CN103980507A - Method for crosslinking oil-soluble epoxy compound and collagen in supercritical carbon dioxide - Google Patents

Method for crosslinking oil-soluble epoxy compound and collagen in supercritical carbon dioxide Download PDF

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CN103980507A
CN103980507A CN201410223524.7A CN201410223524A CN103980507A CN 103980507 A CN103980507 A CN 103980507A CN 201410223524 A CN201410223524 A CN 201410223524A CN 103980507 A CN103980507 A CN 103980507A
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collagen
reactor
soluble epoxy
supercritical
crosslinked
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CN103980507B (en
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但年华
但卫华
陈一宁
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Sichuan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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Abstract

The invention relates to a method for crosslinking an oil-soluble epoxy compound and collagen in supercritical carbon dioxide. The method is characterized in that the supercritical carbon dioxide is taken as a medium, the oil-soluble epoxy compound and the collagen have a crosslinking reaction; after crosslinking is ended, an active substance is added, unreacted epoxy groups are closed and the active substance is grafted to the collagen, finally, the supercritical carbon dioxide is taken as an extraction agent to remove impurities. The method can be used in medical biological materials and leather industry.

Description

The method of oil soluble epoxy compounds crosslinked with collagen in supercritical co
Technical field
The present invention relates to the method for oil soluble epoxy compounds crosslinked with collagen in supercritical CO 2 medium, can be applicable to bio-medical material and leather industry.
Background technology
Collagen is the major structural protein that forms reticular tissue, accounts for 1/ 3 of gross protein in Mammals, is extensively present among animal skin, bone, cartilage, tendon, ligament and vessel wall etc., with the collegen filament form of three-dimensional network, exists.Collagen has the plurality of advantages such as the performance of low immunogenicity, low irritant, low cytotoxicity, good biocompatibility, good Promote cell's growth and biodegradability, increasingly extensive in the application of biomedical sector.Yet the collagen degradation in vivo of Non-crosslinked is too fast, be difficult to mate with the growth phase of destination organization.By physics, chemical process, collagen is cross-linked, be conducive to reduce antigenicity, improve physical and mechanical properties, reduce biological degradability, effectively improve its use properties (but time, but defend China, Zeng Rui, Deng. epoxy compounds and the application in collagen cross-linking [J] thereof. material Leader, 2006,20(6): 119-122).The crosslinked of collagen is one of study hotspot of biomaterial always.
The cross-linking method of collagen comprises physical crosslinking and chemically crosslinked.The physical crosslinking exogenous material that do not induce one, but crosslinking degree is low, lack of homogeneity.The relative crosslinking degree of chemically crosslinked is high, can control crosslinking degree by selecting linking agent and crosslinked condition (consumption, pH, temperature, time etc.), and evenly crosslinked.When the higher crosslinking degree of needs, often adopt chemical crosslink technique.Conventional chemical cross-linking agent has: (the public dimension chrysanthemum such as glutaraldehyde, hexamethylene diisocyanate, carbodiimide, epoxy compounds, nitrine diphenylphosphine, genipin, Li Guoying. the present Research [J] that collagen cross-linking is crosslinked. leather chemical industry, 2007,24 (5): 21-30.).Glutaraldehyde cross-linking agent is organized easy calcification because cytotoxicity is strong, crosslinked, can not meet application needs.Carbodiimide, genipin etc., price is comparatively expensive, has limited its mass-producing application.That epoxy compounds has is simple in structure, be easy to synthesize, cheap, chemical reaction Ying Xinggao, the plurality of advantages such as reactive group is many, designability is strong, good biocompatibility, be considered to a kind of good acceptable biological cross-linked material (Woodroof E A.Use of glutaraldehyde and formaldehyde to process tissue heart valves.J Bioeng, 1978,2:1; Speer D P, Chvapil M, Eskelson C D, et al.Biological effects of residual glutaraldehyde in glutaraldehyde tanned collagen biomaterials. J Biomed Mater Res, 1980,14:753).
