CN115475271B - Preparation method of amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing - Google Patents
Preparation method of amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing Download PDFInfo
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- CN115475271B CN115475271B CN202211001048.5A CN202211001048A CN115475271B CN 115475271 B CN115475271 B CN 115475271B CN 202211001048 A CN202211001048 A CN 202211001048A CN 115475271 B CN115475271 B CN 115475271B
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 64
- 230000002439 hemostatic effect Effects 0.000 title claims abstract description 49
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 37
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 32
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 28
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims abstract description 129
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000004627 regenerated cellulose Substances 0.000 claims abstract description 93
- 230000003647 oxidation Effects 0.000 claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 43
- 238000002166 wet spinning Methods 0.000 claims abstract description 26
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- -1 amino acid compound Chemical class 0.000 claims abstract description 13
- 239000004744 fabric Substances 0.000 claims abstract description 12
- 238000009940 knitting Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 229940024606 amino acid Drugs 0.000 claims description 62
- 229920002678 cellulose Polymers 0.000 claims description 62
- 239000001913 cellulose Substances 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 58
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 54
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 20
- 230000001590 oxidative effect Effects 0.000 claims description 20
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 11
- 230000001954 sterilising effect Effects 0.000 claims description 11
- 238000006467 substitution reaction Methods 0.000 claims description 11
- 230000021736 acetylation Effects 0.000 claims description 10
- 238000006640 acetylation reaction Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229920002521 macromolecule Polymers 0.000 claims description 10
- 239000003094 microcapsule Substances 0.000 claims description 10
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000000412 dendrimer Substances 0.000 claims description 8
- 229920000736 dendritic polymer Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- GQBIVYSGPXCELZ-QMMMGPOBSA-N (4s)-4-benzyl-1,3-oxazolidine-2,5-dione Chemical compound O=C1OC(=O)N[C@H]1CC1=CC=CC=C1 GQBIVYSGPXCELZ-QMMMGPOBSA-N 0.000 claims description 6
- DTETYCNJKAUROO-REOHCLBHSA-N (4s)-4-methyl-1,3-oxazolidine-2,5-dione Chemical compound C[C@@H]1NC(=O)OC1=O DTETYCNJKAUROO-REOHCLBHSA-N 0.000 claims description 6
- XNCNNYXFGGTEMT-BYPYZUCNSA-N (4s)-4-propan-2-yl-1,3-oxazolidine-2,5-dione Chemical compound CC(C)[C@@H]1NC(=O)OC1=O XNCNNYXFGGTEMT-BYPYZUCNSA-N 0.000 claims description 6
- JHWZWIVZROVFEM-UHFFFAOYSA-N 4-(2-methylpropyl)-1,3-oxazolidine-2,5-dione Chemical compound CC(C)CC1NC(=O)OC1=O JHWZWIVZROVFEM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 206010052428 Wound Diseases 0.000 abstract description 15
- 208000027418 Wounds and injury Diseases 0.000 abstract description 15
- 239000008280 blood Substances 0.000 abstract description 7
- 210000004369 blood Anatomy 0.000 abstract description 7
- 230000001737 promoting effect Effects 0.000 abstract description 4
- 102000001690 Factor VIII Human genes 0.000 abstract description 3
- 108010054218 Factor VIII Proteins 0.000 abstract description 3
- 102000001554 Hemoglobins Human genes 0.000 abstract description 3
- 108010054147 Hemoglobins Proteins 0.000 abstract description 3
- 230000023555 blood coagulation Effects 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 description 15
- 238000004659 sterilization and disinfection Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 238000002828 disc diffusion antibiotic sensitivity testing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 241000222122 Candida albicans Species 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 230000017531 blood circulation Effects 0.000 description 4
- 229940095731 candida albicans Drugs 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000002522 swelling effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 208000004210 Pressure Ulcer Diseases 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 206010011985 Decubitus ulcer Diseases 0.000 description 1
- 208000028990 Skin injury Diseases 0.000 description 1
- 206010048038 Wound infection Diseases 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 231100000397 ulcer Toxicity 0.000 description 1
- 230000029663 wound healing Effects 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
- A61L15/20—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic 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
- 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
- A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic 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
- 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
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
-
- 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
- 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
- D01F1/103—Agents inhibiting growth of microorganisms
-
- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Hematology (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a preparation method of an amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing, which comprises the steps of preparation of spherical tree-shaped nanometer lanthanum oxide, synthesis of lanthanum oxide/amino acid compound and oxidation of regenerated cellulose; wet spinning acetyl-containing oxidized regenerated cellulose and knitting into cloth with certain quality; the hemostatic dressing containing the acetyl oxidized regenerated cellulose is prepared after slitting and folding, and then packaged and sterilized to obtain the hemostatic dressing commodity containing the acetyl oxidized regenerated cellulose. In the prepared product, oxidized regenerated cellulose can be combined with iron ions of hemoglobin in blood through carboxyl groups, and the blood coagulation factor VIII is activated, so that the purpose of promoting blood coagulation is achieved. The obtained multifunctional dressing is suitable for curing serious wounds such as large-area burns, car accidents and the like, and is particularly suitable for high-efficiency wound treatment under special conditions (such as war) in the background of the less flat world.
