent and water, the hydration organic solvent can be any ratio.
8. the glycosaminoglycan in the summary of the invention 5 can carry out carboxy methylation according to the technical method in summary of the invention 6 and 7, and the carboxylation degree of product is in 0.7~1.4 scope.
9. carboxymethyl chitin or the carboxymethylamino polyose in the summary of the invention 6 and 8 is dissolved in water, also is dissolvable in water weakly alkaline solution.The concentration of solution can be 200ppm~2%.
10. add emulsifying agent in carboxymethyl chitin in the summary of the invention 9 or the carboxymethylamino polyose solution, this emulsifying agent can be Toween10~80, span20~60, sucrose fatty ester, monoglyceride, odium stearate, quaternary ammonium salt etc.The adding of emulsifying agent can be that single emulsifying agent also can be the mixture of two or more emulsifying agents, and the concentration of emulsifying agent can be 0.001~0.5%.
11. add plant seed extract and fully emulsified even in the carboxymethylamino polyose solution in the summary of the invention 10, this extract can be wheat germ oil, maize germ, grape seed extract, cherry seed extract.The consumption of plant seed extract can be 0.001~1% of a solution.
12. adjust pH value 5~8 with acid or alkali in the carboxymethylamino polyose solution in the summary of the invention 11, the acid of use can be inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, also can be organic acid such as acetic acid, lactic acid, ascorbic acid, citric acid; Alkali can be NaOH, potassium hydroxide.
13. add the little molecular regulation osmotic pressure of organic matter in the carboxymethylamino polyose solution in the summary of the invention 12, the little molecule of organic matter that adds can be sorbierite, sweet mellow wine, glucose, mannose, maltose, glycine, glycerine, and addition can be 0~1%.
14. the carboxymethylamino polyose solution in the summary of the invention 13 has low-viscosity, flowability and film forming, in winter jujube jujube surface compatibility is arranged, biocompatibility is good, can be evenly distributed on winter jujube jujube surface, forms transparent half permeability rete.
15. soak the winter jujube with the carboxymethylamino polyose composite solution in the summary of the invention 13,14, the mode of immersion can be to spray in the tree before the winter jujube is plucked, and also can be to pluck in the fresh-keeping liquid of back to soak, soak time can be 0.1~10 minute.The winter jujube of selecting for use can be first red phase, half red phase and intact red phase.Winter jujube after the processing carries out the dry tack free film forming.Drying mode can be that nature dries, and also can be to dry in the shade or cool breeze dries up, and the baking temperature scope can be 0 ℃~30 ℃, also can be excessive from the high-temperature to low temperature.
16. the winter jujube with dry tack free in the summary of the invention 14 is deposited with the polybag packing of semi-transparent gas.Storage temperature can be-5~15 ℃, and ambient humidity can be 75~98%.Storage life 90 days, no rotting rate is greater than 95%.
The preparation method of carboxymethylamino polyose fresh-keeping of dong jujube film forming agent of the present invention, the one, the raw material that adopts is mainly derived from the ectoskeleton of crustacean and insect, and content is very abundant; The 2nd, the preparation method is simple, easily operation; The 3rd, it is effective to be used for fresh-keeping of dong jujube, easy to use, and storage cycle is long.Storage relative humidity is grasped 80%~85%.90 days shelf-lifves, serviceability rate 97%.
