CN114409828A - Chitosan oligosaccharide aminophenylamide derivatives and preparation method thereof - Google Patents
Chitosan oligosaccharide aminophenylamide derivatives and preparation method thereof Download PDFInfo
- Publication number
- CN114409828A CN114409828A CN202210137616.8A CN202210137616A CN114409828A CN 114409828 A CN114409828 A CN 114409828A CN 202210137616 A CN202210137616 A CN 202210137616A CN 114409828 A CN114409828 A CN 114409828A
- Authority
- CN
- China
- Prior art keywords
- chitosan oligosaccharide
- acid
- aminophenylamide
- benzene
- derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Chitosan oligosaccharide aminophenylamide derivatives Chemical class 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 89
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 claims abstract description 70
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 64
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 32
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 28
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 26
- JTEDVYBZBROSJT-UHFFFAOYSA-N indole-3-butyric acid Chemical compound C1=CC=C2C(CCCC(=O)O)=CNC2=C1 JTEDVYBZBROSJT-UHFFFAOYSA-N 0.000 claims abstract description 25
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 38
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- 238000000502 dialysis Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 11
- 239000007853 buffer solution Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229960004365 benzoic acid Drugs 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000010521 absorption reaction Methods 0.000 abstract description 31
- 239000000126 substance Substances 0.000 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 abstract description 9
- 229920002521 macromolecule Polymers 0.000 abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 20
- 229920001661 Chitosan Polymers 0.000 description 19
- 238000002329 infrared spectrum Methods 0.000 description 15
- 239000005971 1-naphthylacetic acid Substances 0.000 description 10
- 150000001408 amides Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- HNXGGWNCFXZSAI-UHFFFAOYSA-N 2-morpholin-2-ylethanesulfonic acid Chemical compound OS(=O)(=O)CCC1CNCCO1 HNXGGWNCFXZSAI-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229920001542 oligosaccharide Polymers 0.000 description 4
- 150000002482 oligosaccharides Chemical class 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical class NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
- A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a chitosan oligosaccharide aminophenylamide derivative and a preparation method thereof, wherein the chitosan oligosaccharide aminophenylamide derivative is generated by grafting benzene-containing carboxylic acids such as salicylic acid (BHA), alpha-naphthylacetic acid (NAA), 3-indolebutyric acid (IBA) and the like with the capability of improving the stress resistance of plants on chitosan oligosaccharide; the benzene-containing carboxylic acid is greatly hydrophobic because the benzene ring is formed by only C, H, and the groups formed by only C, H elements are hydrophobic; according to international general criteria, the relative contact area of the benzene-containing carboxylic acid to the solvent is less than 7 percent, and the benzene-containing carboxylic acid is hydrophobic; the chitosan oligosaccharide is a macromolecule containing multi-OH, and has excellent hydrophilicity; macromolecules formed after the phenylcarboxylic acid and the chitosan oligosaccharide are crosslinked still have a large amount of hydrophilic groups-OH, and the relative contact area of the side chain of the molecular residue to a solvent is far more than 7 percent, so that the hydrophobicity of the phenylcarboxylic acid is effectively changed by a new substance, and the solubility is greatly increased; is favorable for absorption through the root system or the leaf surface of the plant.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a chitosan oligosaccharide aminophenylamide derivative and a preparation method thereof.
Background
The benzene-containing carboxylic acid has certain capacities of resisting oxidation, promoting plant growth and improving plant stress resistance, such as salicylic acid (BHA), alpha-naphthylacetic acid (NAA) and 3-indolebutyric acid (IBA); however, the excellent lipid solubility of the benzene-containing carboxylic acid greatly limits the exertion of the superior performance of the benzene-containing carboxylic acid on plants, and the benzene-containing carboxylic acid is difficult to absorb through the root systems or leaf surfaces of the plants. Therefore, the biological activity of the substances is fully utilized, and the disadvantages of the substances are reduced, so that the method has important theoretical significance and practical application value for the development of novel phytostimulants.
Disclosure of Invention
In order to improve the water solubility of benzene-containing carboxylic acids such as salicylic acid (BHA), alpha-naphthylacetic acid (NAA), 3-indolebutyric acid (IBA) and the like, the invention provides a chitosan oligosaccharide aminophenylamide derivative and a preparation method thereof, wherein the benzene-containing carboxylic acids such as salicylic acid (BHA), alpha-naphthylacetic acid (NAA), 3-indolebutyric acid (IBA) and the like with the plant stress resistance improving capability are grafted on chitosan oligosaccharide to generate the chitosan oligosaccharide aminophenylamide derivative.
The technical scheme adopted by the invention is as follows: a method for preparing chitooligosaccharide aminophenylamide derivatives comprises mixing carboxyl (-COOH) on benzene-containing carboxylic acid with chitooligosaccharide C2Amino (-NH) group at position2) The reaction generates the chitosan oligosaccharide amino phenyl amide derivatives.
