CN105218700A - A kind of oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent and preparation method thereof - Google Patents
A kind of oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent and preparation method thereof Download PDFInfo
- Publication number
- CN105218700A CN105218700A CN201510443851.8A CN201510443851A CN105218700A CN 105218700 A CN105218700 A CN 105218700A CN 201510443851 A CN201510443851 A CN 201510443851A CN 105218700 A CN105218700 A CN 105218700A
- Authority
- CN
- China
- Prior art keywords
- oligochitosan
- kojic acid
- mannich base
- preparation
- antibacterial agent
- 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.)
- Granted
Links
- 0 CC[C@](C(*)[I+])*(C1N*1(O)OC(C)C(CC1)CCC1C=O)O Chemical compound CC[C@](C(*)[I+])*(C1N*1(O)OC(C)C(CC1)CCC1C=O)O 0.000 description 5
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3562—Sugars; Derivatives thereof
Abstract
The invention belongs to technical field of food additives, particularly relate to a kind of oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent and preparation method thereof, the method comprises the following steps: N methyl piperazine and chloro kojic acid mix and react by (1), obtains product chloro kojic acid-Mannich base; (2) oligochitosan schiff bases is mixed with chloro kojic acid-Mannich base and reacts; obtain oligochitosan schiff bases-O-kojic acid-Mannich base derivative through aftertreatment, obtain oligochitosan-O-kojic acid-Mannich base derivative through amino protective reaction and purifying.The molecule with anti-microbial property is introduced in oligochitosan molecule by the present invention, produce with oligochitosan molecule and act synergistically, enhance the anti-microbial activity of oligochitosan, preparation method is simple, substitution value is high, cost is low, method of purification is easy, stable in properties, the oligochitosan derivative obtained has good aqueous solubility and anti-microbial activity, to intestinal bacteria, gold-coloured staphylococci etc., all there is good anti-microbial activity, be well suited for as anti-biotic material.
Description
Technical field
The invention belongs to technical field of food additives, particularly relate to one
oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent and preparation method thereof.
Background technology
In recent years, food-safety problem has become one of worldwide focal issue of global public priority consideration.Food all may be subjected to some harmful microbes and pollute in the processes such as process for processing, transport, storage and sale, these harmful microorganisms can contaminated food products, make food spoilage, not only can cause the serious waste of food resource, but also can cause serious injury the health of by mistake trencherman, therefore the anti-corrosive fresh-keeping of varieties of food items is a major issue urgently to be resolved hurrily all the time.Natural anticorrosion fungistat is as chitosan and kojic acid, look at the parent that its characteristic such as safety non-toxic, Heat stability is good is subject to people, develop by chemical modification the focus that the antiseptics for natural food with stronger bacteriostatic activity and wider antimicrobial spectrum has become people's research.
Oligochitosan is the lower molecular weight basic amine group oligosaccharides that chitosan main chain obtains after the fracture of physics, chemistry or enzyme liberating.Have biodegradability, biocompatibility, biological non-toxicity and chemical reactivity, to comprising bacterium, a series of microorganisms of fungi have restraining effect, are regarded as exploitation
novelthe ideal material of antiseptics for natural food.
But, because oligochitosan is natural macromolecular product, when using as food antiseptic antiseptic-germicide, compared with traditional conventional Chemical Preservative, still have the shortcomings such as anti-microbial activity is low, so current application is in the food industry not very general.Therefore, can by carrying out chemically modified to the structure of oligochitosan, owing to its molecular chain having amino and the hydroxyl of chemical reactivity, these sites are all the ideal role sites of oligochitosan being carried out to chemical modification, can improve its anti-microbial activity further, this is also the effective ways that research is more both at home and abroad at present.
Because above-mentioned defect, the design people, actively in addition research and innovation, to founding one
oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent and preparation method thereof, make it have more utility value in industry.
Summary of the invention
For solving the problems of the technologies described above, the object of this invention is to provide one
oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent and preparation method thereof, the active antibacterial group-gamma-pyrone base in kojic acid and N methyl piperazine are incorporated in oligochitosan molecular chain, produce with oligochitosan molecule and act synergistically, to strengthen the anti-microbial activity of oligochitosan, obtain the oligochitosan derivative of good, the mutual synergy of solvability.
A kind of oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent that the present invention proposes, its chemical structural formula is as follows, and wherein, n is 6-20, and substitution value is 1.21-1.78.
