CN110156911A - Hydrophobic polysaccharide and its preparation method and application - Google Patents
Hydrophobic polysaccharide and its preparation method and application Download PDFInfo
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- CN110156911A CN110156911A CN201910418160.0A CN201910418160A CN110156911A CN 110156911 A CN110156911 A CN 110156911A CN 201910418160 A CN201910418160 A CN 201910418160A CN 110156911 A CN110156911 A CN 110156911A
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- Prior art keywords
- polysaccharide
- glycylglycine
- propylgallate
- glucan
- hydrophobic
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
- A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
-
- 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
-
- 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
Abstract
The present invention provides a kind of hydrophobic polysaccharide and its preparation method and application.The general structure of the hydrophobic polysaccharide is as follows: G-P-O；Wherein, G is polysaccharide or disaccharides, and P is amino acid or double peptides, and O is oleic acid；It is connect by ester bond with the hydroxyl on polysaccharide between G and P, is keyed between P and O by amide.Hydrophobic polysaccharide provided by the invention has loading performance, can be acted on by hydrogen bond and hydrophobization, propylgallate is loaded and is scattered among water phase, prepares water-soluble propylgallate and carries powder.The present invention successfully solves the problems, such as propylgallate poor biocompatibility, and hydrophobic polysaccharide can play with propylgallate and cooperate with pharmacological action.
Description
Technical field
The present invention relates to high molecular materials and technical field of organic synthesis, specifically, be related to a kind of hydrophobic polysaccharide and
Preparation method and application.
Background technique
Propylgallate is the oil-soluble inhibitor with antibacterial activity, is widely used in food oxydating resistance field.Its
Application method is generally, and propylgallate is first dissolved in vegetable oil, is then added in food.And aqueous emulsion is needed some
Antibacterial, anti-oxidation field, propylgallate fails to be applied.For example, propylgallate is nontoxic, have antibacterial living
Property, but due to lacking emulsion products, it can not be used cooperatively in mouthwash.And it is the antibacterial of food, feed, drug, Chinese medicine, anti-
It is mould and anti-oxidant, it is available also to lack product nontoxic, easy to use.
Heteroauxin is widely used in agricultural production as plant hormone, but heteroauxin is insoluble in water, uses
When need to be dissolved in being diluted with water use after being prepared into sodium salt in sodium hydrate aqueous solution.The strong oxidizing property of sodium hydroxide easily makes Yin
Indolylbutyric acid failure, there is the harm for generating waste and contaminated soil and water body, and urgent need solves the problems, such as that the formulations of pesticide are not good enough.
Summary of the invention
The object of the present invention is to provide a kind of novel hydrophobic polysaccharides and preparation method thereof.
It is a further object of the present invention to provide the applications of the hydrophobic polysaccharide, including are applied in combination with heteroauxin, with
And the purposes of aspect is applied in combination with propylgallate.
In order to achieve the object of the present invention, in a first aspect, the present invention provides a kind of hydrophobic polysaccharide, general structure is as follows: G-
P-O；Wherein, G is polysaccharide or disaccharides (as hydrophilic radical), and P is amino acid or double peptides (as linking arm), and O is that oleic acid (is made
For hydrophobic group)；Preferably, G is glucan, and P is glycylglycine.Pass through the hydroxyl on ester bond and polysaccharide between G and P
Connection is keyed between P and O by amide.
The hydrophobic polysaccharide is glucan and oleic acid base glycylglycine by condensation reaction, and preparation is with glucan
Hydrophilic radical take glycylglycine as the functional polysaccharide of loading property group using oleic acid as hydrophobic group.
In the present invention, it is more that the polysaccharide is selected from glucan, algal polysaccharides, starch, amylopectin, amylose, Propiram
Sugar, ethoxy dextran, mannosan, levulan, synanthrin, chitin, chitosan, chitin, xyloglucan, water-soluble fibre
At least one of dimension element etc..
The disaccharides is sucrose or fructose.
The amino acid or double peptides are selected from glycylglycine, glutamic acid, L-lysine, L-cysteine, the third ammonia of DL-
Acid, DL- METHIONINE, L-Orn, γ-aminobutyric acid, ASPARTIC ACID, L-thiamine, L-arginine, beta Alanine, L- melon
At least one of propylhomoserin, L-Histidine etc..
