CN110483705A - A kind of hemostasis hydrogel and preparation method thereof based on keratin - Google Patents
A kind of hemostasis hydrogel and preparation method thereof based on keratin Download PDFInfo
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- CN110483705A CN110483705A CN201910749963.4A CN201910749963A CN110483705A CN 110483705 A CN110483705 A CN 110483705A CN 201910749963 A CN201910749963 A CN 201910749963A CN 110483705 A CN110483705 A CN 110483705A
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- keratin
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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
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
- A61L24/0031—Hydrogels or hydrocolloids
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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
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/10—Polypeptides; Proteins
- A61L24/108—Specific proteins or polypeptides not covered by groups A61L24/102 - A61L24/106
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/04—Materials for stopping bleeding
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- Chemical & Material Sciences (AREA)
- Surgery (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
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Abstract
The present invention relates to a kind of hemostasis hydrogel and preparation method thereof based on keratin, including the following raw material component: activated monomer, thermal initiator, water cross-linking agent, functional additive, promotor, deionized water, functional additive is keratin, feed concentrations 0.1-0.225g/mL, and the mass ratio of keratin and activated monomer is 33.3-75:100.Preparation method includes the following steps: that keratin is dissolved in deionized water by (1), and adjusts solution PH, stirs to get keratin solution;(2) activated monomer, thermal initiator, water cross-linking agent, promotor are added in keratin solution, stir to get hydrogel precursor solution;(3) hydrogel precursor solution is then placed within 10-14h at room temperature in 30-50 DEG C of polyase 13-5h.Present invention hemostasis hydrogel can be adhered to the surface of various solid materials repeatedly, not only have excellent haemostatic effect, while can also significantly draw high repeatedly without destroying the hydrogel that stops blooding;Its preparation process has many advantages, such as that mild condition, energy conservation, pollution-free, precision is high, easy to operate.
Description
Technical field
The present invention relates to biomedical materials fields, and in particular to a kind of hemostasis hydrogel and its preparation based on keratin
Method.
Background technique
Hemostasis is an important step of emergency medical treatment, sudden wound occurs in patient's operative treatment, daily life
When hurting, it is both needed to carry out quick-acting haemostatic powder, it is real when the war, emergency care of trauma in severe war environment and complicated emergency event are treated
Now quickly and effectively stop blooding particularly important.Due to traditional hemostatic material such as currently used hemostatic material such as gauze, bandage, cotton yarn
It is very unsatisfactory all to there is haemostatic effect in material.Though in addition, having novel hemostatic gauze and styptic sponge haemostatic effect better than tradition hemostasis
Material, but because own material limits, unnecessary secondary injury often is brought to patient during removing again.How to open
Issue efficient and quick hemostatic material and product, bleeding after the accident fast short stopping effectively is carried out to the bleeding surface of a wound
Blood, the key that this, which becomes, reduces risk, saves life, reduces the death rate.
Hydrogel because its can be designed be embedded in Physical interaction (including hydrogen bond, hydrophobic interaction, metal complex and
Pi-pi accumulation) it reversibly adheres in various solid matrixs and biological tissue.Therefore, it is widely studied for manufacturing clinical doctor
Learn adhesive aerogel dressing.Up to the present, a series of tough and tensile and cohesive hydrogel has been developed.Zhao etc. passes through chemical bond
Conjunction is prepared for one kind can be with the tough hydrogel in conjunction with various nonporous solid materials.However, being glued after chemical bond is destroyed
Conjunction ability is irreversible.Hereafter JianyuXu etc. develops a kind of viscous toughness hydrogel driven by lactoprotein.The hydrogel
It can reversibly be adhered on various solid matrixs and biological tissue by possible Physical interaction.But due to its function list
One changes so that it is restricted in practical applications.
Summary of the invention
The invention aims to provide a kind of high to glue tough, stretchable, the good hemostasis water based on keratin of haemostatic effect
Gel and preparation method thereof.
The first purpose of this invention is to provide a kind of hemostasis hydrogel based on keratin comprising the following raw material group
Point: activated monomer, thermal initiator, water cross-linking agent, functional additive, promotor, deionized water, the functional additive
For keratin, concentration of the keratin in the deionized water is 0.1-0.225g/mL, the keratin and the activity
The mass ratio of monomer is 33.3-75:100.