The chemical reactivity of epoxy compounds mainly relies on epoxy group(ing), and the epoxy group(ing) number in single epoxy compounds is more, and obtainable crosslinking degree is higher.Yet epoxy group(ing) is more, it is water-soluble poorer, is not even dissolved in water (as ethylene glycol diglycidylether, butyleneglycol glycidyl ether, tetramethylolmethane glycidyl ether etc.).When take water when medium is cross-linked, oil-soluble epoxy compounds is difficult to be scattered in water, forms the non-homogeneous mixture of oily water separation, and reaction efficiency is low, and rate of crosslinking is slow, is difficult to produce a desired effect.And take organic solvent (as acetone) during as solvent, and although can form homogeneous phase solution, speed of response is fast, rate of crosslinking improves.But because organic solvent is difficult to remove completely, may there is dissolvent residual, the biocompatibility of cross-linked material is had a negative impact.Visible, find a kind of green solvent, in non-water non-organic solvent medium, adopt oil soluble epoxy compounds crosslinked with collagen, be the key overcoming the above problems.
Supercutical fluid refers to that its temperature and pressure, respectively at the fluid of critical temperature and a kind of special state more than emergent pressure, is characterized in having the character of similar gas and liquid.From Theresa Andrews in 1869, find that stagnation point has the history of more than 100 year so far, but to the broad research of supercutical fluid be nearly decades thing (Yu Chenjie, Ma Hongjia, Zhou Zhihua. the applied research progress [J] of supercritical fluid technology. chemistry world, 2007(2): 118-120,124).Supercritical CO 2be a kind of conventional supercutical fluid, have the following advantages: the speed of response that 1. improves chemical reaction; 2. reduce the temperature of reaction of high-temperature chemical reaction; 3. heterogeneous reaction can be become to homogeneous reaction; 4. reduce the deactivation rate of catalyzer; 5. improve the selectivity of reaction; 6. speed of reaction, productive rate, selectivity etc. can regulate by the interpolation of pressure or a small amount of cosolvent; 7. greatly improve the rate of mass transfer of heterogeneous reaction; 8. with eco-friendly solvent, replace hazardous solvent; 9. chemical reaction and sepn process are combined as a whole (Zhang Yuanming. chemical research and application new development outline [M]. Guangzhou: south China. BJ Universithy of Polytech Press, 2000).
Utilize supercritical CO 2as reaction medium, be expected to realize oil soluble epoxy compounds crosslinked with collagen in non-water non-organic solvent medium.
Summary of the invention
The method of oil soluble epoxy compounds crosslinked with collagen in supercritical co, is characterized in that taking the collagen of 100 weight parts, is soaked in the buffered soln of pH7.0 to pH12.0 of 100-1000 weight part, stirs or jolting 5-30min lyophilize; The oil soluble epoxy compounds of above-mentioned collagen and 0.5-20 weight part is joined to supercritical co reactor, closed reactor, adjusting temperature of reactor is 35 ℃-45 ℃, setting reaction pressure is 8-15MPa, inside reactor stirred or rotate, keeping this conditioned response 12-72 h; Off-response device, discharges carbon dioxide in reactor; To the active substance that adds 1-20 weight part in reactor, adjusting temperature of reactor is 35 ℃-45 ℃, increases pressure to 8-15MPa, stirs or rotates, and keeps this conditioned response 12-72 h; Off-response device, discharges carbon dioxide in reactor; Pass into carbon dioxide, again temperature of reactor is adjusted to 35 ℃-45 ℃, pressure is 8-15MPa, stirs or rotates, and keeps this condition 1-48h, reclaims carbon dioxide; Off-response device, takes out crosslinked with collagen.
The method of oil soluble epoxy compounds according to claim 1 crosslinked with collagen in supercritical co, wherein said damping fluid refers to boric acid-borate buffer solution, borax-sodium hydrate buffer solution, sodium hydroxide-sodium carbonate buffer, Sodium phosphate dibasic-sodium hydrate buffer solution, sodium carbonate-sodium bicarbonate buffer liquid, phosphate buffered saline buffer.
