CN112206354A - Polycaprolactone/nano-hydroxyapatite-citric acid composite material and patch absorbable memory elastic ring - Google Patents
Polycaprolactone/nano-hydroxyapatite-citric acid composite material and patch absorbable memory elastic ring Download PDFInfo
- Publication number
- CN112206354A CN112206354A CN202011079825.9A CN202011079825A CN112206354A CN 112206354 A CN112206354 A CN 112206354A CN 202011079825 A CN202011079825 A CN 202011079825A CN 112206354 A CN112206354 A CN 112206354A
- Authority
- CN
- China
- Prior art keywords
- citric acid
- hydroxyapatite
- nano
- polycaprolactone
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 115
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 229960004106 citric acid Drugs 0.000 claims description 95
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000000725 suspension Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003517 fume Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000002074 melt spinning Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 210000004204 blood vessel Anatomy 0.000 abstract description 5
- 210000000683 abdominal cavity Anatomy 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 210000000056 organ Anatomy 0.000 abstract description 4
- 230000007850 degeneration Effects 0.000 abstract description 3
- 210000001519 tissue Anatomy 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 7
- 241000700159 Rattus Species 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 206010021620 Incisional hernias Diseases 0.000 description 4
- 230000003187 abdominal effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- 206010019909 Hernia Diseases 0.000 description 3
- 206010061218 Inflammation Diseases 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000004054 inflammatory process Effects 0.000 description 3
- 210000004303 peritoneum Anatomy 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000001356 surgical procedure Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 210000003815 abdominal wall Anatomy 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 1
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 1
- 208000029836 Inguinal Hernia Diseases 0.000 description 1
- 208000008081 Intestinal Fistula Diseases 0.000 description 1
- 206010022678 Intestinal infections Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010029113 Neovascularisation Diseases 0.000 description 1
- 208000035965 Postoperative Complications Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 210000002744 extracellular matrix Anatomy 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 230000028709 inflammatory response Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 230000002980 postoperative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- 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
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
-
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/34—Materials or treatment for tissue regeneration for soft tissue reconstruction
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Public Health (AREA)
- Dermatology (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Veterinary Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a polycaprolactone/nano-hydroxyapatite-citric acid composite material and a patch absorbable memory elastic ring. The polycaprolactone/nano-hydroxyapatite-citric acid composite material can be used for preparing a Kugel patch with an absorbable memory elastic ring, changes the non-absorbable material of the memory elastic ring of the current Kugel patch, and gradually absorbs the elastic ring after several months of operation, so that the advantages of the current Kugel patch can be kept, the defects of damages to organs, blood vessels and the like in the abdominal cavity caused by degeneration and fracture of the memory elastic ring can be avoided, and the application prospect is good.
Description
Technical Field
The invention relates to the technical field of patches, in particular to a polycaprolactone/nano-hydroxyapatite-citric acid composite material and an absorbable memory elastic ring of a patch.
Background
At present, the Kugel patch is mainly applied to inguinal hernia and abdominal incisional hernia operation, particularly abdominal incisional hernia, part of patients have large hernia sacs, the defect repair difficulty is high, and the patch with high support strength is often required to prevent the hernia sacs and displacement. The Kugel patch is mainly different from other patches in that the Kugel patch is provided with a memory elastic ring, and the memory elastic ring has the function of enabling the patch to be more easily unfolded and laid flat in an operation, so that the Kugel patch is few in suture, easy to fix, convenient to operate and low in recurrence rate. The Kugel patch applied to abdominal incisional hernia at present is an absorbable elastic ring patch, a memory elastic ring is not absorbable, and the material of the Kugel patch can be gradually denatured and even broken along with the passage of time to damage organs, blood vessels and the like in an abdominal cavity, so that intestinal fistula, infection and heavy bleeding are caused, and serious patients can even endanger life. Similar reports are made at home and abroad. Generally speaking, several months after the hernia repair, the surrounding tissue has grown completely into the patch, and the patch does not need the fixing and supporting function of the memory elastic ring. If the memory elastic ring is made of an absorbable material and is gradually absorbed for months after operation, the advantages of the conventional Kugel patch can be kept, and the defects of damages to organs, blood vessels and the like in the abdominal cavity caused by degeneration and fracture of the memory elastic ring can be avoided.
The absorbable elastic ring patch is made of materials such as polycaprolactone and the like, so that the non-absorbable material of the conventional Kugel patch is thoroughly changed, a series of postoperative complications are avoided, the advantages of the conventional Kugel patch are retained, and the absorbable elastic ring patch is mainly applied to repair of abdominal incisional hernia.