Keratin is a kind of and the closely related biocompatibility natural material of vital movement, contains one or more ammonia
Base acid residue long-chain, while its intermolecular energy is crosslinked by the cystine linkage between hydrogen bond, sat linkage and cystine.These macromolecular chains
Orderly natural two of protein folding can be self-assembly of under the non-covalent bonds driving such as hydrophobe interaction or hydrogen bond
Grade, tertiary structure.Simultaneously because it is easy to generate Physical interaction, including hydrogen bond, hydrophobic phase interaction between other materials
With, metal complex and electrostatic effect, therefore keratin can assign hydrogel excellent bond properties.
Keratin can be by Physical interaction in the network architecture by forming interpenetrating with the main matrix of hydrogel
Network stablizes hydrogel, to improve mechanical performance.In addition, the clotting ability of keratin is mainly reflected in two aspect:
1) keratin has good activated blood platelet ability and strong cellular adhesive attraction, further viscous by cell recognition and cell
It is attached to stop blooding;2) keratin can cause the polymerization of fibrinogen to promote to stop blooding in the early onset thereof time of coagulation cascade,
Significant reduction blood plasma blood coagulation lag time.In addition, this mechanism is unrelated with the temperature of coagulation factor and concentration, to can reach fast
Fast hemostatic capability.
In the present invention, keratin is from animal hair.
Preferably, the feed concentrations of the keratin are 0.1-0.225g/mL.
Preferably, the mass ratio of the keratin and the activated monomer is 33.3-58.3:100.
Specifically, the activated monomer is selected from one of acrylamide and acrylamide derivative or a variety of.
Specifically, the thermal initiator is one in potassium peroxydisulfate, azo-bis-isobutyrate hydrochloride and ammonium persulfate
Kind.
Preferably, the mass ratio of the thermal initiator and the activated monomer is 0.33-1:100.
Specifically, the water cross-linking agent is in N, N'- methylene-bisacrylamide, amino resins and isocyanates
One kind.
Preferably, the mass ratio of the water cross-linking agent and the activated monomer is 0.016-0.05:100.
Specifically, the promotor is selected from tetramethylethylenediamine, hexa and diethyl-dithio amino first
One of sour zinc.
Preferably, the mass ratio of the promotor and the activated monomer is 0.48-0.53:100.
Second object of the present invention is to provide a kind of preparation side of hemostasis hydrogel based on keratin as described above
Method includes the following steps:
(1) keratin is dissolved in the deionized water, and adjusts solution PH, stir to get keratin solution;
(2) activated monomer, thermal initiator, water cross-linking agent, promotor are added in the keratin solution, stirring
Obtain hydrogel precursor solution;
(3) by the hydrogel precursor solution in 30-50 DEG C of polyase 13-5h, be then placed at room temperature 10-14h to get
The hemostasis hydrogel.
Specifically, in step (1), PH to 5-7 is adjusted using alkali.
Due to the above technical solutions, the present invention has the following advantages over the prior art: the present invention is based on angle eggs
White hemostasis hydrogel can be adhered to the surface of various solid materials repeatedly, not only have excellent haemostatic effect, simultaneously also
It can significantly draw high repeatedly without destroying the hydrogel that stops blooding;The preparation process of hemostasis hydrogel has mild condition, energy conservation, without dirt
The advantages that dye, precision are high, easy to operate.
Detailed description of the invention
Attached drawing 1 is the coagulating effectiveness figure of the hemostasis hydrogel of the concentration of different keratin;
Attached drawing 2 is the SEM figure of the hemostasis hydrogel of embodiment 1;
Attached drawing 3 is bonding effect figure of the hemostasis hydrogel on different materials surface of embodiment 1;
Attached drawing 4 is macroscopical drawing effect figure of the hemostasis hydrogel of embodiment 1.
Specific embodiment
The preferred embodiment of the invention is described in detail below.
The first purpose of this invention is to provide a kind of hemostasis hydrogel based on keratin comprising the following raw material group
Point: activated monomer, thermal initiator, water cross-linking agent, functional additive, promotor, deionized water, functional additive are angle
Albumen, the feed concentrations of keratin are 0.1-0.225g/mL, and the mass ratio of keratin and activated monomer is 33.3-75:100.