Preferably, in general formula G-P-O, G is glucan, and P is glycylglycine, the structure of the hydrophobic polysaccharide such as formula
(I) shown in:
Wherein, R1、R2Or R3In any two be H, remaining is
N is the arbitrary integer greater than 2.
The hydrophobic polysaccharide is that the hydroxyl of glucan is reacted with the carboxyl of glycylglycine, first prepares the sweet ammonia of glycyl
Sour glucan ester, then hydrophobization glucan is obtained so that the amino of glycylglycine and oleic acid are esterified with elaidin reaction.
Second aspect, the present invention provide the preparation method of the hydrophobic polysaccharide, comprising the following steps:
1) carboxyl of the hydroxyl of polysaccharide or disaccharides and amino acid or double peptides carries out esterification and generates amino acid or double peptide esters
Change polysaccharide；
2) condensation reaction occurs for amino acid or double peptide esterified saccharides and oleic acid, generates hydrophobic polysaccharide.
When the structure of the hydrophobic polysaccharide is as shown in formula (I), preparation method is as follows:
1. reacting glucan with the glycylglycine of amido protecting, proper catalyst is added and taking off
Aqua, 0~60 DEG C of reaction temperature, 1~96h of reaction time obtains glycylglycine glucan ester；
2. the amido protecting of glycylglycine glucan ester is removed, method particularly includes: by above-mentioned glycylglycine
Glucan ester is added in sodium hydrate aqueous solution, and the amino of glycylglycine dissociates rapidly, after being dried under reduced pressure water removal, redissolves
In organic solvent, oleic acid, catalyst and appropriate dehydrating agent is added, in 0~60 DEG C of 1~96h of reaction, water is added to terminate reaction；
3. will 2. gained reaction system be filtered, alcohols solvent is added into filtrate, collects precipitating, is drying to obtain hydrophobic
Change polysaccharide.
Method above-mentioned, 1. the organic solvent is selected from dimethylformamide, dimethyl sulfoxide or methylene chloride etc. to step
At least one of.
Method above-mentioned, 1., 2. the catalyst is DMAP (4-dimethylaminopyridine) and DCC (dicyclohexyl carbon to step
Diimine), dehydrating agent DCC, their dosage is appropriate.In addition, pyridine, the concentrated sulfuric acid also may be selected in catalyst；Dehydrating agent can
Select the inorganic salts such as molecular sieve, calcium chloride, zinc chloride, magnesium sulfate.
Method above-mentioned, 3. the alcohols solvent is dehydrated alcohol or methanol to step, and the dosage of the alcohols solvent is suitable
Amount.
The molar ratio of method above-mentioned, the glucan, glycylglycine and oleic acid is 1:1-2:1-2, wherein sweet ammonia
Acyl glycine and oleic acid are molar ratio mixing.It is preferred that 1:1:1 or 1:2:2.
Method above-mentioned, 3. middle reaction system is filtered step, collects filter residue, after dry, recoverable DMAP and pair
Product dicyclohexylurea (DCU) (DCU).
The third aspect, the present invention provide the hydrophobic polysaccharide, or the hydrophobic polysaccharide prepared according to the method described above with
Under any application:
A. it is used as carrier for active principle；
B. pharmacy or antibacterial agent are used for；
Wherein, the active constituent includes drug, auxin.
Hydrophobic polysaccharide carrier medicament provided by the invention can be used in compounding with other drugs.
Fourth aspect, the present invention, which provides, contains the hydrophobic polysaccharide, or the hydrophobic polysaccharide prepared according to the method described above
And the drug or composition of at least one active constituent.
Preferably, the active constituent is gallic acid and its derivative, more preferable propylgallate.
The weight ratio of the hydrophobic polysaccharide and propylgallate is 10:1-10:100, preferably 10:4-10:50.
It is highly preferred that the dosage form of the drug or composition is aqueous emulsion, Average Particle Diameters are 0~1000nm, preferably
500nm or less.Preferably, the active constituent is heteroauxin and its derivative, more preferable heteroauxin.
The weight ratio of the hydrophobic polysaccharide and heteroauxin is 10:1-10:100, preferably 10:4-10:50.
It is highly preferred that the dosage form of the drug or composition is aqueous solution.
5th aspect, the present invention provide the preparation method of the drug or composition, which comprises hydrophobization is more
Sugar is soluble in water, and propylgallate or heteroauxin is then added, and uses at probe emulsifier or ultrasonic wave after being completely dissolved
Reason until formed needed for partial size aqueous emulsion or solution to get.