The invention allows for the preparation method of oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent, comprise the following steps:
(1) after oligochitosan schiff bases and chloro kojic acid-Mannich base organic solvent being dissolved respectively, mix and stir, reaction terminates rear interpolation organic solvent deposit product, filter, precipitated product organic solvent soxhlet type, namely lyophilize obtains oligochitosan schiff bases-O-kojic acid-Mannich base derivative;
(2) in the oligochitosan schiff bases-O-kojic acid-Mannich base derivative of described step (1), add hydrochloric acid/ethanol (V/V=1:4) mixed solution of 0.25mol/L, mix and stir, reaction terminates rear adjustment pH to neutral, with organic solvent washing, suction filtration, lyophilize obtains sample.
Further, described method is also included in the purification step after step (2), and by described dried product dialysis, add organic solvent deposit, suction filtration, lyophilize finally obtains purified oligochitosan-O-kojic acid-Mannich base derivative.
Further, the mass parts ratio of described oligochitosan schiff bases and chloro kojic acid-Mannich base is 2: (1-5).
Further, the molecular weight of described oligochitosan is 1000 ~ 5000Da, and deacetylation is 90-95%.
Further, in described step (1), dissolved chlorine is methyl-sulphoxide or dimethyl formamide for the organic solvent of kojic acid-Mannich base, and consumption is 2-4 times of chloro kojic acid-Mannich base quality; The organic solvent dissolving oligochitosan schiff bases is dimethyl formamide and pyridine, and the consumption of dimethyl formamide is 2-4 times of oligochitosan schiff bases, and the consumption of pyridine is 2-6 times of oligochitosan schiff bases.
Further, in described step (1), temperature of reaction is-35 DEG C ~ 40 DEG C, and the reaction times is 2 ~ 6h.
Further, in described step (2), temperature of reaction is room temperature, and the reaction times is 12-24h.
Further, in described step (1), the preparation method of described chloro kojic acid-Mannich base comprises the following steps:
N methyl piperazine and chloro kojic acid are dissolved in methyl alcohol and formalin solution, at room temperature rapid stirring, generate tan precipitate, collect, filter, wash several times with anhydrous methanol, with anhydrous methanol recrystallization, drying, namely obtain chloro kojic acid-Mannich base.
Further, the mass parts ratio of described N methyl piperazine and chloro kojic acid is 1: (2-3), and the parts by volume ratio of described methyl alcohol and formalin solution is (10-20): 1.
By such scheme, the present invention at least has the following advantages: the present invention is based on the thought that substructure connects, the active group in kojic acid-gamma-pyrone base and N methyl piperazine are linked in oligochitosan molecular chain, make three have Synergistic antimicrobial activity, develop
novelfood antiseptic fungistat.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technique means of the present invention, and can be implemented according to the content of specification sheets, coordinates below with preferred embodiment of the present invention
accompanying drawingbe described in detail as follows.
Accompanying drawing explanation
fig. 1it is the infrared spectra of oligochitosan
figure;
fig. 2it is the infrared spectra of the oligochitosan derivative of preparation in the embodiment of the present invention one
figure;
fig. 3it is the oligochitosan derivative of preparation in the embodiment of the present invention one
1h-NMR
figure;
fig. 4it is the oligochitosan derivative of preparation in the embodiment of the present invention one
13c-NMR
figure;
fig. 5it is the infrared spectra of the oligochitosan derivative of preparation in the embodiment of the present invention two
figure;
fig. 6it is the infrared spectra of the oligochitosan derivative of preparation in the embodiment of the present invention three
figure.
Embodiment
Below in conjunction with
accompanying drawingand embodiment, the specific embodiment of the present invention is described in further detail.Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
The preparation method with the oligochitosan-O-kojic acid-Mannich base derivative of good aqueous solubility and anti-microbial activity is as follows: adopt N methyl piperazine and chloro kojic acid to be raw material; first chloro kojic acid-Mannich base is obtained through Mannich reaction; then with the oligochitosan schiff bases generation alkylated reaction through amido protecting; obtain the oligochitosan-O-kojic acid-Mannich base derivative of retentive activity amino again through amino deprotection reaction and purifying, its synthetic route is as follows:
Embodiment one:
The preparation method of oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent comprises the following steps:
1, the preparation of chloro kojic acid-Mannich base
N methyl piperazine and chloro kojic acid in mass ratio 1:2 are dissolved in the methyl alcohol of 100mL and the formalin solution of 10mL, rapid stirring at 25 DEG C, generate tan precipitate, collect, filter, wash 5 times with anhydrous methanol, with anhydrous methanol recrystallization, drying, namely obtain chloro kojic acid-Mannich base.
