CN105218700B - A kind of chitosan oligosaccharide O kojic acids Mannich base derivative antibacterial agent and preparation method thereof - Google Patents
A kind of chitosan oligosaccharide O kojic acids Mannich base derivative antibacterial agent and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to technical field of food additives, more particularly to a kind of chitosan oligosaccharide O kojic acids Mannich base derivative antibacterial agent and preparation method thereof, this method comprises the following steps：(1) N methyl piperazines and chloro kojic acid are mixed and reacted, obtain product chloro kojic acid Mannich base；(2) chitosan oligosaccharide schiff bases are mixed and reacted with chloro kojic acid Mannich base, obtained chitosan oligosaccharide schiff bases O kojic acid Mannich base derivatives by post processing, chitosan oligosaccharide O kojic acid Mannich base derivatives are obtained by amino deprotection reaction and purifying.Molecule with anti-microbial property is introduced into chitosan oligosaccharide molecule by the present invention, synergy is produced with chitosan oligosaccharide molecule, enhance the antibacterial activity of chitosan oligosaccharide, preparation method is simple, substitution value is high, cost is low, method of purification is easy, property is stable, obtained chitosan oligosaccharide derivative has good aqueous solubility and antibacterial activity, good antibacterial activity is respectively provided with to Escherichia coli, gold-coloured staphylococci etc., is well suited as anti-biotic material.
Description
Technical field
The invention belongs to technical field of food additives, more particularly to a kind of chitosan oligosaccharide-O- kojic acids-Mannich base derivative
Antiseptic and preparation method thereof.
Background technology
In recent years, food-safety problem has turned into one of worldwide focal issue that global public priority considers.Food exists
The pollution of some harmful microbes is all may suffer from during production and processing, transport, storage and sale etc., these are harmful micro-
Biology can contaminated food products, make food apoilage, not only result in the serious waste of food resource, but also can be to trencherman by mistake
Body cause serious injury, therefore the anti-corrosive fresh-keeping of varieties of food items is a major issue urgently to be resolved hurrily all the time.Naturally
Antiseptic and inhibiting bacteria function agent such as chitosan and kojic acid, with the characteristic such as its is safe and non-toxic, heat endurance is good by the pro-gaze of people, pass through chemistry
The modified focus developed the antiseptics for natural food with stronger bacteriostatic activity and wider antimicrobial spectrum and have become people's research.
Chitosan oligosaccharide is that the low molecule amount basic amine group that chitosan main chain obtains after the degraded fracture of physics, chemistry or enzyme is few
Sugar.With biodegradability, biocompatibility, biological non-toxicity and chemical reactivity, to including bacterium, fungi
A series of microorganisms have inhibitory action, are considered as developing the ideal material of novel natural food preservative.
However, because chitosan oligosaccharide is natural macromolecular product, when as food antiseptic antiseptic in use, with it is traditional normal
Compared with chemical preservative, the shortcoming such as still have antibacterial activity low, so application in the food industry is not very universal at present.
Therefore, can be by being chemically modified to the structure of chitosan oligosaccharide, due to having the amino of chemical reactivity on its strand
And hydroxyl, these sites are the ideal role sites that chemical modification is carried out to chitosan oligosaccharide, the work of its antibacterial can be further improved
Property, this is also to study more effective ways both at home and abroad at present.
In view of it is above-mentioned the defects of, the design people, be actively subject to research and innovation, to found a kind of chitosan oligosaccharide-O- kojic acids-
Mannich base derivative antibacterial agent and preparation method thereof, make it with more the value in industry.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of chitosan oligosaccharide-O- kojic acids-Mannich base derivative
Antiseptic and preparation method thereof, active antibacterial group-gamma-pyrone base in kojic acid and N methyl piperazine are incorporated into shell widow
In sugar subchain, synergy is produced with chitosan oligosaccharide molecule, to strengthen the antibacterial activity of chitosan oligosaccharide, it is good, mutual to obtain dissolubility
The chitosan oligosaccharide derivative of synergy.