Fig. 1 is that hydrophobization glucan loads the load medicine particle diameter formed in aqueous solution after propylgallate and its divides
Cloth state.The particle that is formed in aqueous solution after hydrophobization glucan load propylgallate, mostly at 500 nanometers hereinafter,
Compared with traditional lotion greater than 1 micron grain size, there is apparent advantage.
Fig. 2 is the particle diameter and its distribution that hydrophobization glucan is formed in aqueous solution.Hydrophobization glucan is certainly
Particle diameter is assembled less than 200 nanometers, the partial size after polydispersion, with load medicine is significantly different.
6th aspect, the present invention, which provides the above-mentioned aqueous emulsion prepared by the hydrophobic polysaccharide and propylgallate, (not to be had
Propyl galate lotion) application in antibacterial, anti-oxidation field.
7th aspect, invention provide the above-mentioned aqueous solution prepared by the hydrophobic polysaccharide and heteroauxin in plant growth
Application in adjusting.
By above-mentioned technical proposal, the present invention at least have following advantages and the utility model has the advantages that
(1) hydrophobic polysaccharide provided by the invention has loading performance, can be acted on, will not eaten by hydrogen bond and hydrophobization
Sub- propyl propionate is loaded and is scattered among water phase, is prepared water-soluble propylgallate and is carried powder, can well solve
The problem of propylgallate poor biocompatibility.
(2) hydrophobic polysaccharide provided by the invention not only has hydrophilic polysaccharide segment, hydrophobic oleic acid base, goes back band
There is the linking arm of amino acid or double peptides, gallic acid (or heteroauxin) and its derivative not only generate hydrophobic sample effect, also
There is the bonding action of hydrogen bond, therefore, prepared lotion (or solution) is stablized, and is not also demulsified under low concentration.
(3) hydrophobic polysaccharide synthesis of the present invention is raw materials used, all safe and nontoxic, can be used for food, medicine field.It is hydrophobic
It is nontoxic to change polysaccharide, can be decomposed entirely in nature, no acute toxicity, also without toxicity at a specified future date.Propylgallate lotion can rise antibacterial,
Antioxidation.
Detailed description of the invention
Fig. 1 is that hydrophobization glucan of the present invention loads the load medicine particle diameter formed in aqueous solution after propylgallate
And its distribution.
Fig. 2 is the particle diameter and its distribution that hydrophobization glucan of the present invention is formed in aqueous solution.
Fig. 3 is propylgallate aqueous solution (2.5mg/ml) particles size and distribution state in the embodiment of the present invention 7.
Fig. 4 is propylgallate aqueous solution (1.25mg/ml) particles size and distribution state in the embodiment of the present invention 7.
Fig. 5 is propylgallate aqueous solution (0.62mg/ml) particles size and distribution state in the embodiment of the present invention 7.
Fig. 6 is propylgallate aqueous solution (0.31mg/ml) particles size and distribution state in the embodiment of the present invention 7.
Fig. 7 is propylgallate aqueous solution (0.15mg/ml) particles size and distribution state in the embodiment of the present invention 7.
Fig. 8 is propylgallate aqueous solution (0.08mg/ml) particles size and distribution state in the embodiment of the present invention 7.
Fig. 9 is propylgallate aqueous solution (0.01mg/ml) particles size and distribution state in the embodiment of the present invention 7.
Figure 10 is that propylgallate carries sub (2.5mg/ml) the particles size and distribution state of powder in the embodiment of the present invention 7.
Figure 11 is that propylgallate carries sub (1.25mg/ml) the particles size and distribution state of powder in the embodiment of the present invention 7.
Figure 12 is that propylgallate carries sub (0.62mg/ml) the particles size and distribution state of powder in the embodiment of the present invention 7.
Figure 13 is that propylgallate carries sub (0.31mg/ml) the particles size and distribution state of powder in the embodiment of the present invention 7.
Figure 14 is kohlrabi silk brown stain experimental result in the embodiment of the present invention 8.Wherein, both the above sample is when testing initial
The photo of shooting, a are that the upper spray concentration of kohlrabi silk is that 0.1% propylgallate carries powder subsample, and b is the kohlrabi not sprayed
Silk sample；Following two sample is the photo shot when testing for 24 hours, and a is that the upper spray concentration of kohlrabi silk is 0.1% gallic acid third
Ester carries powder subsample, and b is the kohlrabi silk sample not sprayed.