The method of oil soluble epoxy compounds according to claim 1 crosslinked with collagen in supercritical co, wherein said oil soluble epoxy compounds refers to ethylene glycol diglycidylether, butanediol diglycidyl ether, glycerin triglycidyl ether, tetramethylolmethane four glycidyl ethers, sorbyl alcohol four glycidyl ethers.
The method of oil soluble epoxy compounds according to claim 1 crosslinked with collagen in supercritical co, wherein said active substance refers to amino acid, RGD peptide, RPMI-1640 dehydrated medium.
The method of oil soluble epoxy compounds crosslinked with collagen in supercritical co described in claim 1, is characterized in that this cross-linking method can be used in the processing or the preparation containing the biomedical material of collagen of pig in leather industry, ox, sheep animal skin.
The present invention has advantages of following:
(1) solve Solvent
Supercritical carbon dioxide fluid has very strong dissolving power, the polyepoxy compound that it can dissolved water indissoluble, thus realize the crosslinking reaction under non-water, non-organic solvent condition.Carbonic acid gas can reclaim simultaneously, Reusability;
(2) no solvent residue
Carbonic acid gas is nontoxic, under normal temperature, is gas, and after reaction finishes, carbonic acid gas can evaporate automatically, thereby has avoided the residual of organic solvent (as acetone).This point, concerning collagen is used as biomaterial for medical purpose, seems very important, useful;
(3) improve speed of response
Supercritical carbon dioxide fluid has good mobility and transitivity, and there is larger kinetic energy than liquid, can be as entering into gas among the collegen filament of porous, this has just strengthened the speed that oil soluble epoxy compounds contacts with collagen, improved mass transfer process, increase the probability colliding between active group, thereby can improve speed of response, improved crosslinked homogeneity;
(4) change chemical equilibrium
The overcritical chemical equilibrium that affects reaction.There are at present two kinds of explanations, the one, think that the variation of several orders of magnitude has occurred under super critical condition reaction equilibrium constant; The 2nd, owing to having broken through the restriction of thermodynamic(al)equilibrium condition.By optimizing reaction parameter, be expected to make oil soluble epoxy compounds more complete, efficient with reacting of collagen, obtain higher degree of crosslinking;
(5) improve temperature of reaction
The denaturation temperature of collagen in water is lower; And under anhydrous condition, denaturation temperature can obviously raise.Take supercritical carbon dioxide fluid as medium, is the crosslinking reaction of carrying out under anhydrous condition, and therefore, reaction can be carried out at higher temperature, is conducive to acceleration molecular thermal motion, is conducive to overcome reaction energy barrier, thereby improves speed of reaction;
(6) functionalization of termination reaction and residual epoxy group(ing) is removed
Due to sterically hindered, fibre gap is excessive, react the reason such as incomplete, it is complete that a plurality of epoxy group(ing) in linking agent are difficult to total overall reaction, may be after reaction finishes, exist part epoxy group(ing) residual (in tetramethylolmethane glycidyl ether, may there is the crosslinked of three epoxy group(ing) generations, but have an epoxy group(ing) to fail to react, a thereby residual epoxy group(ing)).These residual chemical active radicals may have a negative impact to the biocompatibility of material.In order effectively to remove these residual crosslinked groups, in supercritical CO 2 medium, add the biologically active substance (as amino acid, RGD, cell culture medium pulvis etc.) that can react with residual epoxy group(ing), seal these active groups.Remove these active groups on the one hand, introduced biologically active substance simultaneously, improved other performance of cross-linked material.When realizing group sealing, reached the object of functionalization;
(7) remove non-collagen tissue
Supercritical CO 2because its good solubility is for as spe medium, utilize this characteristic, after crosslinking reaction completes, pass into a certain amount of supercritical CO 2fluid (not adding other material), just can reach the object of collagen purification.It not only can extract the non-collagen tissue (grease as residual in possibility in collagen, foreign protein etc.) of removing in collagen, meanwhile, can extract and remove unreacted linking agent or other product;
(8) keep structure and form