In the present invention, keratin is 0.1-0.175g/mL, keratin from animal hair, the feed concentrations of keratin
Mass ratio with activated monomer is 33.3-58.3:100.
Activated monomer is selected from one of acrylamide and acrylamide derivative or a variety of;Thermal initiator be selected from
One of potassium sulfate, azo-bis-isobutyrate hydrochloride and ammonium persulfate.The mass ratio of thermal initiator and activated monomer is 0.33-
1:100。
Water cross-linking agent is selected from one of N, N'- methylene-bisacrylamide, amino resins and isocyanates;It is aqueous
The mass ratio of crosslinking agent and activated monomer is 0.016-0.05:100.
Promotor is one in tetramethylethylenediamine, hexa and zinc diethyl dithiocarbamate
Kind;The mass ratio of promotor and activated monomer is 0.48-0.53:100.
Second object of the present invention is to provide a kind of preparation method of as above hemostasis hydrogel based on keratin, packet
Include following steps:
(1) keratin is dissolved in deionized water, and adjusts solution PH, stir to get keratin solution;
(2) activated monomer, thermal initiator, water cross-linking agent, promotor are added in keratin solution, stir to get water-setting
Glue precursor solution;
(3) by hydrogel precursor solution in 30-50 DEG C of polyase 13-5h, be then placed at room temperature 10-14h to get hemostasis
Hydrogel.
Specifically, in step (1), PH to 5-7 is adjusted using alkali.
It is described in detail below in conjunction with to the preferred embodiment of the invention:
Embodiment 1
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it the following steps are included:
(1) 1.0g keratin is added into beaker, is dissolved in 5ml deionized water, stirs evenly and adjusted using NaOH molten
Liquid PH to 6.6, is made keratin solution;
(2) 3g acrylamide, 0.001g water cross-linking agent N, N'- methylene-bisacrylamide and 5ml deionized water is mixed
After closing uniformly, it is uniformly mixed with keratin solution;0.02g potassium peroxydisulfate, 20 μ L tetramethylethylenediamines are added, water is stirred to get
Gel precursors solution;
(3) hydrogel precursor solution is polymerize 4h in 40 DEG C of insulating boxs, be then placed at room temperature 12h to get hemostasis water
Gel.
Embodiment 2
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: joined 1.25g keratin in step (a).
Embodiment 3
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: joined 1.5g keratin in step (a).
Embodiment 4
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: joined 1.75g keratin in step (a).
Embodiment 5
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: joined 2.0g keratin in step (a).
Embodiment 6
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: joined 2.25g keratin in step (a).
Embodiment 7
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: joined 0.03g potassium peroxydisulfate in step (b).
Embodiment 8
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: joined 15 μ L tetramethylethylenediamines in step (b).
Comparative example 1
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: keratin is not added in step (a).
Comparative example 2
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: 0.5g keratin being added in step (a).
Comparative example 3
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: 0.75g keratin being added in step (a).
Comparative example 4
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: 0.04g potassium peroxydisulfate being added in step (b).
Comparative example 5
The preparation method for the hemostasis hydrogel that the present embodiment provides a kind of based on keratin, it with it is basic in embodiment 1
Unanimously, unlike: tetramethylethylenediamine is not added in step (b).
The BCI value that the obtained hemostasis hydrogel of above-described embodiment 1-7 and comparative example 1-5 measures is listed in the table below 1
The BCI value that can be seen that the hemostasis hydrogel of various concentration keratin from the embodiment 1-6 of Fig. 1 and table 1 is different,
With the raising of keratin concentration, BCI value is gradually become smaller, but after increasing to a certain extent, BCI value is gradually increased, and works as angle
When the feed concentrations of albumen are 0.125g/mL, BCI value is minimum.
It can be seen that the increase with initiator content from embodiment 1 and embodiment 7, polymerization rate improves, polymerization
Object molecular weight becomes smaller, and PAM strand shortens so that the hydrogel mesh that stops blooding becomes smaller, therefore stops with the increase of initiator content
The hemostasis efficiency of watery blood gel is deteriorated, and BCI value increases.
From embodiment 1 and embodiment 8 as can be seen that the BCI value of hemostasis hydrogel can't be with the change of the content of promotor
Change has larger fluctuation.
