CN106399416B - A kind of synthetic method of Mei Lade product modification polycaprolactone in ionic liquid - Google Patents
A kind of synthetic method of Mei Lade product modification polycaprolactone in ionic liquid Download PDFInfo
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Abstract
The invention discloses a kind of synthetic method of Mei Lade product modification polycaprolactone in ionic liquid, belong to Polycaprolactone modified technical field.The method of the present invention is to mix the solution of the small molecule reduced sugar containing primary hydroxyl and collagen buffer solution, and freeze-drying obtains mixture, then disperses mixture in ionic liquid, reacts at 60~150 DEG C；After completion of the reaction, 100 DEG C are cooled to and carries out ring-opening polymerization under the catalysis of lipase using Mei Lade product as initiator hereinafter, caprolactone monomer and lipase is added, obtains Mei Lade product modification polycaprolactone.The method of the present invention has synthesized Mei Lade product in ionic liquid and using the modified polycaprolactone of lipase-catalyzed synthesis, has many advantages, such as that reaction condition is mild, non-metallic ion residual.
Description
Technical field
The present invention relates to a kind of synthetic method of Mei Lade product modification polycaprolactone in ionic liquid, belong to and gather in oneself
Ester modified technical field.
Background technique
Polycaprolactone is a kind of important medical bio degradation material, it is widely used as sutures, medicament slow release
Material and Medical rack material.But as medical material, polycaprolactone haves the defects that hydrophobicity is too strong, this will lead to poly-
Caprolactone is not easy to infiltrate with cell culture medium, and adherency growth of the cell on its surface is relatively difficult, will appear foreign matter over time
The reaction of the bio-incompatibilities such as reaction, causes aseptic inflammation.Therefore, in order to improve the cell compatibility of polycaprolactone, having must
It is modified.
There are reports, using groups such as chitin, chitosan, hydroxyethyl cellulose and starch in lipase or
It is introduced into polycaprolactone end under the catalysis of other inorganic metal catalysts, realizes the function modified of polycaprolactone.With it is common
Polysaccharose substance compare, albumen is a kind of macro-molecular protein generally existing in animal body, and cell compatibility is more preferable, because
This, it is more advantageous to its cellular affinity of raising and biocompatibility if albumen can be introduced into polycaprolactone organization material.But
The polycaprolactone that nobody can be modified using lipase-catalyzed method synthetic proteins class, this is because albumen itself lacks enough
Lipase-catalyzed site, therefore its functionalization and modification can not be directly realized by using enzyme law catalysis, if urged using metal ion
Change, then since its hot conditions limits, albumen can be denaturalized in catalytic process, lose modified meaning.
U.S. ladd product is one kind that the amino on reduced sugar terminal carbonyl and protein is formed under simple heating condition
Protein-sugar covalent complex.Due to introducing sugar chain in protein molecule, so after Maillard reaction, protein
Property, such as: dissolubility, emulsibility, foaming characteristic, thermal stability are greatly improved before all relatively modified.At present for beauty
The research of Maillard reaction is mainly used in field of food, this is because Maillard reaction occurs mainly in the process of food
In, Maillard reaction has a major impact food flavor, color, dissolution/emulsification of albumen and the fresh-keeping of food.In addition, most
Recent studies on shows that Mei Lade product also has special antioxygenic property and anti-microbial property, therefore Mei Lade product is used as and is resisted
The research of oxidant and other additives is also gradually paid attention to, and has that researches show that the intracorporal Maillard reactions of body to people recently
Body health also has a major impact, but is applied to Polycaprolactone modified not yet someone's research at present.
In terms of Mei Lade Product formation, existing method is broadly divided into wet process and dry method, wherein wet process be suitable only for sugar and
Albumen is dissolved in the case where water, and reaction speed is slower, and it is more than hour to generally require tens；Dry method mainly uses powdered object
It is heated after matter mixing, method reaction is very fast, and reaction process is violent, can not effectively control substantially, product property is poor.
Recently, researcher discloses a kind of chitosan-xylan maillard reaction product and its preparation method and application
(CN103304682A) in the invention, ionic liquid is utilized as solvent to carry out Maillard reaction in researcher, but this
Kind of method is still the scope for belonging to wet process, can only be for the object that is dissolved in chloro 1- butyl -3- methylimidazole ionic liquid
Matter is useful, and the ionic liquid is limited to the dissolution degree of protein matter, so this application is limited.
