CN110368519A - A kind of orthopaedics adhesive based on sea-mussel mucin - Google Patents
A kind of orthopaedics adhesive based on sea-mussel mucin Download PDFInfo
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- CN110368519A CN110368519A CN201910793366.1A CN201910793366A CN110368519A CN 110368519 A CN110368519 A CN 110368519A CN 201910793366 A CN201910793366 A CN 201910793366A CN 110368519 A CN110368519 A CN 110368519A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K38/00—Medicinal preparations containing peptides
- A61K38/16—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- A61K38/17—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- A61K38/18—Growth factors; Growth regulators
- A61K38/1841—Transforming growth factor [TGF]
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
- A61L24/0015—Medicaments; Biocides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/10—Polypeptides; Proteins
- A61L24/108—Specific proteins or polypeptides not covered by groups A61L24/102 - A61L24/106
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P19/00—Drugs for skeletal disorders
- A61P19/02—Drugs for skeletal disorders for joint disorders, e.g. arthritis, arthrosis
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P19/00—Drugs for skeletal disorders
- A61P19/08—Drugs for skeletal disorders for bone diseases, e.g. rachitism, Paget's disease
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/252—Polypeptides, proteins, e.g. glycoproteins, lipoproteins, cytokines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/602—Type of release, e.g. controlled, sustained, slow
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/04—Materials for stopping bleeding
Abstract
The present invention provides a kind of sea-mussel mucin glycosylation modified comprising D-Gal, Tween 80, the orthopaedics adhesive of BMP-2 and its each ingredient difference packaged adhesive kit and applications.Adhesive of the invention can be sustained BMP-2 in the case where keeping bond properties substantially, realize and preferably promote recovery effects to completeness fracture.
Description
Technical field
The invention belongs to field of biomedical materials and regenerative medicine field containing activated protein, and specifically, the application mentions
The orthopaedics adhesive of a kind of sea-mussel mucin glycosylation modified comprising D-Gal, Tween 80, BMP-2 have been supplied, and
Provide each ingredient difference packaged adhesive kit of the adhesive and the application of the adhesive.
Background technique
Bone morphogenesis protein-2 (bone morphogenetic protein-2, BMP-2) is the pass for promoting ostosis
The key factor belongs to TGF- α family member.BMP-2 is the major signaling molecule that cell differentiation metallogenic material deposits osteoblast, is risen
To the effect of induced osteogenesis cell differentiation.It is expressed in limbs growth, endochondral ossification, fracture, in bone growth and development and again
Raw repair plays an important role, it is considered to be the good agent activity ingredient of the osteopathy such as treatment fracture, bone defect, and there are many phases
It closes filler and injection drug obtains supervision department's approval listing.Main problem in BMP-2 application is its half-life short, quiet
T after arteries and veins injection1/2Only 6-7min, therefore injecting pathway is difficult to the concentration of target area continuous and effective, affected bone is for a long time
The needs for (being greater than 30) growth and restoring.
Sea-mussel mucin (mussel adhesive protein, MAP) is the hatching egg that mussel foot gland secrets out of
White compound, superpower viscosity are the key that mussel can be firmly attached on reef and not be afraid of sea beat.Sea-mussel mucin
The advantages that range is wide, and intensity is high, good waterproof performance, bioaffinity and good degradability with bonding, it is considered to be good biology
Adhesive.The currently the only bioadhesive commercial goods of sea-mussel mucin (non-cosmetics or wound covering liquid) are BD
The CELL-TAK of Bioscience production can be used for tissue adhesion, and gene engineering product is due to lacking mussel foot body of gland
Processing and bond properties is obviously not so good as natural extract product.
Influence mussel adh esive protein is widely applied, and main reason is that it is expensive, (CELL-TAK 1mg needs
It is extracted close to 10,000 mussels, price initially more than 200 dollars, present needs exist for 80 dollars or so).Solve the problems, such as this
Thinking, can also be from the effect for improving mussel adh esive protein other than improving extraction process and genetic engineering process for preparing
Start with, preparation effect is substantially better than the product of existing adhesive (such as Fibrin Glue) so that city's field energy receive such product compared with
High price.Mussel adh esive protein is loaded into upper BMP-2, promotees bone uptake function using its strong bonding characteristic and BMP-2 and controls
The fixed difficult situation such as diseases, the especially comminuted fracture such as fracture is treated, is a kind of promising medicament.
