CN115475271A - 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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- CN115475271A CN115475271A CN202211001048.5A CN202211001048A CN115475271A CN 115475271 A CN115475271 A CN 115475271A CN 202211001048 A CN202211001048 A CN 202211001048A CN 115475271 A CN115475271 A CN 115475271A
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- acetyl
- regenerated cellulose
- oxidized regenerated
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 63
- 230000002439 hemostatic effect Effects 0.000 title claims abstract description 54
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 43
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 28
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 25
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 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 116
- 239000004627 regenerated cellulose Substances 0.000 claims abstract description 98
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- -1 amino acid compound Chemical class 0.000 claims abstract description 19
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 238000004806 packaging method and process Methods 0.000 claims abstract description 13
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- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims abstract 58
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 44
- 239000002244 precipitate Substances 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 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
- 239000012716 precipitator Substances 0.000 claims description 18
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- 238000001035 drying Methods 0.000 claims description 16
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- 238000000576 coating method Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 11
- 238000006467 substitution reaction Methods 0.000 claims description 11
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- 230000015572 biosynthetic process Effects 0.000 claims description 10
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- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229920002521 macromolecule Polymers 0.000 claims description 10
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- 229920000962 poly(amidoamine) Polymers 0.000 claims description 10
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- 238000003786 synthesis reaction Methods 0.000 claims description 10
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- 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
- 239000000047 product Substances 0.000 claims description 8
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- 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
- 239000003513 alkali Substances 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 claims description 2
- 229940081735 acetylcellulose Drugs 0.000 claims description 2
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- 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
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 66
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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
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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
- A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
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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
- A61L15/22—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
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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
- A61L15/22—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
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- 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
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- 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
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- 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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Abstract
The invention relates to a preparation method of an amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing, which comprises the steps of preparing spherical tree-shaped nanometer lanthanum oxide, synthesizing a lanthanum oxide/amino acid compound, and oxidizing regenerated cellulose; carrying out wet spinning on oxidized regenerated cellulose containing acetyl, and knitting the oxidized regenerated cellulose containing acetyl into cloth with certain mass; after cutting and folding, the hemostatic dressing containing acetyl oxidized regenerated cellulose is prepared, and then the hemostatic dressing containing acetyl oxidized regenerated cellulose is obtained after packaging and sterilization. In the prepared product, the 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 aim of promoting blood coagulation is fulfilled. The obtained multifunctional dressing is suitable for curing serious wounds such as large-area burns, car accidents and the like, and particularly for high-efficiency wound treatment in special states (such as war) under the not-flat world background.
Description
Technical Field
The invention relates to a preparation method of an amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing, a preparation method of a multifunctional medical dressing, and belongs 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, plays roles of preventing excessive loss of in-vivo water and electrolyte, maintaining stability of in-vivo environment, regulating body temperature, protecting a wound, preventing external microorganism invasion and the like before skin recovery or reconstruction, and prevents and reduces complications such as wound infection and the like.
Skin injury caused by accidents or operations occurs to tens of millions of people every year in China, and along with the aggravation of aging of the population, chronic wound surfaces such as pressure sores and ulcers which are closely related to the elderly also increase year by year. According to statistics, the market demand of medical dressings in China reaches 400 hundred million yuan in 2010, and the annual composite growth rate exceeds 20%. However, in the medical dressings currently used in China, the market share of the traditional dressings is as high as more than 80%, and the market share of the novel dressings is far lower than that of developed countries in Europe and America. Compared with the traditional dressing, the novel dressing can improve the speed and the quality of wound healing, relieve pain, has lower replacement frequency and lower actual treatment cost, and meets the development requirement of modern wound care medicine. With the rapid development of the medical and health field in China and the improvement of the requirements of the patients on medical conditions and medical care levels in China, the novel medical dressing is favored by the patients and medical care workers. Therefore, the market of medical dressings in China is huge and the development of the medical dressings is very powerful.
At present, enterprises for producing novel medical dressings in China are few, research and development investment of enterprises is insufficient, products lack competitiveness, most of novel medical dressing markets are occupied by imported products (products of companies such as 3M, duPont and Qiangsheng companies) with high price, great economic pressure is brought to patients in China, and the rapid improvement of the wound nursing medical care level in China is also hindered.
Therefore, the research and development of the domestic novel medical dressing with excellent performance, acceptable price and independent intellectual property rights has very important significance undoubtedly for breaking monopoly and technical barriers of foreign products, promoting the development of the domestic medical dressing industry, improving the medical experience of patients, and reducing the medical cost of the patients and the working strength of medical care workers.
Disclosure of Invention
The invention aims to provide a preparation method of an amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing, which is a multifunctional dressing with good biocompatibility, high efficiency, antibacterium, hydrophilicity and real-time monitoring and hemostasis, can be used for curing serious wounds such as large-area burns and traffic accidents, and particularly can be used for high-efficiency wound treatment in special states (such as war) in the world background.
Yet another object of the present invention is to: provides the product obtained by the method.
