CN106349718B - A kind of preparation method of antibiotic property collagen - Google Patents
A kind of preparation method of antibiotic property collagen Download PDFInfo
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- CN106349718B CN106349718B CN201610935790.1A CN201610935790A CN106349718B CN 106349718 B CN106349718 B CN 106349718B CN 201610935790 A CN201610935790 A CN 201610935790A CN 106349718 B CN106349718 B CN 106349718B
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- collagen
- antibiotic property
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- triclosan
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
Abstract
The present invention relates to a kind of preparation method of antibiotic property collagen, include the following steps: (1) by collagenolysis in buffer solution, the mass concentration for controlling collagen is 0.1%~15%, obtains collagen solution；(2) modified triclosan is added in the collagen solution in step (1), is warming up to 25~50 DEG C, reacts 0.1~48h, obtains antibiotic property collagen solution；(3) then the antibiotic property collagen solution for obtaining step (2) is freeze-dried at 0~4 DEG C of 0.5~96h of dialysis to get antibiotic property collagen.Antibiotic property collagen prepared by the present invention, antibacterial components are firmly combined in collagen with covalent bond, antibacterial effect is more lasting, such as be prepared into antimicrobial form collagen gel, collagen sponge, wound dressing, organizational project cytoskeleton biomedical material, then material in entire service life all have antibacterial action.
Description
Technical field
The invention belongs to the modified fields of natural products, are related to a kind of preparation method of antibiotic property collagen.
Background technique
Collagen is the main constituents of Animal Skin, bone, connective tissue etc., has good physicochemical property and bio-compatible
Property, it is widely used in the fields such as food, medicine, cosmetics.Compared with collagen, the glue of triple helix structure is only maintained
Biomedical material made of original molecule or its oligomer just has excellent bioactivity, therefore in terms of preparing biomaterial
Mainly use collagen, rather than its hydrolysate collagen.Cell culture substrate, wound dressing, leatheret are prepared using collagen
When the biomedical materials such as skin, Antimicrobial preservative performance has the application range and application effect of such material very important
It influences.
But current research is concentrated mainly on additional antibacterial components to realize its antibacterial action, carries out chemistry to tropocollagen molecule
It is modified, antibacterial components are introduced in its molecular structure, realize that the research of the anti-microbial property of collagen and its material is less.
Chinese patent document CN 102888027A (application number: 201210364097.5) disclose a kind of bacteria cellulose/
Collagen-chitin composite material and preparation method includes the following steps: (1) preparation and purification of bacterial cellulose；(2) pass through
Collagen is sufficiently submerged in the network of bacteria cellulose by negative-pressure penetration method or positive pressure method, recycles cross-linking agents bacterial fibers
Bacteria cellulose/collagen interpenetrating networks composite material is made in collagen in element/collagen composite materials；(3) by above-mentioned composite material
It after removing unreacted crosslinking agent, then impregnates in chitosan or derivatives thereof class antimicrobial, is prepared with antibacterial
The composite material of effect.But the composite material be only from improve anti-biotic material mechanical strength in terms of to anti-biotic material into
Row processing, does not carry out chemical modification to tropocollagen molecule, fundamentally solves the anti-microbial property of collagen.
Chinese patent document CN101163749A (application number: 200680012963.7) is disclosed a kind of for sterilizing collagen
The method of protein formulation from disinfection, the preparation of antibacterial collagen preparations, and is related to it and is used to prepare especially for medicine
And/or the purposes of cosmetic purpose collagen product (such as sponge, film or gel), and be related to by described from disinfection glue
The product of former protein formulation preparation.The preparation from disinfection, the method for antibacterial collagen preparations, be to collagen aqueous solution or
Water-soluble antibacterial activity agent is added in the aqueous collagen suspension liquid of person.But the antibacterial time of the collagen of above method preparation
Short, antibacterial components are easy to run off, and there are the risks that antibacterial components are absorbed by the body.Importantly, collagen and collagen exist
There are greatest differences in terms of bioactivity, the latter is difficult to realize the former bioactivity；There is also huge differences for the dissolubility of the two
Different, although collagen has hydrophily but is difficult to be dissolved in neutral aqueous solution, cannot obtain the collagen of antibiotic property in aforementioned manners.
Therefore firm antibacterial components are introduced with chemical bond in tropocollagen molecule structure, prepare antibiotic property collagen, biomedical material,
The fields such as cosmetics have wider array of application prospect and better application effect.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of antibiotic property collagen, this method is available
Antibiotic property collagen.
