CN104383584B - A kind of Graphene/oxidized regenerated cellulose compound hemostatic material - Google Patents
A kind of Graphene/oxidized regenerated cellulose compound hemostatic material Download PDFInfo
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- CN104383584B CN104383584B CN201410675529.3A CN201410675529A CN104383584B CN 104383584 B CN104383584 B CN 104383584B CN 201410675529 A CN201410675529 A CN 201410675529A CN 104383584 B CN104383584 B CN 104383584B
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Abstract
A kind of Graphene/oxidized regenerated cellulose compound hemostatic material, it relates to a kind of hemostatic material.The invention aims to solve existing hemostatic material and exist expensive, anthemorrhagic speed is slow, it is impossible to the problem being used in the situation of massive haemorrhage.A kind of Graphene/oxidized regenerated cellulose compound hemostatic material is to be prepared by the filament yarn fabric of redox Graphene and oxidized regenerated cellulose, and described redox Graphene is (0.05～10) with the mass ratio of the filament yarn fabric of oxidized regenerated cellulose: 100.Method: the first, prepare graphene solution；2nd, ultrasonic, freeze-drying, obtains a kind of Graphene/oxidized regenerated cellulose compound hemostatic material.Graphene prepared by the present invention/oxidized regenerated cellulose compound hemostatic material stops blooding, and bleeding stopping period reduces 6%～15%.The present invention can obtain a kind of Graphene/oxidized regenerated cellulose compound hemostatic material.
Description
Technical field
The present invention relates to a kind of hemostatic material.
Background technology
Inevitably there is various accident in daily life, in carrying out emergency treatment and surgical procedure, all may
Because massive haemorrhage causes malpractice even dead.Therefore, the topically effective quick-acting haemostatic powder of patient is then most important, effectively controls
Make blood and reduce the bleeding time become reduce mortality important measures.Clinical conventional hemostatic material such as hemostatic gauze,
Stanch fibre, tourniquet bandage in use have limitation, as bleeding stopping period is longer, easily with wound adhesion and be difficult to change dressings,
To the infection of wound with suppurate helpless.Quick-acting haemostatic powder and feature hemostasis will be the directions of following haemostatic medicament development.
Conventional Absorbable hemostatic material has Fibrin Glue, gelfoam, oxycellulose, microfibrillar collagen, shitosan
And Sorbsan etc..Their mechanism of action and using method are not quite similar, and haemostatic effect also has difference.But, mesh
Before the hemostatic gauze that is widely used clinically be the SURGICEL being produced by Johnson & Johnson of the U.S. (Johnson&Johnson) company
Series absorbable hemostatic product SURGICELTM、SURGICELTM Nu-Knit、SURGICELTMFibrillar,
At home also known as " speed i.e. yarn ", the composition of above product is oxidized regenerated cellulose, and main difference is embodied in external manifestation
Form, SURGICEL series of products have occupied extremely important status in the international market now, and receive medical science
The consistent favorable comment of domain expert.Meanwhile, domestic You Ji company has also produced similar hemostatic gauze, but due to material
Performance can not show a candle to speed i.e. yarn, so main clinically use expensive import hemostatic material.
Oxidized regenerated cellulose is the derivative of cellulose, has good anthemorrhagic performance, biodegradable properties and nontoxic, mesh
Before have been used for multiple industry, including in the medical field, general use nitrogen oxides as oxidant, by cellulose unit
Hydroxyl oxygen on middle C-6 position turns to carboxyl and prepares oxidized regenerated cellulose.When it uses as hemostatic material, carboxyl-content should
It is 16～24%, to ensure its haemostatic effect.Oxidized regenerated cellulose hemostatic mechanism is as follows: oxidized regenerated cellulose contacts
Can adsorb substantial amounts of erythrocyte after blood, then the acidic carboxypolymer in oxidized regenerated cellulose structure can cause haemolysis, i.e.
Erythrocyte dissolves, rupture, and discharges hemoglobin.Simultaneously as hemoglobin contains ferric ion, oxidation
Regenerated cellulose can be with Fe3+In conjunction with forming brown blob of viscose, close, block capillary end and stop blooding.As can be seen here,
The hemostasis of oxidized regenerated cellulose is a series of Biochemical Engineering, and the carboxyl quantity in material structure has
Limit, the anthemorrhagic speed therefore causing oxidized regenerated cellulose material is relatively slow, causes such material cannot be applicable to artery etc.
The massive haemorrhage situation at position.
