CN104383578B - A kind of graphene oxide graft modification regenerated oxycellulose as styptic material and preparation method thereof - Google Patents
A kind of graphene oxide graft modification regenerated oxycellulose as styptic material and preparation method thereof Download PDFInfo
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Abstract
A kind of graphene oxide graft modification regenerated oxycellulose as styptic material and preparation method thereof, it relates to a kind of hemostatic material and preparation method thereof. The object of the invention is to solve existing oxidized regenerated cellulose material modified exist the mechanical strength of material and bio-absorbable poor, anthemorrhagic performance promotes the little problem of amplitude. Prepared by the graphene oxide that a kind of graphene oxide graft modification regenerated oxycellulose as styptic material contains amino group by surface and oxidized regenerated cellulose; Preparation method: one, the graphene oxide of preparation chloride; Two, the graphene oxide that preparation contains amino group; Three, chemical graft, obtains graphene oxide graft modification regenerated oxycellulose as styptic material. The graphene oxide graft modification regenerated oxycellulose as styptic material that uses the present invention to prepare stops blooding, and bleeding stopping period has reduced by 7%～17%. The present invention can obtain a kind of graphene oxide graft modification regenerated oxycellulose as styptic material and preparation method thereof.
Description
Technical field
The present invention relates to a kind of hemostatic material and preparation method thereof.
Background technology
Inevitably can there are in daily life various accidents, carrying out in emergency treatment and surgical procedure, all mayBecause massive haemorrhage causes malpractice even dead. Therefore, patient is local, and effectively quick-acting haemostatic powder is most important, effectively controlMake blood and reduce the important measures that the bleeding time becomes reduction mortality. Clinical conventional hemostatic material as hemostatic gauze,Stanch fibre, tourniquet bandage in use have limitation, as longer in bleeding stopping period, easily and wound adhesion and be difficult for changing dressings,Infection to wound and suppurate helpless. Quick-acting haemostatic powder and functional hemostasis are by the direction that is following haemostatic medicament development.
Conventional absorbable hemostatic material has Fibrin Glue, gelfoam, oxycellulose, microfibre collagen, shitosanAnd Sorbsan etc. Their mechanism of action and using method are not quite similar, and haemostatic effect also has difference. But, orderBefore the hemostatic gauze that is widely used be clinically the SURGICEL being produced by company of Johnson & Johnson of the U.S. (Johnson&Johnson)Series absorbable hemostatic product---SURGICELTM、SURGICELTMNu-Knit、SURGICELTMFibrillar，Claim again at home " speed is yarn ", the composition of above product is oxidized regenerated cellulose, and main difference is embodied in external manifestationForm, SURGICEL series of products have occupied extremely important status in the international market now, and have been subject to medical scienceDomain expert's consistent favorable comment. Meanwhile, domestic You Ji company has also produced similar hemostatic gauze, but due to materialIt is yarn that performance can not show a candle to speed, so mainly adopt clinically expensive import hemostatic material.
Oxidized regenerated cellulose is cellulosic derivative, has good anthemorrhagic performance, biodegradable performance and nontoxic, orderBefore be used to multiple industry, be included in medical field, generally adopt nitrogen oxide as oxidant, by cellulose unitHydroxyl oxidize on middle C-6 position is that carboxyl makes oxidized regenerated cellulose. When it uses as hemostatic material, carboxyl-content shouldBe 16～24%, to ensure its haemostatic effect. Oxidized regenerated cellulose hemostatic mechanism is as follows: oxidized regenerated cellulose contact bloodAfter liquid, can adsorb a large amount of erythrocytes, then the acid carboxyl in oxidized regenerated cellulose structure can cause haemolysis, i.e. bloodErythrocytolysis, break, and discharge hemoglobin. Meanwhile, owing to containing ferric ion in hemoglobin, oxidation againRaw cellulose can with Fe3+In conjunction with forming brown blob of viscose, sealing, stop up capillary end and stopping blooding. As can be seen here, oxygenChange the hemostasis of regenerated cellulose and be a series of Biochemical Engineering, and carboxyl limited amount in material structure,Therefore cause the anthemorrhagic speed of oxidized regenerated cellulose material relatively slow, cause such material cannot be applicable to the positions such as arteryMassive haemorrhage situation.