Technical scheme is as follows:
A kind of preparation method of antibiotic property collagen, includes the following steps:
(1) by collagenolysis in buffer solution, the mass concentration for controlling collagen is 0.1%~15%, obtains collagen solution；
(2) modified triclosan is added in the collagen solution in step (1), is warming up to 25~50 DEG C, reacts 0.1~48h,
Obtain antibiotic property collagen solution；
(3) then the antibiotic property collagen solution for obtaining step (2) is freeze-dried, i.e., at 0~4 DEG C of 0.5~96h of dialysis
Obtain antibiotic property collagen.
, according to the invention it is preferred to, buffer solution described in step (1) is selected from the configuration of at least one of following system
At buffer solution:
Barbiturate-hydrochloric acid system, boric acid-borax system, Glycine-NaOH system, borax-sodium hydroxide body
The buffer solution of pH=7~10 is prepared by system, sodium carbonate-bicarbonate system.The ionic strength of the buffer solution of preparation, which is not done, to be had
Body requirement.
, according to the invention it is preferred to, collagen described in step (1) be maintain triple helix structure tropocollagen molecule or
Its oligomer does not do specific requirement to its source；
It is further preferred that the collagen is the type i collagen extracted from the tissue such as Animal Skin, tendon.
, according to the invention it is preferred to, the mass concentration of collagen solution described in step (1) is 2.5%~7.5%.
, according to the invention it is preferred to, in step (2) dosage of modified triclosan be collagen quality 0.01%~
25%, further preferred 0.05%~10%.
, according to the invention it is preferred to, the reaction temperature of collagen and modified triclosan is 30~40 DEG C in step (2), reaction
Time be 12~for 24 hours.
, according to the invention it is preferred to, after reaction by antibiotic property collagen solution 48~72h of dialysis, freezing in step (3)
The parameters such as dry time, temperature do not do specific requirement, by this field routine operation.
, according to the invention it is preferred to, modification triclosan described in step (2) has structure shown in formula (I),
In formula (I): R be Cl or
It is preferred according to the present invention, in the step (2) modified triclosan the preparation method is as follows:
Triclosan is dissolved in carbon tetrachloride solution, in 4 degrees Celsius with concentrated acid sulfonation 2h~8h, triclosan and the concentrated sulfuric acid
Molar ratio be 1:1.1~1:1.5, neutralized after isolating and purifying, obtain triclosan sulfonated bodies；Then triclosan sulfonated bodies is dissolved in steaming
Cyanuric Chloride is added in distilled water, and the molar ratio of triclosan sulfonated bodies and Cyanuric Chloride is 3:1~1:3, reacted in ice-water bath 1h~
5h is finally neutralized to sodium hydroxide solution neutral to get modified triclosan.
It is modified the preparation method of triclosan according to the present invention, it is preferred that the molar ratio of triclosan sulfonated bodies and Cyanuric Chloride
For 2:1~1:1.
Beneficial effects of the present invention are as follows:
Antibiotic property collagen prepared by the present invention, antibacterial components are firmly combined in collagen with covalent bond, antibacterial effect
Fruit is more lasting, such as be prepared into antimicrobial form collagen gel, collagen sponge, wound dressing, organizational project cytoskeleton
Biomedical material, then material all has antibacterial action in entire service life.Antibiotic property collagen prepared by the present invention
Antibacterial components not easily run off, and there is no the risks that antibacterial components are absorbed by the body.Therefore, antibiotic property collagen tool prepared by the present invention
There are better market prospects.
Detailed description of the invention
Fig. 1 is the antibacterial effect figure in test example of the present invention.
Specific embodiment
The present invention is further described below by way of specific embodiment, it should be pointed out that, following the description is merely to solution
The present invention is released, its content is not defined.
It is raw materials used in embodiment, it is regular market purchase product unless otherwise specified.
Embodiment 1
A kind of preparation method of antibiotic property collagen, includes the following steps:
(1) using the barbiturate aqueous solution of 0.04mol/L and the aqueous hydrochloric acid solution of 0.2mol/L prepare pH be 8.0 it is slow
Rush solution；
It is dissolved in type i collagen is extracted in ox-hide in buffer solution, the mass concentration for controlling collagen is 5%, and it is molten to obtain collagen
Liquid；
(2) the modification triclosan of collagen quality 1.5% is added in the collagen solution of step (1), is warming up to 35 DEG C, reaction
For 24 hours, antibiotic property collagen solution is obtained；
(3) then the antibiotic property collagen solution for obtaining step (2) is freeze-dried at 0~4 DEG C of dialysis 72h to get antibacterial
Property collagen.
In the present embodiment, the modification triclosan is had the following structure:
Preparation process is as follows:
Triclosan is dissolved in carbon tetrachloride solution, in 4 degrees Celsius with concentrated acid sulfonation 4h, triclosan and the concentrated sulfuric acid rub
You neutralize after isolating and purifying than being 1:1.15；Then triclosan sulfonated bodies is dissolved in distilled water, Cyanuric Chloride, triclosan is added
The molar ratio of sulfonated bodies and Cyanuric Chloride is 1:1, and 1h is reacted in ice-water bath, is finally neutralized to neutrality with sodium hydroxide solution.