Disclosure of Invention
Aiming at the conditions of the prior art, the invention aims to provide a polycaprolactone/nano-hydroxyapatite-citric acid composite material and a patch prepared from the material and capable of absorbing memory elastic rings
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the polycaprolactone/nano-hydroxyapatite-citric acid composite material comprises the following steps:
1) adding nano hydroxyapatite into deionized water/ethanol solution, and performing ultrasonic treatment for 1-1.5h to obtain nano hydroxyapatite suspension with the concentration of 0.01 g/mL;
2) dissolving citric acid monohydrate into deionized water/ethanol solution to obtain citric acid solution with concentration of 0.001-0.005g/mL, and adjusting pH value of the citric acid solution to 7-8 with NaOH solution;
3) dropwise adding the citric acid solution with the pH adjusted in the step 2) into the nano-hydroxyapatite suspension in the step 1), and stirring for 3-3.5 hours in a constant-temperature magnetic stirring oil bath;
4) washing the product obtained in the step 3) with ethanol for several times, centrifuging, collecting the solid, and drying to obtain surface-modified nano hydroxyapatite-citric acid powder;
5) weighing polycaprolactone, dissolving the polycaprolactone in dichloromethane to obtain a polycaprolactone solution with the concentration of 0.1g/mL, and dissolving for 6 hours to a uniform state;
6) pouring the weighed nano hydroxyapatite-citric acid powder into dichloromethane, ultrasonically dispersing for 30-40min to obtain a nano hydroxyapatite-citric acid suspension with the concentration of 3mg/mL, and breaking up soft aggregates of the nano hydroxyapatite-citric acid powder by mechanical energy generated by an ultrasonic cleaning machine, so that the nano hydroxyapatite-citric acid powder can be uniformly dispersed in a PCL matrix at the later stage;
7) dropwise adding the nano-hydroxyapatite-citric acid suspension obtained in the step 6) into the polycaprolactone solution obtained in the step 5) in a fume hood, and stirring for 2-2.5 hours on a magnetic stirrer to obtain a polycaprolactone/nano-hydroxyapatite-citric acid mixed solution;
8) pouring the mixed solution of polycaprolactone/nano-hydroxyapatite-citric acid on a dining board in a fume hood, after dichloromethane is completely volatilized, obtaining a polycaprolactone/nano-hydroxyapatite-citric acid composite material which is marked as a PCL/HAP-CA composite material, drying the composite material in a vacuum drying oven at 35 ℃ for at least 24 hours, and storing for later use;
9) placing the PCL/HAP-CA composite material into liquid nitrogen for quick freezing, crushing by a crusher, adding the material conveniently from a feed inlet with the diameter of 1cm, and drying in a vacuum drying oven at 40 ℃ for 24 hours;
10) and carrying out melt spinning on the PCL/HAP-CA composite material.
In the steps 1) and 2), the volume ratio of the deionized water to the ethanol in the deionized water/ethanol solution is 8: 2.
And 2) the molar concentration of the NaOH solution in the step 2) is 2M.
In the step 3), the temperature is set to be 34-38 ℃, and the rotation speed is 500-.
In the step 4), the centrifugal rotating speed is 5500-.
In the step 7), the volume ratio of the nano-hydroxyapatite-citric acid suspension to the polycaprolactone solution in the obtained polycaprolactone/nano-hydroxyapatite-citric acid mixed solution is 1: 3.
The drying temperature of the step 8) is 35 ℃, and the drying time is not less than 24 h; the drying temperature of the step 9) is 40 ℃, and the drying time is not less than 24 h.
And step 10) in the process of melt spinning the PCL/HAP-CA composite material, selecting the spinning temperature of 190-.
The Kugel patch with the absorbable memory elastic ring is characterized in that the absorbable memory elastic ring is made of the polycaprolactone/nano-hydroxyapatite-citric acid composite material.
Compared with the prior art, the invention has the following beneficial effects: the Kugel patch with the absorbable memory elastic ring is made of the polycaprolactone/nano-hydroxyapatite-citric acid composite material, the non-absorbable material of the memory elastic ring of the current Kugel patch is changed, and the elastic ring is gradually absorbed after several months of operation, so that the advantages of the current Kugel patch can be kept, the defects of damages to organs, blood vessels and the like in the abdominal cavity caused by degeneration and breakage of the memory elastic ring can be avoided, and the Kugel patch has a good application prospect.
Drawings
The invention will be further explained with reference to the drawings and the detailed description below:
fig. 1 is a schematic diagram of a patch structure.
FIG. 2 is a graph showing the results of the general observation experiment in example 1, wherein a, b, c and d represent the form of the elastic force ring and the surrounding tissues at 1, 3, 6 and 8 months after the operation, respectively.
FIG. 3 is a graph showing the results of the histopathological observation experiment in example 1, wherein a, b, c, and d represent the inflammatory response of the surrounding tissue, the neovascularization, the fibroblasts, and the extracellular matrix deposition (HEX400) at 1, 3, 6, and 8 months after the operation, respectively.