Oxidized regenerated cellulose as the study on the modification of hemostatic material always in constantly making great efforts to carry out. The people such as Doub discloseThe method that adopts the aqueous solution of sodium acid carbonate or calcium acetate to neutralize oxidized regenerated cellulose, and use fibrin ferment impregnated carbonThe oxidized regenerated cellulose of acid hydrogen sodium neutralization, then freezes to process and be dried under this state, system to the fabric after dippingObtained a kind of efficient oxycellulose class operation hemostatic material. In United States Patent (USP), the people such as Saferstein has narrated useThe alcohol solution of salt of weak acid, as sodium acetate, is neutralized to pH value between 5～8 by oxidized regenerated cellulose, this methodNot only make oxidized regenerated cellulose can ambient-temp-stable store, and the sour sensitive materials of similar fibrin ferment on can load, enterAnd the anthemorrhagic performance of raising oxidized regenerated cellulose material. They also find simultaneously, and the people such as Doub adopt sodium acid carbonate neutralizationMethod can cause the gel of oxidized regenerated cellulose fabrics part, distortion, and cause the oxidation regeneration fiber of final neutralization to be knittedThe hot strength of thing is too low and cannot be applied in actual hemostasis. And the calcium acetate that the people such as Doub mention in patentAlthough the oxidized regenerated cellulose of neutralization has ensured original form of fabric, because material calcium content after neutralization is too high, makeWith producing excitant to the mammal skin of contact position and other body cells in process, and form large sending out in use locationWhite granulation lump, the bio-absorbable that hinders material.
In sum, although above achievement in research all the correlative study of oxidized regenerated cellulose is had a very big significance, simultaneouslyAlso make the anthemorrhagic performance of material obtain lifting to a certain degree, but lifting degree is generally less, improves effect poor;And the improvement method in research also can be to the mechanical strength of regenerated oxycellulose as styptic material and Bioabsorbable in the pastCan cause negative effect, for the anthemorrhagic performance promoting by a small margin, modified effect is lost more than gain.
Summary of the invention
The object of the invention is to solve material modified mechanical strength and the biology that has material of existing oxidized regenerated celluloseAbsorption difference, anthemorrhagic performance promotes the little problem of amplitude, and provides a kind of graphene oxide graft modification oxidized regenerated cellulose onlyBlood material and preparation method thereof.
The graphite oxide that a kind of graphene oxide graft modification regenerated oxycellulose as styptic material contains amino group by surfacePrepared by alkene and oxidized regenerated cellulose; The graphene oxide that amino group is contained on described surface and oxidized regenerated celluloseMass ratio is (0.01～3): 100.