Summary of the invention
Applicants have found that sea-mussel mucin carry out it is a degree of it is glycosylation engineered after, due to sulfhydryl content
The variation of cross-linking properties caused by reducing has more microstructures formation or the reservation with a sequence of position BMP, matching surface
After activating agent (similarly helping to microstructure to be formed), the long-term sustained release performance to BMP-2 may be obtained, while basic holding is made a gift of
The adhesive force of shellfish mucoprotein.The effect that adhesive strength and bone restore when the adhesive is for fixation of bone fragments treatment fracture is obvious
Better than existing similar adhesive product.
On the one hand, the present invention provides a kind of adhesive kits comprising the sea-mussel mucin of the modification of independent packaging,
Tween surfactant, BMP and 5% acetum.
Further, Tween is Tween 80, BMP BMP-2.
Further, the sea-mussel mucin in adhesive containing modification, Tween 80, BMP-2 mass ratio be 1-3:5-10:
0.5-1, the amount of 5% acetum are more than amount needed for sea-mussel mucin is configured to 1mg/mL solution.
Further, the sea-mussel mucin in adhesive containing modification, Tween 80, BMP-2 mass ratio be 1:6:0.5,
The amount of 5% acetum is more than amount needed for sea-mussel mucin is configured to 1.5mg/mL solution.
Further, the sea-mussel mucin of modification is glycosylation modified.
Further, the sea-mussel mucin of modification is that D-Gal is glycosylation modified.
Further, the preparation process of the sea-mussel mucin of modification are as follows: sea-mussel mucin is formulated as the outstanding of 0.5% concentration
Liquid, 5 times of D-Gals of sea-mussel mucin quality are added into suspension and the glutamine of 20U/g sea-mussel mucin turns ammonia
Enzyme adjusts pH to 7.0,4h is reacted at 40 DEG C, and inactivator 5min at 80 DEG C, dialysis removes extra D-Gal for 24 hours, freezes
The sea-mussel mucin for doing to modify.
On the other hand, this application provides a kind of orthopaedics adhesives, are made using above-mentioned adhesive kit
Adhesive product, wherein sea-mussel mucin, Tween 80, BMP-2 with the concentration that 5% acetum is prepared be 1.5mg/mL,
9mg/mL、0.75mg/mL。
On the other hand, this application provides above-mentioned adhesive kits or adhesive in the medicament of preparation treatment fracture
Using.
Further, the fracture is complete fracture, it is preferable that is helicity, comminuted or compression fracture.
The sea-mussel mucin product that sea-mussel mucin in the application can select mussel foot to extract, such as commercially available mussel are viscous
The CELL-TAK of albumen finished product BD Bioscience either voluntarily changes in the method for prior art record or on this basis
Into method extract various types of mussel sea-mussel mucin；Gene work can also be selected in the case where the characteristics such as viscosity allow
The various Mefp albumen of Cheng Fangfa preparation, including but not limited to Mefp-1 to Mefp-6.
Above-mentioned mussel includes but is not limited to Mytilus galloprovincialis, Trachyostracous mussel, Perna viridis etc..
BMP-2 in the application can be various sources, have the active BMP-2 albumen of bon e formation, protein mutant,
Protein active fragment；Source its can be extracted from natural products or with gene engineering method from various host's strains expression obtain
It obtains (gene order can be obtained from approach such as Genbank, EMBL)；BMP-2 can voluntarily extraction/expression obtains by subject of implementation
, it is also possible to the finished product purchased from market.
In addition to the fracture of various severity and form, the adhesive of the application can be also used for other various bone injuries,
The bonding of the needs such as the orthopedic reparation of therapeutic bone, esthetics orthopedic reparation, spinal fusion, joint fusion simultaneously and promotes the feelings of bone uptake
Shape.