Description
Technical Field
The invention relates to a preparation method of an amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing, and relates to a preparation method of a multifunctional medical dressing, belonging to the technical field of medical materials.
Background
The medical dressing is used as an important sanitary material medical product, is used for covering a wound surface under the condition that skin is damaged, and plays roles of preventing excessive loss of in-vivo moisture and electrolyte, maintaining in-vivo environment stable, regulating body temperature, protecting the wound, preventing external microorganism invasion and the like, and preventing and reducing complications such as wound infection and the like before the skin is restored or rebuilt.
Tens of millions of people in China cause skin injury due to accidents or operations every year, and chronic wound surfaces such as pressure sores and ulcers closely related to the aged people are increased year by year along with the aging of population. According to statistics, the market demand of medical dressings in China reaches 400 hundred million yuan in 2010, and the annual average composite growth rate exceeds 20%. However, in medical dressings currently used in China, the market share of the traditional dressing is as high as more than 80%, and the market share of the novel dressing is far lower than that of European and developed countries. Compared with the traditional dressing, the novel dressing can improve the wound healing speed and healing quality, relieve pain, has lower replacement frequency and lower actual treatment cost, and meets the development requirements of modern wound care medicine. With the rapid development of the medical and health field in China and the improvement of the requirements of domestic patients on medical conditions and medical care levels, the novel medical dressing is favored by the patients and medical staff. Therefore, the medical dressing market in China is huge and the development is quite powerful.
At present, enterprises for producing novel medical dressings in China are few, the research and development investment of the enterprises is insufficient, the products are lack of competitiveness, most of novel medical dressing markets are occupied by expensive imported products (products of 3M, duPont, qiangsheng and other companies), great economic pressure is brought to domestic patients, and the quick improvement of wound nursing medical care level in China is also hindered.
Therefore, the research and development of the domestic novel medical dressing with excellent performance and acceptable price and independent intellectual property has very important significance for breaking monopoly and technical barriers of foreign products, promoting the development of the medical dressing industry in China, improving the medical experience of patients, and reducing the medical care cost of the patients and the working intensity of medical care workers.
Disclosure of Invention
The invention aims to provide a preparation method of an amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing, which is a multifunctional dressing with good biocompatibility, high efficiency antibacterial property, hydrophilicity and real-time monitoring and hemostatic property, can be used for curing serious wounds such as large-area burns, car accidents and the like, and particularly can be used for high-efficiency wound treatment in special states (such as war) under the background of the world.
Still another object of the present invention is: the product obtained by the method is provided.
The invention aims at realizing the following scheme: the preparation method of the amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing adopts an in-situ preparation method and comprises the following steps:
1) Preparing spherical tree-shaped nanometer lanthanum oxide: PAMAM macromolecules are used as a template agent, alkali liquor is used as a precipitator, and ultrasonic-assisted precipitation is combined with a hydrothermal method to prepare nano rare earth lanthanum oxide with a spherical tree structure;
2) Synthesis of lanthanum oxide/amino acid complex: coating a positively charged amphiphilic amino acid polymer (AA) on the surface of a nano rare earth compound by adopting a microcapsule polymerization process, namely coating the positively charged amphiphilic amino acid polymer on the surface of lanthanum oxide;
3) Oxidizing regenerated cellulose: acetic anhydride and acetic acid form an acetylation mixed solution, cellulose is placed into the mixed solution, and acetyl-containing cellulose with the acetyl substitution degree of 0.1-3.3 is obtained; oxidizing acetyl-containing cellulose to form an oxidation solution by carbon tetrachloride and nitrogen oxide, soaking the acetyl-containing cellulose into the oxidation solution, and reacting to obtain acetyl-containing oxidized regenerated cellulose with the carboxyl content of 5-26%; grafting the nanometer lanthanum oxide coated with the amino acid on the regenerated cellulose containing acetyl oxidation in situ to obtain wet spinning solution containing the regenerated cellulose containing acetyl oxidation;
4) Wet spinning acetyl-containing oxidized regenerated cellulose and knitting into cloth with certain quality. The hemostatic dressing containing the acetyl oxidized regenerated cellulose is prepared after slitting and folding, and then packaged and sterilized to obtain the hemostatic dressing commodity containing the acetyl oxidized regenerated cellulose.
Based on the scheme, the added alkali in the step (1) is ammonia water with different concentrations. The preferred concentration is 0.2mol/L to 0.75 mol/L.
Based on the above scheme, the positively charged amphiphilic amino acid polymer in the step (2) is one of L-phenylalanine NCA, L-leucine NCA, L-valine NCA and L-alanine NCA.
Based on the scheme, the addition proportion of the nanometer lanthanum oxide in the step (3) is 5% -10%; the substitution degree of acetyl is 0.1-3.3, and the carboxyl content is 5-26%; the length of the fiber is more than 2mm; the linear density is more than or equal to 1dtex; the dry strength is more than or equal to 12cN/tex; the hemostatic dressing containing acetyl oxidized regenerated cellulose has gram weight of 100-350 g/m through the non-woven fabric manufacturing process 2 Within the range.