During oxidized regenerated cellulose is being continually striving to carry out as the study on the modification of hemostatic material always.Doub et al. discloses
The method that oxidized regenerated cellulose is neutralized by the aqueous solution of employing sodium acid carbonate or calcium acetate, and use fibrin ferment impregnated carbon
The oxidized regenerated cellulose that acid hydrogen sodium neutralizes, then carries out freezing to process and be dried in this case to the fabric after dipping, system
Obtained a kind of efficient oxycellulose class operation hemostatic material.In United States Patent (USP), Saferstein et al. describes use
The alcohol solution of salt of weak acid, such as sodium acetate, oxidized regenerated cellulose is neutralized to pH value between 5～8, this method
Not only make oxidized regenerated cellulose can store with ambient-temp-stable, and the acid-sensitive material of similar fibrin ferment can be loaded, enter
And improve the anthemorrhagic performance of oxidized regenerated cellulose material.They also find simultaneously, and Doub et al. uses sodium acid carbonate to neutralize
Method can cause oxidized regenerated cellulose fabrics part gel, deformation, and cause the oxidation regeneration fiber of final neutralization to be knitted
The tensile strength of thing is too low to be applied in the hemostasis of reality.And the calcium acetate that Doub et al. mentions in the patent
Although the oxidized regenerated cellulose neutralizing ensure that original form of fabric, but due to after neutralizing material calcium content too high, make
Excitant can be produced during with to the mammal skin of contact position and other body cells, and using position to form big sending out
White granulation lump, hinders the bio-absorbable of material.Said method utilizes modification can improve the hemostasis of oxidized regenerated cellulose
Performance, but its Bioabsorbable is greatly reduced.
Although the correlative study that above achievement in research is all to oxidized regenerated cellulose has a very big significance, also make material simultaneously
Anthemorrhagic performance has obtained a certain degree of lifting, but it is typically small to be an up degree, i.e. improves effect poor；And, in the past
The mechanical strength of regenerated oxycellulose as styptic material and biological absorbable performance also can be caused negative by the ameliorative way in research
Face rings, and for the anthemorrhagic performance promoting by a small margin, modified effect is lost more than gain.
Content of the invention
The invention aims to solve existing hemostatic material and exist expensive, anthemorrhagic speed is slow, it is impossible to be used in massive haemorrhage
The problem of situation, and provide a kind of Graphene/oxidized regenerated cellulose compound hemostatic material.
A kind of Graphene/oxidized regenerated cellulose compound hemostatic material is by redox Graphene and oxidized regenerated cellulose
Prepared by filament yarn fabric；Described redox Graphene and the mass ratio of the filament yarn fabric of oxidized regenerated cellulose are
(0.05～10): 100.
The preparation method of a kind of Graphene/oxidized regenerated cellulose compound hemostatic material is specifically realized by the following steps:
First, graphene solution is prepared: join in solvent by redox Graphene, then at ultrasonic power be
Under conditions of 160W～400W, ultrasonically treated 10min～60min, obtains graphene solution；
The quality of the redox Graphene described in step one and the volume ratio of solvent are (0.1mg～2mg): 1mL；
2nd, ultrasonic, freeze-drying: be immersed in the filament yarn fabric of oxidized regenerated cellulose in graphene solution, at ultrasonic work(
Ultrasonically treated 10min～60min under conditions of rate is 200W～400W, then re-uses oscillator oscillation treatment 1h～24h,
Again the filament yarn fabric of oxidized regenerated cellulose is taken out from the solution of Graphene, the oxidized regenerated cellulose after being impregnated
Filament yarn fabric；The filament yarn fabric of the oxidized regenerated cellulose after impregnating vacuum freeze drying at temperature is for-70～-20 DEG C
8h～96h, obtains Graphene/oxidized regenerated cellulose compound hemostatic material；
The quality of the filament yarn fabric of the oxidized regenerated cellulose described in step 2 with the volume ratio of graphene solution is
(0.005g～0.04g): 1mL；
Redox Graphene and oxidation regeneration in Graphene described in step 2/oxidized regenerated cellulose compound hemostatic material
The mass ratio of the filament yarn fabric of cellulose is (0.05～10): 100.
Advantages of the present invention:
First, Graphene prepared by the present invention/oxidized regenerated cellulose compound hemostatic material is the long filament at oxidized regenerated cellulose
Nano-graphene is directly adsorbed on the surface of fabric, has both improve the anthemorrhagic performance of material, simultaneously again will not the machine of attacking material
Tool intensity and biological absorbable performance；
2nd, the Graphene/oxidized regenerated cellulose compound hemostatic material using the present invention to prepare stops blooding, and bleeding stopping period drops
Low by 6%～15%.
