CN104383577B - A kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material - Google Patents
A kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material Download PDFInfo
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- CN104383577B CN104383577B CN201410718670.7A CN201410718670A CN104383577B CN 104383577 B CN104383577 B CN 104383577B CN 201410718670 A CN201410718670 A CN 201410718670A CN 104383577 B CN104383577 B CN 104383577B
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- regenerated cellulose
- nanometer gold
- oxidized regenerated
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Abstract
A kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material, it relates to a kind of hemostatic material.The invention aims to solve existing modified oxidized regenerated cellulose little as the anthemorrhagic performance lifting amplitude of hemostatic material, mechanical performance and bioresorbable reduce the problem that amplitude is big.A kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material is prepared by the fabric of nanometer gold and oxidized regenerated cellulose long filament；Preparation method: one, prepare nanometer gold aqueous dispersions；Two, absorption, obtains nanometer gold/oxidized regenerated cellulose compound hemostatic material.Nanometer gold/oxidized regenerated cellulose the compound hemostatic material using the present invention to prepare stops blooding, and bleeding stopping period reduces 3.8%～13%.The present invention can obtain a kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material and preparation method thereof.
Description
Technical field
The present invention relates to a kind of hemostatic material.
Background technology
The most inevitably there is various accident, in carrying out emergency treatment and operation process, all may
Because massive hemorrhage causes malpractice the most dead.Therefore, the topically effective quick-acting haemostatic powder of patient is 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 functional hemostasis will be the directions of following haemostatic medicament development.
Conventional Absorbable hemostatic material has Fibrin Glue, gelfoam, oxidized cellulose, microfibrillar collagen, chitosan
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 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 outward manifestation
Form, SURGICEL series of products have occupied extremely important status the most 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, uses expensive import hemostatic material so main clinically.
Oxidized regenerated cellulose is the derivant 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 oxidize on middle C-6 position is that carboxyl 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 contact blood
Can adsorb substantial amounts of erythrocyte after liquid, then the acidic carboxypolymer in oxidized regenerated cellulose structure can cause haemolysis, i.e. blood
Erythrocytolysis, rupture, and discharge hemoglobin.Simultaneously as containing ferric ion in hemoglobin, oxidation is again
Raw cellulose can be with Fe3+In conjunction with forming brown blob of viscose, close, block blood capillary end and stop blooding.As can be seen here, oxygen
The hemostasis changing regenerated cellulose is a series of Biochemical Engineering, and the carboxyl limited amount in material structure,
Therefore the anthemorrhagic speed causing oxidized regenerated cellulose material is relatively slow, causes such material cannot be applicable to the positions such as tremulous pulse
Massive hemorrhage situation.
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
Use the method that oxidized regenerated cellulose is neutralized by the aqueous solution of sodium bicarbonate or calcium acetate, and use thrombin impregnated carbon
The oxidized regenerated cellulose that acid hydrogen sodium neutralizes, then freezes to process and be dried in this case to the fabric after dipping, system
Obtained a kind of efficient oxidized cellulose class surgical operation hemostatic material.In United States Patent (USP), Saferstein et al. describes use
The alcohol-water solution of salt of weak acid, such as sodium acetate, is neutralized to pH value between 5～8, this method by oxidized regenerated cellulose
Not only make oxidized regenerated cellulose can store with ambient-temp-stable, and the acid-sensitive material of similar thrombin can be loaded, enter
And improve the anthemorrhagic performance of oxidized regenerated cellulose material.They also find simultaneously, and Doub et al. uses sodium bicarbonate 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 hot 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 neutralized ensure that original form of fabric, but due to after neutralizing material calcium content too high, make
The mammal skin of contact position and other somatic cells can be produced zest during with, and use position to form big sending out
White granulation lump, hinders the bio-absorbable of material.
In sum, although the correlational study of oxidized regenerated cellulose is all had a very big significance by above achievement in research, simultaneously
Also the anthemorrhagic performance making material has obtained a certain degree of lifting, but it is typically small to be an up degree, i.e. improves effect poor；
And, the ameliorative way in research also can be to the mechanical strength of regenerated oxycellulose as styptic material and Bioabsorbable in the past
Can adversely affect, for the anthemorrhagic performance promoted by a small margin, modified effect is lost more than gain.
Summary of the invention
The invention aims to the anthemorrhagic performance lifting amplitude solving existing modified oxidized regenerated cellulose as hemostatic material
Little, mechanical performance and bioresorbable reduce the problem that amplitude is big, and provide a kind of nanometer gold/oxidized regenerated cellulose to be combined
Hemostatic material.
A kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material is by nanometer gold and the fabric system of oxidized regenerated cellulose long filament
Standby；The mass ratio of the fabric of described nanometer gold and oxidized regenerated cellulose long filament is (0.35～5): 100.
The preparation method of a kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material, is specifically realized by the following steps:
One, nanometer gold aqueous dispersions is prepared: be added to the water by nanometer gold, super under ultrasonic power is 160W～400W
Sonication 5min～45min, obtains nanometer gold aqueous dispersions；
The quality of the nanometer gold described in step one and the volume ratio of water are (0.5mg～6.5mg): 1mL；
Two, absorption: the fabric of oxidized regenerated cellulose long filament is joined in nanometer gold aqueous dispersions, then at power is
200W～400W supersound process 10min～40min, then re-use agitator concussion and process 1h～48h, obtain nanometer Jinsui River
The fabric of the oxidized regenerated cellulose long filament after dispersion liquid dipping；Oxidation regeneration fiber after again nanometer gold aqueous dispersions being impregnated
The fabric of element long filament is immersed in 2h～24h in dehydrated alcohol, re-uses dehydrated alcohol and carries out washing 5 times～8 times, then in temperature
For vacuum lyophilization 16h～96h at-70 DEG C～-20 DEG C, obtain nanometer gold/oxidized regenerated cellulose compound hemostatic material；
The surface area of the fabric of the oxidized regenerated cellulose long filament described in step 2 with the volume ratio of nanometer gold aqueous dispersions is
1cm2: (0.6mL～1.0mL)；
In nanometer gold described in step 2/oxidized regenerated cellulose compound hemostatic material, nanometer gold and oxidized regenerated cellulose are long
The mass ratio of the fabric of silk is (0.35～5): 100.
Advantages of the present invention:
On the basis of one it is contemplated that maintain oxidized regenerated cellulose Absorbable hemostatic material advantage, one is proposed suitableeer
Oxidized regenerated cellulose is modified by suitable method；The present invention is in oxidized regenerated cellulose material surface physical absorption nanometer
Gold particle, and then improve the anthemorrhagic performance of oxidized regenerated cellulose, simultaneously the most again will not the mechanical strength of attacking material, but also
Can guarantee that the Bioabsorbable of material；
Two, the nanometer gold/oxidized regenerated cellulose compound hemostatic material using the present invention to prepare stops blooding, and bleeding stopping period drops
Low by 3.8%～13%.
The present invention can obtain a kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material and preparation method thereof.
Detailed description of the invention
Detailed description of the invention one: present embodiment is that a kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material is by nanometer gold
Prepare with the fabric of oxidized regenerated cellulose long filament；The quality of the fabric of described nanometer gold and oxidized regenerated cellulose long filament
Than being (0.35～5): 100.
The advantage of present embodiment:
One, on the basis of present embodiment is intended to maintain oxidized regenerated cellulose Absorbable hemostatic material advantage, one is proposed more
Add suitable method oxidized regenerated cellulose is modified；Present embodiment is at oxidized regenerated cellulose material surface physics
Absorption nano Au particle, and then improve the anthemorrhagic performance of oxidized regenerated cellulose, simultaneously the most again will not the mechanical strength of attacking material,
But also can guarantee that the Bioabsorbable of material；
Two, the nanometer gold/oxidized regenerated cellulose compound hemostatic material using present embodiment to prepare stops blooding, during hemostasis
Between reduce 3.8%～13%.
Present embodiment can obtain a kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material and preparation method thereof.
Detailed description of the invention two: the present embodiment difference from detailed description of the invention one is: described oxidized regenerated cellulose
In the fabric of long filament, carboxyl-content is 16%～24%.Other are identical with detailed description of the invention one.
