CN112521527A - Modified oligosaccharide and preparation method thereof - Google Patents
Modified oligosaccharide and preparation method thereof Download PDFInfo
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- CN112521527A CN112521527A CN202011608868.1A CN202011608868A CN112521527A CN 112521527 A CN112521527 A CN 112521527A CN 202011608868 A CN202011608868 A CN 202011608868A CN 112521527 A CN112521527 A CN 112521527A
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- 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
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Abstract
The invention discloses a modified oligosaccharide which is obtained by performing 3-bromo-3, 7-dimethyl-1, 6-octadiene modification reaction on chitosan oligosaccharide and purifying. In addition, a preparation method thereof is also disclosed. The modified oligosaccharide has better antibacterial performance against escherichia coli and staphylococcus aureus; meanwhile, the preparation method has simple reaction steps and higher reaction yield.
Description
Technical Field
The invention belongs to the technical field of oligosaccharides, and particularly relates to a modified oligosaccharide and a preparation method thereof.
Background
With the continuous improvement of the development level of the economic society, large-scale intensification becomes the main direction of the development of the animal husbandry in China. Since the antibiotics are widely used as the growth-promoting feed additive, obvious economic benefits are created for the breeding industry. However, the use of feeding antibiotics in a sub-dosage for a long time has been proved by many researches to form a source of drug resistance of various pathogenic bacteria and cause endogenous infection and superinfection of livestock, so that the health condition of the livestock is seriously influenced. The drug residue in the livestock and poultry product not only influences the quality of the livestock and poultry product, but also can cause pathogenic bacteria in human bodies to generate drug resistance to the residual antibiotics, thereby directly threatening the health of human beings.
For the healthy development of the feed industry and the livestock breeding industry, people have more healthy thinking, antibiotics are cautiously used or even forbidden, and the active development and use of safe, nontoxic and harmless green feed additives are urgent. The green feed additives which are researched more by people at present comprise: oligosaccharide, prebiotics, enzyme preparation, acidifier, antibacterial peptide and Chinese herbal medicine.
Among these, oligosaccharides are a more interesting class of additives. Researches show that the oligosaccharide has the effects of inhibiting the growth of harmful bacteria, promoting the absorption and utilization of trace elements of iron and calcium, improving the production performance and the immune function of animals, strengthening the state of intestinal tissues and regulating the microbial ecology, has the capability of replacing part of antibiotics in animal feed, and provides practical basis for antibiotic-free, green and sustainable culture.
However, when either animal-derived oligosaccharides or plant-derived oligosaccharides are used directly as feed additives, they are often unsatisfactory in bacteriostatic properties due to solubility and group limitations. For this reason, a large number of researchers have been working on improving the antibacterial properties of oligosaccharides by chemical modification. The common idea of chemical modification is to introduce natural molecules, such as polyphenols, polypeptides, organic acids and organic alcohols, etc., on the amino group at position 2 and the hydroxyl groups at positions 3 and 6.
Lin Yue et al prepared geraniol-modified chitosan oligosaccharide derivatives by substitution reaction. In the reaction process, the amino group of the chitosan oligosaccharide is protected and deprotected in sequence, and finally geraniol is introduced into the hydroxyl group of the chitosan oligosaccharide. The results show that the oligosaccharide derivative has good solubility, thermal stability and antibacterial property. However, the modified chitosan oligosaccharide has complicated reaction steps and low reaction yield, and the antibacterial performance of the modified chitosan oligosaccharide against escherichia coli and staphylococcus aureus still needs to be improved.
In view of the above technical defects, a modified oligosaccharide with better antibacterial performance and higher reaction yield against escherichia coli and staphylococcus aureus and a preparation method thereof need to be found.
Disclosure of Invention
One of the objects of the present invention is to provide a modified oligosaccharide. Compared with the prior art, the modified oligosaccharide has better antibacterial performance against escherichia coli and staphylococcus aureus.
The second purpose of the invention is to provide a preparation method of the modified oligosaccharide. Compared with the prior art, the preparation method has the advantages of simple reaction steps and higher reaction yield.
In order to solve the technical problem, on one hand, the invention adopts the following technical scheme: the modified oligosaccharide is characterized in that the modified oligosaccharide is obtained by performing 3-bromo-3, 7-dimethyl-1, 6-octadiene modification reaction on chitosan oligosaccharide and purifying.
The modified oligosaccharide according to the invention, wherein the average molecular weight of the chitosan oligosaccharide is =1000-2000 dalton; the deacetylation degree is more than or equal to 95 percent.