The present invention can obtain a kind of Graphene/oxidized regenerated cellulose compound hemostatic material.
Detailed description of the invention
Detailed description of the invention one: present embodiment be a kind of Graphene/oxidized regenerated cellulose compound hemostatic material be by aoxidizing
Prepared by the filament yarn fabric of reduced graphene and oxidized regenerated cellulose；Described redox Graphene and oxidation regeneration fiber
The mass ratio of the filament yarn fabric of element is (0.05～10): 100.
The advantage of present embodiment:
First, Graphene prepared by present embodiment/oxidized regenerated cellulose compound hemostatic material is at oxidized regenerated cellulose
Nano-graphene is directly adsorbed on the surface of filament yarn fabric, has both improve the anthemorrhagic performance of material, simultaneously again will not attacking material
Mechanical strength and biological absorbable performance；
2nd, the Graphene/oxidized regenerated cellulose compound hemostatic material using present embodiment to prepare stops blooding, during hemostasis
Between reduce 6%～15%.
Present embodiment can obtain a kind of Graphene/oxidized regenerated cellulose compound hemostatic material.
Detailed description of the invention two: the difference from detailed description of the invention one for the present embodiment is: the long filament of oxidized regenerated cellulose
In fabric, carboxyl-content is 16%～24%.Other are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is the preparation side of a kind of Graphene/oxidized regenerated cellulose compound hemostatic material
Method is specifically realized by the following steps:
First, graphene solution is prepared: join in solvent by redox Graphene, then at ultrasonic power be
Under conditions of 160W～400W, ultrasonically treated 10min～60min, obtains graphene solution；
The quality of the redox Graphene described in step one and the volume ratio of solvent are (0.1mg～2mg): 1mL；
2nd, ultrasonic, freeze-drying: be immersed in the filament yarn fabric of oxidized regenerated cellulose in graphene solution, at ultrasonic work(
Ultrasonically treated 10min～60min under conditions of rate is 200W～400W, then re-uses oscillator oscillation treatment 1h～24h,
Again the filament yarn fabric of oxidized regenerated cellulose is taken out from the solution of Graphene, the oxidized regenerated cellulose after being impregnated
Filament yarn fabric；The filament yarn fabric of the oxidized regenerated cellulose after impregnating vacuum freeze drying at temperature is for-70～-20 DEG C
8h～96h, obtains Graphene/oxidized regenerated cellulose compound hemostatic material；
The quality of the filament yarn fabric of the oxidized regenerated cellulose described in step 2 with the volume ratio of graphene solution is
(0.005g～0.04g): 1mL；
Redox Graphene and oxidation regeneration in Graphene described in step 2/oxidized regenerated cellulose compound hemostatic material
The mass ratio of the filament yarn fabric of cellulose is (0.05～10): 100.
Redox Graphene described in step one is to carry out oxidation processes with Hummers method to Graphene, then through washing
Wash, be dried to obtain oxidation product；Then recycle hydrazine hydrate and reduction treatment is carried out to oxidation product, through washing, drying
After the redox Graphene that obtains.
The advantage of present embodiment:
First, Graphene prepared by present embodiment/oxidized regenerated cellulose compound hemostatic material is at oxidized regenerated cellulose
Nano-graphene is directly adsorbed on the surface of filament yarn fabric, has both improve the anthemorrhagic performance of material, simultaneously again will not attacking material
Mechanical strength and biological absorbable performance；
2nd, the Graphene/oxidized regenerated cellulose compound hemostatic material using present embodiment to prepare stops blooding, during hemostasis
Between reduce 6%～15%.
Present embodiment can obtain a kind of Graphene/oxidized regenerated cellulose compound hemostatic material.
Detailed description of the invention four: the difference from detailed description of the invention three for the present embodiment is: the solvent described in step one
For the ethanol solution that water, absolute ethyl alcohol or mass fraction are 20%～80%.Other are identical with detailed description of the invention three.
Detailed description of the invention five: the difference from detailed description of the invention three or four for the present embodiment is: in step one by oxidation also
Former Graphene joins in solvent, then ultrasonically treated 10min～30min under conditions of ultrasonic power is 160W～400W,
Obtain graphene solution.Other are identical with detailed description of the invention three or four.
Detailed description of the invention six: the difference from detailed description of the invention three to five for the present embodiment is: in step one by oxidation also
Former Graphene joins in solvent, then ultrasonically treated 30min～60min under conditions of ultrasonic power is 200W～400W,
Obtain graphene solution.Other are identical with detailed description of the invention three to five.