Detailed description of the invention three: the present embodiment difference from detailed description of the invention one or two is: the grain of described nanometer gold
Footpath is 5nm～40nm.Other are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is the preparation side of a kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material
Method is specifically realized by the following steps:
One, nanometer gold aqueous dispersions is prepared: be added to the water by nanometer gold, super under ultrasonic power is 160W～400W
Sonication 5min～45min, obtains nanometer gold aqueous dispersions；
The quality of the nanometer gold described in step one and the volume ratio of water are (0.5mg～6.5mg): 1mL；
Two, absorption: the fabric of oxidized regenerated cellulose long filament is joined in nanometer gold aqueous dispersions, then at power is
200W～400W supersound process 10min～40min, then re-use agitator concussion and process 1h～48h, obtain nanometer Jinsui River
The fabric of the oxidized regenerated cellulose long filament after dispersion liquid dipping；Oxidation regeneration fiber after again nanometer gold aqueous dispersions being impregnated
The fabric of element long filament is immersed in 2h～24h in dehydrated alcohol, re-uses dehydrated alcohol and carries out washing 5 times～8 times, then in temperature
For vacuum lyophilization 16h～96h at-70 DEG C～-20 DEG C, obtain nanometer gold/oxidized regenerated cellulose compound hemostatic material；
The surface area of the fabric of the oxidized regenerated cellulose long filament described in step 2 with the volume ratio of nanometer gold aqueous dispersions is
1cm2: (0.6mL～1.0mL)；
In nanometer gold described in step 2/oxidized regenerated cellulose compound hemostatic material, nanometer gold and oxidized regenerated cellulose are long
The mass ratio of the fabric of silk is (0.35～5): 100.
The advantage of present embodiment:
One, on the basis of present embodiment is intended to maintain oxidized regenerated cellulose Absorbable hemostatic material advantage, one is proposed more
Add suitable method oxidized regenerated cellulose is modified；Present embodiment is at oxidized regenerated cellulose material surface physics
Absorption nano Au particle, and then improve the anthemorrhagic performance of oxidized regenerated cellulose, simultaneously the most again will not the mechanical strength of attacking material,
But also can guarantee that the Bioabsorbable of material；
Two, the nanometer gold/oxidized regenerated cellulose compound hemostatic material using present embodiment to prepare stops blooding, during hemostasis
Between reduce 3.8%～13%.
Present embodiment can obtain a kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material and preparation method thereof.
Detailed description of the invention five: the present embodiment difference from detailed description of the invention four is: the nanometer gold described in step one
Particle diameter be 5nm～40nm.Other are identical with detailed description of the invention four.
Detailed description of the invention six: the present embodiment difference from detailed description of the invention four or five is: described oxidation regeneration is fine
In the fabric of dimension element long filament, carboxyl-content is 16%～24%.Other are identical with detailed description of the invention four or five.
Detailed description of the invention seven: the present embodiment difference from detailed description of the invention four to six is: receiving described in step one
The quality of meter Jin and the volume ratio of water are (0.5mg～4mg): 1mL.Other are identical with detailed description of the invention four to six.
Detailed description of the invention eight: the present embodiment difference from detailed description of the invention four to seven is: the oxygen described in step 2
The surface area of fabric changing regenerated cellulose filaments is 1cm with the volume ratio of nanometer gold aqueous dispersions2:0.6mL.Other with tool
Body embodiment four to seven is identical.
Detailed description of the invention nine: the present embodiment difference from detailed description of the invention four to eight is: receiving described in step 2
In meter Jin/oxidized regenerated cellulose compound hemostatic material, the mass ratio of the fabric of nanometer gold and oxidized regenerated cellulose long filament is
(0.35～3.5): 100.Other are identical with detailed description of the invention four to eight.
Detailed description of the invention ten: the present embodiment difference from detailed description of the invention four to nine is: receiving described in step 2
In meter Jin/oxidized regenerated cellulose compound hemostatic material, the mass ratio of the fabric of nanometer gold and oxidized regenerated cellulose long filament is
(4～5): 100.Other are identical with detailed description of the invention four to nine.
Employing tests below checking beneficial effects of the present invention:
Test one: the preparation method of a kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material, the most according to the following steps
Complete:
One, nanometer gold aqueous dispersions is prepared: be added to the water by nanometer gold, then supersound process under ultrasonic power is 280W
15min, obtains nanometer gold aqueous dispersions；
The particle diameter of the nanometer gold described in step one is 15nm；
The quality of the nanometer gold described in step one and the volume ratio of water are 0.8mg:1mL；
Two, absorption: the fabric of the oxidized regenerated cellulose long filament of a size of 5cm × 5cm is joined 15mL nanometer Jinsui River
In dispersion liquid, then it is 320W supersound process 20min at power, then re-uses agitator concussion and process 24h, received
The fabric of the oxidized regenerated cellulose long filament after meter Jin Shui dispersion liquid dipping；Oxidation after being impregnated by nanometer gold aqueous dispersions again is again
The fabric of raw cellulosic filaments is immersed in 4h in dehydrated alcohol, re-uses dehydrated alcohol and carries out washing 8 times, then in temperature is
Vacuum lyophilization 32h at-53 DEG C, obtains nanometer gold/oxidized regenerated cellulose compound hemostatic material；
In nanometer gold described in step 2/oxidized regenerated cellulose compound hemostatic material, nanometer gold and oxidized regenerated cellulose are long
The mass ratio of the fabric of silk is 0.41:100；
In oxidized regenerated cellulose described in step 2, carboxyl-content is 17.36%.