The purpose of the invention is realized by the following scheme: a preparation method of amino acid/rare earth nanocrystalline/nano cellulose antibacterial hemostatic dressing adopts an in-situ preparation method, and comprises the following steps:
1) Preparing spherical tree-shaped nano lanthanum oxide: using PAMAM macromolecules as a template agent and alkali liquor as a precipitator, and preparing nano rare earth lanthanum oxide with a spherical tree structure by combining ultrasonic-assisted precipitation and a hydrothermal method;
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) Oxidized regenerated cellulose: forming an acetylation mixed solution by acetic anhydride and acetic acid, and placing cellulose into the mixed solution to obtain acetyl cellulose with an acetyl substitution degree of 0.1 to 3.3; oxidizing acetyl-containing cellulose to form an oxidizing solution from carbon tetrachloride and nitric oxide, soaking the acetyl-containing cellulose in the oxidizing solution, and reacting to obtain oxidized regenerated cellulose containing acetyl, wherein the carboxyl content is 5-26%; in-situ grafting the nano lanthanum oxide coated with the amino acid to acetyl-containing oxidized regenerated cellulose to obtain a wet spinning solution containing the acetyl-containing oxidized regenerated cellulose;
4) The oxidized regenerated cellulose containing acetyl is spun by a wet method and knitted into cloth with certain mass. The acetyl-containing oxidized regenerated cellulose hemostatic dressing is prepared after cutting and folding, and the acetyl-containing oxidized regenerated cellulose hemostatic dressing commodity is obtained after packaging and sterilization.
On the basis of the scheme, the alkali added in the step (1) is ammonia water with different concentrations. The preferred concentration is 0.2mol/L to 0.75 mol/L.
On the basis of the 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.
On the basis of the scheme, the addition proportion of the nano lanthanum oxide in the step (3) is 5-10%; the degree of substitution of acetyl groups is 0.1 to 3.3, and the content of carboxyl groups is 5 to 26 percent; 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 gram weight of the oxidized regenerated cellulose hemostatic dressing containing acetyl is 100 to 350g/m by a non-woven fabric manufacturing process 2 Within the range.
The oxidized regenerated cellulose containing acetyl is spun by a wet method and knitted into cloth with certain quality. The acetyl-containing oxidized regenerated cellulose hemostatic dressing is prepared after cutting and folding, and the acetyl-containing oxidized regenerated cellulose hemostatic dressing commodity is obtained after packaging and sterilization.
The invention also provides the acetyl-containing oxidized regenerated cellulose hemostatic dressing obtained by the method. The hemostatic dressing is prepared from the following components in OH-C 6 upper-COCH 3 The substituted oxidized regenerated cellulose fiber is prepared into the hemostatic dressing through a wet process manufacturing process, slitting, packaging and asepsis.
The principle of the acetyl-containing oxidized regenerated cellulose hemostatic dressing is as follows: the fluorescence responsiveness and antibacterial property of the rare earth nanocrystal and the sterilization and hydrophilicity of amino acid are utilized to realize functional superposition, so that the rare earth nanocrystal has high-efficiency biocompatibility and antibacterial activity (the antibacterial rate is more than 99.9%); sensitive stimulation response to fluorescence is realized, and the fluorescent probe can be used as a hydrophilic group real-time tracer material; meanwhile, the dressing has strong hydrophilicity (the swelling rate can reach 280 percent), and can effectively absorb wound seepage and maintain a healing environment with moderate moisture of the wound; the 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 aim of promoting blood coagulation is fulfilled. The obtained multifunctional dressing is suitable for curing serious wounds such as large-area burns, car accidents and the like, and particularly for high-efficiency wound treatment in special states (such as war) under the not-flat world background.
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 particularly for high-efficiency wound treatment in special states (such as war) under the not-flat world background.
Drawings
FIG. 1: scanning electron microscope images of the amino acid/rare earth nanocrystal/cellulose composite material prepared in example 2.
Example 1
An amino acid/rare earth nanocrystalline/nano cellulose antibacterial hemostatic dressing is prepared by the following steps:
1) Preparing spherical tree-shaped nano lanthanum oxide: taking dendrimer PAMAM macromolecules as a template agent and 0.2mol/L ammonia water as a precipitator, combining an ultrasonic-assisted precipitation method with a hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-neck flask, placing the flask in 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, dropwise adding the solution at the speed of 1 ml/min, after the completion, continuing to process for 1 h in the ultrasonic instrument, and taking out a white precipitate; taking 60 ml of white precipitate, adding the white precipitate into a high-pressure reaction kettle for further treatment, heating the white precipitate at 140 ℃ for 6 hours, separating the obtained sample by using a centrifugal machine, washing the sample for a plurality of times by using ethanol, taking the sample out, drying the sample in a drying oven at 140 ℃ for 2 hours, calcining the sample at 750 ℃ for 5 hours, grinding the sample to prepare nano rare earth lanthanum oxide n-RE powder with a spherical tree-shaped structure, and sealing and storing the nano rare earth lanthanum oxide n-RE powder;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-phenylalanine NCA solution, weighing 0.1gn-RE powder, coating the N-RE prepared in the step (1) with L-phenylalanine NCA on the surface by adopting a microcapsule polymerization process to obtain amino acid coated nano lanthanum oxide, cleaning, and freeze-drying;
3) Oxidized regenerated cellulose: forming acetylation mixed solution by acetic anhydride and acetic acid, placing a certain amount of cellulose into the mixed solution, and substituting OH-C6 on part of cellulose by acetyl to obtain acetyl substitution degree of 1.0; oxidizing acetyl-containing cellulose, forming an oxidizing solution by carbon tetrachloride and nitric oxide, soaking the acetyl-containing cellulose into the oxidizing solution, and reacting to obtain oxidized regenerated cellulose containing acetyl and acetyl-containing cellulose with 17% of carboxyl content; in-situ grafting the nano lanthanum oxide coated with amino acid to oxidized regenerated cellulose containing acetyl; the nano lanthanum oxide is added with the mass percentage of 5 percent to obtain a wet spinning solution containing acetyl oxidized regenerated cellulose;
4) Carrying out wet spinning on the oxidized regenerated cellulose containing acetyl to obtain a filament bundle with the linear density of 1.1dtex, and carrying out S-direction twisting on the oxidized regenerated cellulose containing acetyl with the twist of 15 twists/1 cm,166D; knitting 235g of cloth; after cutting and folding, the hemostatic dressing containing acetyl oxidized regenerated cellulose is prepared, and then the hemostatic dressing containing acetyl oxidized regenerated cellulose is obtained after packaging and sterilization.