A preparation method of chitosan oligosaccharide aminophenylamide derivatives comprises the following specific steps:
step one, activating carboxyl containing benzene carboxylic acid:
dissolving benzene-containing carboxylic acid in anhydrous ethanol and 2-morpholine ethanesulfonic acid buffer solution, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, and stirring for activation.
Further, the benzene-containing carboxylic acid is any one of salicylic acid, alpha-naphthylacetic acid and 3-indolebutyric acid.
Preferably, the 2-morpholinoethanesulfonic acid buffer solution used in the first step has a pH =5.5, a concentration of 0.1mol/L, and a volume ratio of the 2-morpholinoethanesulfonic acid buffer solution to the anhydrous ethanol of 1:1 or 2:3 or 3: 2.
Preferably, the molar ratio of the other reagents is, benzene-containing carboxylic acid: 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride: n-hydroxysuccinimide =1:3: 3.
Step two, carrying out amide reaction on the chitosan oligosaccharide and the activated benzene-containing carboxylic acid:
and (3) adding the chitosan oligosaccharide into the step one, and stirring for reaction, so that the amino group of the chitosan oligosaccharide and the carboxyl group containing the benzene carboxylic acid form amide.
Further, the chitosan oligosaccharide used in the second step is chitosan oligosaccharide (n =15-25) or chitosan oligosaccharide (n =6-8), and the reaction molar ratio of the benzene-containing carboxylic acid to the chitosan oligosaccharide (n =15-25) is 20: 1; the reaction molar ratio of the benzene-containing carboxylic acid to the chitosan oligosaccharide (n =6-8) is 7: 1; the molar ratio of the two reactions is based on the difference of the average molecular weights of the two chitosan oligosaccharides, n =15-25 ≈ 20, n =6-8 ≈ 7, and the ratio is to make the ratio of the amino group of the chitosan oligosaccharide to the carboxyl group containing the benzene carboxylic acid reach 1:1 as much as possible so as to fully perform the amide reaction.
Step three, separating and purifying the target compound:
dialyzing the product obtained after the reaction in the second step in distilled water by using a dialysis bag, concentrating the solution in the dialysis bag, and then freeze-drying to obtain the chitosan oligosaccharide aminophenylamide derivatives.
The aim of dialysis by using distilled water is to remove small molecular impurities more thoroughly; the concentration process can remove redundant water and reduce the volume; since the compound obtained by the invention is easy to decompose at high temperature, the water is completely removed by low-temperature freeze drying, and the liquid state is changed into solid state powder, namely the finished product.
Preferably, the molecular weight cut-off of the dialysis bag used is 500Da for removing the unreacted part containing phenylcarboxylic acid, EDC & HCl and NHS, the chitosan oligosaccharide itself is a macromolecule, Mn is more than 1000Da, and the molecular weight of the target chitosan oligosaccharide derivative is only increased but not reduced after the reaction.
The chitosan oligosaccharide aminophenylamide derivative prepared by the invention has the following structural formula:
wherein R is any one of the following structural formulas:
wherein n is any number from 6 to 25; preferably n =6-8 or n = 15-25.
The process principle of the invention is illustrated as follows:
in the first step, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, EDC & HCl for short, is water-soluble carbodiimide, and the molecule of the water-soluble carbodiimide is in a linear structure and is used for the condensation reaction of carboxyl and primary amine. EDC forms an O-acylurea intermediate that can react with an amino group by reacting with the amino group. If the intermediate does not react with the amino group, it will quickly hydrolyze and re-release the carboxyl group. EDC & HCl can convert carboxyl groups to amino-reactive NHS esters in the presence of N-hydroxysuccinimide (NHS). This reaction is achieved by mixing EDC · HCl, the carboxyl group containing molecule and NHS. EDC & HCl can be used as a condensing agent in the present invention to achieve rapid dehydration condensation.
N-hydroxysuccinimide, referred to as NHS, is synthesized as NHS ester by dehydration reaction in carboxylic acid in the presence of EDC. The presence of NHS increases the efficiency of EDC-mediated coupling and any carboxyl-containing molecule can be used to prepare amine-reactive NHS esters. NHS in the present invention can control the carboxylate activated carbodiimide crosslinking reaction coupled to the amino group of the chitosan oligosaccharide.