2, the preparation of oligochitosan-O-kojic acid-Mannich base derivative
Under rapid stirring, 0.5g chloro kojic acid-Mannich base is dissolved in the methyl-sulphoxide of 2mL, (molecular weight is 1000Da to 1g oligochitosan schiff bases, deacetylation is 90%) be dissolved in the dimethyl formamide of 2mL and the pyridine mixed solution of 2mL, the oligochitosan schiff bases be dissolved in dimethyl formamide and pyridine mixed solution is dropwise added in the chloro kojic acid-Mannich base being dissolved in dimethyl formamide, reaction mixture magnetic agitation after 2 hours in-35 DEG C of water-baths, pouring excessive propanone into makes product precipitate, throw out filters, throw out uses ethanol respectively, acetone carries out surname extraction to remove dimethyl formamide and pyridine, namely lyophilize must obtain 1g oligochitosan schiff bases-O-kojic acid-Mannich base derivative.
Acidic alcohol (V/V=1:4) the mixed solution 20mL of 0.25mol/L is added, after stirring at room temperature 12h, with the Na of 10% in above-mentioned obtained oligochitosan schiff bases-O-kojic acid-Mannich base derivative
2cO
3regulate pH to neutral, with acetone repetitive scrubbing 5 times, suction filtration, lyophilize.
Be suspended from 5mL ultrapure water by 1 gram of crude product, put into dialysis tubing, dialyse 24 hours, concentrated, add enough acetone precipitations, suction filtration, lyophilize finally obtains the oligochitosan-O-kojic acid-Mannich base derivative of purified brown.
The yield of this oligochitosan derivative is 62.1%, uses infrared spectra and nucleus magnetic resonance to characterize it.
fig. 1for the infrared spectra of oligochitosan
figure, wherein, 3422.36cm
-1for the stretching vibration absorption peak of O-H and N-H, 2923.83cm
-1for the absorption peak of C-H stretching vibration, 1628.76cm
-1for NH
2flexural vibration absorption peak, 1155.97cm
-1with 1071.52cm
-1for the absorption peak of C-O stretching vibration, 893.24cm
-1for ring stretching vibration absorption peak.
fig. 2it is the infrared light of this enforcement mesochite oligosaccharide derivative
figurespectrum, wherein, 890.44cm
-1the charateristic avsorption band of β-pyranose form glycosidic link that place is corresponding, 1519.37cm
-1for C=C stretching vibration absorption peak in this derivative, 1223.02cm
-1for C-O-C stretching vibration absorption peak in this derivative, 970.39cm
-1for the absorption peak of chloro kojic acid-Mannich base and oligochitosan covalent bond, 1223.02cm
-1and 970.39cm
-1existence prove the formation of target product.
fig. 3it is the present embodiment mesochite oligosaccharide derivative
1h-NMR
figure, chemical shift appear at the peak at 1.968ppm place corresponding be-CH on acetamido residues
3proton peak; H on what the peak at 2.447-2.796ppm place was corresponding is aminoglucose saccharide residue and acetamido residues
2proton peak; The proton peak at corresponding H3, H4, H5, H6 place on what the peak at 3.089-3.837ppm place was corresponding is glucosamine and acetylglucosamine; The peak at 4.7ppm place is solvent peak; 4.26 and 6.82ppm place there are two new chemical shifts, the chemical shift of-CH2 on kojic acid 5-hydroxy pyrone skeleton (H-7 ') and each proton of H-3 ' can be attributed to respectively; And H on the aminoglucose saccharide residue at δ=2.98ppm place
2chemical shift still exist, this result is consistent with the result of infrared spectra, so these new chemical shifts prove that the amino of 5-hydroxy pyrone and oligochitosan in kojic acid there occurs alkylation; 2.88,3.07 and 3.12ppm place be on N methyl piperazine ring
?chemical shift; Therefore, by the ownership of above chemical shift, can prove, chloro kojic acid-Mannich base and oligochitosan schiff bases there occurs O-alkylated reaction, and oligochitosan-O-kojic acid-Mannich base derivative is successfully prepared.