And (3) detecting the sterilization performance: according to the 'sterilization technical specification' 2002 edition, a disc diffusion method is adopted for detecting the sterilization performance. Test results show that the composite dressing has a killing rate of more than 99.999 percent on escherichia coli (8099 type), a killing rate of more than 99.999 percent on staphylococcus aureus (ATCC 6538 type), a killing rate of more than 99.999 percent on pseudomonas aeruginosa (ATCC 9027 type) and a killing rate of more than 99.999 percent on candida albicans (ATCC 10231 type);
in vitro blood circulation coagulation test: the absorption capacity of the tested 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: by using a weighing method for testing, the swelling ratio of the prepared amino acid/rare earth nanocrystal/acetylated cellulose composite material is 228%, and the composite material has excellent hydrophilicity.
Example 2
An amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing is prepared by the following steps similar to the steps of the embodiment 1:
1) Preparing spherical tree-shaped nano lanthanum oxide: taking dendritic macromolecular PAMAM macromolecules as a template agent, taking 0.4mol/L ammonia water as a precipitator, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-mouth flask by adopting an ultrasonic-assisted hydrothermal method, placing the flask into an ultrasonic instrument, adjusting the temperature to be 20 +/-5 ℃, slowly adding 0.4mol/L ammonia water precipitator into the lanthanum nitrate solution by using a constant-pressure funnel, dropwise adding the solution at the speed of 1 ml/min, continuing to process for 1 h in the ultrasonic instrument after the completion, and taking out the precipitate; taking 60 ml of white precipitate, adding the white precipitate into a high-pressure reaction kettle for further treatment, heating the white precipitate at 140 ℃ for 6 hours, separating the obtained sample by using a centrifugal machine, washing the sample for a plurality of times by using ethanol, taking the sample out, drying the sample in a drying oven at 140 ℃ for 2 hours, calcining the sample at 750 ℃ for 5 hours, grinding the prepared nano rare earth lanthanum oxide n-RE with the spherical tree-shaped structure, and sealing and storing the nano rare earth lanthanum oxide n-RE;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-leucine NCA solution, weighing 0.1g of n-RE powder, coating the n-RE surface 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) Oxidized regenerated cellulose: forming acetylation mixed solution by acetic anhydride and acetic acid, placing a certain amount of cellulose into the mixed solution, and substituting OH-C6 on part of cellulose by acetyl to obtain cellulose containing acetyl, wherein the substitution degree of the acetyl is 0.4; oxidizing acetyl-containing cellulose to form an oxidizing solution from carbon tetrachloride and nitric oxide, soaking the acetyl-containing cellulose in the oxidizing solution, and reacting to obtain oxidized regenerated cellulose containing acetyl with the carboxyl content of 23%; grafting 5% of the nano lanthanum oxide coated by the amino acid obtained in the step 2) to acetyl-containing oxidized regenerated cellulose in situ to obtain a wet spinning solution containing acetyl-containing oxidized regenerated cellulose;
4) Carrying out wet spinning on oxidized regenerated cellulose containing acetyl to obtain long tows with the linear density of 1.6 dtex; twisting oxidized regenerated cellulose filaments containing acetyl in the S direction, wherein the twist is 15 twists/1cm, 166D; knitting 230g of cloth, cutting and folding to prepare the hemostatic dressing containing acetyl oxidized regenerated cellulose, and packaging and sterilizing to obtain the hemostatic dressing product containing acetyl oxidized regenerated cellulose. The hemostatic dressing is an amino acid/rare earth nanocrystalline/cellulose composite material, and a scanning electron microscope picture of the hemostatic dressing is shown in figure 1.
And (3) sterilization performance detection: according to the 'sterilization technical specification' 2002 edition, the disc diffusion method is adopted for detecting the sterilization performance: according to the 'sterilization technical specification' 2002 edition, a disc diffusion method is adopted for sterilization performance detection. Test results show that the composite dressing has a killing rate of more than 99.99 percent on escherichia coli (8099 type), more than 99.999 percent on staphylococcus aureus (ATCC 6538 type), more than 99.999 percent on pseudomonas aeruginosa (ATCC 9027 type) and more than 99.999 percent on candida albicans (ATCC 10231 type);
in vitro blood circulation coagulation test: the absorption capacity of the tested 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: by using a weighing method for testing, the swelling ratio of the prepared amino acid/rare earth nanocrystal/acetylated cellulose composite material is 250%, and the composite material has excellent hydrophilicity.