FIG. 4 is the result of the experiment of example 1, wherein a, b, c, d show the surface absorption and proliferation of peripheral cells of the elastic ring at 1, 3, 6, 8 months after operation.
Detailed Description
Preparation of polycaprolactone/nano-hydroxyapatite-citric acid (PCL/HAP-CA) composite material
1) Adding 0.10g of nano-hydroxyapatite into 10ml of deionized water/ethanol (8:2v/v) solution, and carrying out ultrasonic treatment for 1-1.5h to obtain nano-hydroxyapatite suspension;
2) dissolving 0.01-0.05g of citric acid monohydrate into 10ml of deionized water/ethanol (8:2v/v) solution, adding 2M NaOH solution, and adjusting the pH value of the solution to be 7-8;
3) dropwise adding the solution obtained in the step 2) into the nano hydroxyapatite suspension liquid obtained in the step 1), and stirring for 3-3.5h in a constant-temperature magnetic stirring oil bath at the temperature of 34-38 ℃ and the rotating speed of 500-;
4) washing the product obtained in the step 3) with ethanol for several times, centrifuging for 15-20min in a centrifuge at the speed of 5500-6500r/min, collecting the solid, and drying in a vacuum drying oven at 60-65 ℃ for at least 24h to obtain surface-modified nano hydroxyapatite-citric acid powder;
5) weighing a certain amount of polycaprolactone, dissolving the polycaprolactone in dichloromethane to obtain a polycaprolactone solution with the concentration of 0.1g/mL, and dissolving for 6 hours to a uniform state;
6) weighing nano hydroxyapatite-citric acid powder with the mass according to the corresponding proportion, pouring the nano hydroxyapatite-citric acid powder into a certain amount of dichloromethane (3mg/mL), performing ultrasonic dispersion for 30-40min to obtain a nano hydroxyapatite-citric acid suspension with the concentration of 3mg/mL, and breaking up soft aggregates of the nano hydroxyapatite-citric acid powder by using mechanical energy generated by an ultrasonic cleaning machine, so that the nano hydroxyapatite-citric acid powder can be uniformly dispersed in a PCL matrix at the later stage;
7) dropwise adding the nano-hydroxyapatite-citric acid suspension obtained in the step 6) into the polycaprolactone solution obtained in the step 5) in a fume hood, and stirring for 2-2.5 hours on a magnetic stirrer to obtain a polycaprolactone/nano-hydroxyapatite-citric acid mixed solution;
8) pouring the polycaprolactone/nano-hydroxyapatite-citric acid mixed solution on a dining plate in a fume hood according to the volume ratio of 1:3 of the nano-hydroxyapatite-citric acid suspension to the polycaprolactone solution, after dichloromethane is completely volatilized, obtaining a polycaprolactone/nano-hydroxyapatite-citric acid composite material (PCL/HAP-CA), putting the polycaprolactone/nano-hydroxyapatite-citric acid composite material into a vacuum drying oven, drying at 35 ℃ for at least 24 hours, and storing for later use;
10) placing the PCL/HAP-CA composite material into liquid nitrogen for quick freezing, crushing by a crusher to facilitate adding the material from a feed inlet with the diameter of 1cm, and drying the sample in a vacuum drying oven at 40 ℃ for 24 hours;
11) and (3) carrying out melt spinning on the PCL/HAP-CA composite material: according to the rheological test result, the spinning temperature is 190-.
The polycaprolactone/nano-hydroxyapatite-citric acid composite material is used for preparing a Kugel patch with an elastic ring, and the Kugel patch with an absorbable memory elastic ring is further obtained.