Supercritical CO 2as reaction medium, after crosslinked end, reduce temperature and pressure, CO 2become gas and remove.Whole reaction process can the not induce one aqueous solution or organic solvent, collagen sample can keep original pattern (as profile, hole etc.) substantially, keeps dry state simultaneously, has avoided secondary freeze-drying;
In sum, adopt the super CO that faces 2fluid is medium, has not only overcome the issuable toxic side effect of organic solvent, and can promote mass transfer process, improves speed of response, improves chemical equilibrium, promotes crosslinked.Adopt the method for functionalization, remove residual chemical active radical, and grafting active substance, biocompatibility improved; Finally, adopt the super CO that faces 2fluid extracts, and can remove non-collagen tissue and reaction residue in collagen.Present method will be cross-linked, functionalization and purifying fuse into one, and have obvious novelty.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention; and can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
embodiment 1
(1) take de-10 grams of cell pig dermis matrix (dry weight);
(2) be placed in 100ml pH10.4 sodium hydroxide-sodium carbonate buffered soln, soak 30min, lyophilize is standby;
(3) take 0.8 gram of tetramethylolmethane four glycidyl ether, add supercritical co reactor, the more de-cell pig dermis matrix through above-mentioned processing is put into reactor, closed reactor;
(4) open temperature controlled switch, temperature of reactor is adjusted into 40 ℃;
(5) open to add and compress switch, add carbonic acid gas, be forced into 9.5Mpa, close to add and compress switch;
(6) open whipping appts, under aforementioned temperature and pressure, reaction 48 h;
(7) close heater switch, open carbon dioxide recovery valve, reclaim CO 2gas;
(8) open reactor, add 0.2 gram of RPMI-1640 dehydrated medium, open whipping appts, adjusting temperature is 40 ℃, and pressure is 9.5Mpa, reaction 12 h;
(9) off-response device, discharges CO 2gas;
(10) in reactor, pass into CO 2gas, opens whipping appts, and regulating temperature is 40 ℃, and pressure is 9.5MPa, extraction 8h;
(11) close heater switch, open carbon dioxide recovery valve, reclaim CO 2gas, opens reactor, takes out crosslinked de-cell pig dermis matrix.
embodiment 2
(1) take 100 grams of collagen sponges, put it in supercritical co reactor;
(2) take 4 grams of ethylene glycol diglycidylethers and add in reactor, closed reactor;
(3) open whipping appts, temperature of reactor is adjusted into 37 ℃, passing into carbon dioxide, to make pressure be 8.0Mpa, reaction 12 h;
(4) stop stirring, close temperature controlled switch, open recovery valve, reclaim CO 2gas;
(5) open reactor, take 0.5 gram of RGD and join in reactor, temperature of reactor, for adjusting 37 ℃, is passed into CO 2gas, is forced into 8.0Mpa, reaction 12 h;
(6) open whipping appts, regulating temperature is 40 ℃, adds carbonic acid gas, is pressurized to 9.5MPa, extraction 8h;
(7) close heater switch, open carbon dioxide recovery valve, reclaim CO 2gas, opens reactor, takes out crosslinked with collagen sponge.
embodiment 3
(1) take 1 gram of collagen-based micro-nano fiber, be placed in supercritical co reactor;
(2) add 0.1 gram of glycerin triglycidyl ether to reactor, closed reactor;
(3) open whipping appts, temperature of reactor is adjusted into 35 ℃, passing into carbon dioxide, to make pressure be 8.5MPa, reaction 24 h;
(4) stop stirring, discharge CO 2gas;
(5) open reactor, add 0.3 gram of Methionin, adjusting temperature is 37 ℃, and pressure is 8.5Mpa, reaction 12h;
(6) in reactor, pass into CO 2gas, regulating temperature is 37 ℃, pressure is 8.5MPa, Exhaust Gas after maintenance 8h;
(7) stop stirring, close temperature controller, reclaim carbonic acid gas, open reactor, take out crosslinked with collagen base fiber.
embodiment 4
(1) take 1000 grams of ox pelts after softening, be placed in sodium hydroxide-sodium carbonate buffer of pH10.0, under normal temperature, rotate 30min;
(2) with wringing machine, squeeze and remove excessive moisture;
(3) take 80 grams of tetramethylolmethane four glycidyl ethers and be put in reactor, the pelt after water squeezing is added in reactor to closed reactor;
(4) open wheelwork, temperature of reactor is adjusted into 35 ℃, passing into carbon dioxide, to make pressure be 10MPa, reaction 24 h;
(5) stop stirring, close temperature controller, reclaim carbonic acid gas, open reactor, take out the cattle hide of tanning.