Example 3
An amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing is prepared by the following steps similar to the steps of the example 1:
1) Preparing spherical tree-shaped nano lanthanum oxide: taking dendritic macromolecular PAMAM macromolecules as a template agent, taking 0.6mol/L ammonia water as a precipitator, adopting an ultrasonic-assisted hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-neck flask, placing the flask into an ultrasonic instrument, adjusting the temperature to be 20 +/-5 ℃, slowly adding 0.6mol/L ammonia water precipitator into the lanthanum nitrate solution by using a constant-pressure funnel, dropwise adding the solution at the speed of 1 ml/min, after finishing, continuously treating in the ultrasonic instrument for 1 hour, and taking out the precipitate; taking 60 ml of white precipitate, adding the white precipitate into a high-pressure reaction kettle for further treatment, heating the white precipitate at 140 ℃ for 6 hours, separating the obtained sample by using a centrifugal machine, washing the sample for a plurality of times by using ethanol, taking the sample out, drying the sample in a drying oven at 140 ℃ for 2 hours, calcining the sample at 750 ℃ for 5 hours to obtain the nano rare earth lanthanum oxide n-RE with the spherical tree-shaped structure, grinding, sealing and storing;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-valine NCA solution, weighing 0.1gn-RE powder, coating 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) Oxidized regenerated cellulose: forming acetylation mixed solution by acetic anhydride and acetic acid, placing a certain amount of cellulose into the mixed solution, and substituting OH-C6 on part of cellulose by acetyl to obtain acetyl-containing cellulose with acetyl substitution degree of 2.9; oxidizing acetyl-containing cellulose to form an oxidizing solution from carbon tetrachloride and nitric oxide, soaking the acetyl-containing cellulose in the oxidizing solution, and reacting to obtain oxidized regenerated cellulose containing acetyl with the carboxyl content of 7%; nano lanthanum oxide coated with amino acid with the addition ratio of 10% is in-situ grafted to acetyl-containing oxidized regenerated cellulose to obtain a wet spinning solution containing acetyl-containing oxidized regenerated cellulose;
4) Carrying out wet spinning on the oxidized regenerated cellulose containing acetyl, and spinning the oxidized regenerated cellulose containing acetyl into a filament bundle with linear density of 1.5 dtex; twisting oxidized regenerated cellulose filaments containing acetyl in the S direction, wherein the twist is 15 twists/1cm, 32S; knitting the fabric into 300g, cutting and folding the fabric to prepare the hemostatic dressing containing the acetyl oxidized regenerated cellulose, and packaging and sterilizing the hemostatic dressing to obtain the hemostatic dressing commodity containing the acetyl oxidized regenerated cellulose.
And (3) sterilization performance detection: according to the 'sterilization technical specification' 2002 edition, a disc diffusion method is adopted for detecting the sterilization performance. Test results show that the composite dressing has a killing rate of more than 99.99 percent on escherichia coli (8099 type), more than 99.9 percent on staphylococcus aureus (ATCC 6538 type), more than 99.9 percent on pseudomonas aeruginosa (ATCC 9027 type) and more than 99.99 percent on candida albicans (ATCC 10231 type);
in vitro blood circulation coagulation experiment: the absorption capacity of the tested 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: by using a weighing method for testing, the swelling ratio of the prepared amino acid/rare earth nanocrystal/acetylated cellulose composite material is 180%, and the prepared amino acid/rare earth nanocrystal/acetylated cellulose composite material has good hydrophilicity.
Example 4
An amino acid/rare earth nanocrystalline/nanocellulose antibacterial hemostatic dressing is prepared by the following steps similar to the steps of the example 1:
1) Preparing spherical tree-shaped nano lanthanum oxide: taking dendritic macromolecular PAMAM macromolecules as a template agent, taking 0.75mol/L ammonia water as a precipitator, adopting an ultrasonic-assisted hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-mouth flask, placing the flask into an ultrasonic instrument, adjusting the temperature to 20 +/-5 ℃, slowly adding 0.75mol/L ammonia water precipitator into the lanthanum nitrate solution by using a constant-pressure funnel, dropwise adding the solution at the speed of 1 ml/min, after the completion, continuing to process for 1 h in the ultrasonic instrument, and then taking out the precipitate; taking 60 ml of white precipitate, adding the white precipitate into a high-pressure reaction kettle for further treatment, heating the white precipitate for 6 hours at the temperature of 140 ℃, separating the obtained sample by using a centrifugal machine, washing the sample by using ethanol for a plurality of times, taking out the sample, drying the sample in a drying oven at the temperature of 140 ℃ for 2 hours, calcining the sample at the temperature of 750 ℃ for 5 hours, grinding the prepared nano rare earth lanthanum oxide n-RE with the spherical tree-shaped structure to obtain powder, and sealing and storing the powder;
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 L-alanine NCA on the surface of n-RE prepared in the step (1) to obtain amino acid coated nano lanthanum oxide, cleaning, and freeze-drying;
3) Oxidized regenerated cellulose: forming acetylation mixed liquor by acetic anhydride and acetic acid, placing a certain amount of cellulose into the mixed liquor, and substituting OH-C6 on part of cellulose by acetyl to obtain acetyl-containing cellulose with acetyl substitution degree of 2.2; oxidizing acetyl-containing cellulose to form an oxidizing solution from carbon tetrachloride and nitric oxide, soaking the acetyl-containing cellulose in the oxidizing solution, and reacting to obtain oxidized regenerated cellulose containing acetyl, wherein the carboxyl content is 18%; in-situ grafting the nano lanthanum oxide coated with the amino acid onto acetyl-containing oxidized regenerated cellulose, wherein the addition amount of the nano lanthanum oxide is 8% by mass, so as to obtain a wet spinning solution containing acetyl-containing oxidized regenerated cellulose;
4) Carrying out wet spinning on the oxidized regenerated cellulose containing acetyl, and spinning the oxidized regenerated cellulose containing acetyl into a filament bundle with the linear density of 1.6 dtex; twisting oxidized regenerated cellulose filaments containing acetyl in the S direction with a twist of 15 twists/1cm, 166D; knitting 280g of cloth; after cutting and folding, the hemostatic dressing containing acetyl oxidized regenerated cellulose is prepared, and then the hemostatic dressing containing acetyl oxidized regenerated cellulose is obtained after packaging and sterilization.
