CN118563451A - Preparation method of degradable absorbing fiber based on casein and application of degradable absorbing fiber - Google Patents
Preparation method of degradable absorbing fiber based on casein and application of degradable absorbing fiber Download PDFInfo
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- CN118563451A CN118563451A CN202410769673.7A CN202410769673A CN118563451A CN 118563451 A CN118563451 A CN 118563451A CN 202410769673 A CN202410769673 A CN 202410769673A CN 118563451 A CN118563451 A CN 118563451A
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- 239000000835 fiber Substances 0.000 title claims abstract description 78
- 239000005018 casein Substances 0.000 title claims abstract description 47
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 235000021240 caseins Nutrition 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 9
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- 229940005550 sodium alginate Drugs 0.000 claims abstract description 44
- 239000000661 sodium alginate Substances 0.000 claims abstract description 44
- -1 aldehyde sodium alginate Chemical class 0.000 claims abstract description 30
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 238000009987 spinning Methods 0.000 claims description 21
- 230000001112 coagulating effect Effects 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000002166 wet spinning Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 230000002787 reinforcement Effects 0.000 claims description 5
- 239000011265 semifinished product Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 3
- 239000003356 suture material Substances 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
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- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 abstract description 2
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- 150000004753 Schiff bases Chemical class 0.000 abstract description 2
- 125000003172 aldehyde group Chemical group 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 238000010382 chemical cross-linking Methods 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 125000000879 imine group Chemical group 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 1
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- 229920002647 polyamide Polymers 0.000 description 3
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- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
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Classifications
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/06—At least partially resorbable materials
- A61L17/10—At least partially resorbable materials containing macromolecular materials
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Vascular Medicine (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Surgery (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Toxicology (AREA)
- Artificial Filaments (AREA)
- Materials For Medical Uses (AREA)
Abstract
A degradable absorbing fiber based on casein is prepared through oxidizing the o-diol structure on structural unit of sodium alginate by sodium periodate to form aldehyde group, obtaining aldehyde sodium alginate, generating dynamic imine group by Schiff base reaction of aldehyde group on molecular chain of protein, cross-linking casein by aldehyde sodium alginate to form dynamic chemical cross-linking, and forming stable chemical covalent bond by epoxy group of polyethylene glycol diglycidyl ether, amino group of protein and antelope group to realize two-stage cross-linking of casein and reinforcing casein fiber. Can be used as a baseline for surgical sutures. The suture has enough mechanical strength and good biocompatibility, and can meet the requirements of practical application.
Description
Technical Field
The invention belongs to the technical field of biomedical material preparation, and particularly relates to a preparation method of degradable absorbing fibers based on casein and application of the degradable absorbing fibers.
Background
The market development prospect of the suture line at the current stage is huge, and the practical application of medical suture lines made of different materials still has respective defects, and the current surgical suture lines are divided into two types of natural and synthetic:
The raw materials used for natural sutures are typically animal or vegetable fibers, the most common raw materials being taken mainly from silk and animal gut. The animal intestinal line mainly comprises intestinal submucosa and bovine serosa of goats and sheep, and comprises macromolecular proteins with triple helix structures which are mainly formed by winding three polypeptides. The natural suture line made of the intestinal thread material belongs to an absorbable biological material, and the material has low production cost and wide sources, but at the same time, the strength of the intestinal thread is uneven, the intestinal thread is not even enough when being degraded in a human body, and the problems of poor wear resistance and the like exist. In addition, it should be noted that silk suture is easy to adsorb bacteria, causes wound infection, is not easy to degrade in vivo, and can form granuloma, abscess and even non-healing sinus, which is also a symptom for limiting the development of silk suture.
Synthetic sutures are such as Polyamide (PA) fibers, polyester (PET) fibers, polypropylene (PP) fibers, etc., which have disadvantages in that the softness of single-strand sutures is to be improved, and knotting is difficult; the multi-strand PA suture line has high tissue reactivity and is easy to cause inflammation.
The fiber obtained by spinning casein in the prior art has low strength, poor toughness and good sustainability, and cannot be applied to the field of industry or food and medicine on a large scale.