The invention has the beneficial effects that: the invention grafts benzoic acid containing benzene such as salicylic acid (BHA), alpha-naphthylacetic acid (NAA), 3-indolebutyric acid (IBA) and the like with the capability of improving the stress resistance of plants on chitosan oligosaccharide to generate chitosan oligosaccharide aminophenylamide derivatives; the benzene-containing carboxylic acid is greatly hydrophobic because the benzene ring is composed of only C, H, and the groups composed of only C, H elements are hydrophobic. According to international general criteria, the relative contact area of the benzene-containing carboxylic acid to the solvent is less than 7%, and the benzene-containing carboxylic acid is hydrophobic. Chitosan oligosaccharide is itself a poly-OH-containing macromolecule, and has excellent hydrophilicity. Macromolecules formed after the phenylcarboxylic acid and the chitosan oligosaccharide are crosslinked still have a large amount of hydrophilic groups-OH, and the relative contact area of the side chain of the molecular residue to a solvent is far more than 7 percent, so that the hydrophobicity of the phenylcarboxylic acid is effectively changed by a new substance, and the solubility is greatly increased; is favorable for absorption through the root system or the leaf surface of the plant.
Drawings
FIG. 1 shows the reaction principle of chitosan oligosaccharide and benzene-containing carboxylic acid reaction to prepare chitosan oligosaccharide aminophenylamide derivatives.
FIG. 2 is the structural formula of the chitosan oligosaccharide aminophenylamide derivatives of the present invention.
FIG. 3 is an infrared spectrum of a conventional chitosan oligosaccharide (n = 15-25).
FIG. 4 is an infrared spectrum of a conventional chitosan oligosaccharide (n = 6-8).
FIG. 5 is an infrared spectrum of o-hydroxybenzoyl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide of example 1 (n =15-25) with salicylic acid.
FIG. 6 is an infrared spectrum of o-hydroxybenzoyl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide of example 2 (n =6-8) with salicylic acid.
FIG. 7 is an infrared spectrum of a-naphthylacetyl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide of example 3 (n =15-25) with 1-naphthylacetic acid.
FIG. 8 is an infrared spectrum of a-naphthylacetyl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide of example 4 (n =6-8) with 1-naphthylacetic acid.
FIG. 9 is an infrared spectrum of 3-indolebutyryl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide (n =15-25) with 3-indolebutyric acid.
FIG. 10 is an infrared spectrum of 3-indolebutyryl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide (n =6-8) with 3-indolebutyric acid.
FIG. 11 shows the o-hydroxybenzoyl chitooligosaccharides obtained by reacting chitooligosaccharides (n =6-25) with salicylic acid13C nuclear magnetic resonance spectrum.
FIG. 12 shows the reaction of chitooligosaccharide (n =6-25) with 1-naphthylacetic acid to obtain alpha-naphthylacetyl chitooligosaccharide13C nuclear magnetic resonance spectrum.
FIG. 13 shows 3-indolebutyryl-chitooligosaccharides obtained by reacting chitooligosaccharides (n =6-25) with 3-indolebutyric acid13C nuclear magnetic resonance spectrum.
FIG. 14 is a reaction formula of o-hydroxybenzoyl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide with salicylic acid.
FIG. 15 is a reaction formula of alpha-naphthylacetyl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide with alpha-naphthylacetic acid.
FIG. 16 shows the reaction scheme of 3-indolebutyryl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide with indolebutyric acid.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Unless otherwise stated, all materials and reagents in the following examples are commercially available materials and reagents, such as chitooligosaccharide (n =15-25) from Qingdao Yu Biotech, Inc., DD > 90%.
As shown in figure 1, is a reaction principle diagram of the reaction of chitosan oligosaccharide and benzene-containing carboxylic acid to prepare chitosan oligosaccharide aminophenylamide derivatives; the reaction process is as follows:
the first step is as follows: 1-Ethyl- (3-dimethylaminopropyl) carbodiimides hydrochloride (EDC. HCl) reacts with-COOH on a benzene-containing carboxylic acid to form an O-acylurea intermediate, intermediate 1.
The second step is that: n-hydroxysuccinimide (NHS) was added to convert the O-acylurea intermediate in the reaction system to an active NHS ester that reacts with the amino group, intermediate 2.
Thirdly, Chitosan Oligosaccharide (COS) is added, C-O bond on NHS ester is broken and-NH on the chitosan oligosaccharide is added2Combining to form amide, namely the target product.
Example 1
Method for preparing o-hydroxybenzoyl chitosan oligosaccharide by reaction of chitosan oligosaccharide (n =15-25) and salicylic acid
Step one, salicylic acid carboxyl is activated
Dissolving salicylic acid in an absolute ethyl alcohol and 2-morpholine ethanesulfonic acid buffer solution, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, stirring until the mixture is completely dissolved, and continuously stirring for 3 hours to activate carboxyl. The pH of the used 2-morpholine ethanesulfonic acid buffer solution is =5.5, the concentration is 0.1mol/L, the dosage is 100mL (2-morpholine ethanesulfonic acid buffer solution is excessive), and 100mL of absolute ethyl alcohol is used; other reagent amounts (molar ratio), salicylic acid: 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride: the molar ratio of N-hydroxysuccinimide is 1:3: 3.