And (3) sterilization performance detection: according to the 'sterilization technical specification' 2002 edition, a disc diffusion method is adopted for detecting the sterilization performance. Test results show that the composite dressing has a killing rate of more than 99.99 percent on escherichia coli (8099 type), more than 99.999 percent on staphylococcus aureus (ATCC 6538 type), more than 99.999 percent on pseudomonas aeruginosa (ATCC 9027 type) and more than 99.999 percent on candida albicans (ATCC 10231 type);
in vitro blood circulation coagulation test: the absorption capacity of the tested 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: by using a weighing method for testing, the swelling ratio of the prepared amino acid/rare earth nanocrystal/acetylated cellulose composite material is 210%, and the composite material has excellent hydrophilicity.
Claims (9)
1. A preparation method of an amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing is characterized by comprising the following steps:
1) Preparing spherical tree-shaped nano lanthanum oxide: the nano rare earth lanthanum oxide with the spherical tree structure is prepared by taking PAMAM macromolecules as a template agent and alkali liquor as a precipitator and combining an ultrasonic-assisted hydrothermal method;
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) Oxidized regenerated cellulose: forming an acetylation mixed solution by acetic anhydride and acetic acid, and placing cellulose into the mixed solution to obtain acetyl cellulose with an acetyl substitution degree of 0.1 to 3.3; oxidizing acetyl-containing cellulose to form an oxidizing solution from carbon tetrachloride and nitric oxide, soaking the acetyl-containing cellulose in the oxidizing solution to react to obtain acetyl-containing oxidized regenerated cellulose, wherein the carboxyl content is 5-26%; in-situ grafting the nano lanthanum oxide coated with amino acid to regenerated cellulose containing acetyl oxide to obtain wet spinning solution containing regenerated cellulose containing acetyl oxide;
4) Wet spinning the regenerated cellulose containing acetyl oxide, knitting the spun cellulose into cloth, cutting and folding the cloth to prepare the hemostatic dressing containing the regenerated cellulose containing acetyl oxide, and packaging and sterilizing the hemostatic dressing to obtain the hemostatic dressing product containing the regenerated cellulose containing acetyl oxide.
2. The preparation method of the amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing according to claim 1, characterized in that: in the step (1), the alkali liquor is ammonia water.
3. The preparation method of the amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing according to claim 1, characterized in that: in the step (2), the amphiphilic amino acid polymer with positive charges is one of L-phenylalanine NCA, L-leucine NCA, L-valine NCA or L-alanine NCA.
4. The preparation method of the amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing according to claim 1, characterized in that: in the step (3), the adding 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 gram weight of the oxidized regenerated cellulose hemostatic dressing containing acetyl is 100 to 350g/m by a non-woven fabric manufacturing process 2 Within the range.
5. The method for preparing the amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing according to any one of claims 1 to 4, wherein the method comprises the following steps: the preparation method comprises the following steps:
1) Preparing spherical tree-shaped nano lanthanum oxide: taking dendrimer PAMAM macromolecules as a template agent and 0.2mol/L ammonia water as a precipitator, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate into a four-neck flask and placing the flask into an ultrasonic instrument by combining an ultrasonic-assisted precipitation method with a hydrothermal method, adjusting the temperature to be 20 +/-5 ℃, slowly adding 0.2mol/L ammonia water precipitator into the lanthanum nitrate solution by using a constant-pressure funnel, dropwise adding the solution at the speed of 1 ml/min, continuing to process for 1 h in the ultrasonic instrument after the completion, and taking out a white precipitate; taking 60 ml of white precipitate, adding the white precipitate into a high-pressure reaction kettle for further treatment, heating the white precipitate at 140 ℃ for 6 hours, separating the obtained sample by using a centrifugal machine, washing the sample for a plurality of times by using ethanol, taking the sample out, drying the sample in a drying oven at 140 ℃ for 2 hours, calcining the sample at 750 ℃ for 5 hours, grinding the sample to prepare nano rare earth lanthanum oxide n-RE powder with a spherical tree-shaped structure, and sealing and storing the nano rare earth lanthanum oxide n-RE powder;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-phenylalanine NCA solution, weighing 0.1gn-RE powder, coating the n-RE prepared in the step (1) with L-phenylalanine NCA by adopting a microcapsule polymerization process to obtain amino acid coated nano lanthanum oxide, cleaning, and freeze-drying;
3) Oxidized regenerated cellulose: acetic anhydride and acetic acid form acetylation mixed liquor, a certain amount of cellulose is placed in the mixed liquor, and the acetyl replaces OH-C6 on part of the cellulose to obtain acetyl substitution degree of 1.0; oxidizing acetyl-containing cellulose, forming an oxidation solution by carbon tetrachloride and nitric oxide, soaking the acetyl-containing cellulose into the oxidation solution, and reacting to obtain oxidized regenerated cellulose containing acetyl and acetyl-containing cellulose with 17% of carboxyl content; in-situ grafting the nano lanthanum oxide coated with amino acid to oxidized regenerated cellulose containing acetyl; the nano lanthanum oxide is added with the mass percentage of 5 percent to obtain wet spinning solution containing acetyl oxidized regenerated cellulose;
4) Carrying out wet spinning on the oxidized regenerated cellulose containing acetyl to obtain a filament bundle with the linear density of 1.1dtex, and carrying out S-direction twisting on the oxidized regenerated cellulose containing acetyl with the twist of 15 twists/1 cm,166D; knitting the cloth into 235 g; after cutting and folding, the hemostatic dressing containing acetyl oxidized regenerated cellulose is prepared, and then the hemostatic dressing containing acetyl oxidized regenerated cellulose is obtained after packaging and sterilization.