Embodiment 2
A kind of preparation method of antibiotic property collagen, includes the following steps:
(1) buffering for the use of the boric acid aqueous solution of the borax solution of 0.05mol/L and 0.2mol/L preparation pH being 7.8 is molten
Liquid；
The type i collagen extracted from rat-tail key is dissolved in buffer solution, the mass concentration for controlling collagen is 2.5%,
Obtain collagen solution；
(2) the modification triclosan of collagen quality 5% is added in the collagen solution that step (1) obtains, is warming up to 30 DEG C, instead
36h is answered, antibiotic property collagen solution is obtained；
(3) then the antibiotic property collagen solution for obtaining step (2) is freeze-dried at 0~4 DEG C of dialysis 48h to get antibacterial
Property collagen.
In the present embodiment, the modification triclosan is the mixture with the following two kinds structure:
Preparation process is as follows:
Triclosan is dissolved in carbon tetrachloride solution, in 4 degrees Celsius with concentrated acid sulfonation 5h, triclosan and the concentrated sulfuric acid rub
You neutralize after isolating and purifying than being 1:1.3；Then triclosan sulfonated bodies is dissolved in distilled water, Cyanuric Chloride, triclosan sulphur is added
Compound and the molar ratio of Cyanuric Chloride are 1.5:1, and 3.5h is reacted in ice-water bath, are finally neutralized to sodium hydroxide solution
Property.
Embodiment 3
A kind of preparation method of antibiotic property collagen, includes the following steps:
(1) preparing pH using the sodium hydrate aqueous solution of the glycine solution of 0.2mol/L and 0.2mol/L is 9.2
Buffer solution；
It is 2% by the mass concentration in buffer solution, controlling collagen from the I collagenolysis extracted in pigskin, obtains collagen
Solution；
(2) the modification triclosan of collagen quality 20% is added in the collagen solution that step (1) obtains, is warming up to 37 DEG C,
Reaction for 24 hours, obtains antibiotic property collagen solution；
(3) then the antibiotic property collagen solution for obtaining step (2) is freeze-dried at 0~4 DEG C of dialysis 48h to get antibacterial
Property collagen.
In the present embodiment, the modification triclosan is had the following structure:
Preparation process is as follows:
Triclosan is dissolved in carbon tetrachloride solution, concentrated acid sulfonation 3h is used in ice-water bath, triclosan and the concentrated sulfuric acid
Molar ratio is 1:1.4, is neutralized after isolating and purifying；Then triclosan sulfonated bodies is dissolved in distilled water, Cyanuric Chloride, triclosan is added
The molar ratio of sulfonated bodies and Cyanuric Chloride is 2:1, and 4.5h is reacted in ice-water bath, is finally neutralized to sodium hydroxide solution
Property.
Embodiment 4
A kind of preparation method of antibiotic property collagen, includes the following steps:
(1) preparing pH using the sodium bicarbonate aqueous solution of the aqueous sodium carbonate of 0.1mol/L and 0.1mol/L is 10.5
Buffer solution；
It will be dissolved in buffer solution from the type i collagen extracted in carp skin, the mass concentration for controlling collagen is 15%, is obtained
Collagen solution；
(2) the modification triclosan of collagen quality 10% is added in the collagen solution that step (1) obtains, is warming up to 37 DEG C,
48h is reacted, antibiotic property collagen solution is obtained；
(3) then the antibiotic property collagen solution for obtaining step (2) is freeze-dried at 0~4 DEG C of dialysis 72h to get antibacterial
Property collagen.
In the present embodiment, the modification triclosan is had the following structure:
Preparation process is as follows:
Triclosan is dissolved in carbon tetrachloride solution, concentrated acid sulfonation 3h is used in ice-water bath, triclosan and the concentrated sulfuric acid
Molar ratio is 1:1.4, is neutralized after isolating and purifying；Then triclosan sulfonated bodies is dissolved in distilled water, Cyanuric Chloride, triclosan is added
The molar ratio of sulfonated bodies and Cyanuric Chloride is 2:1, and 4.5h is reacted in ice-water bath, is finally neutralized to sodium hydroxide solution
Property.
Test example
The anti-microbial property of 1,2,3 pair of Escherichia coli of embodiment is determined with filter paper enzyme.By the filter paper of sterilizing to
Upper sample solution is impregnated with, and is placed on the culture medium for being vaccinated with Escherichia coli, culture medium is placed in 37.5 DEG C of incubator and is trained
Support 12h, antibacterial effect as shown in Figure 1, the collagen that synthesizes of the present invention has preferable inhibitory effect as seen from Figure 1, and
Unmodified collagen does not have fungistatic effect then.