Figure 15 is kohlrabi silk brown stain experimental result for 24 hours in the embodiment of the present invention 8.Wherein, a is that the upper spray concentration of kohlrabi silk is
0.1% propylgallate carries powder subsample, and b is the kohlrabi silk sample not sprayed.
Figure 16 is the particles size and distribution state of heteroauxin carrier medicament in the embodiment of the present invention 12.
Figure 17 is that wheat is soaked seed the 3rd day image in the embodiment of the present invention 12.
Figure 18 is that wheat is soaked seed the 4th day image in the embodiment of the present invention 12.
Figure 19 is that wheat is soaked seed the 5th day image in the embodiment of the present invention 12.
Figure 20 is that wheat is soaked seed the 6th day image in the embodiment of the present invention 12.
Figure 21 is that wheat is soaked seed the 7th day image in the embodiment of the present invention 12.
Figure 22 is that wheat is soaked seed the 8th day image in the embodiment of the present invention 12.
Figure 23 is that wheat is soaked seed the 9th day image in the embodiment of the present invention 12.
Figure 24 is that wheat is soaked seed the 10th day image in the embodiment of the present invention 12.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..Unless otherwise specified, embodiment
Used in the conventional means that are well known to those skilled in the art of technological means, raw materials used is commercial goods.
The molecular weight of glucan used is 10000g/mol in following embodiment.
1 hydrophobic polysaccharide of embodiment and preparation method thereof
Hydrophobic polysaccharide manufactured in the present embodiment is that the hydroxyl of glucan is reacted with glycylglycine, first prepares glycyl
Glycine glucan ester, then hydrophobization glucan is obtained so that the carboxyl of glycylglycine is esterified by oleic acid with elaidin reaction.
It is specific the preparation method is as follows:
1,100g (0.01mol) glucan is dissolved in the n,N dimethylformamide (DMF) of 2L, adds 1.6g (0.01mol)
The glycylglycine of amido protecting adds catalyst DMAP 1g and dehydrating agent DCC 10g, in room temperature reaction 48h, filtering removal
By-product of dicyclohexylurea, filtrate add water to terminate reaction on a small quantity, dehydrated alcohol 2L are added, obtaining white depositions is glycyl
Glycine glucan ester.
2, glycylglycine glucan ester 100g is added to the NAOH aqueous solution 1L of 1N, deprotection base makes glycyl
Reaction system vacuum distillation is removed moisture removal by the amino separate out of glycine.
3, the glycylglycine glucan ester 100g of above-mentioned deprotection is redissolved in appropriate 2L DMF, 2.8g is added
(0.01mol) oleic acid adds catalyst DMAP 1g and dehydrating agent DCC 10g, in room temperature reaction 48h, filtering removal two ring of by-product
Hexyl urea, filtrate add water to terminate reaction on a small quantity, dehydrated alcohol 2L are added, obtaining white depositions is hydrophobization glucan.
Step 2, the filter residue that reaction system is collected by filtration in 3 are that by-product of dicyclohexylurea (DCU) can be returned after dry
It receives and utilizes.
2 hydrophobic polysaccharide of embodiment and preparation method thereof
It is specific the preparation method is as follows:
1,100g (0.01mol) glucan is dissolved in the n,N dimethylformamide (DMF) of 4L, adds 3.2g (0.02mol)
The glycylglycine of amido protecting adds catalyst DMAP 2g and dehydrating agent DCC 20g, for 24 hours in 40 DEG C of reactions, filtering removal
By-product of dicyclohexylurea, filtrate add water to terminate reaction on a small quantity, anhydrous methanol 4L are added, obtaining white depositions is glycyl
Glycine glucan ester.
2, glycylglycine glucan ester 100g is added to the NAOH aqueous solution 2L of 1N, deprotection base makes glycyl
Reaction system vacuum distillation is removed moisture removal by the amino separate out of glycine.
3, the glycylglycine glucan ester 100g of above-mentioned deprotection is redissolved in 4L DMF, 5.6g is added
(0.02mol) oleic acid adds catalyst DMAP 2g and dehydrating agent DCC 20g, for 24 hours in 40 DEG C of reactions, filtering removal two ring of by-product
Hexyl urea, filtrate add water to terminate reaction on a small quantity, anhydrous methanol 4L are added, obtaining white depositions is hydrophobization glucan.