In existing Polycaprolactone modified method, natural polymer and polycaprolactone are carried out using biosynthesis technology
Nzymatic synthesis grafting copolymerization is than a kind of attractive green method of modifying.In the process, enzyme must be in water-less environment
It is catalyzed, but traditional non-aqueous system has negative effect to enzyme activity and stability, very mostly based on toxic solvent
The application of this method is limited in big degree.In recent years, with the development of this novel green solvent of ionic liquid, which has
Prestige is resolved.Many studies have shown that ionic liquids are the perfect mediums of lipase-catalyzed synthesis.Most of lipase is in ion
Stability and selectivity in liquid have increase, and the conversion ratio of product is also quite attractive.
The study on the modification of polycaprolactone focuses primarily upon the strong solvability using ionic liquid in existing ionic liquid
After dissolving to natural products such as starch, cellulose or chitosans, homogeneous graft is obtained, then recycles traditional nothing
Machine metal ion catalyst makees initiator to realize the ring-opening polymerisation of caprolactone, and final realization polycaprolactone end-functionalization changes
Property.Such as: cosolvent of the Liu Jiyan using 1- butyl -3- methylimidazole bromide ion liquid as starch and caprolactone, in isooctyl acid
Biodegradable starch/polycaprolactone graft copolymer has been synthesized under the catalysis of stannous, but the molecular weight of product is lower, because
This can be dissolved in water.Huang Qing uses solvent of the ionic liquid at room temperature chloro 1- butyl -3- methylimidazole as konjaku glucomannan,
Using stannous octoate as catalyst, success is in konjaku glucomannan surface grafting polycaprolactone long-chain；Zhaodong Wang exists
Chitosan/polycaprolactone grafting has been catalyzed and synthesized using stannous iso caprylate in 1- ethyl-3-methylimidazole acetate ionic liquid
Copolymer.These researchs are still traditional inorganic metal catalyzed ring opening polymerization in itself, and ionic liquid is only played the part of wherein
The role of solvent.
Summary of the invention
To solve the above-mentioned problems, the invention proposes enzymatic clarification one kind direct in ionic liquid is collagen-modified
The method of polycaprolactone is improved poly- by introducing the preferable collagen macromolecular of cell recognition in polycaprolactone material
The cellular affinity and functionality of caprolactone material.It is suitable for lipase-catalyzed primary hydroxyl position due to lacking in collagen molecules
Point directly can not carry out enzyme process ring-opening polymerisation to caprolactone using it as initiator.For this purpose, the present invention will by Maillard reaction
Small molecule reduced sugar containing primary hydroxyl is grafted on collagen, promotes the primary hydroxyl number on albumen, obtains being suitable for fat
The Mei Lade product of enzymatic, then as initiator, ring-opening polymerization is carried out by means of lipase-catalyzed caprolactone monomer,
Finally obtain Mei Lade product modification polycaprolactone.High temperature is to protein when the method avoids conventional metals catalyst ring-opening polymerisation
Destruction and its metal ion residue problem, and introduce Mei Lade product be a kind of glycoprotein, biocompatibility is more preferable,
The product helps to improve the biocompatibility of polycaprolactone.The method of the present invention also has efficient, good, the action condition temperature of selectivity
With and it is environmental-friendly the features such as.
The method that Mei Lade product modification polycaprolactone is synthesized in ionic liquid of the invention, the method is will to contain
The solution and collagen buffer solution of the small molecule reduced sugar of primary hydroxyl mix, and freeze-drying obtains mixture, then will mix
It closes object to be scattered in ionic liquid, be reacted at 60~150 DEG C；After completion of the reaction, 100 DEG C are cooled to hereinafter, caprolactone is added
Monomer and lipase carry out ring-opening polymerization under the catalysis of lipase, obtain Mei Lade product modification polycaprolactone.
In one embodiment of the invention, the small molecule reduced sugar containing primary hydroxyl be glucose, galactolipin,
In lactose etc. any one or it is a variety of.