fig. 4for the present embodiment mesochite oligosaccharide derivative
13c-NMR
figure, δ=22.74,56.33,60.46,71.03,75.11,76.95,98.63,174.18ppm is attributed to-CH in oligochitosan molecule respectively
3, the chemical shift of C2, C6, C3, C5, C4, C1 and-C=O; δ=45.83,47.08,56.38ppm, is attributed to-the CH2 in derivative on N methyl piperazine ring and-CH respectively
3in C.δ=60.44,114.64,139.82,145.87,159.35 and the chemical shift at 176.99ppm place be attributed in derivative 5-hydroxy pyrone base in C-7 ', C-3 ', C-6 ', C-5 ', C-2 ' and the chemical shift of C-4 ', show that oligochitosan-O-kojic acid-Mannich base derivative is successfully prepared.
Embodiment two:
The preparation method of oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent comprises the following steps:
1, the preparation of chloro kojic acid-Mannich base
N methyl piperazine and chloro kojic acid in mass ratio 1:2.5 are dissolved in the methyl alcohol of 150mL and the formalin solution of 10mL, rapid stirring at 25 DEG C, generate tan precipitate, collect, filter, 5 times are washed with anhydrous methanol, with anhydrous methanol recrystallization, drying, namely obtain chloro kojic acid-Mannich base.
2, the preparation of oligochitosan-O-kojic acid-Mannich base derivative
Under rapid stirring, 1.5g chloro kojic acid-Mannich base is dissolved in the dimethyl formamide of 3mL, (molecular weight is 3000Da to 1g oligochitosan schiff bases, deacetylation is 93%) be dissolved in the dimethyl formamide of 3mL and the pyridine mixed solution of 4mL, the oligochitosan schiff bases be dissolved in dimethyl formamide and pyridine mixed solution is dropwise added in the chloro kojic acid-Mannich base being dissolved in dimethyl formamide, reaction mixture magnetic agitation after 4 hours in-5 DEG C of water-baths, pouring excessive propanone into makes product precipitate, throw out filters, throw out uses ethanol respectively, acetone carries out surname extraction to remove dimethyl formamide and pyridine, finally obtain the product 1.8g after vacuum lyophilization.
Acidic alcohol (V/V=1:4) the mixed solution 36mL of 0.25mol/L is added, after stirring at room temperature 12h, with the Na of 10% in above-mentioned obtained oligochitosan schiff bases-O-kojic acid-Mannich base derivative
2cO
3regulate pH to neutral, with acetone repetitive scrubbing 5 times, suction filtration, lyophilize.
Be suspended from 5mL ultrapure water by 1 gram of crude product, put into dialysis tubing, dialyse 24 hours, concentrated, add enough acetone precipitations, suction filtration, lyophilize finally obtains the oligochitosan-O-kojic acid-Mannich base derivative of purified brown.
The yield of this oligochitosan derivative is 65.2%.
fig. 5for the infrared spectra of this sample
figure, wherein, 892.24cm
-1the charateristic avsorption band of β-pyranose form glycosidic link that place is corresponding, 1518.32cm
-1for C=C stretching vibration absorption peak in this derivative, 1226.23cm
-1for C-O-C stretching vibration absorption peak in this derivative, 971.91cm
-1for the absorption peak of chloro kojic acid-Mannich base and oligochitosan covalent bond, 1226.23cm
-1and 971.91cm
-1existence prove the formation of target product.
Embodiment three:
The preparation method of oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent comprises the following steps:
1, the preparation of chloro kojic acid-Mannich base
N methyl piperazine and chloro kojic acid in mass ratio 1:3 are dissolved in the methyl alcohol of 200mL and the formalin solution of 10mL, rapid stirring at 25 DEG C, generate tan precipitate, collect, filter, wash 5 times with anhydrous methanol, with anhydrous methanol recrystallization, drying, namely obtain chloro kojic acid-Mannich base.