Four, description of drawings: do not have
Five, the specific embodiment:
Fresh snow crab shell is with 20 times of 1N salt acid soak 12 hours, wash neutrality with clear water after, add the 1.5N sodium hydroxide solution and boiled 3 hours, clear water washs pH value neutrality.So alternate treatment is 2 times, uses the salt acid soak 36 hours of 3N then, washs neutrality.Add 20 times of concentration in the chitin polysaccharide that obtains and be 55% sodium hydroxide solution alkali and carry out deacetylation, 110 ℃ of heating-up temperatures were handled 4 hours, washed drying and obtained taking off the acetylamino polysaccharide.Add 50 times of isopropyl alcohols, 1.5 times of solid sodium hydroxides, 0.5 times water and 4 times chloroacetic acid 40 in the glycosaminoglycan and reacted 2 hours, ethanol washing drying obtains the methylamino polysaccharide.Concentration according to 1% is dissolved in the aqueous solution, and 800ppm is arrived with distilled water diluting in centrifugal back.Adding 0.01%Toween60 and 0.1%span60 mixes.Add 0.15% wheat germ oil, stir.The glycerine of adding 1.5% stirs and gets final product.
Carboxymethylamino polyose fresh-keeping of dong jujube film forming agent is used for the fresh-keeping of dong jujube example: as the fresh-keeping film forming agent 1000ml of the carboxymethylamino polyose of above-mentioned manufacturing, select half intact red winter phase jujube 2kg, soaked even 1 minute, dry at shady and cool place.With the packed 250g of atresia 0.025 millimeters thick polyethylene, precooling was preserved after 24 hours, and relative humidity is grasped 88%~95%.90 days shelf-lifves, serviceability rate 98%.

Claims (6)

1, a kind of manufacture method of carboxymethylamino polyose fresh-keeping of dong jujube film forming agent is characterized in that comprising: (one) is raw material with the ectoskeleton of shellfish or insect, carries out washing pH value neutrality with clear water after soda acid handles, and drying obtains chitosan; (2) add concentrated base in the chitosan and carry out deacetylation, the alkali consumption is 10-100 a times of chitosan, the concentration of alkali is 25%-60%, heating-up temperature is-5~25 ℃, or 80~120 ℃, processing time is 2~8 hours, and the washing drying obtains taking off the acetyl chitosan and also is glycosaminoglycan, and the deacetylation of glycosaminoglycan can be 45%~55% also can be 75%~100%; (3) glycosaminoglycan is the mixture of sized molecules amount shitosan through the glycosaminoglycan that acid hydrolysis, oxidative degradation, enzyme degraded or irradiation-induced degradation obtain, the molecular weight of its small-molecular weight shitosan is 2000Da~300,000 Da, the molecular weight of macromolecule shitosan is 40Da~2,000,000 Da, and the ratio of macromolecule glycosaminoglycan in mixture is 0~30%; (4) glycosaminoglycan is reacted with chloroacetic acid in solvent, obtain the carboxymethyl chitin derivative, the carboxylation degree of the product that reaction obtains is in 0.7~1.4 scope; (5) carboxymethyl chitin or the carboxymethylamino polyose after the carboxylation is dissolved in water, also is dissolvable in water weakly alkaline solution, and the concentration of solution is 200ppm~2%; (6) in above-mentioned carboxymethyl chitin or carboxymethylamino polyose solution, add emulsifying agent, this emulsifying agent comprises Toween10~80, span20~60, sucrose fatty ester, monoglyceride, odium stearate, quaternary ammonium salt, the adding of emulsifying agent can be that single emulsifying agent also can be the mixture of two or more emulsifying agents, and the concentration of emulsifying agent can be 0.001-0.5%; (7) the pH value of adjusting in carboxymethyl chitin or the carboxymethylamino polyose solution with acid or alkali is 5~8, and the acid of use can be inorganic acid, also can be organic acid, and alkali can be NaOH, potassium hydroxide; (8) add 0~1% the little molecular regulation osmotic pressure of organic matter in carboxymethyl chitin or carboxymethylamino polyose solution, the little molecule of described organic matter comprises sorbierite, sweet mellow wine, glucose, mannose, maltose, glycine, glycerine.
2, the manufacture method of carboxymethylamino polyose fresh-keeping of dong jujube film forming agent according to claim 1 is characterized in that: the ectoskeleton of shellfish or insect comprises shell or the larva shells such as cicada slough and maggot of crab shell, dried small shrimp, shell-fish insect.