In one embodiment of the invention, the mass ratio of the sugar and collagen is 1:1~1:3.
In one embodiment of the invention, the dispersion is the ratio by mixture according to mass fraction 0.1%~5%
Example is scattered in ionic liquid.
In one embodiment of the invention, the ionic liquid be 1- butyl -3- methylimidazole hexafluorophosphate or
Person's 1- butyl -3- methyl imidazolium tetrafluoroborate ionic liquid.
In one embodiment of the invention, the mass ratio between the ionic liquid and caprolactone monomer is 0.1
~10.
In one embodiment of the invention, the time reacted at described 60~150 DEG C is 5~240 minutes.
In one embodiment of the invention, the cooling is to be cooled to 60~100 DEG C or less.
In one embodiment of the invention, the lipase is candida antarctica lipase B or pig pancreas fat
Enzyme.
In one embodiment of the invention, the lipase additive amount be caprolactone monomer quality 0.1%~
10%.
In one embodiment of the invention, the enzyme activity of the lipase is 3000U/g.
In one embodiment of the invention, the ring-opening polymerization be 60~100 DEG C in temperature at vibrate it is anti-
It answers 1~144 hour.
In one embodiment of the invention, the preparation method further includes, to anti-after ring-opening polymerization finishes
It answers and methylene chloride is added in mixture, be completely dissolved target product, filter, then -20 DEG C of proper volume are added into filtrate
~-4 DEG C of cold methanols stand a period of time in -20 DEG C~-4 DEG C environment, refilter, obtain crude product；It is taken out by solvent of acetone
It puts on and states crude product, obtain Mei Lade product modification polycaprolactone.
In one embodiment of the invention, method of the invention is specifically:
(1) lactose solution and collagen phosphate buffer (pH=7.8) for preparing 1% mass fraction respectively, according to
Volume ratio 1:3 ratio is uniformly mixed, after -20 DEG C are freeze-dried 48 hours, by the mixture according to mass fraction 0.1%~5%
Ratio be scattered in ionic liquid, ionic liquid temperature is risen to 60~150 DEG C later, is reacted 5~240 minutes；
(2) after completion of the reaction, above-mentioned ionic liquid temperature is down to 60 DEG C, is separately added into 6-caprolactone monomer and fat
Enzyme, it is to react 1~144 hour in 60~100 DEG C of constant temperature oscillation reactors that temperature is placed it in after logical nitrogen-sealed；
(3) methylene chloride of 2 times of bulk products is added in Xiang Shangshu product, filters out lipase with filter paper later, then to
- 20 DEG C of cold methanols of 10 times of filtrate volumes are added in filtrate, is filtered after standing 24 hours in -20 DEG C of environment, obtains crude product；
(4) above-mentioned crude product is extracted 24 hours using acetone as solvent, obtains Mei Lade product modification polycaprolactone.
A second object of the present invention is to provide the Mei Lade product modification polycaprolactones obtained according to the method described above.
Third object of the present invention is to provide the applications of the Mei Lade product modification polycaprolactone.
In one embodiment of the invention, the application is used as medical material.
In one embodiment of the invention, the application be specifically be used as sutures, Thermosensitive Material Used for Controlled Releasing of Medicine or
Medical rack material.
Beneficial effects of the present invention:
(1) Mei Lade product modification polycaprolactone synthetic method of the invention, modifying process is environment friendly and pollution-free, passes through ion
Maillard reaction in liquid introduces the reduced sugar small molecule containing primary hydroxyl on collagen, is successfully realized and utilizes fat
Enzyme catalyzes and synthesizes Mei Lade product modification polycaprolactone, and reaction condition is mild, non-metallic ion residual.
(2) in the present invention, selected two kinds of ionic liquids not only can be used as the decentralized medium of Maillard reaction but also can be with
Catalysis reaction medium as lipase.On the one hand ionic liquid is subjected to dry process reaction as heat medium, using in this way
Method, not only contribute to the dispersion and its mixing of reaction substrate, and condition is relatively mild and controllable, obtained Mei Lade is produced
Physical performance is good；On the other hand: such ionic liquid is substantially harmless to lipase, and some researchs also show ionic liquid to lipase
There are also facilitations for catalytic polymerization, therefore can carry out the open loop of next step without removing ionic liquid after Maillard reaction
Polymerization reaction.