Detailed description of the invention seven: the difference from detailed description of the invention three to six for the present embodiment is: the oxygen described in step one
The volume ratio of the quality and solvent of changing reduced graphene is (0.1mg～1mg): 1mL.Other and detailed description of the invention three to six phase
With.
Detailed description of the invention eight: the difference from detailed description of the invention three to seven for the present embodiment is: the oxygen described in step 2
Change the quality of filament yarn fabric of regenerated cellulose and the volume ratio of graphene solution is (0.005g～0.02g): 1mL.Other with tool
Body embodiment three to seven is identical.
Detailed description of the invention nine: the difference from detailed description of the invention three to eight for the present embodiment is: described in step 2
Redox Graphene and the filament yarn fabric of oxidized regenerated cellulose in Graphene/oxidized regenerated cellulose compound hemostatic material
Mass ratio is (0.05～2): 100.Other are identical with detailed description of the invention three to eight.
Detailed description of the invention ten: the difference from detailed description of the invention three to nine for the present embodiment is: the oxygen described in step 2
Changing carboxyl-content in the filament yarn fabric of regenerated cellulose is 16%～24%.Other are identical with detailed description of the invention three to nine.
Employing tests below checking beneficial effects of the present invention:
Test one: the preparation method of a kind of Graphene/oxidized regenerated cellulose compound hemostatic material is complete specifically according to the following steps
Become:
First, graphene solution is prepared: join in 150mL water by 20mg redox Graphene, then at ultrasonic work(
Under conditions of rate is 320W, ultrasonically treated 30min, obtains graphene solution；
2nd, ultrasonic, freeze-drying: the filament yarn fabric of 2.5g oxidized regenerated cellulose is immersed in the stone obtaining in step one
In ink alkene solution, ultrasonically treated 15min under conditions of ultrasonic power is 400W, then re-use oscillator oscillation treatment
4h, then the filament yarn fabric of oxidized regenerated cellulose is taken out from the solution of Graphene, the oxidation regeneration fiber after being impregnated
The filament yarn fabric of element；The filament yarn fabric of the oxidized regenerated cellulose after impregnating vacuum freeze drying at temperature is for-50 DEG C
72h, obtains Graphene/oxidized regenerated cellulose compound hemostatic material；
In the filament yarn fabric of the oxidized regenerated cellulose described in step 2, carboxyl-content is 17.36%；
Redox Graphene and oxidation regeneration in Graphene described in step 2/oxidized regenerated cellulose compound hemostatic material
The mass ratio of the filament yarn fabric of cellulose is 0.28:100.
Bleeding stopping period measures: after slowly injecting Nembutal sodium solution anesthetized animal by 40mg/kg dose intravenous, by its central authorities
Arteria auricularis region preserved skin, sterilization, cut skin along arteria auricularis direction, and blunt separation goes out arteria auricularis, vein and nerve, then uses
Scalpel transversely cutting artery, is pasted on wound surface by 1 layer of test material or control sample and is used immediately after blood is gushed out
Pull and push dynamometer applies the pressure of 3N, observes hemostasis every 10s, until record bleeding stopping period after final hemostasis completely.
Test result is as follows: the bleeding stopping period using the filament yarn fabric of the oxidized regenerated cellulose of carboxyl-content 17.36% is 130s,
Using the bleeding stopping period testing a Graphene/oxidized regenerated cellulose compound hemostatic material obtaining to be 122s, bleeding stopping period drops
Low by 6.2%.
Test two: the preparation method of a kind of Graphene/oxidized regenerated cellulose compound hemostatic material is complete specifically according to the following steps
Become:
First, graphene solution is prepared: join 100mg redox Graphene in 150mL absolute ethyl alcohol, then exist
Under conditions of ultrasonic power is 400W, ultrasonically treated 45min, obtains graphene solution；
2nd, ultrasonic, freeze-drying: the filament yarn fabric of 2.5g oxidized regenerated cellulose is immersed in the stone obtaining in step one
In ink alkene solution, ultrasonically treated 30min under conditions of ultrasonic power is 400W, then re-use oscillator oscillation treatment
24h, then the filament yarn fabric of oxidized regenerated cellulose is taken out from the solution of Graphene, the oxidation regeneration after being impregnated is fine
The filament yarn fabric of dimension element；The filament yarn fabric of the oxidized regenerated cellulose after impregnating vacuum freeze drying at temperature is for-50 DEG C
24h, obtains Graphene/oxidized regenerated cellulose compound hemostatic material；
In the filament yarn fabric of the oxidized regenerated cellulose described in step 2, carboxyl-content is 17.36%；
Redox Graphene and oxidation regeneration in Graphene described in step 2/oxidized regenerated cellulose compound hemostatic material
The mass ratio of the filament yarn fabric of cellulose is 1.36:100.