3, the manufacture method of carboxymethylamino polyose fresh-keeping of dong jujube film forming agent according to claim 1, it is characterized in that: it is that ectoskeleton with shellfish or insect soaks with watery hydrochloric acid that the soda acid that at first carries out is handled, the hydrochloric acid consumption can be raw material 10-100 times, concentration of hydrochloric acid can be 0.1-4N, soak time can be 10-48 hour, and soaking number of times can be 1-3 time; After washing neutrality with clear water, add caustic soda and boil, the 10-100 that adds caustic soda amount and can be raw material crab shell doubly, caustic soda concentration can be 1-4N, can be 2-20 hour heat time heating time, the alkali treatment number of times can be 1-3 time; Above process also can be the soda acid alternate treatment.
4, the manufacture method of carboxymethylamino polyose fresh-keeping of dong jujube film forming agent according to claim 1, it is characterized in that: in carboxymethyl chitin that adds emulsifying agent or carboxymethylamino polyose solution, add plant seed extract and fully emulsified even, this extract can be wheat germ oil, maize germ, grape seed extract, cherry seed extract, and the consumption of plant seed extract is 0.001~1% of a solution.
5, the manufacture method of carboxymethylamino polyose fresh-keeping of dong jujube film forming agent according to claim 1 is characterized in that: glycosaminoglycan can be to react with chloroacetic acid at neutral or alkaline water with the chloroacetic acid reaction condition in solvent; Also can be to react with chloroacetic acid in alkali organic solvent, reaction dissolvent also can be the mixture of organic solvent and water, and wherein alkali is NaOH or potassium hydroxide, and consumption can be 0.5~1.2 times of chitin raw material; The organic solvent of indication can be methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isobutanol, methyl-sulfoxide, pyridine etc., consumption can be chitinous 0~100 times an of raw material, also can use the mixture of organic solvent and water, the hydration organic solvent can be any ratio.
6, the manufacture method of carboxymethylamino polyose fresh-keeping of dong jujube film forming agent according to claim 1, it is characterized in that: adjust pH value 5~8 with acid or alkali in the carboxymethylamino polyose solution, the acid of using can be inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, also can be organic acid such as acetic acid, lactic acid, ascorbic acid, citric acid.
CNB2004100388526A 2003-09-15 2004-05-01 Method for manufacturing carboxymethyl glycosaminoglycan film-forming agent for fresh-keeping of winter jujube Ceased CN100502670C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101971871A (en) * 2010-11-09 2011-02-16 河南农业大学 Shelling variable egg preservative agent and preparation method thereof
CN105166009A (en) * 2015-10-10 2015-12-23 广东海洋大学 Method for prolonging cold storage preservation period of tilapia fillets by means of chitosan with composite molecular weights
CN109354632A (en) * 2018-11-06 2019-02-19 中国科学院烟台海岸带研究所 A kind of carboxymethylamino polyose derivative and its preparation method and application
CN116268083A (en) * 2023-02-02 2023-06-23 响水县村嫂农业科技有限公司 Composite polysaccharide preservative and preparation method and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101971871A (en) * 2010-11-09 2011-02-16 河南农业大学 Shelling variable egg preservative agent and preparation method thereof
CN105166009A (en) * 2015-10-10 2015-12-23 广东海洋大学 Method for prolonging cold storage preservation period of tilapia fillets by means of chitosan with composite molecular weights
CN105166009B (en) * 2015-10-10 2019-01-22 广东海洋大学 A method of Tilapia Fillet refrigerated shelf life is extended using compound molecule amount chitosan
CN109354632A (en) * 2018-11-06 2019-02-19 中国科学院烟台海岸带研究所 A kind of carboxymethylamino polyose derivative and its preparation method and application
CN116268083A (en) * 2023-02-02 2023-06-23 响水县村嫂农业科技有限公司 Composite polysaccharide preservative and preparation method and application thereof

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