2, the preparation of oligochitosan-O-kojic acid-Mannich base derivative
Under rapid stirring, 2.5g chloro kojic acid-Mannich base is dissolved in the methyl-sulphoxide of 4mL, (molecular weight is 5000Da to 1g oligochitosan schiff bases, deacetylation is 95%) be dissolved in the dimethyl formamide of 4mL and the pyridine mixed solution of 6mL, the oligochitosan schiff bases be dissolved in dimethyl formamide and pyridine mixed solution is dropwise added in the chloro kojic acid-Mannich base being dissolved in dimethyl formamide, reaction mixture magnetic agitation after 6 hours in 40 DEG C of water-baths, pouring excessive propanone into makes product precipitate, throw out filters, throw out uses ethanol respectively, acetone carries out surname extraction to remove dimethyl formamide and pyridine, finally obtain the product 3g after vacuum lyophilization.
Acidic alcohol (V/V=1:4) the mixed solution 60mL of 0.25mol/L is added, after stirring at room temperature 12h, with the Na of 10% in above-mentioned obtained oligochitosan schiff bases-O-kojic acid-Mannich base derivative
2cO
3regulate pH to neutral, with acetone repetitive scrubbing 5 times, suction filtration, lyophilize.
Be suspended from 5mL ultrapure water by 1 gram of crude product, put into dialysis tubing, dialyse 24 hours, concentrated, add enough acetone precipitations, suction filtration, lyophilize finally obtains the oligochitosan-O-kojic acid-Mannich base derivative of purified brown.
The yield of this oligochitosan derivative is 63.5%.
fig. 6for the infrared spectra of this sample
figure, wherein, 893.34cm
-1the charateristic avsorption band of β-pyranose form glycosidic link that place is corresponding, 1514.18cm
-1for C=C stretching vibration absorption peak in this derivative, 1223.73cm
-1for C-O-C stretching vibration absorption peak in this derivative, 970.39cm
-1for the absorption peak of chloro kojic acid and oligochitosan covalent bond, 1223.13cm
-1and 970.39cm
-1existence prove the formation of target product.
The detection of germ resistance
1, the preparation of antimicrobial
By called after derivative 1, derivative 2, the derivative 3 respectively of the sample in embodiment one, embodiment two, embodiment three, with deionized water, oligochitosan, kojic acid, derivative 1, derivative 2 and derivative 3 are dissolved, be made into the solution that concentration gradient is 0.01,0.05,0.1,0.5,1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0 and 9.0mg/mL, with the filtering with microporous membrane of 0.22 μm, for subsequent use.
2, Determination of Antibacterial Activity
Cultivated with the nutrient broth after 98mL sterilizing by the initial bacterium liquid of 1mL and mix, then add the above-mentioned antiseptic-germicide of different concns gradient of 1mL wherein, replace antimicrobial as blank using 1mL deionized water, at 37 DEG C, shaking table is cultivated.In culturing process, take out 1mL nutrient solution after 8h, after doubling dilution, spread plate method calculates colony number, and each sample repeats 3 times.Antibiotic rate (I) is according to following formulae discovery:
I(％)＝N
1-N
2/N
1×100
Wherein, N1: the total number of bacterial colony in initial incubation liquid;
N2: containing the total number of bacterial colony in antiseptic-germicide nutrient solution.
With the concentration of antiseptic-germicide for X-coordinate, inhibiting rate is that ordinate zou is done
figure, obtain IC
50value
table 1the detection of antiseptic-germicide performance
From
table 1in can find out, the antiseptic-germicide that the present invention obtains all has good anti-microbial activity to streptococcus aureus, streptococcus pyogenes, subtilis, Salmonella typhimurium, shigella dysenteriae and intestinal bacteria, and anti-microbial property is better than oligochitosan and kojic acid greatly, there is in food antiseptic potential using value.
In sum, principle of the present invention is as follows: have three chemical modification avtive spots in the molecular structure of oligochitosan, if there is alkylated reaction, according to the size of three position activity, first occurring on C-2 bit amino, is secondly on the primary hydroxyl of C-6 position, is finally on the secondary hydroxyl of C-3 position.Due in an acidic solution, after the C-2 protonated amino in oligochitosan molecule, be the active group of anti-microbial effect; therefore, first the active amino phenyl aldehyde of C-2 position is protected, after alkylated reaction be there occurs; deprotection in acid alcohol solution again, release active amino.And the hydroxyl of C-3 position is due to steric effect, do not participate in reaction.Therefore there is O-alkylated reaction in the hydroxyl of C-6 position and chloro kojic acid-Mannich base.