Wet spinning acetyl-containing oxidized regenerated cellulose and knitting into cloth with certain quality. The hemostatic dressing containing the acetyl oxidized regenerated cellulose is prepared after slitting and folding, and then packaged and sterilized to obtain the hemostatic dressing commodity containing the acetyl oxidized regenerated cellulose.
The invention also provides the hemostatic dressing containing acetyl oxidized regenerated cellulose obtained by the method. The hemostatic dressing is prepared from a material containing an amino acid and a hydroxyl group in OH-C 6 Upper-COCH 3 The substituted oxidized regenerated cellulose fiber is prepared into hemostatic dressing through wet process, slitting, packing and sterilizing.
The principle of the hemostatic dressing containing acetyl oxidized regenerated cellulose of the invention is that: by utilizing the fluorescence response and antibacterial property of the rare earth nanocrystalline, the sterilization and hydrophilicity of the amino acid are realized, so that the rare earth nanocrystalline not only has high-efficiency biocompatibility and antibacterial activity (the antibacterial rate is more than 99.9 percent); sensitive stimulus response to fluorescence, can be used as a hydrophilic group real-time tracer material; meanwhile, the dressing has strong hydrophilicity (the swelling rate can reach 280 percent), can effectively absorb wound surface seepage and maintains a healing environment with moderately moist wound surface; oxidized regenerated cellulose can be combined with iron ions of hemoglobin in blood through carboxyl groups, and activates blood coagulation factor VIII, so that the purpose of promoting blood coagulation is achieved. The obtained multifunctional dressing is suitable for curing serious wounds such as large-area burns, car accidents and the like, and is particularly suitable for high-efficiency wound treatment under special conditions (such as war) in the background of the less flat world.
The invention has the advantages that the oxidized regenerated cellulose can be combined with iron ions of hemoglobin in blood through carboxyl groups, and activates blood coagulation factor VIII, thereby achieving the purpose of promoting blood coagulation. The obtained multifunctional dressing is suitable for curing serious wounds such as large-area burns, car accidents and the like, and is particularly suitable for high-efficiency wound treatment under special conditions (such as war) in the background of the less flat world.
Drawings
Fig. 1: scanning electron microscope pictures of the amino acid/rare earth nanocrystalline/cellulose composite material prepared in example 2.
Example 1
An amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing is prepared according to the following steps:
1) Preparing spherical tree-shaped nanometer lanthanum oxide: taking dendrimer PAMAM macromolecules as a template agent, taking 0.2mol/L ammonia water as a precipitator, combining an ultrasonic auxiliary precipitation method with a hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-mouth flask, placing the four-mouth flask into an ultrasonic instrument, adjusting the temperature to 20+/-5 ℃, slowly adding 0.2mol/L ammonia water precipitator into the lanthanum nitrate solution by using a constant pressure funnel, dripping at a speed of 1 ml/min, continuously treating 1 h in the ultrasonic instrument after completion, and taking out white precipitate; taking 60 ml white precipitate, adding into a high-pressure reaction kettle for further treatment, heating at 140 ℃ for 6 h, separating the obtained sample by a centrifuge, washing with ethanol for several times, taking out the sample, drying in a 140 ℃ oven for 2h, calcining at 750 ℃ for 5 h, grinding to prepare nano rare earth lanthanum oxide n-RE powder with a spherical tree structure, and sealing and storing;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-phenylalanine NCA solution, weighing 0.1gn-RE powder, coating the L-phenylalanine NCA on the n-RE surface prepared in the step (1) by adopting a microcapsule polymerization process to obtain amino acid coated nano lanthanum oxide, cleaning and freeze-drying;
3) Oxidizing regenerated cellulose: acetic anhydride and acetic acid form an acetylation mixed solution, a certain amount of cellulose is placed into the mixed solution, and the acetyl replaces OH-C6 on part of cellulose to obtain the degree of substitution of acetyl of 1.0; oxidizing acetyl-containing cellulose, forming an oxidation solution by carbon tetrachloride and nitrogen oxide, soaking the acetyl-containing cellulose into the oxidation solution, and reacting to obtain acetyl-containing oxidized regenerated cellulose, wherein the carboxyl content of the acetyl-containing cellulose is 17%; grafting the nanometer lanthanum oxide coated with the amino acid on the regenerated cellulose containing acetyl oxidation in situ; the nano lanthanum oxide is added with 5 percent by mass to obtain wet spinning solution containing acetyl oxidized regenerated cellulose;
4) Wet spinning acetyl-containing oxidized regenerated cellulose to obtain filament bundles with linear density of 1.1dtex, and twisting the acetyl-containing oxidized regenerated cellulose filaments in S direction, wherein the twist is 15 twists/1 cm and 166D; knitting 235g of cloth; the hemostatic dressing containing the acetyl oxidized regenerated cellulose is prepared after slitting and folding, and then packaged and sterilized to obtain the hemostatic dressing commodity containing the acetyl oxidized regenerated cellulose.