A preparation method for graphene oxide graft modification regenerated oxycellulose as styptic material, specifically complete according to the following stepsBecome:
One, the graphene oxide of preparation chloride: 1., graphene oxide is joined in DMF, thenBe ultrasonic processing 15min～60min under 160W～400W at ultrasonic power, then add thionyl chloride, in temperature beUnder the condition that 60 DEG C～100 DEG C and mixing speed are 300r/min～750r/min, stir 16h～48h, then naturally cool to room temperature,Re-use revolve steam evaporimeter revolve steaming, obtain mixture A; 2., taking carrene as cleaning agent, use Rotary EvaporatorsTo mixture, A revolves steaming; 3., repeating step one 2. 2 times～6 times, obtain the graphene oxide of chloride;
The quality of the graphene oxide described in step 1 and the volume ratio of DMF are(0.004g～0.05g):1mL；
The quality of the graphene oxide described in step 1 and the volume ratio of thionyl chloride are (0.007g～0.03g): 1mL;
Two, the graphene oxide that amino group is contained on preparation surface: in the graphene oxide of chloride, add carrene,Be ultrasonic processing 10min～45min under 200W～400W at ultrasonic power, then with the dropping of 10/min～25 droplet/minSpeed adds 1,3-propane diamine, then is cold under 35 DEG C～60 DEG C and the mixing speed condition that is 350r/min～800r/min in temperatureSolidifying back flow reaction 8h～32h, then naturally cool to room temperature, re-uses to revolve and steams evaporimeter and revolve steaming, obtains mixture B;Respectively taking methyl alcohol, deionized water and absolute ethyl alcohol as cleaning agent, mixture B is distinguished to centrifuge washing 3 times～8 times again, thenBe freeze drying 24h～60h at-70 DEG C～-40 DEG C in temperature, obtain spongy product; Re-using mortar grinds spongy productBe milled to and there is no macroscopic particle, obtain the graphene oxide that amino group is contained on surface;
The quality of the graphene oxide of the chloride described in step 2 and the volume ratio of carrene are(0.002g～0.005g):1mL；
The volume ratio of the quality of the graphene oxide of the chloride described in step 2 and 1,3-propane diamine is(0.0125g～0.033g):1mL；
Three, chemical graft: 1., surface that step 2 the is obtained graphene oxide that contains amino group is distributed in solvent,Then be the ultrasonic processing of 160W～400W 15min～50min at ultrasonic power, obtain the oxidation stone that contains amino group in surfaceChina ink alkene solution; Oxidized regenerated cellulose is immersed in the graphene oxide solution that contains amino group in surface again, then ultrasonicPower is ultrasonic processing 20min～40min under 200W～400W, and then uses oscillator oscillation treatment 1h～24h, thenThe graphene oxide solution that oxidized regenerated cellulose is contained to amino group from surface, take out, obtain the oxidation regeneration after graftingCellulose; 2. be, the oxidized regenerated cellulose after grafting is immersed in deionized water, 200W～320W at ultrasonic powerLower ultrasonic processing 20min～60min; 3., repeating step three 2. 2 times～5 times, then by the oxidized regenerated cellulose after grafting fromIn deionized water, take out, then be vacuum freeze drying 8h～96h at-70 DEG C～-20 DEG C in temperature, obtain graphene oxide graftingModified oxidized regenerated cellulose hemostatic material;
The quality of the graphene oxide that amino group is contained on the surface described in step 3 and the volume ratio of solvent are(0.1mg～1.0mg):1mL；
The body of the graphene oxide solution that amino group is contained on the quality of the oxidized regenerated cellulose described in step 3 and surfaceLong-pending than being (0.002g～0.05g): 1mL;
In graphene oxide graft modification regenerated oxycellulose as styptic material described in step 3, amino group is contained on surfaceGraphene oxide and the mass ratio of oxidized regenerated cellulose be (0.01～3): 100.
In amino group in the graphene oxide that in the present invention, amino group is contained on surface and oxidized regenerated cellulose structureCarboxyl reaction generate amido link, thereby by graphene oxide branch to oxidized regenerated cellulose.
Advantage of the present invention:
One, the present invention is intended to maintain on the basis of oxidized regenerated cellulose absorbable hemostatic material advantage, proposes one suitableeerSuitable method is carried out modification to material; Advantage of the present invention is on chemical graft, to contain on the filament yarn fabric of oxidized regenerated celluloseThere is the graphene oxide of amino group, increased the specific area of the filament yarn fabric of oxidized regenerated cellulose, can obtain structureStable material, can also improve the anthemorrhagic performance of the filament yarn fabric of oxidized regenerated cellulose, can not damage oxidation more again simultaneouslyMechanical strength and the biological absorbable performance of raw cellulosic filament yarn fabric, the while can also be improved the bacteriostasis property of material, carriesRise the organization healing ability that promotes.