Beneficial effect of the present invention is as follows: (1), by the hydroxyl of the C-6 position of oligochitosan and chloro kojic acid-Mannich base, O-alkylated reaction occurs, active antibacterial group-gamma-pyrone base in kojic acid and N methyl piperazine are incorporated in oligochitosan molecular chain, produce with oligochitosan molecule and act synergistically, significantly strengthen its anti-microbial activity.(2) this type of new derivative toxicity is low; and have well water-soluble; be dissolvable in water multiple inorganic with in organic solvent; avoid the use of organic solvent; more be conducive to environment protection; and expand its Application Areas, have a wide range of applications in fields such as medicine, food, makeup and agriculturals.
The above is only the preferred embodiment of the present invention; be not limited to the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (10)
1. oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent, is characterized in that: its chemical structural formula is as follows, and wherein, n is 6-20, and substitution value is 1.21-1.78.
2. the preparation method of oligochitosan-O-kojic acid according to claim 1-Mannich base derivative antibacterial agent, is characterized in that: comprise the following steps:
(1) after oligochitosan schiff bases and chloro kojic acid-Mannich base organic solvent being dissolved respectively, mix and stir, reaction terminates rear interpolation organic solvent deposit product, filter, precipitated product organic solvent soxhlet type, namely lyophilize obtains oligochitosan schiff bases-O-kojic acid-Mannich base derivative;
(2) in the oligochitosan schiff bases-O-kojic acid-Mannich base derivative of described step (1), add hydrochloric acid/ethanol (V/V=1:4) mixed solution of 0.25mol/L, mix and stir, reaction terminates rear adjustment pH to neutral, with organic solvent washing, suction filtration, lyophilize obtains sample.
3. the preparation method of oligochitosan-O-kojic acid according to claim 2-Mannich base derivative antibacterial agent, it is characterized in that: described method is also included in the purification step after step (2), by described dried product dialysis, add organic solvent deposit, suction filtration, lyophilize finally obtains purified oligochitosan-O-kojic acid-Mannich base derivative.
4. the preparation method of oligochitosan-O-kojic acid according to claim 2-Mannich base derivative antibacterial agent, is characterized in that: the mass parts ratio of described oligochitosan schiff bases and chloro kojic acid-Mannich base is 2: (1-5).
5. the preparation method of oligochitosan-O-kojic acid according to claim 4-Mannich base derivative antibacterial agent, is characterized in that: the molecular weight of described oligochitosan is 1000 ~ 5000Da, and deacetylation is 90-95%.
6. the preparation method of oligochitosan-O-kojic acid according to claim 2-Mannich base derivative antibacterial agent, it is characterized in that: in described step (1), dissolved chlorine is methyl-sulphoxide or dimethyl formamide for the organic solvent of kojic acid-Mannich base, and consumption is 2-4 times of chloro kojic acid-Mannich base quality; The organic solvent dissolving oligochitosan schiff bases is dimethyl formamide and pyridine, and the consumption of dimethyl formamide is 2-4 times of oligochitosan schiff bases, and the consumption of pyridine is 2-6 times of oligochitosan schiff bases.
7. the preparation method of oligochitosan-O-kojic acid according to claim 2-Mannich base derivative antibacterial agent, is characterized in that: in described step (1), temperature of reaction is-35 DEG C ~ 40 DEG C, and the reaction times is 2 ~ 6h.
8. the preparation method of oligochitosan-O-kojic acid according to claim 2-Mannich base derivative antibacterial agent, it is characterized in that: in described step (2), temperature of reaction is room temperature, and the reaction times is 12-24h.
9. the preparation method of oligochitosan-O-kojic acid according to claim 2-Mannich base derivative antibacterial agent, is characterized in that: in described step (1), and the preparation method of described chloro kojic acid-Mannich base comprises the following steps:
N methyl piperazine and chloro kojic acid are dissolved in methyl alcohol and formalin solution, at room temperature rapid stirring, generate tan precipitate, collect, filter, wash several times with anhydrous methanol, with anhydrous methanol recrystallization, drying, namely obtain chloro kojic acid-Mannich base.