(3) product cell compatibility is more preferable.Using the Mei Lade product addressed of the present invention to Polycaprolactone modified, can obtain
Better cellular affinity, the maillard reaction product of collagen and lactose, have it is amphipathic, using the substance to gathering oneself
It is lactone-modified to promote its cellular affinity, and it is more multi-functional to assign it.
Specific embodiment
Wetability test method:
Drip method test is carried out using JC2000D4 contact angle measurement.Modified polycaprolactone is pressed using tablet press machine
The thin slice of thickness about 2mm is made in piece.When test, it is fixed on sample is smooth on instrument platform.It drips at sample 10mm
Deionized water drop, measures the contact angle that water droplet and sample room are formed after 60 seconds, each sample is surveyed 5 times, is averaged.
MTT detection is cytotoxicity assay (non-direct contact):
Sample impregnates 36h with DMEM after the sterilization of ultraviolet disinfection for 24 hours, is removed by filter (0.22 μm of pore size)
Sample obtains dipping culture medium, for use.NIH/3T3 cell suspending liquid (the 5* of 100 μ L is added in the tissue culture plate in 96 holes
104A/mL), it is placed in 37 DEG C, 5%CO2, saturated humidity incubator in cultivate for 24 hours, make cell completely it is adherent after remove culture plate
In culture medium, be added dipping culture medium continue culture for 24 hours, be eventually adding MTT (tetramethyl azo azoles salt) solution of 10 μ L extremely
It in every hole, is put into incubator and continues to be incubated for 4h, the absorbance at 450nm, each sample test are measured by ELISA microplate reader
It is repeated 5 times.
Cytotoxicity assay result indicates are as follows:
Cell survival percentage (%)=A1/A0*100
Wherein, A1, A0 are respectively the absorbance of sample and blank
Grafting efficiency:
It is calculated using weight method, grafting efficiency=[graft monomer quality/(graft monomer quality+homopolymerization substance
Amount)] * 100%
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1:
(1) lactose solution and collagen phosphate buffer (pH=7.8) for preparing 1% mass fraction respectively, according to
Volume ratio 1:3 ratio is uniformly mixed, after -20 DEG C are freeze-dried 48 hours, by the mixture according to the ratio of mass fraction 0.1%
It is scattered in 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid, ionic liquid temperature is risen to 150 DEG C later, reaction 5
Minute；
(2) after completion of the reaction, above-mentioned ionic liquid temperature is down to 60 DEG C, is separately added into 6-caprolactone monomer and the South Pole is false
Silk Yeast-lipase B, it is to react 1 hour in 100 DEG C of constant temperature oscillation reactors that temperature is placed it in after logical nitrogen-sealed；
(3) methylene chloride of 2 times of bulk products is added in Xiang Shangshu product, filters out lipase with filter paper later, then to
- 20 DEG C of cold methanols of 10 times of filtrate volumes are added in filtrate, is filtered after standing 24 hours in -20 DEG C of environment, obtains crude product；
(4) above-mentioned crude product is extracted 24 hours using acetone as solvent, obtains Mei Lade product modification polycaprolactone.
Mei Lade product modification polycaprolactone is obtained through the above method, being computed its grafting efficiency is about 70%, is pressed it
Contact angle test is carried out after piece, shows that its water droplet wetting contact angle is 45 °, mtt assay detection shows 95% or more cell survival rate.
Embodiment 2:
(1) lactose solution and collagen phosphate buffer (pH=7.8) for preparing 1% mass fraction respectively, according to
Volume ratio 1:3 ratio is uniformly mixed, after -20 DEG C are freeze-dried 48 hours, by the mixture according to the ratio of mass fraction 0.1%
It is scattered in 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid, ionic liquid temperature is risen to 60 DEG C later, reaction
240 minutes；
(2) after completion of the reaction, above-mentioned ionic liquid temperature is down to 60 DEG C, is separately added into 6-caprolactone monomer and pig pancreas rouge
Fat enzyme, it is to react 144 hours in 60 DEG C of constant temperature oscillation reactors that temperature is placed it in after logical nitrogen-sealed；
(3) methylene chloride of 2 times of bulk products is added in Xiang Shangshu product, filters out lipase with filter paper later, then to
- 20 DEG C of cold methanols of 10 times of filtrate volumes are added in filtrate, is filtered after standing 24 hours in -20 DEG C of environment, obtains crude product；
(4) above-mentioned crude product is extracted 24 hours using acetone as solvent, obtains Mei Lade product modification polycaprolactone.