Preferably, the average molecular weight of the chitosan oligosaccharide is =1200 and 1800 daltons; the deacetylation degree is more than or equal to 96 percent.
In a specific embodiment, the chitosan oligosaccharide has an average molecular weight of =1500 daltons; degree of deacetylation = 97%.
The modified oligosaccharide of the invention, wherein the molar ratio of the chitosan oligosaccharide to the 3-bromo-3, 7-dimethyl-1, 6-octadiene is 1: (2-4).
Preferably, the molar ratio of the chitosan oligosaccharide to 3-bromo-3, 7-dimethyl-1, 6-octadiene is 1: (2.5-3.5).
In a specific embodiment, the molar ratio of the chitosan oligosaccharide to 3-bromo-3, 7-dimethyl-1, 6-octadiene is 1: 3.
in the present invention, 3-bromo-3, 7-dimethyl-1, 6-octadiene is a known compound having CAS number 169912-98-4; see JP 61-83114A.
The modified oligosaccharide according to the invention, wherein the catalyst of the modification reaction is trialkylamine.
Preferably, the catalyst of the modification reaction is trimethylamine, triethylamine and tripropylamine.
In a specific embodiment, the catalyst of the modification reaction is triethylamine.
The modified oligosaccharide of the invention has a molar ratio of the chitosan oligosaccharide to the catalyst of 1: (0.01-0.05).
Preferably, the molar ratio of the chitosan oligosaccharide to the catalyst is 1: (0.02-0.04).
In a specific embodiment, the chitosan oligosaccharide to catalyst molar ratio is 1: 0.03.
the modified oligosaccharide of the invention is prepared by the following steps: the reaction temperature is 50-70 ℃; the reaction time is 2-6 h.
Preferably, the conditions of the modification reaction are: the reaction temperature is 55-65 ℃; the reaction time is 3-5 h.
In one embodiment, the conditions of the modification reaction are: the reaction temperature is 60 ℃; the reaction time was 4 h.
The modified oligosaccharide is prepared by adding acetone to precipitate after the modification reaction is finished, and drying in vacuum to obtain a crude product.
The modified oligosaccharide according to the invention, wherein the purification conditions are: soxhlet extraction of petroleum ether for 8-16 h; dialyzing with distilled water for 12-36 h.
Preferably, the purification conditions are: soxhlet extraction of petroleum ether for 10-14 h; dialyzing with distilled water for 18-30 h.
In one embodiment, the purification conditions are: soxhlet extraction of petroleum ether for 12 h; dialyzing with distilled water for 24 h.
On the other hand, the invention also provides a preparation method of the modified oligosaccharide, which is characterized in that the preparation method takes chitosan oligosaccharide and 3-bromo-3, 7-dimethyl-1, 6-octadiene as raw materials and comprises the steps of modification reaction and purification.
The preparation method according to the present invention further comprises a freeze-drying step.
The inventors found that the specific modified oligosaccharide of the invention has better antibacterial performance against escherichia coli and staphylococcus aureus; the preparation method has simple reaction steps and higher reaction yield.
Without wishing to be bound by any theory, the specific modifier and the method of preparation thereof bring about the above-mentioned technical effect.
Detailed Description
The invention will be further illustrated with reference to specific embodiments.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
In the present invention, all parts are parts by weight unless otherwise specified.
Example 1
Dissolving chitosan oligosaccharide (average molecular weight =1500 dalton; degree of deacetylation = 97%) in DMSO, adding catalyst triethylamine dropwise, and stirring until the solution is clear and transparent. Dissolving 3-bromo-3, 7-dimethyl-1, 6-octadiene in DMF, and adding dropwise into the chitosan oligosaccharide solution under stirring condition to perform modification reaction. The molar ratio of the chitosan oligosaccharide, the 3-bromo-3, 7-dimethyl-1, 6-octadiene and the triethylamine is 1: 3: 0.03. the conditions of the modification reaction are as follows: the reaction temperature is 60 ℃; the reaction time was 4 h. And after the modification reaction is finished, cooling to room temperature, adding acetone to separate out a precipitate, standing, centrifuging, collecting the precipitate, and drying in vacuum at 40 ℃ for 6 hours to obtain a crude product. The crude product was further purified. The purification conditions are as follows: soxhlet extraction of petroleum ether for 12 h; dialyzing with distilled water for 24 h. Finally, the modified oligosaccharide is obtained by freeze drying.