And (3) detecting sterilization performance: according to the 2002 edition of the disinfection technical Specification, a disc diffusion method is adopted for detecting the disinfection performance. Test results show that the composite dressing has a killing rate of more than 99.999% on escherichia coli (8099 type), more than 99.999% on staphylococcus aureus (ATCC 6538 type), more than 99.999% on pseudomonas aeruginosa (ATCC 9027 type), and more than 99.999% on candida albicans (ATCC 10231 type);
extracorporeal blood circulation coagulation experiment: the adsorption capacity of the test protein is obviously reduced, the OD value and the cell compatibility are obviously improved, and excellent blood compatibility and biocompatibility are shown;
swelling property test: the swelling rate of the prepared amino acid/rare earth nanocrystalline/acetylated cellulose composite material is 228% by using a weighing method, and the amino acid/rare earth nanocrystalline/acetylated cellulose composite material has excellent hydrophilicity.
Example 2
An amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing is prepared by the steps similar to those in example 1 as follows:
1) Preparing spherical tree-shaped nanometer lanthanum oxide: 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution is put into a four-mouth flask and placed into an ultrasonic instrument by adopting an ultrasonic auxiliary combined hydrothermal method by taking dendrimer PAMAM macromolecules as a template agent and 0.4mol/L ammonia water as a precipitant, the temperature is adjusted to be 20+/-5 ℃, the 0.4mol/L ammonia water precipitant is slowly added into the lanthanum nitrate solution by using a constant pressure funnel, the solution is dropwise added at the speed of 1 ml/min, after the completion, the solution is continuously treated in the ultrasonic instrument for 1 h, and then the precipitate is taken out; taking 60 ml white precipitate, adding into a high-pressure reaction kettle for further treatment, heating at 140 ℃ for 6 h, separating the obtained sample by a centrifuge, washing with ethanol for several times, taking out the sample, drying in a 140 ℃ oven for 2h, calcining at 750 ℃ for 5 h, and grinding, sealing and preserving the prepared nano rare earth lanthanum oxide n-RE with spherical tree structure;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-leucine NCA solution, weighing 0.1g n-RE powder, coating the surface of the n-RE prepared in the step (1) with L-leucine NCA by adopting a microcapsule polymerization process to obtain amino acid coated nano lanthanum oxide, cleaning, and freeze-drying;
3) Oxidizing regenerated cellulose: acetic anhydride and acetic acid form an acetylation mixed solution, a certain amount of cellulose is placed in the mixed solution, and acetyl replaces OH-C6 on part of cellulose to obtain cellulose containing acetyl, wherein the degree of substitution of acetyl is 0.4; oxidizing acetyl-containing cellulose, forming an oxidation solution by carbon tetrachloride and nitrogen oxide, soaking the acetyl-containing cellulose into the oxidation solution, and reacting to obtain acetyl-containing oxidized regenerated cellulose with the carboxyl content of 23%; grafting 5% of the nano lanthanum oxide coated with the amino acid obtained in the step 2) onto the regenerated cellulose containing acetyl oxidation in situ to obtain a wet spinning solution containing the regenerated cellulose containing acetyl oxidation;
4) Wet spinning acetyl-containing oxidized regenerated cellulose to obtain filament bundles with linear density of 1.6 dtex; s-direction twisting is carried out on the regenerated cellulose filaments containing acetyl oxidation, and the twist is 15 twists/1 cm and 166D; knitting 230g cloth, cutting and folding to obtain hemostatic dressing containing acetyl oxidized regenerated cellulose, packaging, and sterilizing to obtain hemostatic dressing commodity containing acetyl oxidized regenerated cellulose. The hemostatic dressing is an amino acid/rare earth nanocrystalline/cellulose composite material, and a scanning electron microscope image of the hemostatic dressing is shown in figure 1.
And (3) detecting sterilization performance: according to the 2002 edition of the disinfection technical Specification, a disc diffusion method is adopted for detecting the disinfection performance: according to the 2002 edition of the disinfection technical Specification, a disc diffusion method is adopted for detecting the disinfection performance. Test results show that the composite dressing has a killing rate of more than 99.99% for escherichia coli (8099 type), more than 99.999% for staphylococcus aureus (ATCC 6538 type), more than 99.999% for pseudomonas aeruginosa (ATCC 9027 type), and more than 99.999% for candida albicans (ATCC 10231 type);
extracorporeal blood circulation coagulation experiment: the adsorption capacity of the test protein is obviously reduced, the OD value and the cell compatibility are obviously improved, and excellent blood compatibility and biocompatibility are shown;
swelling property test: the swelling ratio of the prepared amino acid/rare earth nanocrystalline/acetylated cellulose composite material is 250% by using a weighing method, and the amino acid/rare earth nanocrystalline/acetylated cellulose composite material has excellent hydrophilicity.