Mei Lade product modification polycaprolactone is obtained through the above method, being computed its grafting efficiency is about 60%, is pressed it
Contact angle test is carried out after piece, shows that its water droplet wetting contact angle is 50 °, mtt assay detection shows 90% or more cell survival rate.
Embodiment 3:
(1) lactose solution and collagen phosphate buffer (pH=7.8) for preparing 1% mass fraction respectively, according to
Volume ratio 1:3 ratio is uniformly mixed, after -20 DEG C are freeze-dried 48 hours, by the mixture according to the ratio of mass fraction 0.1%
It is scattered in 1- butyl -3- methyl imidazolium tetrafluoroborate ionic liquid, ionic liquid temperature is risen to 150 DEG C later, reaction 5
Minute；
(2) after completion of the reaction, above-mentioned ionic liquid temperature is down to 60 DEG C, is separately added into 6-caprolactone monomer and pig pancreas rouge
Fat enzyme, it is to react 1 hour in 100 DEG C of constant temperature oscillation reactors that temperature is placed it in after logical nitrogen-sealed；
(3) methylene chloride of 2 times of bulk products is added in Xiang Shangshu product, filters out porcine pancreatic lipase with filter paper later,
- 20 DEG C of cold methanols of 10 times of filtrate volumes are added into filtrate again, are filtered after standing 24 hours in -20 DEG C of environment, obtain thick
Product；
(4) above-mentioned crude product is extracted 24 hours using acetone as solvent, obtains Mei Lade product modification polycaprolactone.
Mei Lade product modification polycaprolactone is obtained through the above method, being computed its grafting efficiency is about 63%, is pressed it
Contact angle test is carried out after piece, shows that its water droplet wetting contact angle is 50 °, mtt assay detection shows 90% or more cell survival rate.
Embodiment 4:
(1) lactose solution and collagen phosphate buffer (pH=7.8) for preparing 1% mass fraction respectively, according to
Volume ratio 1:3 ratio is uniformly mixed, after -20 DEG C are freeze-dried 48 hours, by the mixture according to the ratio of mass fraction 0.1%
It is scattered in 1- butyl -3- methyl imidazolium tetrafluoroborate ionic liquid, ionic liquid temperature is risen to 60 DEG C later, reaction
240 minutes；
(2) after completion of the reaction, above-mentioned ionic liquid temperature is down to 60 DEG C, is separately added into 6-caprolactone monomer and the South Pole is false
Silk Yeast-lipase B, it is to react 144 hours in 60 DEG C of constant temperature oscillation reactors that temperature is placed it in after logical nitrogen-sealed；
(3) methylene chloride of 2 times of bulk products is added in Xiang Shangshu product, filters out antarctic candida with filter paper later
Lipase B, then into filtrate be added 10 times of filtrate volumes -20 DEG C of cold methanols, mistake after standing 24 hours in -20 DEG C of environment
Filter, obtains crude product；
(4) above-mentioned crude product is extracted 24 hours using acetone as solvent, obtains Mei Lade product modification polycaprolactone.
Mei Lade product modification polycaprolactone is obtained through the above method, being computed its grafting efficiency is about 72%, is pressed it
Contact angle test is carried out after piece, shows that its water droplet wetting contact angle is 58 °, mtt assay detection shows 85% or more cell survival rate.
Comparative examples 1:
The ionic liquid of (1) the step of embodiment 1 is substituted with aqueous solution, reaction obtains Mei Lade product, then again will
Product is scattered in ionic liquid, other steps and parameter and embodiment 1 are unanimously.As the result is shown: the method obtains Mei Lade product
Color is shallower, this illustrates that reduced sugar is lower to collagen grafting degree, and the modification further reacted using the product is poly-
Caprolactone, being computed its grafting efficiency is about 58%, to Contact-angle measurement is carried out after its tabletting, its wetting contact angle as the result is shown
It is 70 °, the cell survival rate of mtt assay measurement is 75% or so, obtains Mei Lade product modification in too late ionic liquid and gathers oneself
Lactone is good.Above the result shows in ionic liquid Maillard reaction it is more more efficient than in aqueous solution, obtained product
Wetability and cellular affinity can be also more preferable.