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 tremulous pulse, is pasted on wound surface with 1 layer of test material or control sample and uses immediately after blood is gushed out
Pull and push dynamometer applies the pressure of 3N, observes hemostasis every 10s, until recording 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,
The bleeding stopping period using test one to obtain nanometer gold/oxidized regenerated cellulose compound hemostatic material is 125s.
Test two: the preparation method of a kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material, the most according to the following steps
Complete:
One, nanometer gold aqueous dispersions is prepared: be added to the water by nanometer gold, then supersound process under ultrasonic power is 400W
45min, obtains nanometer gold aqueous dispersions；
The quality of the nanometer gold described in step one and the volume ratio of water are 5mg:1mL；
The particle diameter of the nanometer gold described in step one is 32nm；
Two, absorption: the fabric of the oxidized regenerated cellulose long filament of a size of 5cm × 5cm is joined 20mL nanometer Jinsui River
In dispersion liquid, then it is 360W supersound process 40min at power, then re-uses agitator concussion and process 48h, received
The fabric of the oxidized regenerated cellulose long filament after meter Jin Shui dispersion liquid dipping；Oxidation after being impregnated by nanometer gold aqueous dispersions again is again
The fabric of raw cellulosic filaments is immersed in 12h in dehydrated alcohol, re-uses dehydrated alcohol and carries out washing 6 times, then in temperature is
Vacuum lyophilization 48h at-53 DEG C, obtains nanometer gold/oxidized regenerated cellulose compound hemostatic material；
In nanometer gold described in step 2/oxidized regenerated cellulose compound hemostatic material, nanometer gold and oxidized regenerated cellulose are long
The mass ratio of the fabric of silk is 3.26:100；
In oxidized regenerated cellulose described in step 2, carboxyl-content is 17.36%.
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 tremulous pulse, is pasted on wound surface with 1 layer of test material or control sample and uses immediately after blood is gushed out
Pull and push dynamometer applies the pressure of 3N, observes hemostasis every 10s, until recording 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 the two nanometer gold/oxidized regenerated cellulose compound hemostatic materials obtained is 113s.
Claims (1)
1. nanometer gold/oxidized regenerated cellulose compound hemostatic material, it is characterised in that a kind of nanometer gold/oxidized regenerated cellulose compound hemostatic material is prepared by the fabric of nanometer gold and oxidized regenerated cellulose long filament；The mass ratio of the fabric of described nanometer gold and oxidized regenerated cellulose long filament is (0.35～5): 100；
In the fabric of described oxidized regenerated cellulose long filament, carboxyl-content is 16%～24%；
The particle diameter of described nanometer gold is 5nm～40nm；
The preparation method of above-mentioned compound hemostatic material is specifically realized by the following steps:
One, nanometer gold aqueous dispersions is prepared: be added to the water by nanometer gold, then supersound process 5min～45min under ultrasonic power is 160W～400W, obtain nanometer gold aqueous dispersions；
The particle diameter of the nanometer gold described in step one is 5nm～40nm；
The quality of the nanometer gold described in step one and the volume ratio of water are (0.5mg～6.5mg): 1mL；
Two, absorption: the fabric of oxidized regenerated cellulose long filament is joined in nanometer gold aqueous dispersions, it is 200W～400W supersound process 10min～40min at power again, then re-use agitator concussion and process 1h～48h, obtain the fabric of the oxidized regenerated cellulose long filament after nanometer gold aqueous dispersions dipping；The fabric of the oxidized regenerated cellulose long filament after being impregnated by nanometer gold aqueous dispersions again is immersed in 2h～24h in dehydrated alcohol, re-use dehydrated alcohol to carry out washing 5 times～8 times, vacuum lyophilization 16h～96h at temperature is-70 DEG C～-20 DEG C again, obtains nanometer gold/oxidized regenerated cellulose compound hemostatic material；
The surface area of the fabric of the oxidized regenerated cellulose long filament described in step 2 and the volume ratio of nanometer gold aqueous dispersions are 1cm2: (0.6mL～1.0mL).
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| CN101824778A (en) * | 2010-05-05 | 2010-09-08 | 南通茂林医用材料有限公司 | Processing method for surface nano functionalization of cellulose reel |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824778A (en) * | 2010-05-05 | 2010-09-08 | 南通茂林医用材料有限公司 | Processing method for surface nano functionalization of cellulose reel |
| 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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