Step two, the chitosan oligosaccharide and the activated salicylic acid are subjected to amide reaction
Adding 1.0g of chitosan oligosaccharide (n =15-25) into the step one, and continuing stirring and reacting for 24 hours at room temperature to enable the amino group of the chitosan oligosaccharide and the carboxyl group of the salicylic acid to form amide; the reaction molar ratio of salicylic acid to chitosan oligosaccharide (n =15-25) was 20: 1.
Step three, separating and purifying the target compound
And (3) dialyzing the product obtained after the reaction in the second step in distilled water for 4 days by using a dialysis bag, concentrating the solution in the dialysis bag to 50mL, and freeze-drying for 48 hours to obtain the o-hydroxybenzoyl chitosan oligosaccharide. The cut-off molecular weight of the dialysis bag used was 500 Da.
The o-hydroxybenzoyl chitosan oligosaccharide prepared in example 1 has a structural formula shown in FIG. 2,
wherein R =
，n=15-25。
Example 2
Method for preparing o-hydroxybenzoyl chitosan oligosaccharide by reaction of chitosan oligosaccharide (n =6-8) and salicylic acid
Step one, salicylic acid carboxyl is activated
Dissolving salicylic acid in an absolute ethyl alcohol and 2-morpholine ethanesulfonic acid buffer solution, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, stirring until the mixture is completely dissolved, and continuously stirring for 3 hours to activate carboxyl. The pH of the used 2-morpholine ethanesulfonic acid buffer solution is =5.5, the concentration is 0.1mol/L, the dosage is 100mL (2-morpholine ethanesulfonic acid buffer solution is excessive), and 100mL of absolute ethyl alcohol is used; other reagent amounts (molar ratio), salicylic acid: 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride: the molar ratio of N-hydroxysuccinimide is 1:3: 3.
Step two, the chitosan oligosaccharide and the activated salicylic acid are subjected to amide reaction
Adding 1.0g of chitosan oligosaccharide (n =6-8) into the step one, and continuing stirring and reacting at room temperature for 24h to enable the amino group of the chitosan oligosaccharide and the carboxyl group of the salicylic acid to form amide; the reaction molar ratio of salicylic acid to chitosan oligosaccharide (n =15-25) was 7: 1.
Step three, separating and purifying the target compound
And (3) dialyzing the product obtained after the reaction in the second step in distilled water for 4 days by using a dialysis bag, concentrating the solution in the dialysis bag to 50mL, and freeze-drying for 48 hours to obtain the o-hydroxybenzoyl chitosan oligosaccharide. The cut-off molecular weight of the dialysis bag used was 500 Da.
The structural formula of the o-hydroxybenzoyl chitosan oligosaccharide prepared in example 2 is shown in figure 2,
wherein R =
，n=6-8。
Infrared spectrogram of existing chitosan oligosaccharide
As shown in FIG. 3, it is an infrared spectrum of a conventional chitosan oligosaccharide (n =15-25), and its characteristic infrared (cm)-1）：3245.1，2885.49，1604.2，1507.02，1378.26，1062.63。
As shown in fig. 4, is an infrared spectrum of the existing chitosan oligosaccharide (n = 6-8); it is characterized by infrared (cm)-1）：3244.9，2886.93，1613.4，1511.75，1380.27，1064.73。
By infrared spectroscopic analysis
As shown in FIG. 5, it is an infrared spectrum of o-hydroxybenzoyl chitooligosaccharide obtained by reacting chitooligosaccharide (n =15-25) of example 1 with salicylic acid, and its characteristic infrared (cm)-1）：3313.2，2882.98，1706.40，1648.49，1548.40，1375.33，1215.20，1025.31，901.39，760.58，652.23，566.04。
FIG. 5Compared with the graph in FIG. 3, the concentration is 3500-3200cm-1The characteristic broad peaks of O-H and N-H are obviously shifted, which indicates that N-H can possibly react; at 1507cm-1Of (a) NH of (b)2The characteristic absorption peak of (A) is enhanced, indicating-NH2An amide reaction has occurred; at 1649.48cm in FIG. 5-1The characteristic absorption peak of C = O appears at 2882.98cm-1A significant saturated-CH stretching vibration absorption peak is appeared at 1375.33cm-1The saturated-CH deformation vibration absorption peak appears at 760.58cm-1The ortho-position disubstituted characteristic absorption peak of the benzene ring appears.