6. The method for preparing the amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing according to any one of claims 1 to 4, wherein the method comprises the following steps: the preparation method comprises the following steps:
1) Preparing spherical tree-shaped nano lanthanum oxide: taking dendritic macromolecular PAMAM macromolecules as a template agent, taking 0.4mol/L ammonia water as a precipitator, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-mouth flask by adopting an ultrasonic-assisted hydrothermal method, placing the flask into an ultrasonic instrument, adjusting the temperature to be 20 +/-5 ℃, slowly adding 0.4mol/L ammonia water precipitator into the lanthanum nitrate solution by using a constant-pressure funnel, dropwise adding the solution at the speed of 1 ml/min, continuing to process for 1 h in the ultrasonic instrument after the completion, and taking out the precipitate; taking 60 ml of white precipitate, adding the white precipitate into a high-pressure reaction kettle for further treatment, heating the white precipitate at 140 ℃ for 6 hours, separating the obtained sample by using a centrifugal machine, washing the sample for a plurality of times by using ethanol, taking the sample out, drying the sample in a drying oven at 140 ℃ for 2 hours, calcining the sample at 750 ℃ for 5 hours, grinding the prepared nano rare earth lanthanum oxide n-RE with the spherical tree-shaped structure, and sealing and storing the nano rare earth lanthanum oxide n-RE;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-leucine NCA solution, weighing 0.1g of n-RE powder, coating the n-RE surface 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) Oxidized regenerated cellulose: forming acetylation mixed solution by acetic anhydride and acetic acid, placing a certain amount of cellulose into the mixed solution, and substituting OH-C6 on part of cellulose by acetyl to obtain cellulose containing acetyl, wherein the substitution degree of the acetyl is 0.4; oxidizing acetyl-containing cellulose to form an oxidizing solution from carbon tetrachloride and nitric oxide, soaking the acetyl-containing cellulose in the oxidizing solution, and reacting to obtain oxidized regenerated cellulose containing acetyl with the carboxyl content of 23%; grafting 5% of the nano lanthanum oxide coated by the amino acid obtained in the step 2) to acetyl-containing oxidized regenerated cellulose in situ to obtain a wet spinning solution containing acetyl-containing oxidized regenerated cellulose;
4) Carrying out wet spinning on oxidized regenerated cellulose containing acetyl to obtain long tows with the linear density of 1.6 dtex; twisting oxidized regenerated cellulose filaments containing acetyl in the S direction with a twist of 15 twists/1cm, 166D; knitting 230g of cloth, cutting and folding to prepare the hemostatic dressing containing acetyl oxidized regenerated cellulose, and packaging and sterilizing to obtain the hemostatic dressing product containing acetyl oxidized regenerated cellulose.