Example 3
An amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing is prepared by the steps similar to those in example 1 as follows:
1) Preparing spherical tree-shaped nanometer lanthanum oxide: taking dendrimer PAMAM macromolecules as a template agent and 0.6mol/L ammonia water as a precipitant, adopting an ultrasonic-assisted hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-mouth flask and placing the four-mouth flask into an ultrasonic instrument, adjusting the temperature to 20+/-5 ℃, slowly adding 0.6mol/L ammonia water precipitant into the lanthanum nitrate solution by using a constant-pressure funnel, dripping at a speed of 1 ml/min, continuously treating 1 h in the ultrasonic instrument after completion, and taking out the precipitate; taking 60 ml white precipitate, adding into a high-pressure reaction kettle for further treatment, heating at 140 ℃ for 6 h, separating the obtained sample by a centrifuge, washing with ethanol for several times, taking out the sample, drying in a 140 ℃ oven for 2h, calcining at 750 ℃ for 5 h to obtain nano rare earth lanthanum oxide n-RE with a spherical tree structure, grinding, and sealing for preservation;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-valine NCA solution, weighing 0.1gn-RE powder, coating the surface of the n-RE prepared in the step (1) with L-valine NCA by adopting a microcapsule polymerization process to obtain amino acid coated nano lanthanum oxide, cleaning and freeze-drying;
3) Oxidizing regenerated cellulose: acetic anhydride and acetic acid form an acetylation mixed solution, a certain amount of cellulose is placed in the mixed solution, and the acetyl replaces OH-C6 on part of cellulose to obtain acetyl-containing cellulose with the degree of substitution of acetyl of 2.9; oxidizing acetyl-containing cellulose, forming an oxidation solution by carbon tetrachloride and nitrogen oxide, soaking the acetyl-containing cellulose into the oxidation solution, and reacting to obtain acetyl-containing oxidized regenerated cellulose with 7% of carboxyl; the nanometer lanthanum oxide coated with 10% of amino acid is grafted to regenerated cellulose containing acetyl oxide in situ to obtain wet spinning solution containing regenerated cellulose containing acetyl oxide;
4) Wet spinning the regenerated cellulose containing acetyl oxide, and spinning into filament bundles with linear density of 1.5dtex by wet spinning the regenerated cellulose containing acetyl oxide; s-direction twisting is carried out on the regenerated cellulose filaments containing acetyl oxidation, and the twist is 15 twists/1 cm and 32S; knitting 300g cloth, cutting and folding to obtain hemostatic dressing containing acetyl oxidized regenerated cellulose, packaging, and sterilizing to obtain hemostatic dressing commodity containing acetyl oxidized regenerated cellulose.
And (3) detecting sterilization performance: according to the 2002 edition of the disinfection technical Specification, a disc diffusion method is adopted for detecting the disinfection performance. Test results show that the composite dressing has a killing rate of more than 99.99% for escherichia coli (8099 type), more than 99.9% for staphylococcus aureus (ATCC 6538 type), more than 99.9% for pseudomonas aeruginosa (ATCC 9027 type), and more than 99.99% for candida albicans (ATCC 10231 type);
extracorporeal blood circulation coagulation experiment: the adsorption capacity of the test protein is obviously reduced, the OD value and the cell compatibility are also obviously improved, and excellent blood compatibility and biocompatibility are shown;
swelling property test: the swelling ratio of the prepared amino acid/rare earth nanocrystalline/acetylated cellulose composite material is 180% by using a weighing method, and the prepared amino acid/rare earth nanocrystalline/acetylated cellulose composite material has good hydrophilicity.
Example 4
An amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing is prepared by the steps similar to those in example 1 as follows:
1) Preparing spherical tree-shaped nanometer lanthanum oxide: taking dendrimer PAMAM macromolecules as a template agent and 0.75mol/L ammonia water as a precipitant, adopting an ultrasonic-assisted hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-mouth flask and placing the four-mouth flask into an ultrasonic instrument, adjusting the temperature to 20+/-5 ℃, slowly adding 0.75mol/L ammonia water precipitant into the lanthanum nitrate solution by using a constant-pressure funnel, dripping at a speed of 1 ml/min, continuously treating 1 h in the ultrasonic instrument after completion, and taking out the precipitate; taking 60 ml white precipitate, adding into a high-pressure reaction kettle for further treatment, heating at 140 ℃ for 6 h, separating the obtained sample by a centrifuge, washing with ethanol for several times, taking out the sample, drying in a 140 ℃ oven for 2h, calcining at 750 ℃ for 5 h, grinding to obtain powder, and sealing and storing;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-alanine NCA solution, weighing 0.1gn-RE powder, coating a positively charged amphiphilic amino acid polymer on the surface of lanthanum oxide by adopting a microcapsule polymerization process, namely coating the surface of n-RE prepared in the step (1) with L-alanine NCA to obtain amino acid coated nano lanthanum oxide, and cleaning and freeze-drying;
3) Oxidizing regenerated cellulose: acetic anhydride and acetic acid form an acetylation mixed solution, a certain amount of cellulose is placed in the mixed solution, and the acetyl replaces OH-C6 on part of cellulose to obtain acetyl-containing cellulose with the degree of substitution of acetyl of 2.2; oxidizing cellulose containing acetyl, forming an oxidation solution by carbon tetrachloride and nitrogen oxide, soaking the cellulose containing acetyl into the oxidation solution, and reacting to obtain regenerated cellulose containing acetyl oxidation, wherein the carboxyl content is 18%; grafting the nanometer lanthanum oxide coated with the amino acid onto cellulose regenerated by acetyl oxidation in situ, wherein the adding amount of the nanometer lanthanum oxide is 8% by mass, and obtaining wet spinning solution containing cellulose regenerated by acetyl oxidation;
4) Wet spinning the regenerated cellulose containing acetyl oxide, and spinning into filament bundles with linear density of 1.6dtex by wet spinning the regenerated cellulose containing acetyl oxide; s-direction twisting is carried out on the regenerated cellulose filaments containing acetyl oxidation, and the twist is 15 twists/1 cm and 166D; knitting 280g of cloth; the hemostatic dressing containing the acetyl oxidized regenerated cellulose is prepared after slitting and folding, and then packaged and sterilized to obtain the hemostatic dressing commodity containing the acetyl oxidized regenerated cellulose.