A kind of chitosan oligosaccharide-O- kojic acids-Mannich base derivative antibacterial agent proposed by the present invention, the following institute of its chemical structural formula
Show, wherein, n 6-20, substitution value 1.21-1.78.
The invention also provides the preparation method of chitosan oligosaccharide-O- kojic acids-Mannich base derivative antibacterial agent, including following step
Suddenly：
(1) after dissolving chitosan oligosaccharide schiff bases and chloro kojic acid-Mannich base respectively with organic solvent, it is mixed and stirred for,
Organic solvent precipitated product is added in reaction after terminating, filtering, precipitated product organic solvent soxhlet type, be freeze-dried and produce shell
Oligosaccharides schiff bases-O- kojic acids-Mannich base derivative；
(2) add 0.25mol/L's into chitosan oligosaccharide schiff bases-O- kojic acids-Mannich base derivative of the step (1)
Hydrochloric acid/ethanol (V/V=1:4) mixed liquor, it is mixed and stirred for, reaction adjusts pH to neutrality after terminating, with organic solvent washing, take out
Filter, freeze-drying obtain sample.
Further, methods described is additionally included in the purification step after step (2), and the dried product is saturating
Analysis, organic solvent deposit is added, filtered, freeze-drying finally gives purified chitosan oligosaccharide-O- kojic acids-Mannich base and derived
Thing.
Further, the chitosan oligosaccharide schiff bases and the mass parts ratio of chloro kojic acid-Mannich base are 2: (1-5).
Further, the molecular weight of the chitosan oligosaccharide is 1000~5000Da, deacetylation 90-95%.
Further, in the step (1), the organic solvent of dissolving chloro kojic acid-Mannich base is dimethyl sulfoxide or two
NMF, dosage are 2-4 times of chloro kojic acid-Mannich base quality；The organic solvent for dissolving chitosan oligosaccharide schiff bases is two
NMF and pyridine, the dosage of dimethylformamide are 2-4 times of chitosan oligosaccharide schiff bases, and the dosage of pyridine is wished for chitosan oligosaccharide
2-6 times of husband's alkali.
Further, in the step (1), reaction temperature is -35 DEG C~40 DEG C, and the reaction time is 2~6h.
Further, in the step (2), reaction temperature is room temperature, reaction time 12-24h.
Further, in the step (1), the preparation method of the chloro kojic acid-Mannich base comprises the following steps：
N methyl piperazine and chloro kojic acid are dissolved in methanol and formalin solution, quick stirring, raw at room temperature
Into tan precipitate, collect, filtering, washed several times with absolute methanol, recrystallized, dried with absolute methanol, that is, obtain chloro song
Acid-Mannich base.
Further, the mass parts ratio of N methyl piperazine and the chloro kojic acid is 1: (2-3), the methanol and Fu Er
The parts by volume ratio of Malin's solution is (10-20): 1.