Example 1
Preparation of polycaprolactone/nano-hydroxyapatite-citric acid (PCL/HAP-CA) composite material
1) Adding 0.10g of nano hydroxyapatite into 10ml of deionized water/ethanol (8:2v/v) solution, and carrying out ultrasonic treatment for 1h to obtain nano hydroxyapatite suspension;
2) dissolving 0.01g of citric acid monohydrate into 10ml of deionized water/ethanol (8:2v/v) solution, adding 2M NaOH solution, and adjusting the pH value of the solution to 7;
3) dropwise adding the solution obtained in the step 2) into the nano hydroxyapatite suspension in the step 1), and stirring for 3 hours in a constant-temperature magnetic stirring oil bath kettle at the temperature of 34 ℃ and the rotating speed of 00 r/min;
4) washing the product obtained in the step 3) with ethanol for several times, centrifuging the product in a centrifuge at a speed of 5500r/min for 20min, collecting solids, and drying the solids in a vacuum drying oven at the temperature of 60 ℃ for 24h to obtain surface-modified nano hydroxyapatite-citric acid powder;
5) weighing a certain amount of polycaprolactone, dissolving the polycaprolactone in dichloromethane to obtain a polycaprolactone solution with the concentration of 0.1g/mL, and dissolving for 6 hours to a uniform state;
6) weighing nano hydroxyapatite-citric acid powder with the mass according to the corresponding proportion, pouring the nano hydroxyapatite-citric acid powder into a certain amount of dichloromethane (3mg/mL), performing ultrasonic dispersion for 30min to obtain a nano hydroxyapatite-citric acid suspension with the concentration of 3mg/mL, and breaking up soft aggregates of the nano hydroxyapatite-citric acid powder by using mechanical energy generated by an ultrasonic cleaner, so that the nano hydroxyapatite-citric acid powder can be uniformly dispersed in a PCL matrix at the later stage;
7) dropwise adding the nano-hydroxyapatite-citric acid suspension obtained in the step 6) into the polycaprolactone solution obtained in the step 5) in a fume hood, and stirring for 2 hours on a magnetic stirrer to obtain a polycaprolactone/nano-hydroxyapatite-citric acid mixed solution;
8) pouring the polycaprolactone/nano-hydroxyapatite-citric acid mixed solution on a dining plate in a fume hood according to the volume ratio of 1:3 of the nano-hydroxyapatite-citric acid suspension to the polycaprolactone solution, after dichloromethane is completely volatilized, obtaining a polycaprolactone/nano-hydroxyapatite-citric acid composite material (PCL/HAP-CA), putting the polycaprolactone/nano-hydroxyapatite-citric acid composite material into a vacuum drying oven, drying for 24 hours at 35 ℃, and storing for later use;
10) placing the PCL/HAP-CA composite material into liquid nitrogen for quick freezing, crushing by a crusher to facilitate adding the material from a feed inlet with the diameter of 1cm, and drying the sample in a vacuum drying oven at 40 ℃ for 24 hours;
11) and (3) carrying out melt spinning on the PCL/HAP-CA composite material: according to the rheological test result, the spinning temperature is 190 ℃, the rotating speed of a double screw is 20r/min, the stirring time is 30min, the PCL/HAP-CA composite material is melt extruded to obtain nascent fiber, and the pyrolysis temperature of the material is more than 350 ℃.
Example 2
Preparation of polycaprolactone/nano-hydroxyapatite-citric acid (PCL/HAP-CA) composite material
1) Adding 0.10g of nano hydroxyapatite into 10ml of deionized water/ethanol (8:2v/v) solution, and carrying out ultrasonic treatment for 1.5h to obtain nano hydroxyapatite suspension;
2) dissolving 0.05g of citric acid monohydrate into 10ml of deionized water/ethanol (8:2v/v) solution, adding 2M NaOH solution, and adjusting the pH value of the solution to 8;
3) dropwise adding the solution obtained in the step 2) into the nano hydroxyapatite suspension liquid obtained in the step 1), and stirring for 3.5 hours in a constant-temperature magnetic stirring oil bath kettle at the temperature of 38 ℃ and the rotating speed of 500 r/min;
4) washing the product obtained in the step 3) with ethanol for several times, centrifuging for 15min in a centrifuge at the speed of 6500r/min, collecting solids, and drying in a vacuum drying oven at 65 ℃ for 24h to obtain surface-modified nano hydroxyapatite-citric acid powder;
5) weighing a certain amount of polycaprolactone, dissolving the polycaprolactone in dichloromethane to obtain a polycaprolactone solution with the concentration of 0.1g/mL, and dissolving for 6 hours to a uniform state;
6) weighing nano hydroxyapatite-citric acid powder with the mass according to the corresponding proportion, pouring the nano hydroxyapatite-citric acid powder into a certain amount of dichloromethane (3mg/mL), performing ultrasonic dispersion for 40min to obtain a nano hydroxyapatite-citric acid suspension with the concentration of 3mg/mL, and breaking up soft aggregates of the nano hydroxyapatite-citric acid powder by using mechanical energy generated by an ultrasonic cleaning machine, so that the nano hydroxyapatite-citric acid powder can be uniformly dispersed in a PCL matrix at the later stage;
7) dropwise adding the nano-hydroxyapatite-citric acid suspension obtained in the step 6) into the polycaprolactone solution obtained in the step 5) in a fume hood, and stirring for 2.5 hours on a magnetic stirrer to obtain a polycaprolactone/nano-hydroxyapatite-citric acid mixed solution;
8) pouring the polycaprolactone/nano-hydroxyapatite-citric acid mixed solution on a dining plate in a fume hood according to the volume ratio of 1:3 of the nano-hydroxyapatite-citric acid suspension to the polycaprolactone solution, after dichloromethane is completely volatilized, obtaining a polycaprolactone/nano-hydroxyapatite-citric acid composite material (PCL/HAP-CA), putting the polycaprolactone/nano-hydroxyapatite-citric acid composite material into a vacuum drying oven, drying for 24 hours at 35 ℃, and storing for later use;
10) placing the PCL/HAP-CA composite material into liquid nitrogen for quick freezing, crushing by a crusher to facilitate adding the material from a feed inlet with the diameter of 1cm, and drying the sample in a vacuum drying oven at 40 ℃ for 24 hours;
11) and (3) carrying out melt spinning on the PCL/HAP-CA composite material: according to the rheological test result, the spinning temperature is 195 ℃, the rotating speed of a double screw is 25r/min, the stirring time is 35min, the PCL/HAP-CA composite material is melt extruded to obtain nascent fiber, and the pyrolysis temperature of the material is more than 350 ℃.