And (3) detecting sterilization performance: according to the 2002 edition of the disinfection technical Specification, a disc diffusion method is adopted for detecting the disinfection performance. Test results show that the composite dressing has a killing rate of more than 99.99% for escherichia coli (8099 type), more than 99.999% for staphylococcus aureus (ATCC 6538 type), more than 99.999% for pseudomonas aeruginosa (ATCC 9027 type), and more than 99.999% for candida albicans (ATCC 10231 type);
extracorporeal blood circulation coagulation experiment: the adsorption capacity of the test protein is obviously reduced, the OD value and the cell compatibility are also obviously improved, and excellent blood compatibility and biocompatibility are shown;
swelling property test: the swelling ratio of the prepared amino acid/rare earth nanocrystalline/acetylated cellulose composite material is 210% by using a weighing method, and the amino acid/rare earth nanocrystalline/acetylated cellulose composite material has excellent hydrophilicity.
Claims (6)
1. The preparation method of the amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing is characterized by comprising the following steps of:
1) Preparing spherical tree-shaped nanometer lanthanum oxide: PAMAM macromolecules are used as a template agent, alkali liquor is used as a precipitator, and ultrasonic assistance is combined with a hydrothermal method to prepare the nano rare earth lanthanum oxide with the spherical tree structure;
2) Synthesis of lanthanum oxide/amino acid complex: coating a positively charged amphiphilic amino acid polymer on the surface of lanthanum oxide by adopting a microcapsule polymerization process to obtain amino acid coated nano lanthanum oxide;
3) Oxidizing regenerated cellulose: acetic anhydride and acetic acid form an acetylation mixed solution, cellulose is placed into the mixed solution, and acetyl-containing cellulose with the acetyl substitution degree of 0.1-3.3 is obtained; oxidizing acetyl-containing cellulose to form an oxidation solution by carbon tetrachloride and nitrogen oxide, soaking the acetyl-containing cellulose into the oxidation solution, and reacting to obtain acetyl-containing oxidized regenerated cellulose with the carboxyl content of 5-26%; grafting the nanometer lanthanum oxide coated with the amino acid on the regenerated cellulose containing acetyl oxidation in situ to obtain wet spinning solution containing the regenerated cellulose containing acetyl oxidation;
4) Wet spinning the acetyl-containing oxidized regenerated cellulose, knitting into cloth, cutting and folding to obtain acetyl-containing oxidized regenerated cellulose hemostatic dressing, packaging and sterilizing to obtain acetyl-containing oxidized regenerated cellulose hemostatic dressing commodity;
in the step (1), the alkali liquor is ammonia water;
in the step (2), the positively charged amphiphilic amino acid polymer is one of L-phenylalanine NCA, L-leucine NCA, L-valine NCA or L-alanine NCA;
in the step (3), the addition proportion of the nano lanthanum oxide is 5% -10%; the length of the fiber is not less than 2mm; the linear density is more than or equal to 1dtex; the dry strength is more than or equal to 12cN/tex; the hemostatic dressing containing acetyl oxidized regenerated cellulose has gram weight of 100-350 g/m through the non-woven fabric manufacturing process 2 Within the range.