Two, the graphene oxide graft modification regenerated oxycellulose as styptic material that uses the present invention to prepare stops blooding, hemostasisTime has reduced by 7%～17%.
The present invention can obtain a kind of graphene oxide graft modification regenerated oxycellulose as styptic material and preparation method thereof.
Detailed description of the invention
Detailed description of the invention one: present embodiment be a kind of graphene oxide graft modification regenerated oxycellulose as styptic material byPrepared by the graphene oxide that amino group is contained on surface and oxidized regenerated cellulose; The oxygen that amino group is contained on described surfaceThe mass ratio of functionalized graphene and oxidized regenerated cellulose is (0.01～3): 100.
Graphene oxide described in present embodiment is, with Hummers method, Graphene is carried out to oxidation processes, then through washing,Dry, grinding, obtain oxidation product; Again oxidation product is joined in DMF, ultrasonic processing, thenUse Rotary Evaporators to remove DMF, obtain graphene oxide.
Amino group and oxidized regenerated cellulose structure in the graphene oxide that in present embodiment, amino group is contained on surfaceIn carboxyl reaction generate amido link, thereby by graphene oxide branch to oxidized regenerated cellulose.
The advantage of present embodiment:
One, present embodiment is intended to maintain on the basis of oxidized regenerated cellulose absorbable hemostatic material advantage, proposes one moreAdd suitable method material is carried out to modification; The advantage of present embodiment is chemical graft upper surface on oxidized regenerated celluloseThe graphene oxide that contains amino group, has increased the specific area of oxidized regenerated cellulose, can obtain constitutionally stable materialExpect, can also improve the anthemorrhagic performance of oxidized regenerated cellulose, can not damage again the mechanical strength of oxidized regenerated cellulose simultaneouslyWith biological absorbable performance, can also improve the bacteriostasis property of oxidized regenerated cellulose simultaneously, promote the organization healing ability that promotes.
Two, the graphene oxide graft modification regenerated oxycellulose as styptic material that uses present embodiment to prepare stops blooding,Bleeding stopping period has reduced by 7%～17%.
Present embodiment can obtain a kind of graphene oxide graft modification regenerated oxycellulose as styptic material and preparation method thereof.
Detailed description of the invention two: present embodiment and detailed description of the invention one difference are: in described oxidized regenerated celluloseCarboxyl-content is 16%～24%; Described oxidized regenerated cellulose is to exist with the form of short silk, long filament or fabric. OtherStep is identical with detailed description of the invention one.
Detailed description of the invention three: one of present embodiment and detailed description of the invention one or two difference is: described surface is containedThe preparation method of the graphene oxide of amino group completes according to the following steps:
One, the graphene oxide of preparation chloride: 1., graphene oxide is joined in DMF, thenBe ultrasonic processing 15min～60min under 160W～400W at ultrasonic power, then add thionyl chloride, in temperature beUnder the condition that 60 DEG C～100 DEG C and mixing speed are 300r/min～750r/min, stir 16h～48h, then naturally cool to room temperature,Re-use revolve steam evaporimeter revolve steaming, obtain mixture A; 2., taking carrene as cleaning agent, use Rotary EvaporatorsTo mixture, A revolves steaming; 3., repeating step one 2. 2 times～6 times, obtain the graphene oxide of chloride;
The quality of the graphene oxide described in step 1 and the volume ratio of DMF are(0.004g～0.05g):1mL；
The quality of the graphene oxide described in step 1 and the volume ratio of thionyl chloride are (0.007g～0.03g): 1mL;
Two, the graphene oxide that amino group is contained on preparation surface: in the graphene oxide of chloride, add carrene,Be ultrasonic processing 10min～45min under 200W～400W at ultrasonic power, then with the dropping of 10/min～25 droplet/minSpeed adds 1,3-propane diamine, then is cold under 35 DEG C～60 DEG C and the mixing speed condition that is 350r/min～800r/min in temperatureSolidifying back flow reaction 8h～32h, then naturally cool to room temperature, re-uses to revolve and steams evaporimeter and revolve steaming, obtains mixture B;Respectively taking methyl alcohol, deionized water and absolute ethyl alcohol as cleaning agent, mixture B is distinguished to centrifuge washing 3 times～8 times again, thenBe freeze drying 24h～60h at-70 DEG C～-40 DEG C in temperature, obtain spongy product; Re-using mortar grinds spongy productBe milled to and there is no macroscopic particle, obtain the graphene oxide that amino group is contained on surface;