7. The method for preparing the amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing according to any one of claims 1 to 4, wherein the method comprises the following steps: the preparation method comprises the following steps:
1) Preparing spherical tree-shaped nano lanthanum oxide: taking dendritic macromolecular PAMAM macromolecules as a template agent, taking 0.6mol/L ammonia water as a precipitator, adopting an ultrasonic-assisted hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-neck flask, placing the flask into an ultrasonic instrument, adjusting the temperature to be 20 +/-5 ℃, slowly adding 0.6mol/L ammonia water precipitator into the lanthanum nitrate solution by using a constant-pressure funnel, dropwise adding the solution at the speed of 1 ml/min, after finishing, continuously treating in the ultrasonic instrument for 1 hour, and taking out the precipitate; taking 60 ml of white precipitate, adding the white precipitate into a high-pressure reaction kettle for further treatment, heating the white precipitate at 140 ℃ for 6 hours, separating the obtained sample by using a centrifugal machine, washing the sample for a plurality of times by using ethanol, taking the sample out, drying the sample in a drying oven at 140 ℃ for 2 hours, calcining the sample at 750 ℃ for 5 hours to obtain the nano rare earth lanthanum oxide n-RE with the spherical tree-shaped structure, grinding, sealing and storing;
2) Synthesis of lanthanum oxide/amino acid complex: preparing 0.1 mol/L-valine NCA solution, weighing 0.1gn-RE powder, coating 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) Oxidized regenerated cellulose: forming acetylation mixed liquor by acetic anhydride and acetic acid, placing a certain amount of cellulose into the mixed liquor, and substituting OH-C6 on part of cellulose by acetyl to obtain acetyl-containing cellulose with acetyl substitution degree of 2.9; oxidizing acetyl-containing cellulose to form an oxidizing solution from carbon tetrachloride and nitric oxide, soaking the acetyl-containing cellulose in the oxidizing solution, and reacting to obtain oxidized regenerated cellulose containing acetyl with the carboxyl content of 7%; the nanometer lanthanum oxide coated by amino acid with the addition proportion of 10 percent is in-situ grafted to the acetyl-containing oxidized regenerated cellulose to obtain a wet spinning solution containing the acetyl-containing oxidized regenerated cellulose;
4) Carrying out wet spinning on the oxidized regenerated cellulose containing acetyl, and spinning the oxidized regenerated cellulose containing acetyl into a filament bundle with the linear density of 1.5 dtex; twisting oxidized regenerated cellulose filaments containing acetyl in the S direction, wherein the twist is 15 twists/1cm, 32S; knitting the fabric into 300g of cloth, cutting and folding the cloth to prepare the acetyl-containing oxidized regenerated cellulose hemostatic dressing, and packaging and sterilizing the acetyl-containing oxidized regenerated cellulose hemostatic dressing to obtain a hemostatic dressing commodity.
8. The method for preparing the amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing according to any one of claims 1 to 4, wherein the method comprises the following steps: the preparation method comprises the following steps:
1) Preparing spherical tree-shaped nano lanthanum oxide: taking dendritic macromolecular PAMAM macromolecules as a template agent, taking 0.75mol/L ammonia water as a precipitator, adopting an ultrasonic-assisted hydrothermal method, putting 50ml of 0.2mol/L lanthanum nitrate hexahydrate solution into a four-mouth flask, placing the flask into an ultrasonic instrument, adjusting the temperature to 20 +/-5 ℃, slowly adding 0.75mol/L ammonia water precipitator into the lanthanum nitrate solution by using a constant-pressure funnel, dropwise adding the solution at the speed of 1 ml/min, after the completion, continuing to process for 1 h in the ultrasonic instrument, and then taking out the precipitate; taking 60 ml of white precipitate, adding the white precipitate into a high-pressure reaction kettle for further treatment, heating the white precipitate for 6 hours at the temperature of 140 ℃, separating the obtained sample by using a centrifugal machine, washing the sample by using ethanol for a plurality of times, taking out the sample, drying the sample in a drying oven at the temperature of 140 ℃ for 2 hours, calcining the sample at the temperature of 750 ℃ for 5 hours, grinding the prepared nano rare earth lanthanum oxide n-RE with the spherical tree-shaped structure to obtain powder, and sealing and storing the powder;
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 L-alanine NCA on the surface of n-RE prepared in the step (1) to obtain amino acid coated nano lanthanum oxide, cleaning, and freeze-drying;
3) Oxidized regenerated cellulose: forming acetylation mixed solution by acetic anhydride and acetic acid, placing a certain amount of cellulose into the mixed solution, and substituting OH-C6 on part of cellulose by acetyl to obtain acetyl-containing cellulose with acetyl substitution degree of 2.2; oxidizing acetyl-containing cellulose to form an oxidizing solution from carbon tetrachloride and nitric oxide, soaking the acetyl-containing cellulose in the oxidizing solution, and reacting to obtain oxidized regenerated cellulose containing acetyl, wherein the carboxyl content is 18%; in-situ grafting the nano lanthanum oxide coated with amino acid to regenerated cellulose containing acetyl oxide, wherein the addition amount of the nano lanthanum oxide is 8% by mass, so as to obtain wet spinning solution containing regenerated cellulose containing acetyl oxide;
4) Carrying out wet spinning on the oxidized regenerated cellulose containing acetyl, and spinning the oxidized regenerated cellulose containing acetyl into a filament bundle with the linear density of 1.6 dtex; twisting oxidized regenerated cellulose filaments containing acetyl in the S direction with a twist of 15 twists/1cm, 166D; knitting 280g of cloth; after cutting and folding, the hemostatic dressing containing acetyl oxidized regenerated cellulose is prepared, and then the hemostatic dressing containing acetyl oxidized regenerated cellulose is obtained after packaging and sterilization.