FIG. 6 is a chart showing the infrared spectrum of o-hydroxybenzoyl chitooligosaccharide obtained by reacting chitooligosaccharide (n =6-8) of example 2 with salicylic acid; it is characterized by infrared (cm)-1）：3312.89，2972.85，2705.77，1777.22，1731.72，1642.42，1562.36，1470.50，1376.48，1210.34，1070.73，1036.40，904.89，858.79，812.61，761.77，648.51。
FIG. 6 is located at 3500-3200cm compared with FIG. 4-1The characteristic broad peaks of O-H and N-H are obviously shifted, which indicates that N-H can possibly react; is located at 1511cm-1Of (a) NH of (b)2The characteristic absorption peak of (A) is enhanced, indicating-NH2An amide reaction has occurred; at 1642.42cm in FIG. 6-1The characteristic absorption peak of C = O appears at 2972.85cm-1A significant saturated-CH stretching vibration absorption peak is appeared at 1376.48cm-1The peak is a saturated-CH deformation vibration absorption peak at 761.77cm-1The ortho-position disubstituted characteristic peak of the benzene ring appears.
Carbon spectrum analysis by nuclear magnetic resonance
As shown in FIG. 11, it is the o-hydroxybenzoyl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide (n =6-25) with salicylic acid13C nuclear magnetic resonance spectrogram; its characteristic chemical shifts (ppm): 177.41, 174.61, 172.66, 160.53, 159.74, 133.99, 130.51, 124.69, 119.37, 116.43, 98.02, 76.42, 74.83, 72.00, 69.61, 64.22, 62.56, 62.29, 61.83, 60.39, 55.37, 52.07, 45.17, 42.74, 36.49, 35.68, 34.99, 31.30, 25.03, 14.50, 13.33.
Analysis shows that: 174.61ppm is the chemical shift of C = O carbon for the amide bond; 98.02(C1), 76.42(C4), 74.83(C5), 72.00(C3), 60.39(C6), 55.37(C2) ppm are the chemical shifts of the oligosaccharide sugar ring of chitosan; 116.43-160.53ppm is the chemical shift of benzene ring skeleton of salicylic acid. From the above results, formation of the objective compound can be confirmed.
Example 3
Method for preparing alpha-naphthylacetyl chitosan oligosaccharide by reacting chitosan oligosaccharide (n =15-25) with 1-naphthylacetic acid
The preparation process is the same as that of example 1, and 1-naphthylacetic acid is used instead of salicylic acid.
The structural formula of the alpha-naphthylacetyl chitosan oligosaccharide prepared in example 3 is shown in figure 2,
wherein R =
，n=15-25。
Example 4
Method for preparing alpha-naphthylacetyl chitosan oligosaccharide by reacting chitosan oligosaccharide (n =6-8) with 1-naphthylacetic acid
The preparation process is the same as that of example 2, and 1-naphthylacetic acid is used instead of salicylic acid.
The structural formula of the alpha-naphthylacetyl chitosan oligosaccharide prepared in example 4 is shown in figure 2,
wherein R =
，n=6-8。
By infrared spectroscopic analysis
FIG. 7 is a chart showing an infrared spectrum of a-naphthylacetyl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide (n =15-25) of example 3 with 1-naphthylacetic acid; it is characterized by infrared (cm)-1）：3278.93，2936.98，1726.17，1640.53，1555.14，1378.98，1214.11，1186.77，1067.21，1027.90，779.93，651.41，566.43。
FIG. 7 is located at 3500-3200cm compared with FIG. 3-1The characteristic broad peaks of O-H and N-H are obviously shifted, which indicates that N-H can possibly react; at 1507cm-1Of (a) NH of (b)2The characteristic absorption peak of (A) is enhanced, indicating-NH2An amide reaction has occurred; at 1640.53cm in FIG. 7-1Where C = O appearsA characteristic absorption peak; at 2936.98cm-1A significant saturated-CH stretching vibration absorption peak is appeared at 1214.11cm-1The peak is a saturated-CH deformation vibration absorption peak at 779.93cm-1And 651.41cm-1The position is a characteristic absorption peak of naphthalene ring.
FIG. 8 is a chart showing an infrared spectrum of a-naphthylacetyl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide of example 4 (n =6-8) with 1-naphthylacetic acid; it is characterized by infrared (cm)-1）：3334.63，2978.10，1779.18，1725.84，1639.17，1619.01，1562.83，1466.25，1440.77，1422.54，1373.81，1352.55，1211.66，1185.63，1071.21，1030.07，901.18，856.32，784.11，630.62，587.24，540.08，418.20。
FIG. 8 is 3500-3200cm-1The characteristic broad peaks of O-H and N-H are obviously shifted, which indicates that N-H can possibly react; is located at 1511cm-1Of (a) NH of (b)2The characteristic absorption peak of (A) is enhanced, indicating-NH2An amide reaction has occurred; at 1639.17cm in FIG. 8-1A characteristic absorption peak of C = O appears; at 2978.10cm-1A significant saturated-CH stretching vibration absorption peak is appeared at 1373.81cm-1The peak is a saturated-CH deformation vibration absorption peak at 784.11cm-1And 639.62cm-1A naphthalene ring characteristic absorption peak appears.