Detailed description of the invention
The slice map of Fig. 1 adhesive treatment fracture model；
Fig. 2 compares the slice map that adhesive 1 handles fracture model；
Fig. 3 compares the slice map that adhesive 2 handles fracture model；
The slice map of Fig. 4 blank fracture model.
Embodiment
Main agents and instrument
The natural sea-mussel mucin extract product of CELL-TAK: BD Bioscience production is marked as Mytilus galloprovincialis product,
Containing Mefp-2, Mefp-2, Mefp-3；
BMP-2 is voluntarily produced by enterprise, and specific production process is referring to applicant CN201910030649.0 Chinese patent
In application production method (expression in escherichia coli, cation exchange chromatography, detection escherichia coli host residual protein <
0.005%), inhibition zone method detects antibiotic residue < 0.1ppm；
D-Gal, glutamine transaminage/TGase, Tween 80 are purchased from SIGMA/MERCK；
Fibrin Glue (FG) is produced by Guangzhou Beixiu Biological Technology Co., Ltd；
Escherichia coli host residual protein detection kit is produced by Shanghai Cheng Shao Biotechnology Co., Ltd；
CCK-8 cell Proliferation toxicity detection kit is produced by Dalian U.S. logical sequence Science and Technology Ltd.；
People BMP-2 ELISA detection kit is produced by Tianjin An Nuoruikang Bioisystech Co., Ltd；
MC-949B-KD mechanics machine is produced by Guangzhou Ming Chi Science and Technology Ltd.；
Part chemical modification operation commission Shanghai KaiTuoZhe Chemical Research Management Co., Ltd carries out；
Some Animals experiment commission Beijing University of Chinese Medicine's scientific experiment center/Experimental Animal Center carries out；
Remaining reagent (mostly analyzing pure) and instrument are domestic conventional brand and model.
The preparation of the sea-mussel mucin of the preparation modification of 1 adhesive kit of embodiment and adhesive
The natural sea-mussel mucin mussel of CELL-TAK is formulated as to the suspension of 0.5% concentration using distilled water, into suspension
The glutamine transaminage of sea-mussel mucin quality 5 times of D-Gals and 20U/g sea-mussel mucin is added, NaOH is added
The directly reaction (suspension pH has been approached 7 under certain batches) of 1M tune pH to 7.0/, reacts 4h in 40 DEG C of water-baths；Subsequent 80 DEG C of water-baths
Middle inactivation glutamine transaminage 5min；Extra D-Gal is removed for 24 hours to distilled water dialysis using the film of 1000Da
(changing liquid 3 times)；The sea-mussel mucin for being lyophilized to modify.
The preparation of adhesive
It is stored refrigerated that the sea-mussel mucin of modification needs independent 4 DEG C before use, in use, it is protected with same 4 DEG C of refrigeration
Deposit Tween 80, BMP-2 be cooled in advance 4 DEG C 5% acetum prepare composite adhesives, wherein sea-mussel mucin, Tween 80,
BMP-2 concentration need to be used in 5min with postponing for 1.5mg/mL, 9mg/mL, 0.75mg/mL respectively.
In addition to above-mentioned adhesive, directly matched with the unmodified natural sea-mussel mucin of CELL-TAK, Tween 80, BMP-2
System control adhesive 1；
Control adhesive 2 is prepared with Guangzhou Beixiu Biological Technology Co., Ltd's production fibrin glue agent box.
According to kit specification (CCK-8 cell Proliferation toxicity detection kit, the limited public affairs of Dalian U.S. logical sequence science and technology
Department) the CCK-8 cell Proliferation toxicity test that carries out shows that the cytotoxicity of the adhesive is CTS 0-I grades, tentative confirmation its
Safety.
The bond properties test of 2 adhesive of embodiment and control adhesive
Male New Zealand large ear rabbit 12 for choosing 2.5kg or so, take the complete ulna of left fore, middle section immediately after execution
It is vertically cut off with electric saw, adhesive, control adhesive 1 and control 2 product of adhesive then prepared using 60 μ L embodiments 1 is viscous
Breaking part is closed, pressing 10min stands 30min for testing.