By such scheme, the present invention at least has advantages below：Thought of the present invention based on substructure connection, kojic acid
In active group-gamma-pyrone base and N methyl piperazine be linked into chitosan oligosaccharide strand, make three that there is Synergistic antimicrobial
Activity, develop new food antiseptic bacteriostatic agent.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of chitosan oligosaccharide；
Fig. 2 is the infrared spectrogram of the chitosan oligosaccharide derivative prepared in the embodiment of the present invention one；
Fig. 3 is the chitosan oligosaccharide derivative prepared in the embodiment of the present invention one1H-NMR schemes；
Fig. 4 is the chitosan oligosaccharide derivative prepared in the embodiment of the present invention one13C-NMR schemes；
Fig. 5 is the infrared spectrogram of the chitosan oligosaccharide derivative prepared in the embodiment of the present invention two；
Fig. 6 is the infrared spectrogram of the chitosan oligosaccharide derivative prepared in the embodiment of the present invention three.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
The preparation method of chitosan oligosaccharide-O- kojic acids-Mannich base derivative with good aqueous solubility and antibacterial activity is as follows：
Use N methyl piperazine and chloro kojic acid to obtain chloro kojic acid-Mannich base through Mannich reaction first for raw material, then with warp
Alkylated reaction occurs for the chitosan oligosaccharide schiff bases of amido protecting, then obtains retentive activity amino through amino deprotection reaction and purifying
Chitosan oligosaccharide-O- kojic acids-Mannich base derivative, its synthetic route is as follows：
Embodiment one：
The preparation method of chitosan oligosaccharide-O- kojic acids-Mannich base derivative antibacterial agent comprises the following steps：
1st, the preparation of chloro kojic acid-Mannich base
N methyl piperazine and chloro kojic acid in mass ratio 1:2 are dissolved in 100mL methanol and 10mL formalin solution
In, quickly stirred at 25 DEG C, generate tan precipitate, collected, filtering, washed 5 times with absolute methanol, tied again with absolute methanol
It is brilliant, dry, that is, obtain chloro kojic acid-Mannich base.
2nd, the preparation of chitosan oligosaccharide-O- kojic acids-Mannich base derivative
Under quick stirring, 0.5g chloros kojic acid-Mannich base is dissolved in 2mL dimethyl sulfoxide, 1g chitosan oligosaccharide schiff bases
(molecular weight 1000Da, deacetylation 90%) is dissolved in 2mL dimethylformamide and 2mL pyridine mixed liquor, will be molten
Chitosan oligosaccharide schiff bases in dimethylformamide and pyridine mixed liquor be added dropwise be dissolved in the chloro kojic acid of dimethylformamide-
In Mannich base, for magnetic agitation after 2 hours, pour into excessive propanone precipitates product to reactant mixture in -35 DEG C of water-baths, precipitation
Thing filters, and sediment carries out surname extraction to remove dimethylformamide and pyridine with ethanol, acetone respectively, and being freeze-dried must be i.e.
Obtain 1g chitosan oligosaccharide schiff bases-O- kojic acids-Mannich base derivative.
0.25mol/L hydrochloric acid second is added in chitosan oligosaccharide schiff bases-O- kojic acids-Mannich base derivative obtained above
Alcohol (V/V=1:4) mixed liquor 20mL, after 12h is stirred at room temperature, with 10% Na2CO3PH is adjusted to neutrality, is washed repeatedly with acetone
5 times, filter, freeze-drying.
1 gram of crude product is suspended from 5mL ultra-pure waters, is put into bag filter, is dialysed 24 hours, concentration, adds enough acetone
Precipitation, filter, freeze-drying finally gives chitosan oligosaccharide-O- kojic acids-Mannich base derivative of purified brown.
The yield of the chitosan oligosaccharide derivative is 62.1%, and it is characterized using infrared spectrum and nuclear magnetic resonance.
Fig. 1 is the infrared spectrogram of chitosan oligosaccharide, wherein, 3422.36cm-1For O-H and N-H stretching vibration absworption peak,
2923.83cm-1For the absworption peak of C-H stretching vibrations, 1628.76cm-1For NH2Flexural vibrations absworption peak, 1155.97cm-1With
1071.52cm-1For the absworption peak of C-O stretching vibrations, 893.24cm-1For ring stretching vibration absworption peak.
Fig. 2 is the infrared light collection of illustrative plates of chitosan oligosaccharide derivative in this implementation, wherein, 890.44cm-1β-pyranoid form corresponding to place
The characteristic absorption peak of glycosidic bond, 1519.37cm-1For C=C stretching vibration absworption peaks in the derivative, 1223.02cm-1Spread out for this
C-O-C stretching vibration absworption peaks in biology, 970.39cm-1For the suction of chloro kojic acid-Mannich base and chitosan oligosaccharide covalent bond
Receive peak, 1223.02cm-1And 970.39cm-1Presence prove target product formation.