With the development of material preparation technology and the progress of medical level, the suture is expected to play roles in antibiosis, anti-inflammation, wound monitoring and the like so as to better promote wound healing and relieve the pain of wounded. Therefore, improvement of the properties of the raw material fiber and multifunctionality of the suture in suture development are important research directions in the future.
Disclosure of Invention
The invention provides a preparation method of degradable absorbing fiber based on casein, which aims to improve the spinnability of the casein and solve the problems of low mechanical strength of the casein fiber and the like.
The degradable absorbing fiber prepared by the method is used as a surgical suture material.
The technical scheme adopted by the invention is as follows:
A preparation method of degradable absorbing fiber based on casein, which comprises the following steps:
(1) Preparing aldehyde sodium alginate; preparing a sodium alginate solution with the solubility of 3%, adding sodium periodate with the same mass as sodium alginate, carrying out light-proof reaction for 12 hours, and adding ethylene glycol with the same mass as the sodium periodate to terminate the reaction for 1 hour after the reaction is finished.
Adding 3 parts of sodium chloride and 100 parts of ethanol by weight of the sodium alginate solution to obtain a crude product, dissolving the crude product in 100 parts of water, adding 3 parts of sodium chloride and 100 parts of ethanol again, collecting precipitate, and drying to obtain the aldehyde sodium alginate.
(2) Preparing a spinning solution: adding 0.5-2 parts of sodium carbonate and 0.5-2 parts of sodium bicarbonate into 70-100 parts of deionized water, adding casein and aldehyde sodium alginate, so that the mass ratio of the aldehyde sodium alginate to the casein is 1:1-1:10, and mechanically stirring uniformly to form a viscous spinning stock solution.
(3) And (3) discharging bubbles: and (3) discharging bubbles by using a vacuum pump filtering device to obtain the uniform bubble-free spinning solution, wherein the pressure of the vacuum pump is 0.3-0.6 mpa.
(4) Wet spinning: wet spinning is carried out on the defoamed spinning solution, the first coagulating bath is 25wt% ammonium sulfate solution, the pH value is regulated to 4.6 by a small amount of acetic acid, and the fiber residence time is 2h; after the fiber passes through the first coagulating bath, the fiber continuously enters a second coagulating bath, wherein the second coagulating bath comprises 5 weight percent of ethylene glycol and 75 weight percent of ethanol water solution, and the fiber stays in the second coagulating bath for 6-8 hours;
(5) And (3) secondary crosslinking reinforcement: after the first coagulating bath and the second coagulating bath, collecting fibers, putting the fibers into an ethylene glycol diglycidyl ether ethanol aqueous solution with the concentration of 0.4% -0.8%, and reacting overnight at 30-50 ℃.
(6) Rinsing and drying to obtain a semi-finished product: and collecting the fibers, rinsing with clear water for 1-2 h, and naturally airing to obtain a finished product of the degradable and absorbable fibers based on casein.
Use of casein-based degradable absorbent fibres obtained by the method according to the invention as a surgical stapling material.
The invention has the advantages that:
Sodium Alginate (SA) is extracted from brown algae, has good biocompatibility and wide application. The method comprises the steps of oxidizing an o-glycol structure on a sodium alginate structural unit by sodium periodate to form an aldehyde functional group to obtain aldehyde sodium alginate, generating Schiff base reaction when the aldehyde group encounters an amino functional group carried on a molecular chain of protein to generate a dynamic imine group, namely, performing one-stage crosslinking on casein by using the aldehyde sodium alginate to form a dynamic chemical crosslinking, and then forming a stable chemical covalent bond by using an epoxy group carried by polyethylene glycol diglycidyl ether, an amino group and a antelope group of the protein to realize two-stage crosslinking on casein, and reinforcing casein fibers to obtain the degradable multi-aldehyde sodium alginate-casein absorbable fibers.
In addition, sodium chloride with a certain concentration is added in the casein crosslinking process, and the sodium chloride changes the secondary structure of protein and improves the mechanical strength of the fiber by influencing the intermolecular interaction and crosslinking degree of the polyaldehyde sodium alginate-casein composite system. The method provided by the invention improves the defects of no mechanical property and poor stability of the original pure casein fiber, improves the strength of the fiber, has the characteristics of safety and no toxicity, and can be used as a base line of an operation suture line. The suture has enough mechanical strength and good biocompatibility, and can meet the requirements of practical application. The application prospect of casein in the medical field is widened, and a new preparation idea is provided for the field of absorbable fibers.