Test mechanical property (three-point bending resistance test, acceleration 1mm/min, pivot distance 2cm) is tested with mechanical test instrument,
Three samples are averaged.The results are shown in Table 1.
The bending strength of 1 adhesive bonding bone specimen of table
The bond properties of visible sea-mussel mucin is repaired significantly more than existing Fibrin Glue by glycosylation from upper table
It is little that the bond properties of sea-mussel mucin after decorations still reduces amplitude, is still substantially better than existing Fibrin Glue.
The extracorporeal releasing experiment of embodiment 3BMP2
Adhesive and the control each 0.5mL of adhesive 1 prepared by embodiment 1 is obtained, the thin slice of diameter about 1cm is manually depressed into
Shape places it in bag filter after solidifying 1h, and bag filter is placed in 15ml containing 0.2% sodium azide, the PBS buffer solution of pH7.0
In；Be statically placed at 37 DEG C, in 12h, for 24 hours, the separately sampled 1ml of 120h, 240h, 480h, 720h, 960h (then supplement contain 0.2%
Sodium azide, the PBS buffer solution 1ml of pH7.0), according to explanation (people's BMP-2ELISA detection kit, the Tianjin of kit
The production of An Nuoruikang Bioisystech Co., Ltd) with ELISA method measurement BMP-2 concentration, the accumulative release percentage of Conversion Calculation.Knot
Fruit is as shown in table 2:
Promote the formation of the microstructures such as sea-mussel mucin spherical shape lamella is white to BMP-2 to play it can be seen that tween 80 is added
Certain slow releasing function further enhances this slow releasing function (mechanism may be to the glycosylation modified of sugared sea-mussel mucin
Cross-linking properties caused by the reduction of sulfhydryl content changes after glycosylation, have more microstructures formed or with BMP in succession
Position reservation), the BMP-2 releasability for extending to 30 days or more can should more effectively support the reparation at fractured bones damage
(mainly the phase of repairing is generally acknowledged that at 60 days or more after people's bone folding).
The preparation of the rabbit fracture model test rabbit fracture model of 4 adhesive of embodiment and control adhesive
Male New Zealand large ear rabbit 12 for choosing 2.5kg or so are equally divided into 4 groups of (adhesives 1, control adhesive
1, adhesive 2, blank are compareed).Use fixed after the ketalar auricular vein injecting anesthetic of 10mg/kg, left fore depilation
And it sterilizes.
2cm notch is done in left fore ulnar side middle section, and after separating its hetero-organization, with electric saw, vertically sawed-off ulna causes fracture type
It destroys.
The processing of rabbit fracture model
After normal saline flushing fracture and wound, the bonding of 40 μ L embodiments 1 preparation is applied between fracture fracture end
Agent, control adhesive 1 and control adhesive 2 product or without any processing, subsequent pressurized fracture stitch after being broken both ends 180s
Wound is closed with the fixed injury of medical adhesive tape.
Antibiotic (1,000,000 unit of penicillin) treatment on the three is given after operation.
Observation of curative effect
Normal raising is put to death after 90 days, takes the sample in an interception breaking part both ends 1cm；10% formalin is fixed
For 24 hours, paraffin embedding, HE slice dyeing observation, as a result as shown in Figs 1-4；Other two take the ulna of modeling side according to implementation
The method of example 2 detects bending strength.The results are shown in Table 3:
The bending strength of 3 adhesive treatment rabbit fracture model of table
| Adhesive | Average bending strength (MPa) |
| Adhesive | 98.77 |
| Compare adhesive 1 | 74.42 |
| Compare adhesive 2 | 69.38 |
| Blank | 47.26 |
Degradation situation in slice map after visible three kinds of adhesives 90 days is good, does not remain significantly.It is sustained BMP-
Adhesive reparation fracture effect on the 30th is substantially better than the poor control adhesive 1 of slow release effect and control adhesive 2 (compares viscous
Mixture 1 and control 2 effect of adhesive are close, the effect or a with sample that the short BMP of slow-release time does not have auxiliary to repair substantially
Body difference is related), it shows as poroma and disappears substantially, cell arrangement is closely neat.The healing of bending strength and slice display
Effect corresponds to substantially.