Carbon spectrum analysis by nuclear magnetic resonance
As shown in FIG. 12, it is alpha-naphthylacetyl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide (n =6-25) with 1-naphthylacetic acid13C nuclear magnetic resonance spectrogram; its characteristic chemical shifts (ppm): 177.26, 174.77, 172.71, 160.61, 133.61, 98.05, 76.43, 74.84, 72.11, 69.64, 64.15, 62.55, 61.83, 55.38, 52.07, 45.06, 42.72, 36.46, 35.00, 31.28, 25.04, 14.47, 13.38.
Analysis shows that: 174.77ppm is the chemical shift of C = O carbon for the amide bond; 98.05(C1), 76.43(C4), 74.84(C5), 72.11(C3), 61.83(C6), 55.38(C2) ppm are the chemical shifts of the oligosaccharide sugar ring of chitosan; 160.61-133.61ppm is the chemical shift of the alpha-naphthylacetic acid aromatic ring skeleton. From the above results, formation of the objective compound can be confirmed.
Example 5
Method for preparing 3-indolebutyryl chitosan oligosaccharide by reacting chitosan oligosaccharide (n =15-25) with 3-indolebutyric acid
The preparation process is the same as that in example 1, and 3-indolebutyric acid is used instead of salicylic acid.
The structural formula of the 3-indolebutyryl chitosan oligosaccharide prepared in example 5 is shown in figure 2,
wherein R =
，n=15-25。
Example 6
Method for preparing 3-indolebutyryl chitosan oligosaccharide by reacting chitosan oligosaccharide (n =6-8) with 3-indolebutyric acid
The preparation process is the same as that of example 2, and 3-indolebutyric acid is used instead of salicylic acid.
The structural formula of the 3-indolebutyryl chitosan oligosaccharide prepared in example 6 is shown in figure 2,
wherein R =
，n=6-8。
By infrared spectroscopic analysis
FIG. 9 shows an infrared spectrum of 3-indolebutyryl chitosan oligosaccharide obtained by reacting chitosan oligosaccharide (n =15-25) with 3-indolebutyric acid; it is characterized by infrared (cm)-1）：3328.47，2936.06，1724.55，1641.99，1557.11，1374.18，1186.92，1067.23，1026.46，899.02，654.53，586.31。
FIG. 9 is 3500-3200cm-1The characteristic broad peaks of O-H and N-H are obviously shifted, which indicates that N-H can possibly react; at 1507cm-1Of (a) NH of (b)2The characteristic absorption peak of (A) is enhanced, indicating-NH2An amide reaction has occurred; at 1641.99cm in FIG. 9-1A characteristic absorption peak of C = O appears; at 2936.06cm-1A significant saturated-CH stretching vibration absorption peak is appeared at 1374.18cm-1The peak is a saturated-CH deformation vibration absorption peak at 654.53cm-1The position is an indole ring characteristic absorption peak.
As shown in FIG. 10, it is chitooligosaccharide (n =6-8) and 3-An infrared spectrogram of the 3-indolebutyryl chitosan oligosaccharide obtained by the reaction of indolebutyric acid; it is characterized by infrared (cm)-1）：3335.77，2979.46，1778.85，1726.16，1619.26，1566.44，1440.15，1422.21，1373.71，1352.39，1185.61，1070.79，1028.27，901.01，855.26，745.59，652.06，630.87，587.54，426.53。
FIG. 10 is located at 3500-3200cm compared with FIG. 4-1The characteristic broad peaks of O-H and N-H are obviously shifted, which indicates that N-H can possibly react; is located at 1511cm-1Of (a) NH of (b)2The characteristic absorption peak of (A) is enhanced, indicating-NH2An amide reaction has occurred; at 1619cm in FIG. 10-1A characteristic absorption peak of C = O appears; at 2979.46cm-1A clear absorption peak of saturated-CH stretching vibration, 1211cm-1The peak is a saturated-CH deformation vibration absorption peak at 652.06cm-1An indole ring characteristic absorption peak appears.
Carbon spectrum analysis by nuclear magnetic resonance
As shown in FIG. 13, it is 3-indolebutyryl-chitooligosaccharide obtained by reacting chitooligosaccharide (n =6-25) with 3-indolebutyric acid13C nuclear magnetic resonance spectrogram; its characteristic chemical shifts (ppm): 177.45, 174.62, 172.67, 160.55, 159.75, 136.29, 127.01, 118.98, 102.22, 98.07, 97.62, 76.44, 72.04, 64.26, 62.57, 61.80, 55.38, 52.07, 45.06, 42.72, 36.49, 35.75, 31.30, 25.05, 14.53, 13.39, 13.35.