Example 3
Preparation of polycaprolactone/nano-hydroxyapatite-citric acid (PCL/HAP-CA) composite material
1) Adding 0.10g of nano hydroxyapatite into 10ml of deionized water/ethanol (8:2v/v) solution, and carrying out ultrasonic treatment for 1h to obtain nano hydroxyapatite suspension;
2) dissolving 0.03g of citric acid monohydrate into 10ml of deionized water/ethanol (8:2v/v) solution, adding 2M NaOH solution, and adjusting the pH value of the solution to 7.5;
3) dropwise adding the solution obtained in the step 2) into the nano hydroxyapatite suspension liquid obtained in the step 1), and stirring for 3 hours in a constant-temperature magnetic stirring oil bath kettle, wherein the temperature is set to be 35 ℃, and the rotating speed is 500 r/min;
4) washing the product obtained in the step 3) with ethanol for several times, centrifuging for 15min in a centrifuge at the speed of 6000r/min, collecting solids, and drying in a vacuum drying oven at 60 ℃ for at least 24h to obtain surface-modified nano-hydroxyapatite-citric acid powder;
5) weighing a certain amount of polycaprolactone, dissolving the polycaprolactone in dichloromethane to obtain a polycaprolactone solution with the concentration of 0.1g/mL, and dissolving for 6 hours to a uniform state;
6) weighing nano hydroxyapatite-citric acid powder with the mass according to the corresponding proportion, pouring the nano hydroxyapatite-citric acid powder into a certain amount of dichloromethane (3mg/mL), performing ultrasonic dispersion for 30min to obtain a nano hydroxyapatite-citric acid suspension with the concentration of 3mg/mL, and breaking up soft aggregates of the nano hydroxyapatite-citric acid powder by using mechanical energy generated by an ultrasonic cleaner, so that the nano hydroxyapatite-citric acid powder can be uniformly dispersed in a PCL matrix at the later stage;
7) dropwise adding the nano-hydroxyapatite-citric acid suspension obtained in the step 6) into the polycaprolactone solution obtained in the step 5) in a fume hood, and stirring for 2 hours on a magnetic stirrer to obtain a polycaprolactone/nano-hydroxyapatite-citric acid mixed solution;
8) pouring the polycaprolactone/nano-hydroxyapatite-citric acid mixed solution on a dining plate in a fume hood according to the volume ratio of 1:3 of the nano-hydroxyapatite-citric acid suspension to the polycaprolactone solution, after dichloromethane is completely volatilized, obtaining a polycaprolactone/nano-hydroxyapatite-citric acid composite material (PCL/HAP-CA), putting the polycaprolactone/nano-hydroxyapatite-citric acid composite material into a vacuum drying oven, drying for 24 hours at 35 ℃, and storing for later use;
10) placing the PCL/HAP-CA composite material into liquid nitrogen for quick freezing, crushing by a crusher to facilitate adding the material from a feed inlet with the diameter of 1cm, and drying the sample in a vacuum drying oven at 40 ℃ for 24 hours;
11) and (3) carrying out melt spinning on the PCL/HAP-CA composite material: according to the rheological test result, the spinning temperature is 190 ℃, the rotating speed of a double screw is 20r/min, the stirring time is 30-35min, the PCL/HAP-CA composite material is melt extruded to obtain nascent fiber, and the pyrolysis temperature of the material is more than 350 ℃.
Experimental example 1
Animal experiments
The PCL/HAP-CA composite material is ground into absorbable elastic rings (cut off, the diameter is 1.5mm, the length is 20mm) and buried in the preperitoneal gaps of rats, and the elastic rings and surrounding tissues are taken for pathological examination (gross grade, histopathological examination and transmission electron microscope examination) respectively at 1, 3, 6 and 8 months after the operation.