2. The method for preparing the amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing as claimed in claim 1, wherein the method comprises the following steps: the preparation method comprises the following steps:
1) Preparing spherical tree-shaped nanometer lanthanum oxide: taking dendrimer PAMAM macromolecules as a template agent, taking 0.2mol/L ammonia water as a precipitator, combining an ultrasonic auxiliary precipitation method with a hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-mouth flask, placing the four-mouth flask into an ultrasonic instrument, adjusting the temperature to 20+/-5 ℃, slowly adding 0.2mol/L ammonia water precipitator into the lanthanum nitrate solution by using a constant pressure funnel, dripping at a speed of 1 ml/min, continuously treating 1 h in the ultrasonic instrument after completion, and taking out white precipitate; taking 60 ml white precipitate, adding into a high-pressure reaction kettle for further treatment, heating at 140 ℃ for 6 h, separating the obtained sample by a centrifuge, washing with ethanol for several times, taking out the sample, drying in a 140 ℃ oven for 2h, calcining at 750 ℃ for 5 h, grinding to prepare nano rare earth lanthanum oxide n-RE powder with a spherical tree structure, and sealing and storing;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-phenylalanine NCA solution, weighing 0.1gn-RE powder, coating the L-phenylalanine NCA on the n-RE surface prepared in the step (1) by adopting a microcapsule polymerization process to obtain amino acid coated nano lanthanum oxide, cleaning and freeze-drying;
3) Oxidizing regenerated cellulose: acetic anhydride and acetic acid form an acetylation mixed solution, a certain amount of cellulose is placed into the mixed solution, and the acetyl replaces OH-C6 on part of cellulose to obtain the degree of substitution of acetyl of 1.0; oxidizing acetyl-containing cellulose, forming an oxidation solution by carbon tetrachloride and nitrogen oxide, soaking the acetyl-containing cellulose into the oxidation solution, and reacting to obtain acetyl-containing oxidized regenerated cellulose, wherein the carboxyl content of the acetyl-containing cellulose is 17%; grafting the nanometer lanthanum oxide coated with the amino acid on the regenerated cellulose containing acetyl oxidation in situ; the nano lanthanum oxide is added with 5 percent by mass to obtain wet spinning solution containing acetyl oxidized regenerated cellulose;
4) Wet spinning acetyl-containing oxidized regenerated cellulose to obtain filament bundles with linear density of 1.1dtex, and twisting the acetyl-containing oxidized regenerated cellulose filaments in S direction, wherein the twist is 15 twists/1 cm and 166D; knitting 235g of cloth; the hemostatic dressing containing the acetyl oxidized regenerated cellulose is prepared after slitting and folding, and then packaged and sterilized to obtain the hemostatic dressing commodity containing the acetyl oxidized regenerated cellulose.
3. The method for preparing the amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing as claimed in claim 1, wherein the method comprises the following steps: the preparation method comprises the following steps:
1) Preparing spherical tree-shaped nanometer lanthanum oxide: 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution is put into a four-mouth flask and placed into an ultrasonic instrument by adopting an ultrasonic auxiliary combined hydrothermal method by taking dendrimer PAMAM macromolecules as a template agent and 0.4mol/L ammonia water as a precipitant, the temperature is adjusted to be 20+/-5 ℃, the 0.4mol/L ammonia water precipitant is slowly added into the lanthanum nitrate solution by using a constant pressure funnel, the solution is dropwise added at the speed of 1 ml/min, after the completion, the solution is continuously treated in the ultrasonic instrument for 1 h, and then the precipitate is taken out; taking 60 ml white precipitate, adding into a high-pressure reaction kettle for further treatment, heating at 140 ℃ for 6 h, separating the obtained sample by a centrifuge, washing with ethanol for several times, taking out the sample, drying in a 140 ℃ oven for 2 hours, calcining at 750 ℃ for 5 h, and grinding, sealing and preserving the prepared nano rare earth lanthanum oxide n-RE with spherical tree structure;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-leucine NCA solution, weighing 0.1g n-RE powder, coating the surface of the n-RE prepared in the step (1) with L-leucine NCA by adopting a microcapsule polymerization process to obtain amino acid coated nano lanthanum oxide, cleaning, and freeze-drying;
3) Oxidizing regenerated cellulose: acetic anhydride and acetic acid form an acetylation mixed solution, a certain amount of cellulose is placed in the mixed solution, and acetyl replaces OH-C6 on part of cellulose to obtain cellulose containing acetyl, wherein the degree of substitution of acetyl is 0.4; oxidizing acetyl-containing cellulose, forming an oxidation solution by carbon tetrachloride and nitrogen oxide, soaking the acetyl-containing cellulose into the oxidation solution, and reacting to obtain acetyl-containing oxidized regenerated cellulose with the carboxyl content of 23%; grafting 5% of the nano lanthanum oxide coated with the amino acid obtained in the step 2) onto the regenerated cellulose containing acetyl oxidation in situ to obtain a wet spinning solution containing the regenerated cellulose containing acetyl oxidation;
4) Wet spinning acetyl-containing oxidized regenerated cellulose to obtain filament bundles with linear density of 1.6 dtex; s-direction twisting is carried out on the regenerated cellulose filaments containing acetyl oxidation, and the twist is 15 twists/1 cm and 166D; knitting 230g cloth, cutting and folding to obtain hemostatic dressing containing acetyl oxidized regenerated cellulose, packaging, and sterilizing to obtain hemostatic dressing commodity containing acetyl oxidized regenerated cellulose.