10. the preparation method of oligochitosan-O-kojic acid according to claim 9-Mannich base derivative antibacterial agent, it is characterized in that: the mass parts ratio of described N methyl piperazine and chloro kojic acid is 1:(2-3), the parts by volume ratio of described methyl alcohol and formalin solution is (10-20): 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510443851.8A CN105218700B (en) | 2015-07-24 | 2015-07-24 | A kind of chitosan oligosaccharide O kojic acids Mannich base derivative antibacterial agent and preparation method thereof |
| PCT/CN2015/088398 WO2017016022A1 (en) | 2015-07-24 | 2015-08-28 | Chito-oligosaccharide-o-kojic acid-mannich base derivative antibacterial agent and preparation method thereof |
| AU2015403788A AU2015403788B2 (en) | 2015-07-24 | 2015-08-28 | Chito-oligosaccharide-O-kojic acid-Mannich base derivative antibacterial agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510443851.8A CN105218700B (en) | 2015-07-24 | 2015-07-24 | A kind of chitosan oligosaccharide O kojic acids Mannich base derivative antibacterial agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105218700A true CN105218700A (en) | 2016-01-06 |
| CN105218700B CN105218700B (en) | 2018-03-06 |
Family
ID=54988023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510443851.8A Active CN105218700B (en) | 2015-07-24 | 2015-07-24 | A kind of chitosan oligosaccharide O kojic acids Mannich base derivative antibacterial agent and preparation method thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN105218700B (en) |
| AU (1) | AU2015403788B2 (en) |
| WO (1) | WO2017016022A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107441494A (en) * | 2017-07-28 | 2017-12-08 | 中国科学院过程工程研究所 | A kind of chitosan oligosaccharide of antibacterial film activity and antibiotic and its application |
| CN109503732A (en) * | 2018-11-26 | 2019-03-22 | 江南大学 | A kind of Preparation method and use of 2,4 dichlorophenoxyacetic acid chitosan oligosaccharide ester |
| CN111333750A (en) * | 2020-03-24 | 2020-06-26 | 江南大学 | Chitosan oligosaccharide-N-geraniol derivative and preparation method and application thereof |
| CN113068744A (en) * | 2021-04-28 | 2021-07-06 | 高培（广州）乳业有限公司 | Modified milk powder with antioxidant and anti-aging effects |
| CN115433292A (en) * | 2022-09-30 | 2022-12-06 | 大连民族大学 | COS-O-octanoyl chloride derivative, preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746658B (en) * | 2019-11-05 | 2020-09-08 | 江南大学 | Chitosan/kojic acid/chlorinated kojic acid composite bacteriostatic preservative film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304683A (en) * | 2013-06-09 | 2013-09-18 | 江南大学 | Chitosan oligosaccharide kojic acid derivative and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532345B (en) * | 2010-12-24 | 2014-05-07 | 大连中科格莱克生物科技有限公司 | O-unsaturated fatty acid acylated chitosan oligosaccharides as well as preparation and application thereof |
| CN102321196B (en) * | 2011-10-11 | 2013-06-05 | 北京联合大学生物化学工程学院 | O-salicylic acid esterified oligo-chitosan salicylaldehyde Schiff base bacteriostatic agent and preparation method thereof |
| CN104558244B (en) * | 2014-12-19 | 2017-01-04 | 华南理工大学 | A kind of O-pyridine acid esters chitosan and preparation method and application |
| CN105085712B (en) * | 2015-08-21 | 2017-10-31 | 江南大学 | A kind of chitosan oligosaccharide N kojic acids Mannich base derivative and its preparation method and application |
-
2015
- 2015-07-24 CN CN201510443851.8A patent/CN105218700B/en active Active
- 2015-08-28 AU AU2015403788A patent/AU2015403788B2/en active Active
- 2015-08-28 WO PCT/CN2015/088398 patent/WO2017016022A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304683A (en) * | 2013-06-09 | 2013-09-18 | 江南大学 | Chitosan oligosaccharide kojic acid derivative and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| XIAOLI LIU, ET AL.: "Synthesis, Characterization, and Antimicrobial Activity of Kojic Acid Grafted Chitosan Oligosaccharide", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 * |
| XIAOLI LIU,ET AL.: "Binding of a novel bacteriostatic agent—chitosan oligosaccharides–kojic acid graft copolymer to bovine serum albumin: spectroscopic and conformation investigations", 《EUR FOOD RES TECHNOL》 * |