It is above-mentioned the experiment proves that the application adhesive excellent adhesion performance and promote bone recovery capability, treatment fracture,
Especially helicity, comminuted or compression fracture when should have the effect of being substantially better than traditional binders.
Using CELL-TAK sea-mussel mucin finished product costly main reason is that lacking it on the market in embodiment
His high-quality natural extraction sea-mussel mucin.Although applicant is using the sea-mussel mucin voluntarily extracted, also multipotency obtains similar effect
Fruit, but be not possible to provide the sea-mussel mucin source of effect stability due to mussel species/season, it is not easy to study.Therefore
Applicant uses always CELL-TAK sea-mussel mucin finished product in experiment, can be considered when introducing to the market and further stablizes and optimize
Mucoprotein extracts and modification, uses the sea-mussel mucin from extraction.
Claims (10)
1. a kind of adhesive kit, it is characterised in that the sea-mussel mucin of the modification including independent packaging, Tween surface-active
Agent, BMP and 5% acetum.
2. adhesive kit according to claim 1, wherein Tween is Tween 80, BMP BMP-2.
3. adhesive kit according to claim 2, wherein the sea-mussel mucin in adhesive containing modification, Tween 80,
The mass ratio of BMP-2 is 1-3:5-10:0.5-1, and the amount of 5% acetum is more than that sea-mussel mucin is configured to 1mg/mL solution
Required amount.
4. adhesive kit according to claim 3, wherein the sea-mussel mucin in adhesive containing modification, Tween 80,
The mass ratio of BMP-2 is 1:6:0.5, and the amount of 5% acetum is more than that sea-mussel mucin is configured to needed for 1.5mg/mL solution
Amount.
5. any one of -4 adhesive kit according to claim 1, wherein the sea-mussel mucin modified is glycosylation modified.
6. adhesive kit according to claim 5, wherein the sea-mussel mucin modified is that D-Gal glycosylation is repaired
Decorations.
7. adhesive kit according to claim 6, wherein the preparation process for the sea-mussel mucin modified are as follows: mussel is glued egg
5 times of D-Gals of sea-mussel mucin quality and 20U/g mussel are added into suspension for the white suspension for being formulated as 0.5% concentration
The glutamine transaminage of mucoprotein adjusts pH to 7.0,4h is reacted at 40 DEG C, and inactivator 5min at 80 DEG C, dialysis removes for 24 hours
Extra D-Gal, the sea-mussel mucin for being lyophilized to modify.
8. a kind of orthopaedics adhesive is the adhesive product made using according to claim 1-7 adhesive kit,
Wherein sea-mussel mucin, Tween 80, BMP-2 with the concentration that 5% acetum is prepared be 1.5mg/mL, 9 mg/mL, 0.75
mg/mL。
9. any one of -7 adhesive kit or adhesive according to claim 8 are in preparation treatment bone according to claim 1
Application in the medicament of folding.
10. application according to claim 9, the fracture is complete fracture, it is preferable that is helicity, comminuted or compressibility
Fracture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910793366.1A CN110368519B (en) | 2019-08-26 | 2019-08-26 | Orthopedic adhesive based on mussel mucin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910793366.1A CN110368519B (en) | 2019-08-26 | 2019-08-26 | Orthopedic adhesive based on mussel mucin |
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| CN110368519B CN110368519B (en) | 2021-09-21 |
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| CN110882424A (en) * | 2019-12-13 | 2020-03-17 | 浙江瑞谷生物科技有限公司 | Oral cavity guided bone regeneration barrier membrane |
| CN110882424B (en) * | 2019-12-13 | 2021-07-06 | 浙江瑞谷生物科技有限公司 | Oral cavity guided bone regeneration barrier membrane |
| CN117447611A (en) * | 2023-12-26 | 2024-01-26 | 英特菲尔(成都)生物制品有限责任公司 | Recombinant mussel mucin with natural activity and preparation method and application thereof |
| CN117447611B (en) * | 2023-12-26 | 2024-04-05 | 英特菲尔(成都)生物制品有限责任公司 | Recombinant mussel mucin with natural activity and preparation method and application thereof |
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