The quality of the graphene oxide of the chloride described in step 2 and the volume ratio of carrene are(0.002g～0.005g):1mL；
The volume ratio of the quality of the graphene oxide of the chloride described in step 2 and 1,3-propane diamine is(0.0125g～0.033g): 1mL. Other steps are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is a kind of graphene oxide graft modification regenerated oxycellulose as styptic materialPreparation method, specifically completes according to the following steps:
One, the graphene oxide of preparation chloride: 1., graphene oxide is joined in DMF, thenBe ultrasonic processing 15min～60min under 160W～400W at ultrasonic power, then add thionyl chloride, in temperature beUnder the condition that 60 DEG C～100 DEG C and mixing speed are 300r/min～750r/min, stir 16h～48h, then naturally cool to room temperature,Re-use revolve steam evaporimeter revolve steaming, obtain mixture A; 2., taking carrene as cleaning agent, use Rotary EvaporatorsTo mixture, A revolves steaming; 3., repeating step one 2. 2 times～6 times, obtain the graphene oxide of chloride;
The quality of the graphene oxide described in step 1 and the volume ratio of DMF are(0.004g～0.05g):1mL；
The quality of the graphene oxide described in step 1 and the volume ratio of thionyl chloride are (0.007g～0.03g): 1mL;
Two, the graphene oxide that amino group is contained on preparation surface: in the graphene oxide of chloride, add carrene,Be ultrasonic processing 10min～45min under 200W～400W at ultrasonic power, then with the dropping of 10/min～25 droplet/minSpeed adds 1,3-propane diamine, then is cold under 35 DEG C～60 DEG C and the mixing speed condition that is 350r/min～800r/min in temperatureSolidifying back flow reaction 8h～32h, then naturally cool to room temperature, re-uses to revolve and steams evaporimeter and revolve steaming, obtains mixture B;Respectively taking methyl alcohol, deionized water and absolute ethyl alcohol as cleaning agent, mixture B is distinguished to centrifuge washing 3 times～8 times again, thenBe freeze drying 24h～60h at-70 DEG C～-40 DEG C in temperature, obtain spongy product; Re-using mortar grinds spongy productBe milled to and there is no macroscopic particle, obtain the graphene oxide that amino group is contained on surface;
The quality of the graphene oxide of the chloride described in step 2 and the volume ratio of carrene are(0.002g～0.005g):1mL；
The volume ratio of the quality of the graphene oxide of the chloride described in step 2 and 1,3-propane diamine is(0.0125g～0.033g):1mL；
Three, chemical graft: 1., surface that step 2 the is obtained graphene oxide that contains amino group is distributed in solvent,Then be the ultrasonic processing of 160W～400W 15min～50min at ultrasonic power, obtain the oxidation stone that contains amino group in surfaceChina ink alkene solution; Oxidized regenerated cellulose is immersed in the graphene oxide solution that contains amino group in surface again, then ultrasonicPower is ultrasonic processing 20min～40min under 200W～400W, and then uses oscillator oscillation treatment 1h～24h, thenThe graphene oxide solution that oxidized regenerated cellulose is contained to amino group from surface, take out, obtain the oxidation regeneration after graftingCellulose; 2. be, the oxidized regenerated cellulose after grafting is immersed in deionized water, 200W～320W at ultrasonic powerLower ultrasonic processing 20min～60min; 3., repeating step three 2. 2 times～5 times, then by the oxidized regenerated cellulose after grafting fromIn deionized water, take out, then be vacuum freeze drying 8h～96h at-70 DEG C～-20 DEG C in temperature, obtain graphene oxide graftingModified oxidized regenerated cellulose hemostatic material;
The quality of the graphene oxide that amino group is contained on the surface described in step 3 and the volume ratio of solvent are(0.1mg～1.0mg):1mL；
The body of the graphene oxide solution that amino group is contained on the quality of the oxidized regenerated cellulose described in step 3 and surfaceLong-pending than being (0.002g～0.05g): 1mL;
In graphene oxide graft modification regenerated oxycellulose as styptic material described in step 3, amino group is contained on surfaceGraphene oxide and the mass ratio of oxidized regenerated cellulose be (0.01～3): 100.