The surgical suture prepared by combining casein and sodium alginate is easy to absorb or drain, so that the pain of a patient caused by secondary surgery is avoided, inflammatory reaction can be reduced, and the recovered wound surface is smooth and flat. Not only can the healing effect similar to that of the non-absorbable suture be ensured, but also the hospitalization time and the economic cost can be obviously reduced.
Drawings
FIG. 1 is a graph showing the effect of sodium chloride addition on fiber strength;
FIG. 2 is a casein based degradable absorbent fiber product resulting from the process of the present invention;
FIG. 3 is a graph of cell viability versus cytotoxicity test of the finished product of the present invention.
Detailed Description
The following detailed description of the invention is further detailed in connection with the following examples, which are intended to be illustrative, not limiting, and are not intended to limit the scope of the invention.
The test methods used in the examples below are all conventional, all materials, reagents, methods, apparatus, not specifically described, of ordinary specifications, and commercially available to those skilled in the art.
Example 1, a method for preparing a casein based degradable absorbent fiber, comprising the steps of:
(1) Preparing aldehyde sodium alginate; preparing a sodium alginate solution with the solubility of 3%, adding sodium periodate with the same mass as sodium alginate, carrying out light-proof reaction for 12 hours, and adding ethylene glycol with the same mass as the sodium periodate to terminate the reaction for 1 hour after the reaction is finished.
Adding 3 parts of sodium chloride and 100 parts of ethanol by weight of the sodium alginate solution to obtain a crude product, dissolving the crude product in 100 parts of water, adding 3 parts of sodium chloride and 100 parts of ethanol again, collecting precipitate, and drying to obtain the aldehyde sodium alginate.
(2) Preparing a spinning solution: adding 0.5 part of sodium carbonate and 0.5 part of sodium bicarbonate into 70 parts of deionized water, adding casein and aldehyde sodium alginate to make the mass ratio of the aldehyde sodium alginate to the casein be 1:1, and mechanically stirring uniformly to form a viscous spinning stock solution.
(3) And (3) discharging bubbles: discharging bubbles by using a vacuum pump filtering device to obtain uniform bubble-free spinning solution, wherein the pressure of the vacuum pump is 0.3Mpa;
(4) Wet spinning: wet spinning is carried out on the defoamed spinning solution, the first coagulating bath is 25wt% ammonium sulfate solution, the pH value is regulated to 4.6 by a small amount of acetic acid, and the fiber residence time is 2h; after passing through the first coagulation bath, the fiber continues to a second coagulation bath consisting of 5wt% ethylene glycol and 75wt% aqueous ethanol in which the fiber resides for 6 hours.
(5) And (3) secondary crosslinking reinforcement: after passing through the first and second coagulating baths, the collected fibers are put into an aqueous solution of ethylene glycol diglycidyl ether ethanol with concentration of 0.4% -0.8%, the concentration of ethanol is 75%, and the reaction is carried out at 30 ℃ overnight.
(6) Rinsing and drying to obtain a semi-finished product: collecting the fibers, rinsing with clear water for 1h, and naturally airing to obtain a finished product of the degradable and absorbable fiber based on casein.
Example 2, a method for preparing a casein based degradable absorbent fiber, comprising the steps of:
(1) Preparing aldehyde sodium alginate; preparing a sodium alginate solution with the solubility of 3%, adding sodium periodate with the same mass as sodium alginate, carrying out light-proof reaction for 12 hours, and adding ethylene glycol with the same mass as the sodium periodate to terminate the reaction for 1 hour after the reaction is finished.
Adding 3 parts of sodium chloride and 100 parts of ethanol by weight of the sodium alginate solution to obtain a crude product, dissolving the crude product in 100 parts of water, adding 3 parts of sodium chloride and 100 parts of ethanol again, collecting precipitate, and drying to obtain the aldehyde sodium alginate.