Analysis shows that: 174.62ppm is the chemical shift of C = O carbon of the amide bond; 98.07(C1), 76.44(C4), 74.26(C5), 72.04(C3), 60.40(C6), 55.38(C2) ppm are chemical shifts of the oligosaccharide sugar ring; 160.55-102.22ppm is the chemical shift of the aromatic ring skeleton of 3-indolebutyric acid. From the above results, formation of the objective compound can be confirmed.
The chitosan oligosaccharide aminophenylamide derivatives prepared by the invention are yellow brown or dark brown powder. The chitosan oligosaccharide molecule and the accessed group are effectively combined to form the chitosan oligosaccharide amino phenyl amide derivative by adopting infrared spectroscopy, nuclear magnetic resonance carbon spectrum and elemental analysis for verification, wherein the reacted amino accounts for 28.62-74.47% of the total amount of the groups in the chitosan oligosaccharide, namely, the degree of substitution of the benzene-containing carboxylic acid is 28.62-74.47%.
Description of Water solubility of Chitosan oligosaccharide aminophenylamide derivatives prepared by the present invention
As shown in FIGS. 14, 15 and 16, the reaction formula of the present invention is that salicylic acid, alpha-naphthylacetic acid and indolebutyric acid are grafted on chitosan oligosaccharide to generate chitosan oligosaccharide aminophenylamide derivatives. The benzene-containing carboxylic acid is greatly hydrophobic because the benzene ring is composed of only C, H, and the groups composed of only C, H elements are hydrophobic. According to international general criteria, the relative contact area of the benzene-containing carboxylic acid to the solvent is less than 7%, and the benzene-containing carboxylic acid is hydrophobic. Chitosan oligosaccharide is itself a poly-OH-containing macromolecule, and has excellent hydrophilicity. Macromolecules formed after the phenylcarboxylic acid and the chitosan oligosaccharide are crosslinked still have a large amount of hydrophilic groups-OH, and the relative contact area of the side chain of the molecular residue to a solvent is far more than 7 percent, so that the hydrophobicity of the phenylcarboxylic acid is effectively converted by the new substance, and the solubility is greatly increased.
It is to be understood that the present invention has been described with reference to certain embodiments, and that various changes in the features and embodiments, or equivalent substitutions may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (9)
1. A chitosan oligosaccharide aminophenylamide derivative is characterized in that the structural formula is as follows:
wherein R is any one of the following structural formulas:
wherein n is any number from 6 to 25.
2. The chitosan oligosaccharide aminophenylamide derivative according to claim 1, wherein: n =6-8 or n = 15-25.
3. A preparation method of chitosan oligosaccharide aminophenylamide derivatives is characterized by comprising the following steps: mixing carboxyl (-COOH) on benzene-containing carboxylic acid with chitosan oligosaccharide C2Amino (-NH) group at position2) The reaction generates the chitosan oligosaccharide amino phenyl amide derivatives.
4. The process for preparing a chitosan oligosaccharide aminophenylamide derivative as claimed in claim 3, which comprises the steps of dissolving a benzene-containing carboxylic acid in a buffer solution of anhydrous ethanol and 2-morpholinoethanesulfonic acid, adding 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride and N-hydroxysuccinimide, stirring and activating; then adding chitosan oligosaccharide, stirring and reacting to ensure that the amino group of the chitosan oligosaccharide and carboxyl containing benzene carboxylic acid form amide; then dialyzing in distilled water by using a dialysis bag, concentrating the solution in the dialysis bag, and freeze-drying to obtain the chitosan oligosaccharide aminophenylamide derivatives.
5. The process for preparing a chitosan oligosaccharide aminophenylamide derivative as claimed in claim 4, wherein: the benzene-containing carboxylic acid is any one of salicylic acid, alpha-naphthylacetic acid and 3-indolebutyric acid.
6. The process for preparing a chitosan oligosaccharide aminophenylamide derivative as claimed in claim 4, wherein: the 2-morpholinoethanesulfonic acid buffer solution used had a pH =5.5 and a concentration of 0.1 mol/L.
7. The process for preparing a chitosan oligosaccharide aminophenylamide derivative as claimed in claim 4, wherein: containing benzene carboxylic acid: 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride: n-hydroxysuccinimide =1:3: 3.
8. The process for preparing a chitosan oligosaccharide aminophenylamide derivative as claimed in claim 4, wherein: the molar ratio of the amino group of the chitosan oligosaccharide to the carboxyl group containing the benzene carboxylic acid is 1: 1.