The V-Vis absorption spectrum of the modified oligosaccharide shows an absorption peak at 189nm relative to the unmodified chitosan oligosaccharide. In an IR spectrum, the carbonyl stretching vibration peak of the modified oligosaccharide is shifted to 1628cm-1(ii) a And 1515cm-1The peak of the amino group stretching vibration of (2) is weakened. In HNMR spectra, the modified oligosaccharides increased four C = C-H chemical shift values of 5.01ppm, 5.09ppm, 5.21ppm and 5.77 ppm.
The antibacterial performance of the modified oligosaccharide on escherichia coli and staphylococcus aureus is researched by a plate diffusion method. 100 μ L105CFU/mL of the bacterial suspensions of Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 29273) were mixed with 22mL of the solid medium, and cooled to solidify. The wells were punched with a 9mm punch and 200. mu.L of 8mg/mL modified oligosaccharide antibacterial solution was added to the wells and prediffused in a refrigerator at 4 ℃ for 2 h. Culturing in an incubator at 37 ℃ for 24h, measuring the diameter of a bacteriostatic circle, and taking an average value for three times of each pore size test. The diameters of the inhibition zones of the modified oligosaccharide to escherichia coli and staphylococcus aureus are 11.8 +/-0.1 mm and 14.6 +/-0.2 mm respectively.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The modified oligosaccharide is characterized in that the modified oligosaccharide is obtained by performing 3-bromo-3, 7-dimethyl-1, 6-octadiene modification reaction on chitosan oligosaccharide and purifying.
2. The modified oligosaccharide of claim 1, wherein the chitosan oligosaccharide has an average molecular weight of =1000 and 2000 daltons; the deacetylation degree is more than or equal to 95 percent.
3. The modified oligosaccharide of claim 2, wherein the molar ratio of chitosan oligosaccharide to 3-bromo-3, 7-dimethyl-1, 6-octadiene is 1: (2-4).
4. The modified oligosaccharide of claim 1, wherein the catalyst of the modification reaction is a trialkylamine.
5. The modified oligosaccharide of claim 4, wherein the molar ratio of chitosan oligosaccharide to catalyst is 1: (0.01-0.05).
6. The modified oligosaccharide of claim 1, wherein the modification reaction conditions are: the reaction temperature is 50-70 ℃; the reaction time is 2-6 h.
7. The modified oligosaccharide of claim 1 or 6, wherein after the modification reaction is finished, acetone is added to precipitate, and the crude product is obtained after vacuum drying.
8. The modified oligosaccharide of claim 1, wherein the purification conditions are: soxhlet extraction of petroleum ether for 8-16 h; dialyzing with distilled water for 12-36 h.
9. A process for the preparation of a modified oligosaccharide according to any one of claims 1 to 8, starting from chitosan oligosaccharide and 3-bromo-3, 7-dimethyl-1, 6-octadiene, comprising modification reactions and purification steps.
10. The method of claim 9, further comprising a step of freeze-drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114223786A (en) * | 2021-12-31 | 2022-03-25 | 重庆市六九畜牧科技股份有限公司 | Application of nerolidol modified oligosaccharide as feed additive |
| CN114230687A (en) * | 2021-12-31 | 2022-03-25 | 重庆市六九畜牧科技股份有限公司 | Nerolidol modified oligosaccharide and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333750A (en) * | 2020-03-24 | 2020-06-26 | 江南大学 | Chitosan oligosaccharide-N-geraniol derivative and preparation method and application thereof |
| CN111620966A (en) * | 2020-06-23 | 2020-09-04 | 江南大学 | Chitosan oligosaccharide-N-linalool copolymer and preparation method and application thereof |
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- 2020-12-30 CN CN202011608868.1A patent/CN112521527A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333750A (en) * | 2020-03-24 | 2020-06-26 | 江南大学 | Chitosan oligosaccharide-N-geraniol derivative and preparation method and application thereof |
| CN111620966A (en) * | 2020-06-23 | 2020-09-04 | 江南大学 | Chitosan oligosaccharide-N-linalool copolymer and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114223786A (en) * | 2021-12-31 | 2022-03-25 | 重庆市六九畜牧科技股份有限公司 | Application of nerolidol modified oligosaccharide as feed additive |
| CN114230687A (en) * | 2021-12-31 | 2022-03-25 | 重庆市六九畜牧科技股份有限公司 | Nerolidol modified oligosaccharide and preparation method and application thereof |
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