Comparative examples 2:
(1) the step of embodiment 1 is omitted, directly by lactose dispersion in 1- butyl -3- methylimidazole hexafluorophosphate from
In sub- liquid, other steps and parameter and embodiment 1 are unanimously.As the result is shown: the lactose modification polycaprolactone that the method obtains connects
Branch efficiency is about 47%, and the wetting contact angle of pressed disc method measurement is 60 °, and the cell survival rate of mtt assay measurement is 70% or so,
It is good not as good as Mei Lade product modification polycaprolactone.The result shows the wetabilitys of Mei Lade product and cellular affinity energy above
Also more preferable.
Comparative examples 3:
(1) the step of embodiment 1 is omitted, directly disperses 1- butyl -3- methylimidazole hexafluorophosphoric acid for collagen
In ionic liquid, other steps and parameter and embodiment 1 are unanimously.As the result is shown: the method obtains collagen-modified gather in oneself
Ester products amount is less, and being computed its grafting efficiency is about 4%, and the wetting contact angle of pressed disc method measurement is 74 °, mtt assay measurement
Cell survival rate is 70% or so, good not as good as Mei Lade product modification polycaprolactone.If this explanation is on collagen molecules
The small molecule reduced sugar containing primary hydroxyl is not introduced, and lipase can not complete the catalysis to polycaprolactone using collagen as substrate
Ring-opening polymerization, most of caprolactone monomer are catalyzed into as polycaprolactone homopolymer.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (9)
1. a kind of method of modified polycaprolactone, which is characterized in that the method is by the small molecule reduced sugar containing primary hydroxyl
Solution and collagen buffer solution mixing, freeze-drying obtain mixture, then disperse mixture in ionic liquid,
Reaction obtains Mei Lade product at 60 ~ 150 DEG C；After completion of the reaction, 100 DEG C are cooled to hereinafter, caprolactone monomer and rouge is added
Fat enzyme carries out ring-opening polymerization under the catalysis of lipase, obtains Mei Lade product modification polycaprolactone；The lipase is
Candida antarctica lipase B or porcine pancreatic lipase.
2. the method according to claim 1, wherein the small molecule reduced sugar containing primary hydroxyl is following
Any one is a variety of: glucose, galactolipin, lactose.
3. the method according to claim 1, wherein the ionic liquid is 1- butyl -3- methylimidazole hexafluoro
Phosphate or 1- butyl -3- methyl imidazolium tetrafluoroborate ionic liquid.
4. the method according to claim 1, wherein it is described dispersion be by mixture according to mass fraction 0.1% ~
5% ratio is scattered in ionic liquid；Mass ratio between the ionic liquid and caprolactone monomer is 0.1 ~ 10.
5. the method according to claim 1, wherein the ring-opening polymerization is in the case where temperature is 60 ~ 100 DEG C
Oscillating reactions 1 ~ 144 hour.
6. the method according to claim 1, wherein the lipase additive amount is caprolactone monomer quality
0.1%~10%。
7. complete in ring-opening polymerization the method according to claim 1, wherein the preparation method further includes
Methylene chloride is added in Bi Houxiang reaction mixture, is completely dissolved target product, filters, then proper volume is added into filtrate
- 20 DEG C ~ -4 DEG C cold methanols, in -20 DEG C ~ -4 DEG C environment stand a period of time, refilter, obtain crude product；It is with acetone
The above-mentioned crude product of solvent extraction obtains glycosylating collagen-modified polycaprolactone.
8. the Mei Lade product modification polycaprolactone obtained according to any the method for claim 1 ~ 7.
9. U.S. ladd product modification polycaprolactone according to any one of claims 8 is preparing sutures, Thermosensitive Material Used for Controlled Releasing of Medicine or doctor
With the application in timbering material.
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