Bleeding stopping period measures: after slowly injecting Nembutal sodium solution anesthetized animal by 40mg/kg dose intravenous, by its central authorities
Arteria auricularis region preserved skin, sterilization, cut skin along arteria auricularis direction, and blunt separation goes out arteria auricularis, vein and nerve, then uses
Scalpel transversely cutting artery, is pasted on wound surface by 1 layer of test material or control sample and is used immediately after blood is gushed out
Pull and push dynamometer applies the pressure of 3N, observes hemostasis every 10s, until record bleeding stopping period after final hemostasis completely.
Test result is as follows: carboxyl-content be the bleeding stopping period of the filament yarn fabric of 17.36% oxidized regenerated cellulose be 130s, use
The bleeding stopping period of Graphene/oxidized regenerated cellulose compound hemostatic material that test two obtains is 117s, and bleeding stopping period reduces
10%.
Claims (1)
1. Graphene/oxidized regenerated cellulose compound hemostatic material, it is characterised in that a kind of Graphene/oxidation regeneration fiber
Element compound hemostatic material is to be prepared by the filament yarn fabric of redox Graphene and oxidized regenerated cellulose；Described oxidation is also
Former Graphene is (0.05～10) with the mass ratio of the filament yarn fabric of oxidized regenerated cellulose: 100；Described oxidized regenerated cellulose
Filament yarn fabric in carboxyl-content be 16%～24%；
The preparation method of above-mentioned compound hemostatic material is specifically realized by the following steps:
First, prepare graphene solution: join in solvent by redox Graphene, be then 160W～400W at ultrasonic power
Under conditions of ultrasonically treated 10min～60min, obtain graphene solution；
The quality of the redox Graphene described in step one and the volume ratio of solvent are (0.1mg～2mg): 1mL；
Solvent described in step one is the ethanol solution that water, absolute ethyl alcohol or mass fraction are 20%～80%；
2nd, ultrasonic, freeze-drying: be immersed in the filament yarn fabric of oxidized regenerated cellulose in graphene solution, at ultrasonic work(
Ultrasonically treated 10min～60min under conditions of rate is 200W～400W, then re-uses oscillator oscillation treatment 1h～24h,
Again the filament yarn fabric of oxidized regenerated cellulose is taken out from the solution of Graphene, the oxidized regenerated cellulose after being impregnated
Filament yarn fabric；The filament yarn fabric of the oxidized regenerated cellulose after impregnating vacuum freeze drying at temperature is for-70～-20 DEG C
8h～96h, obtains Graphene/oxidized regenerated cellulose compound hemostatic material；
The quality of the filament yarn fabric of the oxidized regenerated cellulose described in step 2 with the volume ratio of graphene solution is
(0.005g～0.04g): 1mL.
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| CN106806049B (en) * | 2015-12-02 | 2018-10-16 | 珠海和凡医药股份有限公司 | A kind of preparation method and medical application of novel graphite alkene material |
| CN108568034A (en) * | 2018-03-14 | 2018-09-25 | 广西中医药大学 | A kind of graphene strengthens medicine infrared treatment head-shield and its preparation, purposes and application process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2517772A (en) * | 1945-05-11 | 1950-08-08 | Parke Davis & Co | Neutralized oxidized cellulose products |
| CN103418019A (en) * | 2013-08-13 | 2013-12-04 | 威海洁瑞医用制品有限公司 | Zwitterionic modified oxidized regenerated cellulose absorbable hemostatic material and preparation method thereof |
| CN104072809A (en) * | 2014-06-20 | 2014-10-01 | 南京林业大学 | Preparation method of graphene oxide/bacterial cellulose antibacterial compound material |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2517772A (en) * | 1945-05-11 | 1950-08-08 | Parke Davis & Co | Neutralized oxidized cellulose products |
| CN103418019A (en) * | 2013-08-13 | 2013-12-04 | 威海洁瑞医用制品有限公司 | Zwitterionic modified oxidized regenerated cellulose absorbable hemostatic material and preparation method thereof |
| CN104072809A (en) * | 2014-06-20 | 2014-10-01 | 南京林业大学 | Preparation method of graphene oxide/bacterial cellulose antibacterial compound material |
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