Fig. 3 is chitosan oligosaccharide derivative in the present embodiment1H-NMR schemes, peak pair of the chemical shift at 1.968ppm
That answer is-the CH on acetamido residues3Proton peak；2.447-2.796ppm it is aminoglucose saccharide residue corresponding to the peak at place
With H on acetamido residues2Proton peak；3.089-3.837ppm it is Glucosamine and acetylamino Portugal corresponding to the peak at place
Proton peak at grape sugar upper corresponding H3, H4, H5, H6；Peak at 4.7ppm is solvent peak；Occur at 4.26 and 6.82ppm
Two new chemical shifts, the change of-CH2 (H-7 ') and each protons of H-3 ' on kojic acid 5- hydroxy pyrone skeletons can be attributed to respectively
Displacement study；And H on the aminoglucose saccharide residue at δ=2.98ppm2Chemical shift still have, this result and infrared spectrum
Result it is consistent, so these new chemical shifts prove that there occurs alkyl for the amino of 5- hydroxy pyrones and chitosan oligosaccharide in kojic acids
Change；It is the chemical shift on N methyl piperazine ring at 2.88,3.07 and 3.12ppm；Therefore, returning by above chemical shift
Category, can be proved, chloro kojic acid-Mannich base and chitosan oligosaccharide schiff bases there occurs O- alkylated reactions, chitosan oligosaccharide-O- kojic acids-
Mannich base derivative is successfully prepared.
Fig. 4 is chitosan oligosaccharide derivative in the present embodiment13C-NMR schemes, δ=22.74, and 56.33,60.46,71.03,
75.11,76.95,98.63,174.18ppm are attributed to-CH in chitosan oligosaccharide molecule respectively3, C2, C6, C3, C5, C4, C1 and-C=
O chemical shift；δ=45.83,47.08,56.38ppm, be attributed to respectively-CH2 in derivative on N methyl piperazine ring and-
CH3In C.Chemical shift at δ=60.44,114.64,139.82,145.87,159.35 and 176.99ppm is attributed to spread out
C-7 ', C-3 ', C-6 in 5- hydroxy pyrone bases in biology ', C-5 ', C-2 ' and C-4 ' chemical shift, show chitosan oligosaccharide-
O- kojic acids-Mannich base derivative is successfully prepared.
Embodiment two：
The preparation method of chitosan oligosaccharide-O- kojic acids-Mannich base derivative antibacterial agent comprises the following steps：
1st, the preparation of chloro kojic acid-Mannich base
N methyl piperazine and chloro kojic acid in mass ratio 1:2.5 are dissolved in 150mL methanol and 10mL formalin is molten
In liquid, quickly stirred at 25 DEG C, generate tan precipitate, collected, filtering, washed 5 times with absolute methanol, tied again with absolute methanol
It is brilliant, dry, that is, obtain chloro kojic acid-Mannich base.
2nd, the preparation of chitosan oligosaccharide-O- kojic acids-Mannich base derivative
Under quick stirring, 1.5g chloros kojic acid-Mannich base is dissolved in 3mL dimethylformamide, 1g chitosan oligosaccharides are wished
Husband's alkali (molecular weight 3000Da, deacetylation 93%) is dissolved in 3mL dimethylformamide and 4mL pyridine mixed liquor,
The chitosan oligosaccharide schiff bases being dissolved in dimethylformamide and pyridine mixed liquor are added dropwise to the chloro for being dissolved in dimethylformamide
In kojic acid-Mannich base, for magnetic agitation after 4 hours, pour into excessive propanone precipitates product to reactant mixture in -5 DEG C of water-baths,
Sediment filters, and sediment carries out surname extraction to remove dimethylformamide and pyridine with ethanol, acetone respectively, finally obtained
Product 1.8g after vacuum freeze drying.