4. The method for preparing the amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing as claimed in claim 1, wherein the method comprises the following steps: the preparation method comprises the following steps:
1) Preparing spherical tree-shaped nanometer lanthanum oxide: taking dendrimer PAMAM macromolecules as a template agent and 0.6mol/L ammonia water as a precipitant, adopting an ultrasonic-assisted hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-mouth flask and placing the four-mouth flask into an ultrasonic instrument, adjusting the temperature to 20+/-5 ℃, slowly adding 0.6mol/L ammonia water precipitant into the lanthanum nitrate solution by using a constant-pressure funnel, dripping at a speed of 1 ml/min, continuously treating 1 h in the ultrasonic instrument after completion, and taking out the precipitate; taking 60 ml white precipitate, adding into a high-pressure reaction kettle for further treatment, heating at 140 ℃ for 6 h, separating the obtained sample by a centrifuge, washing with ethanol for several times, taking out the sample, drying in a 140 ℃ oven for 2h, calcining at 750 ℃ for 5 h to obtain nano rare earth lanthanum oxide n-RE with a spherical tree structure, grinding, and sealing for preservation;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-valine NCA solution, weighing 0.1gn-RE powder, coating the surface of the n-RE prepared in the step (1) with L-valine NCA by adopting a microcapsule polymerization process to obtain amino acid coated nano lanthanum oxide, cleaning and freeze-drying;
3) Oxidizing regenerated cellulose: acetic anhydride and acetic acid form an acetylation mixed solution, a certain amount of cellulose is placed in the mixed solution, and the acetyl replaces OH-C6 on part of cellulose to obtain acetyl-containing cellulose with the degree of substitution of acetyl of 2.9; oxidizing acetyl-containing cellulose, forming an oxidation solution by carbon tetrachloride and nitrogen oxide, soaking the acetyl-containing cellulose into the oxidation solution, and reacting to obtain acetyl-containing oxidized regenerated cellulose with 7% of carboxyl; the nanometer lanthanum oxide coated with 10% of amino acid is grafted to regenerated cellulose containing acetyl oxide in situ to obtain wet spinning solution containing regenerated cellulose containing acetyl oxide;
4) Wet spinning the regenerated cellulose containing acetyl oxide, and spinning into filament bundles with linear density of 1.5dtex by wet spinning the regenerated cellulose containing acetyl oxide; s-direction twisting is carried out on the regenerated cellulose filaments containing acetyl oxidation, and the twist is 15 twists/1 cm and 32S; knitting 300g cloth, cutting and folding to obtain hemostatic dressing containing acetyl oxidized regenerated cellulose, packaging, and sterilizing to obtain hemostatic dressing commodity containing acetyl oxidized regenerated cellulose.
5. The method for preparing the amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing as claimed in claim 1, wherein the method comprises the following steps: the preparation method comprises the following steps:
1) Preparing spherical tree-shaped nanometer lanthanum oxide: taking dendrimer PAMAM macromolecules as a template agent and 0.75mol/L ammonia water as a precipitant, adopting an ultrasonic-assisted hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-mouth flask and placing the four-mouth flask into an ultrasonic instrument, adjusting the temperature to 20+/-5 ℃, slowly adding 0.75mol/L ammonia water precipitant into the lanthanum nitrate solution by using a constant-pressure funnel, dripping at a speed of 1 ml/min, continuously treating 1 h in the ultrasonic instrument after completion, and taking out the precipitate; taking 60 ml white precipitate, adding into a high-pressure reaction kettle for further treatment, heating at 140 ℃ for 6 h, separating the obtained sample by a centrifuge, washing with ethanol for several times, taking out the sample, drying in a 140 ℃ oven for 2h, calcining at 750 ℃ for 5 h, grinding to obtain powder, and sealing and storing;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-alanine NCA solution, weighing 0.1gn-RE powder, coating a positively charged amphiphilic amino acid polymer on the surface of lanthanum oxide by adopting a microcapsule polymerization process, namely coating the surface of n-RE prepared in the step (1) with L-alanine NCA to obtain amino acid coated nano lanthanum oxide, and cleaning and freeze-drying;
3) Oxidizing regenerated cellulose: acetic anhydride and acetic acid form an acetylation mixed solution, a certain amount of cellulose is placed in the mixed solution, and the acetyl replaces OH-C6 on part of cellulose to obtain acetyl-containing cellulose with the degree of substitution of acetyl of 2.2; oxidizing cellulose containing acetyl, forming an oxidation solution by carbon tetrachloride and nitrogen oxide, soaking the cellulose containing acetyl into the oxidation solution, and reacting to obtain regenerated cellulose containing acetyl oxidation, wherein the carboxyl content is 18%; grafting the nanometer lanthanum oxide coated with the amino acid onto cellulose regenerated by acetyl oxidation in situ, wherein the adding amount of the nanometer lanthanum oxide is 8% by mass, and obtaining wet spinning solution containing cellulose regenerated by acetyl oxidation;
4) Wet spinning the regenerated cellulose containing acetyl oxide, and spinning into filament bundles with linear density of 1.6dtex by wet spinning the regenerated cellulose containing acetyl oxide; s-direction twisting is carried out on the regenerated cellulose filaments containing acetyl oxidation, and the twist is 15 twists/1 cm and 166D; knitting 280g of cloth; the hemostatic dressing containing the acetyl oxidized regenerated cellulose is prepared after slitting and folding, and then packaged and sterilized to obtain the hemostatic dressing commodity containing the acetyl oxidized regenerated cellulose.
6. An amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing obtainable by the process according to any one of claims 1 to 5.
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| 纳米稀土形态结构控制对其热塑性聚氨酯复合弹性体影响研究;刘东伟;《中国优秀硕士学位论文全文数据库 工程科技I辑》;正文21-22页和第3.4小节 * |
| 细菌纤维素与纳米银复合制备创伤敷料;南方;赖琛;奚廷斐;;中国组织工程研究(43);全文 * |
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