Claims (10)
1. a kind of preparation method of antibiotic property collagen, includes the following steps:
(1) by collagenolysis in buffer solution, the mass concentration for controlling collagen is 0.1% ~ 15%, obtains collagen solution；
(2) modified triclosan is added in the collagen solution in step (1), is warming up to 25 ~ 50oC reacts 0.1 ~ 48 h, obtains antibacterial
Property collagen solution；
The modification triclosan has structure shown in formula (I),
(I),
In formula (I): R be Cl or；
(3) the antibiotic property collagen solution for obtaining step (2) is 0 ~ 4oC 0.5 ~ 96h of dialysis, is then freeze-dried to get antibiotic property
Collagen.
2. the preparation method of antibiotic property collagen according to claim 1, which is characterized in that buffering as described in step (1)
Solution is selected from the buffer solution that at least one of following system is configured to:
Barbiturate-hydrochloric acid system, boric acid-borax system, Glycine-NaOH system, borax-sodium hydroxide system, carbon
Sour sodium-sodium bicarbonate system prepares the buffer solution of pH=7 ~ 10.
3. the preparation method of antibiotic property collagen according to claim 1, which is characterized in that collagen as described in step (1)
For the tropocollagen molecule or its oligomer for maintaining triple helix structure.
4. the preparation method of antibiotic property collagen according to claim 3, which is characterized in that collagen as described in step (1)
For the type i collagen extracted from Animal Skin or tendon tissue.
5. the preparation method of antibiotic property collagen according to claim 1, which is characterized in that collagen as described in step (1)
The mass concentration of solution is 2.5% ~ 7.5%.
6. the preparation method of antibiotic property collagen according to claim 1, which is characterized in that modified triclosan in step (2)
Dosage be collagen quality 0.01% ~ 25%.
7. the preparation method of antibiotic property collagen according to claim 1, which is characterized in that modified triclosan in step (2)
Dosage be collagen quality 0.05% ~ 10%.
8. the preparation method of antibiotic property collagen according to claim 1, which is characterized in that collagen and modification in step (2)
The reaction temperature of triclosan is 30 ~ 40oC, the reaction time be 12 ~ for 24 hours.
9. the preparation method of antibiotic property collagen according to claim 1, which is characterized in that in step (3) after reaction
By 48 ~ 72h of antibiotic property collagen solution dialysis.
10. the preparation method of antibiotic property collagen according to claim 1, which is characterized in that modified three in the step (2)
Chlorine it is raw the preparation method is as follows:
Triclosan is dissolved in carbon tetrachloride solution, in 4 degrees Celsius with concentrated acid sulfonation 2h ~ 8h, triclosan and the concentrated sulfuric acid rub
You neutralize after isolating and purifying than being 1:1.1 ~ 1:1.5, obtain triclosan sulfonated bodies；Then triclosan sulfonated bodies is dissolved in distilled water,
The molar ratio of addition Cyanuric Chloride, triclosan sulfonated bodies and Cyanuric Chloride is 3:1 ~ 1:3,1h ~ 5h is reacted in ice-water bath, finally
It is neutralized to sodium hydroxide solution neutral to get modified triclosan.
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| CN107903322B (en) * | 2017-10-10 | 2022-03-08 | 宜宾学院 | Method for preparing antibacterial collagen based on safrole epoxidation modification |
| CN108434514A (en) * | 2018-04-18 | 2018-08-24 | 华中农业大学 | It is a kind of to have both antibacterial and biological inducing action collagen hydrogel preparation method |
| CN111187443B (en) * | 2020-03-17 | 2022-05-10 | 陕西科技大学 | Collagen-sodium humate compound suitable for hemostatic material and preparation method thereof |
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| CN103787997A (en) * | 2014-02-18 | 2014-05-14 | 江南大学 | Reaction type antibacterial agent as well as synthetic method and application thereof |
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| CN103787997A (en) * | 2014-02-18 | 2014-05-14 | 江南大学 | Reaction type antibacterial agent as well as synthetic method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Association of Triclosan to Casein Proteins Through Solvent-Mediated High-Pressure Homogenization;A. Roach et al;《Journal of Food Science》;20091231;第74卷(第2期);第23-29页 |
| Preparation and characterization of a novel tobramycin-containing antibacterial collagen film for corneal tissue engineering;Yang Liu et al;《Acta Biomaterialia》;20130905;第289-299页 |
| The Synthesis of Reactive Antibacterial Agents and Their Antibacterial Activities;The Synthesis of Reactive Antibacterial Agents and Their Antibac;《Journal of China Textile University(Eng.Ed.)》;19981231;第15卷(第4期);第1-5页 |
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