Hemostasis hydrogel of the invention is by using specific activated monomer and water cross-linking agent, thermal initiator, keratin
Cooperated with deionized water etc., is prepared for a kind of high gluing tough, stretchable hemostasis hydrogel by heat initiation.Stop blooding hydrogel
Internal keratin is that a kind of there are leucine-aspartic acid-valine (LDV) and glutamic acid asparate-serines (EDS)
Peptide domain, with excellent tolerance, biocompatibility, biological degradability, non-immunogenic, cell attachment, proliferation and
Vigor feature, while can join by the way that simply change total protein concentration, the crosslink density of keratin used related to other
Number, can control physics, the chemistry and biology behavior of these gel rubber materials.Peptides molecule in keratin is with amino acid backbone
For the assembly of unit non-covalent bond orderly second level, tertiary structure can be formed as driving force and then is formed using in keratin molecule
Stable regional space space network, therefore keratin/hydrogel tensile property and toughness improve a lot;Simultaneously only
The preparation process of watery blood gel has many advantages, such as that mild condition, energy conservation, pollution-free, precision is high, easy to operate.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of hemostasis hydrogel based on keratin, which is characterized in that it includes the following raw material component: activated monomer, heat are drawn
Agent, water cross-linking agent, functional additive, promotor, deionized water are sent out, the functional additive is keratin, the angle
The feed concentrations of albumen are 0.1-0.225g/mL, and the mass ratio of the keratin and the activated monomer is 33.3-75:100.
2. hemostasis hydrogel according to claim 1, it is characterised in that: the activated monomer is selected from acrylamide and third
One of alkenylamide derivative is a variety of.
3. hemostasis hydrogel according to claim 1, it is characterised in that: the thermal initiator is selected from potassium peroxydisulfate, idol
One of two NSC 18620 hydrochloride of nitrogen and ammonium persulfate.
4. hemostasis hydrogel according to claim 3, it is characterised in that: the matter of the thermal initiator and the activated monomer
Amount is than being 0.33-1:100.
5. hemostasis hydrogel according to claim 1, it is characterised in that: the water cross-linking agent is selected from N, N'- methylene
One of base bisacrylamide, amino resins and isocyanates.
6. hemostasis hydrogel according to claim 5, it is characterised in that: the water cross-linking agent and the activated monomer
Mass ratio is 0.016-0.05:100.
7. hemostasis hydrogel according to claim 1, it is characterised in that: the promotor be selected from tetramethylethylenediamine,
One of hexa and zinc diethyl dithiocarbamate.
8. hemostasis hydrogel according to claim 7, it is characterised in that: the quality of the promotor and the activated monomer
Than for 0.48-0.53:100.
9. a kind of preparation method of the hemostasis hydrogel as described in any in claim 1-8 based on keratin, which is characterized in that
Include the following steps:
(1) keratin is dissolved in the deionized water, and adjusts solution PH, stir to get keratin solution;
(2) activated monomer, thermal initiator, water cross-linking agent, promotor are added in the keratin solution, are stirred to get
Hydrogel precursor solution;
(3) by the hydrogel precursor solution in 30-50 DEG C of polyase 13-5h, be then placed at room temperature 10-14h to get described
Stop blooding hydrogel.
10. preparation method according to claim 9, it is characterised in that: in step (1), adjust PH to 5-7 using alkali.
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Cited By (1)
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CN111825858A (en) * | 2020-07-02 | 2020-10-27 | 南京师范大学 | Composite hydrogel based on zwitterion and keratin and preparation method thereof |
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CN103524759A (en) * | 2013-09-27 | 2014-01-22 | 西北师范大学 | Method for preparing animal keratin base macromolecular hydrogel and application of hydrogel serving as medicine carrier |
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2019
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Patent Citations (2)
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CN103524759A (en) * | 2013-09-27 | 2014-01-22 | 西北师范大学 | Method for preparing animal keratin base macromolecular hydrogel and application of hydrogel serving as medicine carrier |
CN105218835A (en) * | 2015-09-25 | 2016-01-06 | 西北师范大学 | A kind of preparation of keratin based sensitive high-molecular gel and the application as pharmaceutical carrier |
Non-Patent Citations (1)
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