(2) Preparing a spinning solution: adding 1 part of sodium carbonate and 1 part of sodium bicarbonate into 100 parts of deionized water, adding casein and aldehyde sodium alginate to make the mass ratio of the aldehyde sodium alginate to the casein be 1:5, and mechanically stirring uniformly to form a viscous spinning solution.
(3) And (3) discharging bubbles: discharging bubbles by using a vacuum pump filtering device to obtain uniform bubble-free spinning solution, wherein the pressure of the vacuum pump is 0.6Mpa;
(4) Wet spinning: wet spinning is carried out on the defoamed spinning solution, the first coagulating bath is 25wt% ammonium sulfate solution, the pH value is regulated to 4.6 by a small amount of acetic acid, and the fiber residence time is 2h; after passing through the first coagulation bath, the fiber continues to a second coagulation bath consisting of 5wt% ethylene glycol and 75wt% aqueous ethanol in which the fiber resides for 8 hours.
(5) And (3) secondary crosslinking reinforcement: after passing through the first and second coagulation baths, the collected fibers were placed in an aqueous solution of ethylene glycol diglycidyl ether ethanol having a concentration of 0.8% and ethanol having a concentration of 75% and reacted overnight at 50 ℃.
(6) Rinsing and drying to obtain a semi-finished product: collecting the fibers, rinsing with clear water for 2 hours, and naturally airing to obtain a finished product of the degradable and absorbable fiber based on casein.
Example 3, a method for preparing a casein based degradable absorbent fiber, comprising:
(1) Preparing aldehyde sodium alginate; preparing a sodium alginate solution with the solubility of 3%, adding sodium periodate with the same mass as sodium alginate, carrying out light-proof reaction for 12 hours, and adding ethylene glycol with the same mass as the sodium periodate to terminate the reaction for 1 hour after the reaction is finished.
Adding 3 parts of sodium chloride and 100 parts of ethanol by weight of the sodium alginate solution to obtain a crude product, dissolving the crude product in 100 parts of water, adding 3 parts of sodium chloride and 100 parts of ethanol again, collecting precipitate, and drying to obtain the aldehyde sodium alginate.
(2) Preparing a spinning solution: adding 2 parts of sodium carbonate and 2 parts of sodium bicarbonate into 80 parts of deionized water, adding casein and aldehyde sodium alginate to make the mass ratio of the aldehyde sodium alginate to the casein be 1:10 respectively, and mechanically stirring uniformly to form a viscous spinning solution.
(3) And (3) discharging bubbles: discharging bubbles by using a vacuum pump filtering device to obtain uniform bubble-free spinning solution, wherein the pressure of the vacuum pump is 0.5Mpa;
(4) Wet spinning: wet spinning is carried out on the defoamed spinning solution, the first coagulating bath is 25wt% ammonium sulfate solution, the pH value is regulated to 4.6 by a small amount of acetic acid, and the fiber residence time is 2h; after passing through the first coagulation bath, the fiber continues to a second coagulation bath consisting of 5% by weight ethylene glycol and 75% by weight aqueous ethanol, where the fiber resides for 7 hours.
(5) And (3) secondary crosslinking reinforcement: after passing through the first and second coagulation baths, the collected fibers were placed in an aqueous solution of ethylene glycol diglycidyl ether ethanol at a concentration of 0.6% and ethanol at a concentration of 75% and reacted overnight at 50 ℃.
(6) Rinsing and drying to obtain a semi-finished product: collecting the fibers, rinsing with clear water for 1.5h, and naturally airing to obtain a finished product of the degradable and absorbable fibers based on casein.
The degradable casein-based absorbing fiber prepared by the method can be used as a surgical suture material. The proof experiment is as follows:
1. Cytotoxicity test
The fibers obtained in the test were sterilized, immersed in a DMEM medium, and cultured at 37℃for 2 days to obtain a fiber extract, and fibroblasts were inoculated onto a fiberboard at a density of 1X 105 cells/mL (1 mL per well). The culture was continued for 7 days at 37℃with a small amount of CCK-8 reagent added, the culture was continued for 2-4 hours, followed by washing with PBS buffer, absorbance at 450nm was measured with a microplate reader, and cell viability was calculated from the absorbance.