0.25mol/L hydrochloric acid second is added in chitosan oligosaccharide schiff bases-O- kojic acids-Mannich base derivative obtained above
Alcohol (V/V=1:4) mixed liquor 36mL, after 12h is stirred at room temperature, with 10% Na2CO3PH is adjusted to neutrality, is washed repeatedly with acetone
5 times, filter, freeze-drying.
1 gram of crude product is suspended from 5mL ultra-pure waters, is put into bag filter, is dialysed 24 hours, concentration, adds enough acetone
Precipitation, filter, freeze-drying finally gives chitosan oligosaccharide-O- kojic acids-Mannich base derivative of purified brown.
The yield of the chitosan oligosaccharide derivative is 65.2%.Fig. 5 is the infrared spectrogram of the sample, wherein, 892.24cm-1Place
The characteristic absorption peak of corresponding β-pyranoid form glycosidic bond, 1518.32cm-1For C=C stretching vibration absworption peaks in the derivative,
1226.23cm-1For C-O-C stretching vibration absworption peaks in the derivative, 971.91cm-1It is few for chloro kojic acid-Mannich base and shell
The absworption peak of sugared covalent bond, 1226.23cm-1And 971.91cm-1Presence prove target product formation.
Embodiment three：
The preparation method of chitosan oligosaccharide-O- kojic acids-Mannich base derivative antibacterial agent comprises the following steps：
1st, the preparation of chloro kojic acid-Mannich base
N methyl piperazine and chloro kojic acid in mass ratio 1:3 are dissolved in 200mL methanol and 10mL formalin solution
In, quickly stirred at 25 DEG C, generate tan precipitate, collected, filtering, washed 5 times with absolute methanol, tied again with absolute methanol
It is brilliant, dry, that is, obtain chloro kojic acid-Mannich base.
2nd, the preparation of chitosan oligosaccharide-O- kojic acids-Mannich base derivative
Under quick stirring, 2.5g chloros kojic acid-Mannich base is dissolved in 4mL dimethyl sulfoxide, 1g chitosan oligosaccharide schiff bases
(molecular weight 5000Da, deacetylation 95%) is dissolved in 4mL dimethylformamide and 6mL pyridine mixed liquor, will be molten
Chitosan oligosaccharide schiff bases in dimethylformamide and pyridine mixed liquor be added dropwise be dissolved in the chloro kojic acid of dimethylformamide-
In Mannich base, for magnetic agitation after 6 hours, pour into excessive propanone precipitates product to reactant mixture in 40 DEG C of water-baths, precipitation
Thing filters, and sediment carries out surname extraction to remove dimethylformamide and pyridine with ethanol, acetone respectively, finally obtained through true
Product 3g after vacuum freecing-dry.
0.25mol/L hydrochloric acid second is added in chitosan oligosaccharide schiff bases-O- kojic acids-Mannich base derivative obtained above
Alcohol (V/V=1:4) mixed liquor 60mL, after 12h is stirred at room temperature, with 10% Na2CO3PH is adjusted to neutrality, is washed repeatedly with acetone
5 times, filter, freeze-drying.
1 gram of crude product is suspended from 5mL ultra-pure waters, is put into bag filter, is dialysed 24 hours, concentration, adds enough acetone
Precipitation, filter, freeze-drying finally gives chitosan oligosaccharide-O- kojic acids-Mannich base derivative of purified brown.
The yield of the chitosan oligosaccharide derivative is 63.5%.Fig. 6 is the infrared spectrogram of the sample, wherein, 893.34cm-1Place
The characteristic absorption peak of corresponding β-pyranoid form glycosidic bond, 1514.18cm-1For C=C stretching vibration absworption peaks in the derivative,
1223.73cm-1For C-O-C stretching vibration absworption peaks in the derivative, 970.39cm-1Covalently tied with chitosan oligosaccharide for chloro kojic acid
Close the absworption peak of key, 1223.13cm-1And 970.39cm-1Presence prove target product formation.