| 许敏: "曲酸衍生物的合成及其对酪氨酸酶活性的影响", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107441494A (en) * | 2017-07-28 | 2017-12-08 | 中国科学院过程工程研究所 | A kind of chitosan oligosaccharide of antibacterial film activity and antibiotic and its application |
| CN109503732A (en) * | 2018-11-26 | 2019-03-22 | 江南大学 | A kind of Preparation method and use of 2,4 dichlorophenoxyacetic acid chitosan oligosaccharide ester |
| CN109503732B (en) * | 2018-11-26 | 2020-12-01 | 江南大学 | Preparation method and application of 2, 4-dichlorophenoxyacetic acid chitosan oligosaccharide ester |
| CN111333750A (en) * | 2020-03-24 | 2020-06-26 | 江南大学 | Chitosan oligosaccharide-N-geraniol derivative and preparation method and application thereof |
| CN111333750B (en) * | 2020-03-24 | 2021-05-04 | 江南大学 | Chitosan oligosaccharide-N-geraniol derivative and preparation method and application thereof |
| CN113068744A (en) * | 2021-04-28 | 2021-07-06 | 高培（广州）乳业有限公司 | Modified milk powder with antioxidant and anti-aging effects |
| CN115433292A (en) * | 2022-09-30 | 2022-12-06 | 大连民族大学 | COS-O-octanoyl chloride derivative, preparation method and application thereof |
| CN115433292B (en) * | 2022-09-30 | 2023-05-09 | 大连民族大学 | COS-O-octanoyl chloride derivative, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017016022A1 (en) | 2017-02-02 |
| AU2015403788B2 (en) | 2018-06-07 |
| AU2015403788A1 (en) | 2017-11-09 |
| CN105218700B (en) | 2018-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105218700A (en) | A kind of oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent and preparation method thereof | |
| CN100360036C (en) | Preparation method of chitin/metal copper composite antibactericidal agent | |
| CN100360035C (en) | Preparation method of chitin/zinc compound bactericide | |
| Foroughnia et al. | Synthesis of new chitosan Schiff base and its Fe2O3 nanocomposite: Evaluation of methyl orange removal and antibacterial activity | |
| CN111620966B (en) | Chitosan oligosaccharide-N-linalool copolymer and preparation method and application thereof | |
| CN108262018B (en) | Method for removing tetracycline in water by adsorption of leaf-shaped two-dimensional lamellar structure | |
| CN101701044B (en) | Chitosan hyamine and preparation and application thereof | |
| CN103497275B (en) | A kind of antibacterial, antiviral guanidinesalt star polymer and its preparation method and application | |
| CN107902736B (en) | Preparation method of composite flocculation algistat and composite flocculation algistat | |
| CN103450369B (en) | The preparation method of poly glycol monomethyl ether-chitosan derivatives | |
| CN105237655A (en) | Marine organism polysaccharide Schiff base derivative, preparation method thereof, and application thereof as agricultural bactericide | |
| CN101235099A (en) | Carboxymethyl chitosan quaternary ammonium salt derivatives and preparation method thereof | |
| CN111732674A (en) | Chitosan oligosaccharide-M-cinnamyl alcohol derivative, preparation method and application thereof | |
| CN101649007A (en) | Chitosan quaternary phosphonium salt derivative and preparation method thereof | |
| CN103304683A (en) | Chitosan oligosaccharide kojic acid derivative and preparation method thereof | |
| CN101781374A (en) | Preparation method and application of copper compound with chitosan and/or derivatives thereof | |
| CN110903488A (en) | Preparation method of chitosan @ metal organic framework antibacterial material | |
| CN105131152A (en) | Marine organism polysaccharide copper compound, preparation thereof and application of marine organic polysaccharide copper compound serving as agricultural bactericide | |
| CN106967184A (en) | A kind of chitosan oligosaccharide O spiceleaf 01 derivatives and its production and use | |
| Sang et al. | Synthesis and preservative application of quaternized carboxymethyl chitosan containing guanidine groups | |
| CN103319750A (en) | Carboxymethyl chitosan quaternary ammonium salt/modified zirconium phosphate nanometer composite material | |
| CN106380526A (en) | O-alpha-methyl mandelate-N-trimethyl chitosan quaternary ammonium salt as well as preparation method and application thereof | |
| CN113527538B (en) | Preparation method and application of cinnamic acid modified hydroxypropyl chitosan derivative | |
| CN101139404A (en) | Method for preparing chitosan lactate | |
| CN107602726B (en) | Low molecular weight C6-carboxyl chitin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |