CN115192762B - Medical composite material and preparation method and application thereof - Google Patents
Medical composite material and preparation method and application thereof Download PDFInfo
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- CN115192762B CN115192762B CN202210974361.0A CN202210974361A CN115192762B CN 115192762 B CN115192762 B CN 115192762B CN 202210974361 A CN202210974361 A CN 202210974361A CN 115192762 B CN115192762 B CN 115192762B
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- zirconium
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- based metal
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 73
- 239000013096 zirconium-based metal-organic framework Substances 0.000 claims abstract description 62
- 239000003814 drug Substances 0.000 claims abstract description 54
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 40
- 229940079593 drug Drugs 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000013110 organic ligand Substances 0.000 claims abstract description 22
- 150000003754 zirconium Chemical class 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- PTTPUWGBPLLBKW-UHFFFAOYSA-M sodium;2-[4-(2-methylpropyl)phenyl]propanoate Chemical compound [Na+].CC(C)CC1=CC=C(C(C)C([O-])=O)C=C1 PTTPUWGBPLLBKW-UHFFFAOYSA-M 0.000 claims description 20
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 17
- 235000010413 sodium alginate Nutrition 0.000 claims description 17
- 239000000661 sodium alginate Substances 0.000 claims description 17
- 229940005550 sodium alginate Drugs 0.000 claims description 17
- 238000009987 spinning Methods 0.000 claims description 15
- -1 2',5' -dimethyl-p-terphenyl dicarboxylic acid Chemical compound 0.000 claims description 14
- FZTIWOBQQYPTCJ-UHFFFAOYSA-N 4-[4-(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(O)=O)C=C1 FZTIWOBQQYPTCJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910007926 ZrCl Inorganic materials 0.000 claims description 7
- 229940124599 anti-inflammatory drug Drugs 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229920000858 Cyclodextrin Polymers 0.000 claims description 6
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002166 wet spinning Methods 0.000 claims description 6
- 229920002101 Chitin Polymers 0.000 claims description 5
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 claims description 5
- 229960003022 amoxicillin Drugs 0.000 claims description 5
- 239000002260 anti-inflammatory agent Substances 0.000 claims description 5
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000202 analgesic effect Effects 0.000 claims description 4
- 229940035676 analgesics Drugs 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000730 antalgic agent Substances 0.000 claims description 3
- 238000000578 dry spinning Methods 0.000 claims description 3
- 238000010041 electrostatic spinning Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 206010061218 Inflammation Diseases 0.000 abstract description 3
- 230000004054 inflammatory process Effects 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 abstract description 2
- 230000003467 diminishing effect Effects 0.000 abstract description 2
- 239000012567 medical material Substances 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000003110 anti-inflammatory effect Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001356 surgical procedure Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001760 anti-analgesic effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000005182 global health Effects 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/425—Porous materials, e.g. foams or sponges
-
- 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
-
- 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/44—Medicaments
-
- 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
-
- 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
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
-
- 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
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/005—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters containing a biologically active substance, e.g. a medicament or a biocide
-
- 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
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/06—At least partially resorbable materials
- A61L17/10—At least partially resorbable materials containing macromolecular materials
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/04—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of alginates
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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
- 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
- A61L2300/402—Anaestetics, analgesics, e.g. lidocaine
-
- 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
- A61L2300/404—Biocides, antimicrobial agents, antiseptic 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
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/41—Anti-inflammatory agents, e.g. NSAIDs
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Materials Engineering (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Textile Engineering (AREA)
- Hematology (AREA)
- Mechanical Engineering (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention relates to the field of medical materials, and discloses a medical composite material, and a preparation method and application thereof. The preparation method comprises the following steps: (1) Dissolving zirconium salt and an organic ligand in an organic solvent to obtain a mixed solution, then mixing the mixed solution with acetic acid, and then reacting at 100-150 ℃ for 22-28 hours to obtain a zirconium-based metal-organic framework material; (2) Soaking the zirconium-based metal-organic framework material in the solution in which the medicine is dissolved for 72-96 hours at 50-70 ℃ to obtain a metal-organic framework material loaded with the medicine; (3) The drug loaded metal-organic framework material is mixed with a solution containing a polymer and spun. The medical composite material has good biocompatibility and stability, can achieve the effects of diminishing inflammation and resisting bacteria, can not generate obvious side effects, and has good application prospect.
Description
Technical Field
The invention relates to the field of medical materials, in particular to a medical composite material and a preparation method and application thereof.
Background
With the diversification of diseases and the continuous development of medical technology, surgery plays an important role in medical treatment, and surgery has become an important component of global health care, and medical composite materials with anti-inflammatory and antibacterial effects have become a hot spot for current research. However, the conventional medical composite material has various disadvantages, such as poor tissue compatibility, and is generally prone to adverse effects such as rejection, inflammation, and tissue reactions with different degrees at the wound site.
The metal-organic framework Materials (MOFs) are porous crystal materials formed by self-assembling metal ions or metal clusters and organic ligands in a coordination mode, have the advantages of size adjustability, structural diversity, functional modifier, high porosity, large specific surface area and the like, and are often used as carriers of medicines for preparing medical composite materials. However, since most metal-organic framework materials are generally not acid-resistant, when the use environment of the medical composite material is acidic, the drug-carrying structure of the non-acid-resistant metal-organic framework material is easily damaged, so that the loaded drug is burst released, and research shows that excessive burst release can even cause poisoning, thereby causing safety problems. However, when the wound is inflamed, some colonies secrete acidic components, so that the overall environment is slightly acidic, and research and development of a drug delivery system with a slow release effect in an acidic environment are of great significance.
In addition, the fiber membrane obtained by adopting cyclodextrin, chitin and sodium alginate as spinning stock solution has the advantages of high strength, high biocompatibility and the like.
Disclosure of Invention
The invention aims to solve the problems of unstable drug release amount under acidic conditions, complex preparation process of medical composite materials and the like in the prior art by adopting a zirconium-based metal-organic framework material, and provides a medical composite material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides a method for preparing a medical composite material, the method comprising the steps of:
(1) Dissolving zirconium salt and an organic ligand in an organic solvent to obtain a mixed solution, then mixing the mixed solution with acetic acid, and then reacting for 20-30 hours at 100-150 ℃ to obtain a zirconium-based metal-organic framework material;
(2) Mixing the zirconium-based metal-organic framework material with the solution dissolved with the drug for 48-96 hours at 50-70 ℃ to obtain the zirconium-based metal-organic framework material loaded with the drug;
(3) Mixing the zirconium-based metal-organic framework material loaded with the drug with a solution containing a polymer, and then spinning;
wherein the molar ratio of the zirconium salt to the amount of the organic ligand is (0.9-1.2): 1;
the organic ligand is selected from one or more than two of 1, 4-di (4-carboxyphenyl) benzene, 2',5' -dimethyl-p-terphenyl dicarboxylic acid and (1, 1':4',1 '-triphenyl) -2', 4', 5' -tetracarboxylic acid.
Preferably, the zirconium salt is selected from ZrOCl 2 ·8H 2 O and/or ZrCl 4 。
Preferably, in the step (1), the molar concentration of zirconium ions in the mixed solution is 0.012 to 0.015mol/L.
Preferably, in step (1), the molar concentration of the organic ligand in the mixed solution is 0.012 to 0.015mol/L.
Preferably, the weight ratio of the zirconium-based metal-organic framework material to the drug is 1:2-8, preferably 1:4-5.
Preferably, the drug is an analgesic and/or an anti-inflammatory drug, the anti-inflammatory drug is amoxicillin, and the analgesic drug is sodium ibuprofen.
Preferably, the organic solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide.
Preferably, the concentration of the acetic acid is 99.5 to 99.99wt%.
Preferably, the molar ratio of acetic acid to zirconium salt is 1:9-10.
Preferably, in the solution containing the polymer, the polymer is selected from one or more of sodium alginate, cyclodextrin and chitin.
Preferably, the concentration of the polymer in the polymer-containing solution is 1 to 5wt%.
Preferably, the spinning method is selected from wet spinning, electrospinning or dry spinning.
The second aspect of the invention provides a medical composite material obtained by the preparation method.
The third aspect of the invention provides an application of the medical composite material in preparing medical gauze or medical suture.
The zirconium-based metal-organic framework material (Zr-MOF) prepared by the method has a porous structure, has good biocompatibility and stability, and can be used as a carrier of anti-inflammatory and antibacterial drugs for carrying out chemical drug treatment on patients. In addition, more importantly, when the medicine is released into an acidic environment, the zirconium-based metal-organic framework material loaded with the medicine still has a good slow release effect under the acidic condition, and can not generate obvious side effects while achieving the effects of diminishing inflammation and resisting bacteria, so that medical resources can be saved, and the zirconium-based metal-organic framework material has a good application prospect. Furthermore, the medical composite material prepared by the method has good physical and mechanical properties, can be well applied to medical gauze or medical suture, is simple and convenient to operate, safe, easy to obtain raw materials, mild in condition and has a great industrial application prospect.
Drawings
FIG. 1 is a photograph of a medical composite S1 prepared in example 1;
FIG. 2 is an XRD pattern of the zirconium-based metal-organic framework material C1 and the sodium ibuprofen-loaded zirconium-based metal-organic framework material D1 prepared in example 1;
fig. 3 is a graph showing the drug release profile of the sodium ibuprofen-loaded zirconium-based metal-organic framework material D1 prepared in example 1 in PBS solution at a temperature of 42 ℃ and a pH of 5.0.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention firstly provides a preparation method of a medical composite material, which is characterized by comprising the following steps:
(1) Dissolving zirconium salt and an organic ligand in an organic solvent to obtain a mixed solution, then mixing the mixed solution with acetic acid, and then reacting for 20-30 hours at 100-150 ℃ to obtain a zirconium-based metal-organic framework material;
(2) Mixing the zirconium-based metal-organic framework material with the solution dissolved with the drug for 48-96 hours at 50-70 ℃ to obtain the zirconium-based metal-organic framework material loaded with the drug;
(3) The drug-loaded zirconium-based metal-organic framework material is mixed with a solution containing a polymer and then spun.
In a specific embodiment, the molar ratio of the zirconium salt to the amount of the organic ligand is (0.9-1.2): 1, preferably (1-1.2): 1, more preferably 1.03:1. Specifically, the molar ratio of the zirconium salt to the amount of the organic ligand may be 1:1, 1.03:1, 1:1.5, 1:2, 1:2.5 or 1:3.
In the method of the invention, the zirconium-based metal-organic framework material has the chemical formula of Zr 3 (L) 3 Wherein L is an organic ligand. Different organic ligands and metal ions are selected to obtain metal-organic framework materials with different structures, so that different ligand types can be selected according to specific applications, and the zirconium-based metal-organic framework materials have different physicochemical properties. In order to control the molar ratio of the zirconium salt to the organic ligand, the structure or internal metal coordination of the obtained zirconium-based metal-organic framework material is different from that of the zirconium-based metal-organic framework material when the molar ratio of the zirconium salt to the organic ligand is changed within the range not limited by the invention.
In the method of the invention, the organic ligand is selected from one or more than two of 1, 4-di (4-carboxyphenyl) benzene, 2',5' -dimethyl-p-terphenyl dicarboxylic acid or (1, 1':4',1 '-triphenyl) -2', 4', 5' -tetracarboxylic acid. And the zirconium-based-metal organic framework material has good slow release effect under the acidic condition after carrying the medicine, so that the condition of burst release of the medicine is avoided.
In a specific embodiment, in step (1), the molar concentration of the organic ligand in the mixed solution is 0.012-0.015mol/L. Specifically, it may be 0.012mol/L, 0.0125mol/L, 0.013mol/L, 0.014mol/L or 0.015mol/L.
In a preferred embodiment, the zirconium salt is selected from ZrOCl 2 ·8H 2 O and/or ZrCl 4 。
In a specific embodiment, in step (1), the molar concentration of zirconium ions in the mixed solution is 0.012 to 0.015mol/L. Specifically, it may be 0.012mol/L, 0.01286mol/L, 0.013mol/L, 0.014mol/L or 0.015mol/L.
In a preferred embodiment, the organic solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide.
In a preferred embodiment, in step (1), in order to ensure that the zirconium salt and the organic ligand in the raw material are uniformly mixed in the organic solvent, the zirconium salt may be first dissolved in the organic solvent to obtain solution a, and the organic ligand may be dissolved in the organic solvent to obtain solution B, where the organic solvents selected from the solution a and the solution B are the same. Then mixing the solution A and the solution B to obtain a mixed solution, adding acetic acid into the mixed solution, and then performing solvothermal reaction to obtain the Zr-based metal-organic framework material.
In a specific embodiment, step (1) further comprises washing, centrifuging and drying the Zr-based metal-organic framework material obtained by the reaction in sequence.
In a specific embodiment, the concentration of acetic acid is 99.5 to 99.99wt%.
In a preferred embodiment, the molar ratio of acetic acid to Zr salt is in the range of 1:9 to 10. Specifically, it may be 1:9, 1:9.5, 1:9.8 or 1:10.
In the method of the invention, the drug is selected from anti-inflammatory and/or analgesic drugs.
In the method, the Zr-based metal-organic framework material has the advantages of simple synthesis steps, easily available raw materials, safe operation and mild conditions, and can be loaded with different types of analgesic and anti-inflammatory drugs according to specific purposes when the drugs are loaded, so as to prepare medical composite materials with different applications.
In a preferred embodiment, the anti-inflammatory agent is amoxicillin.
In a preferred embodiment, the analgesic is sodium ibuprofen.
In the method of the invention, the mass ratio of the Zr based metal-organic framework material to the drug is 1:2-8, preferably 1:4-5. Specifically, it may be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8.
In a specific embodiment, step (2) further comprises sequentially washing, centrifuging and drying the drug-loaded metal-organic framework material obtained after mixing.
In a preferred embodiment, the polymer is selected from one or more of sodium alginate, cyclodextrin and chitin in a solution containing the polymer.
In the method of the present invention, the concentration of the polymer in the polymer-containing solution needs to be strictly controlled within a proper range, and if the concentration of the polymer is too high or too low, a medical composite material cannot be obtained. When the concentration of the polymer is low, the material cannot be molded during spinning, and when the concentration of the polymer is high, the obtained fiber is too thick to be in a linear shape.
In a specific embodiment, the concentration of the polymer in the polymer-containing solution is 1 to 5wt%, preferably 3wt%. Specifically, the concentration of the polymer in the polymer-containing solution may be 1wt%, 2wt%, 3wt%, 4wt%, or 5wt%.
In the method, the type of the polymer in the spinning precursor solution can be selected so as to obtain medical composite materials with different physical forms, and the medical composite materials are more convenient to be applied to the preparation of medical gauze or medical suture.
Specifically, when the sodium alginate solution is selected to be mixed with the metal-organic framework material loaded with the medicine and then used as the spinning precursor solution, the film-shaped medical composite material can be finally obtained.
In a specific embodiment, when sodium alginate is used as the polymer in the precursor solution, it is necessary to use a solution of CaCl 2 Spinning in solution, ca 2+ Can play a role in fixing the form of sodium alginate, and finally, the linear medical composite material is obtained by spinning.
When the cyclodextrin solution is selected to be mixed with the metal-organic framework material loaded with the medicine and then used as the spinning precursor solution, the fiber film sheet-shaped medical composite material can be finally obtained.
When the chitin solution is selected to be mixed with the metal-organic framework material loaded with the medicine and then used as the spinning precursor solution, the fiber-shaped medical composite material can be finally obtained.
In the method of the present invention, the spinning method is selected from wet spinning, electrostatic spinning or dry spinning.
The invention also provides the medical composite material obtained by adopting the preparation method.
The invention further provides application of the medical composite material in preparing medical gauze or medical suture.
In the method, the zirconium-based metal-organic framework material is prepared by selecting a specific organic ligand and zirconium salt, has a large specific surface area and a porous structure, has good biocompatibility, can be automatically biodegraded, can be very well used for loading medicines, is combined with medicines with specific functions to obtain the zirconium-based metal-organic framework material loaded with medicines, has high medicine loading capacity, has no influence on the medicine release amount in organisms, and can play a very good slow release role when the use environment of the zirconium-based metal-organic framework material loaded with medicines is acidic, so that the zirconium-based metal-organic framework material loaded with medicines can be very well used for carrying out chemical medicine treatment on patients. In addition, the medical composite material obtained by combining the medical composite material with the spinning fiber membrane can be better used for preparing medical gauze, medical suture and the like, and has very wide application prospect.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, zrCl 4 Sodium alginate and N, N-dimethylformamide are purchased from national medicine reagent; sodium ibuprofen, amoxicillin, 1, 4-bis (4-carboxyphenyl) benzene, 2',5' -dimethyl-p-terphenyl dicarboxylic acid were purchased from ala Ding Shiji.
Example 1
(1) 9.6mg of ZrCl 4 Dissolving in 1mL of N, N-dimethylformamide to obtain a mixed solution A1; 13mg of 1, 4-bis (4-carboxyphenyl) benzene was dissolved in 2.2mL of N, N-dimethylformamide to obtain a mixed solution B1; mixing the mixed solution A1 with the mixed solution B1Mixing to obtain a mixed solution, adding 0.24mL of acetic acid (the concentration is 99.5%) into the mixed solution, performing solvothermal reaction in a reaction kettle, cooling to normal temperature after reacting for 24 hours at the reaction temperature of 120 ℃, centrifuging, washing a precipitate by using N, N-dimethylformamide and absolute ethyl alcohol, and finally drying to obtain a zirconium-based metal-organic framework material C1;
(2) Dissolving 15mg of a zirconium-based metal-organic framework material C1 and 60mg of sodium ibuprofen in 6mL of water, standing at 60 ℃ for 72 hours, cooling to normal temperature, centrifuging, washing a precipitate with absolute ethyl alcohol, and finally drying to obtain a zirconium-based metal-organic framework material D1 loaded with sodium ibuprofen;
(3) 0.5g of sodium alginate was dissolved in 9.5g of water to prepare an aqueous sodium alginate solution (polymer concentration: 5 wt%), then 50mg of sodium ibuprofen-loaded zirconium-based metal-organic framework material D1 was added to the aqueous sodium alginate solution, and finally, 5wt% of CaCl was added 2 Wet spinning is adopted in the aqueous solution to obtain the medical composite material S1.
Wherein the molar concentration of zirconium ions in the mixed solution is 12.86mmol/L, the molar concentration of 1, 4-di (4-carboxyphenyl) benzene is 12.5mmol/L, the molar ratio of zirconium ions to 1, 4-di (4-carboxyphenyl) benzene is 1:1.03, the mass ratio of zirconium-based metal-organic framework material C1 to sodium ibuprofen is 1:4, and the mass ratio of acetic acid to ZrCl 4 The molar ratio of (2) was 1:9.85.
Example 2
(1) 9.6mg of ZrCl 4 Dissolving in 1mL of N, N-dimethylformamide to obtain a mixed solution A2; 14.27mg of 2',5' -dimethyl-p-terphenyl dicarboxylic acid was dissolved in 2.2mL of N, N-dimethylformamide to obtain a mixed solution B2; mixing the mixed solution A2 with the mixed solution B2 to obtain a mixed solution, adding 0.24mL of acetic acid (the concentration is 99.9 percent) into the mixed solution, performing solvothermal reaction in a reaction kettle, cooling to normal temperature after reacting for 24 hours at the reaction temperature of 120 ℃, centrifuging, washing a precipitate by using N, N-dimethylformamide and absolute ethyl alcohol, and finally drying to obtain a zirconium-based metal-organic framework material C2;
(2) Dissolving 15mg of a zirconium-based metal-organic framework material C2 and 60mg of sodium ibuprofen in 6mL of water, standing at 70 ℃ for 72 hours, cooling to normal temperature, centrifuging, washing a precipitate with absolute ethyl alcohol, and finally drying to obtain a zirconium-based metal-organic framework material D2 loaded with sodium ibuprofen;
(3) 0.5g of sodium alginate was dissolved in 9.5g of water to prepare an aqueous sodium alginate solution (polymer concentration: 5 wt%), then 50mg of sodium ibuprofen-loaded zirconium-based metal-organic framework material D2 was added to the aqueous sodium alginate solution, and finally, 5wt% of CaCl was added 2 Wet spinning is adopted in the aqueous solution to obtain the medical composite material S2.
Wherein the molar concentration of zirconium ions in the mixed solution is 12.86mmol/L, the molar concentration of 2',5' -dimethyl-p-terphenyl dicarboxylic acid is 12.5mmol/L, the molar ratio of zirconium ions to 2',5' -dimethyl-p-terphenyl dicarboxylic acid is 1:1.03, the mass ratio of zirconium-based metal-organic framework material C2 to sodium ibuprofen is 1:4, and the mass ratio of acetic acid to ZrCl 4 The molar ratio of (2) was 1:9.85.
Example 3
The procedure of example 1 was carried out as described above, except that in step (3), 0.3g of sodium alginate was dissolved in 9.7g of water to prepare an aqueous sodium alginate solution (polymer concentration: 3 wt%) to finally obtain a medical composite material S3.
Example 4
The procedure of example 1 was followed, except that in step (2), the drug sodium ibuprofen was replaced with amoxicillin in an equal weight, and finally a medical composite material S4 was obtained.
Example 5
The procedure of example 1 was followed, except that in step (3), sodium alginate was replaced with cyclodextrin of equal weight and wet spinning was directly performed in water to obtain a medical composite material S5.
Test case
Test example 1
The photographed picture of the medical composite material prepared in the embodiment 1 is shown in fig. 1, and after the medicine-carrying zirconium-based metal-organic framework material is mixed with the polymer for spinning, the obtained medical composite material can be more conveniently applied to preparing a medical suture line or a medical gauze.
The zirconium-based metal-organic framework material C1 prepared in example 1 and the sodium ibuprofen-loaded zirconium-based metal-organic framework material D1 were characterized by X-ray powder diffraction, and the results are shown in fig. 2.
As can be seen from fig. 2, the characteristic peak positions of the zirconium-based metal-organic framework material prepared by the method of the present invention are completely identical to the characteristic peak positions of the theoretical spectrogram of the zirconium-based metal-organic framework material, which indicates that the zirconium-based metal-organic framework material is successfully prepared by the method of the present invention. In addition, as can be seen from the spectrogram of the zirconium-based metal-organic framework material D1 loaded with the ibuprofen sodium, the framework structure of the zirconium-based metal-organic framework material is not affected after the zirconium-based metal-organic framework material is subjected to drug loading.
Test example 2
The sodium ibuprofen-loaded zirconium-based metal-organic framework material D1 prepared in example 1 was tested for drug release content: the sodium ibuprofen-loaded zirconium-based metal-organic framework material D1 obtained in example 1 was subjected to analysis of drug release content in PBS solution at 42 ℃ and ph=5.0, and the drug release profile is shown in fig. 3.
As can be seen from fig. 3, the sodium ibuprofen-loaded zirconium-based metal-organic framework material D1 prepared by the method of the present invention does not have a drug burst phenomenon under an acidic condition, and only 20% of the drug is released after 72 hours, which indicates that the drug-loaded zirconium-based metal-organic framework material prepared by the method of the present invention still has a good slow release effect under an acidic condition, and also has a good anti-inflammatory effect, and can be well applied to biological medicines.
The test shows that the drug release performance of the zirconium-based metal-organic framework materials loaded with the drugs obtained in examples 2, 3, 4 and 5 is equivalent to that of the result of example 1, and the zirconium-based metal-organic framework materials loaded with the drugs can have good drug release effect under acidic conditions and good anti-inflammatory and analgesic effects.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
1. A method of preparing a medical composite material, the method comprising the steps of:
(1) Dissolving zirconium salt and an organic ligand in an organic solvent to obtain a mixed solution, then mixing the mixed solution with acetic acid, and then reacting at 100-150 ℃ for 22-28 hours to obtain a zirconium-based metal-organic framework material;
(2) Soaking the zirconium-based metal-organic framework material in the solution in which the medicine is dissolved for 72-96 hours at 50-70 ℃ to obtain the zirconium-based metal-organic framework material loaded with the medicine;
(3) Mixing the zirconium-based metal-organic framework material loaded with the drug with a solution containing a polymer, and then spinning;
wherein the molar ratio of the zirconium salt to the amount of the organic ligand is (0.9-1.2): 1;
the organic ligand is selected from one or more than two of 1, 4-di (4-carboxyphenyl) benzene, 2',5' -dimethyl-p-terphenyl dicarboxylic acid and (1, 1':4',1 '-triphenyl) -2', 4', 5' -tetracarboxylic acid;
in step (3), the weight ratio of the zirconium-based metal-organic framework material to the drug is 1:2-4;
in the step (3), in the solution containing the polymer, the polymer is one or more selected from sodium alginate, cyclodextrin and chitin.
2. The method for preparing a medical composite material according to claim 1, wherein the zirconium salt is selected from ZrOCl 2 ·8H 2 O and/or ZrCl 4 。
3. The method of producing a medical composite according to claim 1, wherein in the step (1), the molar concentration of zirconium ions in the mixed solution is 0.012 to 0.015mol/L.
4. The method of producing a medical composite according to claim 1, wherein in the step (1), the molar concentration of the organic ligand in the mixed solution is 0.012 to 0.015mol/L.
5. The method for preparing a medical composite according to claim 1, wherein the drug is an analgesic and/or an anti-inflammatory drug, the anti-inflammatory drug is amoxicillin, and the analgesic drug is sodium ibuprofen.
6. The method for producing a medical composite material according to claim 1, wherein the organic solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide.
7. The method for preparing a medical composite material according to claim 1, wherein the molar ratio of the acetic acid to the zirconium salt is 1:9-10.
8. The method of preparing a medical composite according to claim 1, wherein the concentration of acetic acid is 99.5-99.99wt%.
9. The method of preparing a medical composite according to claim 1, wherein the concentration of the polymer in the polymer-containing solution is 1-5wt%.
10. The method for preparing a medical composite material according to claim 1, wherein the spinning method is selected from wet spinning, electrostatic spinning or dry spinning.
11. A medical composite material obtained by the method for producing a medical composite material according to any one of claims 1 to 10.
12. Use of the medical composite material of claim 11 for the preparation of medical gauze or medical suture.
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