3 hydrophobic polysaccharide of embodiment and preparation method thereof
It is specific the preparation method is as follows:
1,100g (0.01mol) glucan is dissolved in the n,N dimethylformamide (DMF) of 1L, adds 2.4g
The glycylglycine of (0.015mol) amido protecting adds catalyst DMAP 0.5g and dehydrating agent DCC 5g, reacts in 50 DEG C
12h, filtering removal by-product of dicyclohexylurea, filtrate add water to terminate reaction on a small quantity, dehydrated alcohol 1L are added, obtains white precipitate
Object is glycylglycine glucan ester.
2, glycylglycine glucan ester 100g is added to the NAOH aqueous solution 500ml of 1N, deprotection base makes sweet ammonia
Reaction system vacuum distillation is removed moisture removal by the amino separate out of acyl glycine.
3, the glycylglycine glucan ester 100g of above-mentioned deprotection is redissolved in 1LDMF, 4.2g is added
(0.015mol) oleic acid adds catalyst DMAP 0.5g and dehydrating agent DCC 5g, in 50 DEG C of reaction 12h, filtering removal by-product two
Cyclohexyl urea, filtrate add water to terminate reaction on a small quantity, dehydrated alcohol 1L are added, obtaining white depositions is hydrophobization glucan.
4 propylgallate lotion of embodiment and preparation method thereof
Hydrophobic polysaccharide 30g prepared by embodiment 1 is dissolved in water 1L, propylgallate 10g is then added, it is completely molten
Add water 3L after solution at room temperature, using probe emulsifier or ultrasonication until formation Average Particle Diameters are
615.1nm, the aqueous emulsion of polydispersion, as propylgallate lotion.
5 propylgallate lotion of embodiment and preparation method thereof
Hydrophobic polysaccharide 30g prepared by embodiment 2 is dissolved in water 500mL, propylgallate 20g is then added, it is complete
Add water 500mL after fully dissolved at room temperature, using probe emulsifier or ultrasonication until formation partial size is less than 1 μm,
The aqueous emulsion of polydispersion, as propylgallate lotion.
6 propylgallate lotion of embodiment and preparation method thereof
Hydrophobic polysaccharide 30g prepared by embodiment 3 is dissolved in water 2L, propylgallate 5g is then added, it is completely molten
Add water 2L after solution at room temperature, using probe emulsifier or ultrasonication until formation Average Particle Diameters are
240.1nm (79.3%) and 3.1 (20.7%) nm, the aqueous emulsion of polydispersion, as propylgallate lotion.
The solubilising of 7 propylgallate emulsion intercalation method of embodiment and hydrophobization glucan is investigated
The propylgallate emulsion intercalation method of embodiment 4-6 preparation and the solubilising of hydrophobization glucan are investigated.
Gallic acid is that the trihydroxy phenol with hydrophobic group (propyl) exists in aqueous solution with aggregate form,
Thus it is insoluble in water.Fig. 3~Fig. 9 is the particle diameter that the propylgallate under various concentration is formed in aqueous solution and its divides
Cloth, even if being diluted to the concentration of 0.01mg/ml, gallic acid is also with the aggregate form of micron order and nanoscale polydispersion
In the presence of in aqueous solution, unimolecule solution cannot be formed.
10g propylgallate and 30g hydrophobization glucan are dissolved in 4L water, emulsifies, is prepared into propylgallate
Concentration is the sub- aqueous emulsion of load powder of 2.5mg/ml, and dilution detects, particles size and distribution such as Figure 10~figure through particles distribution instrument
Shown in 13.Propylgallate concentration is that the load medicine particle diameter of 2.5mg/ml is respectively less than 700nm, polydispersion, carry powder with
Aggregate form exists, and partial size and distribution are significantly different with propylgallate aqueous solution.And propylgallate concentration is
The load medicine particle diameter of 2.5mg/ml is respectively less than 500nm, polydispersion, carries powder and exists with aggregate form, partial size with point
Cloth and propylgallate aqueous solution are significantly different.And propylgallate carries medicine particle concentration and is less than after 0.62mg/ml, cream
Go out in liquid without detection of particles.Illustrate, carries powder and exist at high concentrations with aggregate form, after dilution, aggregation can be equal
It is even to be distributed in aqueous solution.Propylgallate carries medicine particle concentration and is less than after 0.62mg/ml, there are no propylgallate
Self-aggregate occurs.Hydrophobization glucan carrier solubilization is obvious.