The detection of antibiotic property
1st, the preparation of antimicrobial
Sample in embodiment one, embodiment two, embodiment three is respectively designated as derivative 1, derivative 2, derivative
3, chitosan oligosaccharide, kojic acid, derivative 1, derivative 2 and derivative 3 are dissolved with deionized water, be made into concentration gradient for 0.01,
0.05th, 0.1,0.5,1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0 and 9.0mg/mL solution, filtered with 0.22 μm of micropore
Membrane filtration, it is standby.
2nd, Determination of Antibacterial Activity
Nutrient broth culture after 1mL initial bacterium solution is sterilized with 98mL mixes, then adds the different dense of 1mL thereto
The above-mentioned antiseptic of gradient is spent, antimicrobial is replaced as blank using 1mL deionized waters, shaking table culture at 37 DEG C.Cultivating
During, 1mL nutrient solutions are taken out after 8h, spread plate method calculates clump count after doubling dilution, and each sample is repeated 3 times.Antibacterial
Rate (I) calculates according to below equation：
I (%)=N1-N2/N1×100
Wherein, N1：Total plate count in initial incubation liquid；
N2：Contain the total plate count in antiseptic nutrient solution.
Using the concentration of antiseptic as abscissa, inhibiting rate is mapped for ordinate, obtains IC50Value
The detection of the antiseptic performance of table 1
From table 1 it follows that antiseptic produced by the present invention is to staphylococcus aureus, streptococcus pyogenes, withered grass bud
Spore bacillus, salmonella typhimurium, shigella dysenteriae and Escherichia coli all have good antibacterial activity, and anti-microbial property
Chitosan oligosaccharide and kojic acid are significantly better than, there is potential application value in terms of food antiseptic.
In summary, principle of the invention is as follows：There are three chemical modification avtive spots in the molecular structure of chitosan oligosaccharide, such as
Alkylated reaction occurs for fruit, according to the size of three position activity, first occurs on C-2 bit aminos, next to that the primary hydroxyl in C-6 positions
It is finally on the secondary hydroxyl of C-3 positions on base.Due in an acidic solution, after the C-2 protonated aminos in chitosan oligosaccharide molecule, being
The active group of antibacterial action is played, therefore, the active amino of C-2 positions is protected with benzaldehyde first, treats that there occurs alkyl
Change reaction and then be deprotected in acid alcohol solution, discharge active amino.Therefore the hydroxyl of C-6 positions and C-3 positions and chloro are bent
O- alkylated reactions occur for acid-Mannich base.
Beneficial effects of the present invention are as follows：(1) the C-6 positions of chitosan oligosaccharide and the hydroxyl of C-3 positions and chloro kojic acid-Manny are passed through
O- alkylated reactions occur for uncommon alkali, and active antibacterial group-gamma-pyrone base in kojic acid and N methyl piperazine are incorporated into shell
In oligosaccharide molecular chain, synergy is produced with chitosan oligosaccharide molecule, significantly increases its antibacterial activity.(2) such new derivative poison
Property it is low, and have good water solubility, be dissolvable in water in a variety of inorganic and organic solvent, avoid the use of organic solvent, more have
Beneficial to environmental protection, and its application field is expanded, be widely used in fields such as medicine, food, cosmetics and agriculturals
Value.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is some improvement and
Modification, these improvement and modification also should be regarded as protection scope of the present invention.