1. General observation
1 month post-operation (fig. 2 a): the elastic ring is wrapped by a small amount of surrounding tissues, the elastic ring is not deformed, and the surrounding tissues are not punctured and the peritoneum penetrates through the abdominal wall; 3 months post-surgery (fig. 2 b): the elastic ring is cut off and is basically integrated with host tissues, the elastic ring is not deformed, and peripheral tissues are not punctured, and the peritoneum penetrates through the abdominal wall; post-operative 6 months (fig. 2 c): the elastic ring is completely integrated with host tissues after being cut off, and is deformed and not broken. 8 months post-surgery (fig. 2 d): the elastic ring is cut off and tightly adhered to the surrounding tissues, and the elastic ring is cut off and broken but does not puncture the surrounding tissues and peritoneum.
2. Tissue pathology
The tissue can show mild inflammatory reaction after 1-3 months of operation, the inflammation gradually subsides along with the prolonging of time, and no inflammatory reaction exists at all in 8 months after the operation; the deposition of collagen is gradually increased, obvious collagen regeneration deposition can be seen in 3 months, and the collagen deposition is increased and aged along with the change of time and is arranged in sequence; with time, new blood vessels increased, and no significant changes were observed after 3 months of surgery (fig. 3).
3. Electron microscope
The surface of the elastic ring is not obviously absorbed and dissolved within 3 months after the operation, and is gradually absorbed along with the time, and the absorption becomes obvious from 6 months. A small amount of surrounding tissue proliferated at 1 month, and over time, the surrounding tissue proliferated significantly, gradually covering the tissue surface (fig. 4).
Experimental example 2
Viscosity test experiment of elastic ring
Grinding PCL/HAP-CA composite material into absorbable elastic ring
Respectively measuring the flow-out time t at 25 deg.C and 0.1 deg.C0(blank solvent) and tr(sample liquid), six times each, taking the average (the difference between the two readings must not exceed 0.2s), and then calculating the relative viscosity: etar＝tr/t0Specific viscosity etasp＝ηr-1。
TABLE 1
Determining the relative viscosity eta of the sample liquidrAnd specific viscosity ηspIntrinsic viscosity was calculated as follows:
TABLE 2 intrinsic viscosity/100 ml g－
| A | B | C | D | E | F | G |
| 13.49 | 11.22 | 7.07 | 6.63 | 6 | 5 | 4 |
Note: samples a, B, C, D, E, F, G are the degradation time of the elastic ring in rats for 0 weeks, 4 weeks, 8 weeks, 12 weeks, 16 weeks, 18 weeks, 22 weeks, 26 weeks, respectively.
The experimental results are as follows: the viscosity of the sample was seen to decrease in the rat body over time by testing.
Experimental example 3
Micro tensile test of elastic ring
Grinding PCL/HAP-CA composite material into absorbable elastic ring
Adopting an electronic universal tensile testing machine to test the tensile property, wherein the length of a sample is as follows: 15.76mm, thickness: 1.42mm, and a drawing speed of 10 mm/min.
TABLE 3 maximum load of the elastic ring
| A | B | C | D | E | F | G | H |
| 38.7N | 37N | 36.4N | 33.5N | 31.8N | 31.1N | 25N | 23.9N |
A, B, C, D, E, F and G are maximum load values of the degradation time of the circular ring in rats of 0 week, 4 weeks, 8 weeks, 12 weeks, 16 weeks, 18 weeks, 22 weeks and 26 weeks respectively.
Table 4 tensile strength values for the elastic ring.
| A | B | C | D | E | F | G | H |
| 1.73Mpa | 1.65Mpa | 1.63Mpa | 1.50Mpa | 1.42Mpa | 1.39Mpa | 1.12Mpa | 1.07Mpa |
A, B, C, D, E, F and G are tensile strengths of 0 week, 4 weeks, 8 weeks, 12 weeks, 16 weeks, 18 weeks, 22 weeks and 26 weeks of degradation time of the elastic ring in rats respectively.
From the above results, it was found that the elastic ring was gradually degraded in the rat body with time, and the tensile strength was gradually decreased.
The foregoing is directed to embodiments of the present invention, and equivalents, modifications, substitutions and variations such as will occur to those skilled in the art, which fall within the scope and spirit of the appended claims.