The application of 8 propylgallate lotion of embodiment
The concrete application of the propylgallate lotion of embodiment 4-6 preparation is as follows: to investigate propylgallate lotion
Antioxidant activity, carried out propylgallate carry powder on kohlrabi silk brown stain influence experiment.As a result such as Figure 14, Tu15Suo
Show.Figure 14 a is that the upper spray concentration of kohlrabi silk is that 0.1% propylgallate carries powder subsample, and Figure 14 b is control kohlrabi silk sample
Product.Upper two samples are the photo for initially starting experiment, and lower two samples are the photo of rear sample for 24 hours.After for 24 hours, control group kohlrabi
Blue silk brown stain simultaneously starts to decay, and spray group is in good condition.Figure 15 is the photo of Figure 14 amplification.
9 heteroauxin aqueous solution of embodiment and preparation method thereof
Hydrophobic polysaccharide 30g prepared by embodiment 1 is dissolved in water 1L, heteroauxin 10g is then added, after being completely dissolved
At room temperature plus water 3L, using probe emulsifier or ultrasonication until forming aqueous solution.
10 heteroauxin aqueous solution of embodiment and preparation method thereof
Hydrophobic polysaccharide 30g prepared by embodiment 1 is dissolved in water 0.5L, heteroauxin 20g is then added, is completely dissolved
Add water 0.5L at room temperature afterwards, using probe emulsifier or ultrasonication until forming aqueous solution.
11 heteroauxin aqueous solution of embodiment and preparation method thereof
Hydrophobic polysaccharide 30g prepared by embodiment 1 is dissolved in water 2L, heteroauxin 5g is then added, after being completely dissolved
At room temperature plus water 3L, using probe emulsifier or ultrasonication until forming aqueous solution.
The load pharmacological property and drug release property of 12 hydrophobization glucan of embodiment are investigated
The load pharmacological property of hydrophobization glucan is investigated with the heteroauxin of embodiment 9-12 preparation/hydrophobization glucan aqueous solution
With drug release property.
In order to investigate the load pharmacological property and drug release property of hydrophobization glucan, by slightly solubility heteroauxin 10mg, hydrophobization Portugal is poly-
For sugared 50mg with being dissolved in 2ml water, ultrasound prepares heteroauxin carrier medicament.It is diluted to the carrier medicament solution of 0.5mg/ml, is passed through
Particles distribution instrument detection there are no particle detection, illustrate, heteroauxin is uniformly distributed in water.Testing result is shown in Figure 16.
The drug release that heteroauxin carries powder is investigated, is tested and is carried out using wheat seedling raising.Select plump-eared wheat
Seed is respectively placed in slot, is soaked in water while being carried the sub- medical fluid intervention of powder with heteroauxin.High concentration medical fluid group (Yin is set
Indolylbutyric acid concentration 16mg/ml), middle concentration liquid group (heteroauxin concentration 4mg/ml)), (heteroauxin is dense for low concentration medical fluid group
Spend 1mg/ml)) and control group.Wheat growth state is as shown in Figure 17~Figure 24.High concentration medical fluid group obviously inhibits the life of wheat
Long, low concentration medication group and control group indifference illustrate that heteroauxin carries powder and can play drug action.
Propylgallate and this kind of insoluble drug of heteroauxin are solved at present, are mainly carried out using conventional emulsifier
Solubilising is simultaneously used in compounding with other medicines.If CN201710812180.7 discloses a kind of compound antioxidant, quenched by free radical
Go out agent, peroxide decomposer, synergist, emulsifier, assistant for emulsifying agent and water is prepared, and exists with microemulsion form.Institute
The emulsifier stated is Arlacel-20, Tween-60, Tween-80, fatty acid glyceride, methyl glycol fatty acid ester, sorbitan fatty
One of acid esters, sucrose fatty ester limited emulsifying capacity are a variety of.The assistant for emulsifying agent be ethyl alcohol, ethylene glycol, propylene glycol,
One of glycerol is a variety of.Though these emulsifiers are food and medicine emulsifier, solubilization is limited, and toxicity is bigger than normal.Phase
Than for, it is more superior to carry pharmacological property, drug release property and good security, performance to hydrophobic polysaccharide of the invention.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be modified or is improved, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. hydrophobic polysaccharide, which is characterized in that general structure is as follows: G-P-O；
Wherein, G is polysaccharide or disaccharides, and P is amino acid or double peptides, and O is oleic acid；Pass through the hydroxyl on ester bond and polysaccharide between G and P
Connection is keyed between P and O by amide.