The test result in fig. 3 shows that with the increase of the culture time, the cells show good growth trend, and the growth of the cells is not obviously inhibited in the presence of the composite fiber, which indirectly indicates that the fiber obtained by the multi-formylated sodium alginate-casein composite has no cytotoxicity, has high safety and can be used for subsequent sustainable research.
2. Fiber strength test:
the measuring method comprises the steps of stretching the fiber at a constant speed of 50mm/min by using a stretcher at a temperature of 20 ℃ and a humidity of 65% until the fiber breaks, and obtaining breaking strength and breaking elongation. The mechanical property data of the wet fibers were measured from suture samples after 5 minutes of immersion in phosphate buffer. Each data was obtained from the same four samples. The measurement results are shown in the following table:
The casein is obtained by fiber strength test (each data is obtained from the same four samples), the fiber fineness of the casein can be absorbed and is 10.4+/-0.45 dtex, the dry strength is 1.53+/-0.23N/dtex, the fiber strength is high, the wet strength is 1.21+/-0.52N/dtex, the wet elongation at break is 18.3+/-0.23%, and the toughness is slightly improved in a wet state, so that the requirements of clinical medical suture lines are completely met. By combining with cytotoxicity test, the invention is nontoxic and easy to be absorbed or excreted, avoids the pain of patients caused by secondary operation, reduces the influence of foreign matters after degradation, can reduce inflammatory reaction, and ensures that the recovered wound surface is smooth and even. Not only can the healing effect similar to that of the non-absorbable suture be ensured, but also the hospitalization time and the economic cost can be obviously reduced.
The above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention, but are intended to cover modifications, alternatives, improvements, and the like.
Claims (2)
1. A preparation method of degradable absorbing fiber based on casein, which is characterized by comprising the following steps:
(1) Preparing aldehyde sodium alginate; preparing a sodium alginate solution with the solubility of 3%, adding sodium periodate with the same mass as sodium alginate, reacting for 12 hours in a dark place, and adding ethylene glycol with the same mass as sodium periodate to terminate the reaction for 1 hour after the reaction is finished;
Adding 3 parts of sodium chloride and 100 parts of ethanol by weight of a sodium alginate solution to obtain a crude product, dissolving the crude product in 100 parts of water, adding 3 parts of sodium chloride and 100 parts of ethanol again, collecting precipitate, and drying to obtain aldehyde sodium alginate;
(2) Preparing a spinning solution: adding 0.5-2 parts of sodium carbonate and 0.5-2 parts of sodium bicarbonate into 70-100 parts of deionized water, adding casein and aldehyde sodium alginate to ensure that the mass ratio of the aldehyde sodium alginate to the casein is 1:1-1:10 respectively, and mechanically stirring uniformly to form a viscous spinning stock solution;
(3) And (3) discharging bubbles: discharging bubbles by using a vacuum pump filtering device to obtain uniform bubble-free spinning solution, wherein the pressure of the vacuum pump is 0.3-0.6 mpa;
(4) Wet spinning: wet spinning is carried out on the defoamed spinning solution, the first coagulating bath is 25wt% ammonium sulfate solution, the pH value is regulated to 4.6 by a small amount of acetic acid, and the fiber residence time is 2h; after the fiber passes through the first coagulating bath, the fiber continuously enters a second coagulating bath, wherein the second coagulating bath comprises 5 weight percent of ethylene glycol and 75 weight percent of ethanol water solution, and the fiber stays in the second coagulating bath for 6-8 hours;
(5) And (3) secondary crosslinking reinforcement: after the first coagulating bath and the second coagulating bath, collecting fibers, putting the fibers into an ethylene glycol diglycidyl ether ethanol aqueous solution with the concentration of 0.4% -0.8%, and reacting overnight at 30-50 ℃ with the concentration of 75%;
(6) Rinsing and drying to obtain a semi-finished product: and collecting the fibers, rinsing with clear water for 1-2 h, and naturally airing to obtain a finished product of the degradable and absorbable fibers based on casein.
2. Use of a casein based degradable absorbent fiber obtained by the method of claim 1, characterized in that the fiber is used as a surgical suture material.
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