Claims (10)
1. The preparation method of the polycaprolactone/nano-hydroxyapatite-citric acid composite material is characterized by comprising the following steps: which comprises the following steps:
1) adding nano hydroxyapatite into deionized water/ethanol solution, and performing ultrasonic treatment for 1-1.5h to obtain nano hydroxyapatite suspension with the concentration of 0.01 g/mL;
2) dissolving citric acid monohydrate into deionized water/ethanol solution to obtain citric acid solution with concentration of 0.001-0.005g/mL, and adjusting pH value of the citric acid solution to 7-8 with NaOH solution;
3) dropwise adding the citric acid solution with the pH adjusted in the step 2) into the nano-hydroxyapatite suspension in the step 1), and stirring for 3-3.5 hours in a constant-temperature magnetic stirring oil bath;
4) washing the product obtained in the step 3) with ethanol for several times, centrifuging, collecting the solid, and drying to obtain surface-modified nano hydroxyapatite-citric acid powder;
5) weighing polycaprolactone and dissolving the polycaprolactone in dichloromethane to obtain a polycaprolactone solution with the concentration of 0.1 g/mL;
6) weighing nano hydroxyapatite-citric acid powder, pouring into dichloromethane, and ultrasonically dispersing for 30-40min to obtain nano hydroxyapatite-citric acid suspension;
7) dropwise adding the nano-hydroxyapatite-citric acid suspension obtained in the step 6) into the polycaprolactone solution obtained in the step 5) in a fume hood, and stirring for 2-2.5 hours on a magnetic stirrer to obtain a polycaprolactone/nano-hydroxyapatite-citric acid mixed solution;
8) pouring the polycaprolactone/nano-hydroxyapatite-citric acid mixed solution on a dining plate in a fume hood, and after dichloromethane is completely volatilized, obtaining a polycaprolactone/nano-hydroxyapatite-citric acid composite material which is marked as a PCL/HAP-CA composite material, and drying for later use;
9) placing the PCL/HAP-CA composite material into liquid nitrogen for quick freezing, and then crushing the PCL/HAP-CA composite material by using a crusher and drying the crushed PCL/HAP-CA composite material;
10) and carrying out melt spinning on the PCL/HAP-CA composite material.
2. The preparation method of the polycaprolactone/nano-hydroxyapatite-citric acid composite material according to claim 1, characterized in that: in the steps 1) and 2), the volume ratio of deionized water to ethanol in the deionized water/ethanol solution is 8:2, and the molar concentration of the NaOH solution in the step 2) is 2M.
3. The preparation method of the polycaprolactone/nano-hydroxyapatite-citric acid composite material according to claim 1, characterized in that: in the step 3), the temperature is set to be 34-38 ℃, and the rotation speed is 500-.
4. The preparation method of the polycaprolactone/nano-hydroxyapatite-citric acid composite material according to claim 1, characterized in that: in the step 4), the centrifugal rotating speed is 5500-.
5. The preparation method of the polycaprolactone/nano-hydroxyapatite-citric acid composite material according to claim 1, characterized in that: in the step 7), the volume ratio of the nano-hydroxyapatite-citric acid suspension to the polycaprolactone solution in the obtained polycaprolactone/nano-hydroxyapatite-citric acid mixed solution is 1: 3.
6. The preparation method of the polycaprolactone/nano-hydroxyapatite-citric acid composite material according to claim 1, characterized in that: the drying temperature of the step 8) is 35 ℃, and the drying time is not less than 24 h; the drying temperature of the step 9) is 40 ℃, and the drying time is not less than 24 h.
7. The preparation method of the polycaprolactone/nano-hydroxyapatite-citric acid composite material according to claim 1, characterized in that: in the step 10), the spinning temperature is 190-.
8. The polycaprolactone/nano-hydroxyapatite-citric acid composite material obtained by the method according to any one of claims 1 to 7.
9. Use of the polycaprolactone/nanohydroxyapatite-citric acid composite material according to claim 8 in a patch.
10. A patch absorbable memory elastic ring is characterized in that: which is prepared from the polycaprolactone/nano-hydroxyapatite-citric acid composite material of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011079825.9A CN112206354A (en) | 2020-10-10 | 2020-10-10 | Polycaprolactone/nano-hydroxyapatite-citric acid composite material and patch absorbable memory elastic ring |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011079825.9A CN112206354A (en) | 2020-10-10 | 2020-10-10 | Polycaprolactone/nano-hydroxyapatite-citric acid composite material and patch absorbable memory elastic ring |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112206354A true CN112206354A (en) | 2021-01-12 |
Family
ID=74053144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011079825.9A Pending CN112206354A (en) | 2020-10-10 | 2020-10-10 | Polycaprolactone/nano-hydroxyapatite-citric acid composite material and patch absorbable memory elastic ring |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112206354A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112914785A (en) * | 2021-03-19 | 2021-06-08 | 百迈思(重庆)医疗科技有限公司 | Hernia patch |