2. hydrophobic polysaccharide according to claim 1, which is characterized in that the polysaccharide is selected from glucan, algal polysaccharides, shallow lake
Powder, amylopectin, amylose, pulullan polysaccharide, ethoxy dextran, mannosan, levulan, synanthrin, chitin, shell
At least one of glycan, chitin, xyloglucan, water-soluble cellulose；And/or
The disaccharides is sucrose or fructose；And/or
The amino acid or double peptides are selected from glycylglycine, glutamic acid, L-lysine, L-cysteine, DL-Alanine, DL-
Methionine, L-Orn, γ-aminobutyric acid, ASPARTIC ACID, L-thiamine, L-arginine, beta Alanine, L-citrulline,
At least one of L-Histidine；
Preferably, G is glucan, and P is glycylglycine, shown in the structure of the hydrophobic polysaccharide such as formula (I):
Wherein, R1、R2Or R3In any two be H, remaining isN is
Arbitrary integer greater than 2.
3. the preparation method of hydrophobic polysaccharide as claimed in claim 1 or 2, which comprises the following steps:
1) carboxyl of the hydroxyl of polysaccharide or disaccharides and amino acid or double peptides carries out esterification generation amino acid or the esterification of double peptides is more
Sugar；
2) condensation reaction occurs for amino acid or double peptide esterified saccharides and oleic acid, generates hydrophobic polysaccharide.
4. according to the method described in claim 3, it is characterized in that, when the structure of the hydrophobic polysaccharide is as shown in formula (I),
Preparation method is as follows:
1. reacting glucan with the glycylglycine of amido protecting, proper catalyst and dehydration is added
Agent, reacts 1~96h, obtains glycylglycine glucan ester by 0~60 DEG C of reaction temperature；
2. the amido protecting of glycylglycine glucan ester is removed, method particularly includes: above-mentioned glycylglycine Portugal is gathered
Sugar ester is added in sodium hydrate aqueous solution, and the amino of glycylglycine dissociates rapidly, after being dried under reduced pressure water removal, redissolves in having
Oleic acid, catalyst and appropriate dehydrating agent is added in solvent, in 0~60 DEG C of 1~96h of reaction, water is added to terminate reaction；
3. will 2. gained reaction system be filtered, alcohols solvent is added into filtrate, collects precipitating, it is more to be drying to obtain hydrophobization
Sugar.
5. according to the method described in claim 4, it is characterized in that, step 1. the organic solvent be selected from dimethylformamide,
At least one of dimethyl sulfoxide or methylene chloride；And/or
1., 2. the catalyst is dimethylamino naphthyridine to step, and the dehydrating agent is dicyclohexylcarbodiimide；And/or
3. the alcohols solvent is dehydrated alcohol or methanol to step；And/or
The molar ratio of the glucan, glycylglycine and oleic acid is 1:1-2:1-2, and wherein glycylglycine and oleic acid are
Molar ratio mixing.
6. hydrophobic polysaccharide as claimed in claim 1 or 2, or the hydrophobization prepared according to any one of claim 3-5 the method
Following any application of polysaccharide:
A. it is used as carrier for active principle；
B. pharmacy or antibacterial agent are used for；
Wherein, the active constituent includes drug, auxin.
7. containing hydrophobic polysaccharide as claimed in claim 1 or 2, or dredging according to the preparation of any one of claim 3-5 the method
The drug or composition of aquation polysaccharide and at least one active constituent；
Preferably, the active constituent is gallic acid and its derivative, heteroauxin and its derivative, more preferable gallic acid
Propyl ester, heteroauxin or indolebutyric acid.
8. drug according to claim 7 or composition, which is characterized in that the hydrophobic polysaccharide and propylgallate
Weight ratio be 10:1-10:100, preferably 10:4-10:50；The weight ratio of the hydrophobic polysaccharide and heteroauxin is 10:1-
10:100, preferably 10:4-10:50.
9. drug according to claim 8 or composition, which is characterized in that the dosage form of the drug or composition is water and milk
Agent, Average Particle Diameters are 0~1000nm.
10. the preparation method of drug or composition described in claim 9, which is characterized in that the described method includes: hydrophobization is more
Sugar is soluble in water, and propylgallate or heteroauxin is then added, and uses at probe emulsifier or ultrasonic wave after being completely dissolved
Reason until formed needed for partial size aqueous emulsion or solution to get.
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