9. An amino acid/rare earth nanocrystal/nanocellulose antibacterial hemostatic dressing obtained by the preparation method of any one of claims 1 to 8.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010076418A (en) * | 2000-01-24 | 2001-08-11 | 나카무라 하사오 | Water-swellable polymer gel and process for preparing the same |
| US20040101546A1 (en) * | 2002-11-26 | 2004-05-27 | Gorman Anne Jessica | Hemostatic wound dressing containing aldehyde-modified polysaccharide and hemostatic agents |
| US20060216759A1 (en) * | 2004-10-29 | 2006-09-28 | Imad Naasani | Functionalized fluorescent nanocrystals, and methods for their preparation and use |
| CN101462708A (en) * | 2008-12-30 | 2009-06-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Nano antibacterial hydroxylapatite and preparation thereof |
| US20100298264A1 (en) * | 2009-05-20 | 2010-11-25 | Huizhou Foryou Medical Devices Co., Ltd | Biodegradable and water-soluble hemostatic material and a method for preparing the same |
| CN102504245A (en) * | 2011-11-01 | 2012-06-20 | 中国药科大学 | Amphipathic amino acid block copolymer and preparation method and application thereof |
| US20120294921A1 (en) * | 2010-01-27 | 2012-11-22 | Xiaozhong Huang | Antibacterial agent and method of preparing the same |
| BR302012003681S1 (en) * | 2012-07-20 | 2013-12-17 | TENNIS CONFIGURATION | |
| US20140220082A1 (en) * | 2011-06-28 | 2014-08-07 | University Of Utah Research Foundation | Adhesive complex coacervates and methods of making and using thereof |
| US20140248310A1 (en) * | 2012-12-20 | 2014-09-04 | Frank A. Robey | Cationic metal oxides for use as vaccine adjuvants |
| CN104383586A (en) * | 2014-12-01 | 2015-03-04 | 哈尔滨工业大学 | Nanogold/lysine/oxidized regenerated cellulose composite hemostatic material and preparation method thereof |
| US20200230283A1 (en) * | 2019-01-23 | 2020-07-23 | Central South University | Nano-oxide/kaolin composite hemostatic antibacterial material, hemostatic healing-promoting dressing and preparation method thereof |
| CN112603908A (en) * | 2020-12-02 | 2021-04-06 | 中山大学 | Nano drug-loading system based on amino acid polymer and preparation method and application thereof |
| CN112604025A (en) * | 2020-11-05 | 2021-04-06 | 西安交通大学 | Rare earth-based nano composite hydrogel wound dressing and preparation method and application thereof |
| CN114010834A (en) * | 2021-10-29 | 2022-02-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Acetyl-containing oxidized regenerated cellulose hemostatic dressing |
-
2022
- 2022-08-19 CN CN202211001048.5A patent/CN115475271B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010076418A (en) * | 2000-01-24 | 2001-08-11 | 나카무라 하사오 | Water-swellable polymer gel and process for preparing the same |
| US20040101546A1 (en) * | 2002-11-26 | 2004-05-27 | Gorman Anne Jessica | Hemostatic wound dressing containing aldehyde-modified polysaccharide and hemostatic agents |
| US20060216759A1 (en) * | 2004-10-29 | 2006-09-28 | Imad Naasani | Functionalized fluorescent nanocrystals, and methods for their preparation and use |
| CN101462708A (en) * | 2008-12-30 | 2009-06-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Nano antibacterial hydroxylapatite and preparation thereof |
| US20100298264A1 (en) * | 2009-05-20 | 2010-11-25 | Huizhou Foryou Medical Devices Co., Ltd | Biodegradable and water-soluble hemostatic material and a method for preparing the same |
| US20120294921A1 (en) * | 2010-01-27 | 2012-11-22 | Xiaozhong Huang | Antibacterial agent and method of preparing the same |
| US20140220082A1 (en) * | 2011-06-28 | 2014-08-07 | University Of Utah Research Foundation | Adhesive complex coacervates and methods of making and using thereof |
| CN102504245A (en) * | 2011-11-01 | 2012-06-20 | 中国药科大学 | Amphipathic amino acid block copolymer and preparation method and application thereof |
| BR302012003681S1 (en) * | 2012-07-20 | 2013-12-17 | TENNIS CONFIGURATION | |
| US20140248310A1 (en) * | 2012-12-20 | 2014-09-04 | Frank A. Robey | Cationic metal oxides for use as vaccine adjuvants |
| CN104383586A (en) * | 2014-12-01 | 2015-03-04 | 哈尔滨工业大学 | Nanogold/lysine/oxidized regenerated cellulose composite hemostatic material and preparation method thereof |
| US20200230283A1 (en) * | 2019-01-23 | 2020-07-23 | Central South University | Nano-oxide/kaolin composite hemostatic antibacterial material, hemostatic healing-promoting dressing and preparation method thereof |
| CN112604025A (en) * | 2020-11-05 | 2021-04-06 | 西安交通大学 | Rare earth-based nano composite hydrogel wound dressing and preparation method and application thereof |
| CN112603908A (en) * | 2020-12-02 | 2021-04-06 | 中山大学 | Nano drug-loading system based on amino acid polymer and preparation method and application thereof |
| CN114010834A (en) * | 2021-10-29 | 2022-02-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Acetyl-containing oxidized regenerated cellulose hemostatic dressing |
Non-Patent Citations (6)
| Title |
|---|
| FURONG CHEN ET AL: "Effect of La2O3 particle size on the microstructure and properties of Al Si alloys deposited via wire arc additive manufacturing", 《JOURNAL OF MANUFACTURING PROCESSES》 * |
| 刘东伟: "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", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, pages 21 - 22 * |
| 南方;赖琛;奚廷斐;: "细菌纤维素与纳米银复合制备创伤敷料", 中国组织工程研究, no. 43 * |
| 林琳: "氧化钴及其复合材料在储能领域的研究进展", 《电源技术》 * |
| 贺金梅;王凤文;张华威;吴亚东;谷红波;黄玉东;: "医用可吸收止血材料的功能化改性研究进展", 现代化工, no. 12 * |
| 黄方言: "《现代实用中药新剂型新技术》", 人民卫生出版社 * |
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