9. The process for preparing a chitosan oligosaccharide aminophenylamide derivative as claimed in claim 4, wherein: the cut-off molecular weight of the dialysis bag used was 500 Da.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210137616.8A CN114409828A (en) | 2022-02-15 | 2022-02-15 | Chitosan oligosaccharide aminophenylamide derivatives and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210137616.8A CN114409828A (en) | 2022-02-15 | 2022-02-15 | Chitosan oligosaccharide aminophenylamide derivatives and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114409828A true CN114409828A (en) | 2022-04-29 |
Family
ID=81261045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210137616.8A Pending CN114409828A (en) | 2022-02-15 | 2022-02-15 | Chitosan oligosaccharide aminophenylamide derivatives and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114409828A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775815A (en) * | 2005-11-10 | 2006-05-24 | 侯益民 | 2-chitose-salicylic acid graft compound and its preparing method |
| CN101314622A (en) * | 2008-06-26 | 2008-12-03 | 浙江大学 | Salicylic-g-chitosan oligosaccharide grafts and synthesizing process |
| CN103430956A (en) * | 2013-09-15 | 2013-12-11 | 海南正业中农高科股份有限公司 | Composition containing chitosan oligosaccharide and plant growth regulator and application thereof |
| CN111171086A (en) * | 2020-01-19 | 2020-05-19 | 中国科学院海洋研究所 | Wheat stress-resistant preparation and application thereof |
-
2022
- 2022-02-15 CN CN202210137616.8A patent/CN114409828A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775815A (en) * | 2005-11-10 | 2006-05-24 | 侯益民 | 2-chitose-salicylic acid graft compound and its preparing method |
| CN101314622A (en) * | 2008-06-26 | 2008-12-03 | 浙江大学 | Salicylic-g-chitosan oligosaccharide grafts and synthesizing process |
| CN103430956A (en) * | 2013-09-15 | 2013-12-11 | 海南正业中农高科股份有限公司 | Composition containing chitosan oligosaccharide and plant growth regulator and application thereof |
| CN111171086A (en) * | 2020-01-19 | 2020-05-19 | 中国科学院海洋研究所 | Wheat stress-resistant preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王猛等著: "《手印显现技术前沿》", vol. 1, 东北大学出版社, pages: 140 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2333321A1 (en) | Drug complex | |
| US7432239B2 (en) | Polyoxyalkylene compound and method for making | |
| CN107417752B (en) | Compound with anticancer activity and preparation method and application thereof | |
| CN114437248B (en) | Chitosan oligosaccharide nonpolar amino amide derivative and preparation method thereof | |
| CN103221431A (en) | Method for producing pseudopolyrotaxane | |
| JP5371067B2 (en) | Method for producing high-purity polyethylene glycol aldehyde derivative | |
| EP1076671B1 (en) | Non cross-linked block polyetherester, preparation and uses | |
| EP0354836B1 (en) | Iodopolymers with a dextran skeleton, their processes of preparation and their applications as contrast agents | |
| CN102675484A (en) | Synthetic method of 4-hydrazoic benzoyl chitosan | |
| CN114409828A (en) | Chitosan oligosaccharide aminophenylamide derivatives and preparation method thereof | |
| CN111040180B (en) | Biological cascade reaction type photodynamic integrated biopolymer and preparation method and application thereof | |
| WO1988006162A1 (en) | Iodized polymers, processes for their preparation and their applications as contrast products | |
| WO2008141452A1 (en) | Chitosan salts, methods of manufacture and uses thereof | |
| JPH07216002A (en) | Production of cyclodextrin derivative, and cyclodextrin derivative | |
| CN114478836B (en) | Chitosan oligosaccharide diamino caproamide derivative and preparation method thereof | |
| WO2003046014A1 (en) | Method for sulphonation of compounds comprising free hydroxyl (oh) groups or primary or secondary amines | |
| CN101361982A (en) | Preparation method of folacin coupled chitosan | |
| CN108676105A (en) | A kind of synanthrin triazolium salt and its preparation method and application | |
| CN114437250B (en) | Chitosan oligosaccharide amino hydroxy propionamide derivative and preparation method thereof | |
| Broström et al. | Covalent binding of proteins to polysaccharides by cyanogen bromide and organic cyanates. III. Structural studies on the linkage region | |
| JPH04288304A (en) | High-molecular mitomycin c derivative and production thereof | |
| KR20030026191A (en) | The Method for Preparation of Water Soluble Free Amine Chitosan | |
| JP3898850B2 (en) | Gelling agent comprising sugar derivative having metal coordination ability | |
| Li et al. | Synthesis and characterization of lactobionic acid grafted phenylalanyl-glycyl-chitosan | |
| PL239299B1 (en) | Method of preparation of chitosan with covalently bonded Rhodamine-B |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220429 |
|
| RJ01 | Rejection of invention patent application after publication |