Claims (7)
- A kind of 1. chitosan oligosaccharide-O- kojic acids-Mannich base derivative antibacterial agent, it is characterised in that：Its chemical structural formula is as follows, Wherein, n 6-20, substitution value 1.21-1.78,Its preparation method comprises the following steps：(1) after dissolving chitosan oligosaccharide schiff bases and chloro kojic acid-Mannich base respectively with organic solvent, it is mixed and stirred for, reacts Organic solvent precipitated product is added after end, filtering, precipitated product organic solvent soxhlet type, is freeze-dried and produces chitosan oligosaccharide Schiff bases-O- kojic acids-Mannich base derivative；(2) 0.25mol/L salt is added into chitosan oligosaccharide schiff bases-O- kojic acids-Mannich base derivative of the step (1) Acid/alcohol mixeding liquid, is mixed and stirred for, and reaction adjusts pH to neutrality after terminating, with organic solvent washing, filter, freeze-drying Sample is obtained, the volume ratio of the hydrochloric acid/alcohol mixeding liquid is 1：4；In the step (1), the preparation method of the chloro kojic acid-Mannich base comprises the following steps：N methyl piperazine and chloro kojic acid are dissolved in methanol and formalin solution, quick stirring, generation are brown at room temperature Color precipitates, and collects, filtering, wash several times with absolute methanol, is recrystallized with absolute methanol, drying, that is, obtains chloro kojic acid-graceful Buddhist nun wishes alkali；The mass parts ratio of N methyl piperazine and the chloro kojic acid is 1：(2-3), the body of the methanol and formalin solution Product part ratio is (10-20)：1.
- 2. chitosan oligosaccharide-O- kojic acids according to claim 1-Mannich base derivative antibacterial agent, it is characterised in that：The side Method is additionally included in the purification step after step (2), and the dried product is dialysed, adds organic solvent deposit, is filtered, Freeze-drying finally gives purified chitosan oligosaccharide-O- kojic acids-Mannich base derivative.
- 3. chitosan oligosaccharide-O- kojic acids according to claim 1-Mannich base derivative antibacterial agent, it is characterised in that：The shell Oligosaccharides schiff bases and the mass parts ratio of chloro kojic acid-Mannich base are 2: (1-5).
- 4. chitosan oligosaccharide-O- kojic acids according to claim 3-Mannich base derivative antibacterial agent, it is characterised in that：The shell The molecular weight of oligosaccharides is 1000~5000Da, deacetylation 90-95%.
- 5. chitosan oligosaccharide-O- kojic acids according to claim 1-Mannich base derivative antibacterial agent, it is characterised in that：The step Suddenly in (1), the organic solvent of dissolving chloro kojic acid-Mannich base is dimethyl sulfoxide or dimethylformamide, and dosage is that chloro is bent 2-4 times of acid-Mannich base quality；The organic solvent of dissolving chitosan oligosaccharide schiff bases is dimethylformamide and pyridine, dimethyl The dosage of formamide is 2-4 times of chitosan oligosaccharide schiff bases, and the dosage of pyridine is 2-6 times of chitosan oligosaccharide schiff bases.
- 6. chitosan oligosaccharide-O- kojic acids according to claim 1-Mannich base derivative antibacterial agent, it is characterised in that：The step Suddenly in (1), reaction temperature is -35 DEG C~40 DEG C, and the reaction time is 2~6h.
- 7. chitosan oligosaccharide-O- kojic acids according to claim 1-Mannich base derivative antibacterial agent, it is characterised in that：The step Suddenly in (2), reaction temperature is room temperature, reaction time 12-24h.
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| 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 |
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| CN107441494B (en) * | 2017-07-28 | 2020-03-17 | 中国科学院过程工程研究所 | Chitosan oligosaccharide and antibiotic with antibacterial film activity and application thereof |
| CN109503732B (en) * | 2018-11-26 | 2020-12-01 | 江南大学 | Preparation method and application of 2, 4-dichlorophenoxyacetic acid chitosan oligosaccharide ester |
| 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 |
| 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 |
| CN115433292B (en) * | 2022-09-30 | 2023-05-09 | 大连民族大学 | COS-O-octanoyl chloride derivative, preparation method and application thereof |
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| 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 |
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