Claims (5)

1. the method for oil soluble epoxy compounds crosslinked with collagen in supercritical co, is characterized in that taking the collagen of 100 weight parts, is soaked in the buffered soln of pH7.0 to pH12.0 of 100-1000 weight part, stirs or jolting 5-30min lyophilize; The oil soluble epoxy compounds of above-mentioned collagen and 0.5-20 weight part is joined to supercritical co reactor, closed reactor, adjusting temperature of reactor is 35 ℃-45 ℃, setting reaction pressure is 8-15MPa, inside reactor stirred or rotate, keeping this conditioned response 12-72 h; Off-response device, discharges carbon dioxide in reactor; To the active substance that adds 1-20 weight part in reactor, adjusting temperature of reactor is 35 ℃-45 ℃, increases pressure to 8-15MPa, stirs or rotates, and keeps this conditioned response 12-72 h; Off-response device, discharges carbon dioxide in reactor; Pass into carbon dioxide, again temperature of reactor is adjusted to 35 ℃-45 ℃, pressure is 8-15MPa, stirs or rotates, and keeps this condition 1-48h, reclaims carbon dioxide; Off-response device, takes out crosslinked with collagen.
2. the method for oil soluble epoxy compounds according to claim 1 crosslinked with collagen in supercritical co, wherein said damping fluid refers to boric acid-borate buffer solution, borax-sodium hydrate buffer solution, sodium hydroxide-sodium carbonate buffer, Sodium phosphate dibasic-sodium hydrate buffer solution, sodium carbonate-sodium bicarbonate buffer liquid, phosphate buffered saline buffer.
3. the method for oil soluble epoxy compounds according to claim 1 crosslinked with collagen in supercritical co, wherein said oil soluble epoxy compounds refers to ethylene glycol diglycidylether, butanediol diglycidyl ether, glycerin triglycidyl ether, tetramethylolmethane four glycidyl ethers, sorbyl alcohol four glycidyl ethers.
4. the method for oil soluble epoxy compounds according to claim 1 crosslinked with collagen in supercritical co, wherein said active substance refers to amino acid, RGD peptide, RPMI-1640 dehydrated medium.
5. the method for oil soluble epoxy compounds crosslinked with collagen in supercritical co described in claim 1, is characterized in that this cross-linking method can be used in the processing or the preparation containing the biomedical material of collagen of pig in leather industry, ox, sheep animal skin.
CN201410223524.7A 2014-05-26 2014-05-26 The method of oil soluble epoxy compounds crosslinked with collagen in supercritical co Active CN103980507B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110479216A (en) * 2019-08-26 2019-11-22 西南科技大学 The preparation method of collagen fiber supported tannin load nano zero-valence Fe-Ni bimetallic ball absorbing and reducing material
CN114086390A (en) * 2021-12-08 2022-02-25 四川大学 Epoxidized soybean oil modified collagen fiber and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54142183A (en) * 1978-04-06 1979-11-06 Diamond Shamrock Corp Method of coagulating chemically and*or biologically active substance
CN101289539A (en) * 2007-04-17 2008-10-22 四川大学 Process for modifying leather collagen of animals through epoxides
CN103505759A (en) * 2013-07-04 2014-01-15 四川大学 Method used for modifying collagen with epoxy quaternary ammonium salt

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54142183A (en) * 1978-04-06 1979-11-06 Diamond Shamrock Corp Method of coagulating chemically and*or biologically active substance
CN101289539A (en) * 2007-04-17 2008-10-22 四川大学 Process for modifying leather collagen of animals through epoxides
CN103505759A (en) * 2013-07-04 2014-01-15 四川大学 Method used for modifying collagen with epoxy quaternary ammonium salt

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110479216A (en) * 2019-08-26 2019-11-22 西南科技大学 The preparation method of collagen fiber supported tannin load nano zero-valence Fe-Ni bimetallic ball absorbing and reducing material
CN110479216B (en) * 2019-08-26 2022-01-28 西南科技大学 Preparation method of collagen fiber immobilized tannin loaded nano zero-valent Fe-Ni bimetallic ball adsorption reduction material
CN114086390A (en) * 2021-12-08 2022-02-25 四川大学 Epoxidized soybean oil modified collagen fiber and preparation method and application thereof

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