| CN116515269A (en) * | 2023-07-03 | 2023-08-01 | 汕头市雷氏塑化科技有限公司 | Superfine bamboo powder modified biodegradable polyester and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626861A (en) * | 1994-04-01 | 1997-05-06 | Massachusetts Institute Of Technology | Polymeric-hydroxyapatite bone composite |
| CN103387756A (en) * | 2013-07-30 | 2013-11-13 | 浙江微度医疗器械有限公司 | Modification method and application of hydroxyapatite |
| CN108210996A (en) * | 2016-12-14 | 2018-06-29 | 三维天工（北京）科技有限公司 | A kind of preparation method of high elastic and strength nanometer hydroxyapatite/polycaprolactone composite material |
| CN108221079A (en) * | 2017-12-20 | 2018-06-29 | 东华大学 | Nanometer hydroxyapatite polycaprolactone nanocrystal composite fibre and preparation method thereof |
-
2020
- 2020-10-10 CN CN202011079825.9A patent/CN112206354A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626861A (en) * | 1994-04-01 | 1997-05-06 | Massachusetts Institute Of Technology | Polymeric-hydroxyapatite bone composite |
| CN103387756A (en) * | 2013-07-30 | 2013-11-13 | 浙江微度医疗器械有限公司 | Modification method and application of hydroxyapatite |
| CN108210996A (en) * | 2016-12-14 | 2018-06-29 | 三维天工（北京）科技有限公司 | A kind of preparation method of high elastic and strength nanometer hydroxyapatite/polycaprolactone composite material |
| CN108221079A (en) * | 2017-12-20 | 2018-06-29 | 东华大学 | Nanometer hydroxyapatite polycaprolactone nanocrystal composite fibre and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112914785A (en) * | 2021-03-19 | 2021-06-08 | 百迈思(重庆)医疗科技有限公司 | Hernia patch |
| CN116515269A (en) * | 2023-07-03 | 2023-08-01 | 汕头市雷氏塑化科技有限公司 | Superfine bamboo powder modified biodegradable polyester and preparation method thereof |
| CN116515269B (en) * | 2023-07-03 | 2023-09-01 | 汕头市雷氏塑化科技有限公司 | Superfine bamboo powder modified biodegradable polyester and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112206354A (en) | Polycaprolactone/nano-hydroxyapatite-citric acid composite material and patch absorbable memory elastic ring | |
| CN1101405C (en) | Hyaluronic acid gel, process for producing same and medical material cotng. same | |
| Shishatskaya et al. | Degradation of P (3HB) and P (3HB-co-3HV) in biological media | |
| WO2015144056A1 (en) | Freeze-dried powder of high molecular weight silk fibroin, preparation method therefor and use thereof | |
| CN106479195A (en) | A kind of nano-cellulose strengthens fibroin albumen composite material and preparation method thereof | |
| CN102493021B (en) | A kind of preparation method of cellulose nanocrystal reinforced PHBV nanofiber | |
| Chen et al. | Study on the cross-linking effect of a natural derived oxidized chitosan oligosaccharide on the porcine acellular dermal matrix | |
| Varshosaz et al. | Effect of bassorin (derived from gum tragacanth) and halloysite nanotubes on physicochemical properties and the osteoconductivity of methylcellulose-based injectable hydrogels | |
| Liao et al. | Nano-chitin reinforced agarose hydrogels: Effects of nano-chitin addition and acidic gas-phase coagulation | |
| de Souza et al. | Effect of pH variation and crosslinker absence on the gelling mechanism of high acyl gellan: Morphological, thermal and mechanical approaches | |
| CN110698719A (en) | Preparation of polyvinyl alcohol-based hydrogel | |
| CN107638590B (en) | A kind of chitosan-based gradient biomimetic composite scaffold material and its construction method | |
| CN101693124B (en) | Preparation method of polylactic acid/chitosan/carbon fiber porous supports | |
| CN106928375A (en) | A kind of preparation method of aquagel | |
| Xu et al. | Preparation and characterization of mussel-inspired hydrogels based on methacrylated catechol-chitosan and dopamine methacrylamide | |
| Yuan et al. | A bioinspired injectable antioxidant hydrogel for prevention of postoperative adhesion | |
| CN109078228B (en) | Shape memory composite bone nail and preparation, use method and application thereof | |
| Jia et al. | One-pot synthesis of highly mechanical and redox-degradable polyurethane hydrogels based on tetra-PEG and disulfide/thiol chemistry | |
| Zhao et al. | Enhanced osteogenic and ROS-scavenging MXene nanosheets incorporated gelatin-based nanocomposite hydrogels for critical-sized calvarial defect repair | |
| Zhou et al. | Nanogel-electrospinning for controlling the release of water-soluble drugs | |
| CN107569722A (en) | A kind of chitin hydroxyapatite complex screw and preparation method thereof | |
| CN114561125A (en) | Preparation method of biodegradable starch-based film material | |
| CN113694256A (en) | Acellular matrix fiber and preparation method thereof | |
| Babicheva et al. | Influence of the salting-out agent nature on the strength properties of chitosan microtubes. | |
| CN101816805B (en) | Method for preparing bone tissue repairing material by using Arabic gum |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210112 |