Graphene oxide described in present embodiment is, with Hummers method, Graphene is carried out to oxidation processes, then through washing,Dry, grinding, obtain oxidation product; Again oxidation product is joined in DMF, ultrasonic processing, thenUse Rotary Evaporators to remove DMF, obtain graphene oxide.
Amino group and oxidized regenerated cellulose structure in the graphene oxide that in present embodiment, amino group is contained on surfaceIn carboxyl reaction generate amido link, thereby by graphene oxide branch to oxidized regenerated cellulose.
The advantage of present embodiment:
One, present embodiment is intended to maintain on the basis of oxidized regenerated cellulose absorbable hemostatic material advantage, proposes one moreAdd suitable method material is carried out to modification; The advantage of present embodiment is chemical graft upper surface on oxidized regenerated celluloseThe graphene oxide that contains amino group, has increased the specific area of oxidized regenerated cellulose, can obtain constitutionally stable materialExpect, can also improve the anthemorrhagic performance of oxidized regenerated cellulose, can not damage again the mechanical strength of oxidized regenerated cellulose simultaneouslyWith biological absorbable performance, can also improve the bacteriostasis property of oxidized regenerated cellulose simultaneously, promote the organization healing ability that promotes.
Two, the graphene oxide graft modification regenerated oxycellulose as styptic material that uses present embodiment to prepare stops blooding,Bleeding stopping period has reduced by 7%～17%.
Present embodiment can obtain a kind of graphene oxide graft modification regenerated oxycellulose as styptic material and preparation method thereof.
Detailed description of the invention five: the difference of present embodiment and detailed description of the invention four is: the solvent described in step 3 isWater, absolute ethyl alcohol or mass fraction are 20%～80% ethanolic solution. Other steps are identical with detailed description of the invention four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention four to five difference is: described in step 3In oxidized regenerated cellulose, carboxyl-content is 16%～24%. Other steps are identical with detailed description of the invention four to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention four to six difference is: described in step 3Oxidized regenerated cellulose is to exist with the form of short silk, long filament or fabric. Other steps are identical with detailed description of the invention four to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention four to seven difference is: described in step 3The quality of the graphene oxide that amino group is contained on surface and the volume ratio of solvent are (0.1mg～0.5mg): 1mL. Other stepsIdentical with detailed description of the invention four to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention four to eight difference is: described in step 3The quality of oxidized regenerated cellulose with the volume ratio of the graphene oxide solution that amino group is contained on surface is(0.01g～0.05g): 1mL. Other steps are identical with detailed description of the invention four to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention four to nine difference is: described in step 3Graphene oxide and oxidation that in graphene oxide graft modification regenerated oxycellulose as styptic material, amino group is contained on surfaceThe mass ratio of regenerated cellulose is (0.01～2): 100. Other steps are identical with detailed description of the invention four to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: below a kind of preparation method of graphene oxide graft modification regenerated oxycellulose as styptic material specifically pressesStep completes:
One, the graphene oxide of preparation chloride: 1., graphene oxide is joined in DMF, thenBeing ultrasonic processing 45min under 400W at ultrasonic power, then adding thionyl chloride, is that 75 DEG C and mixing speed are in temperatureUnder the condition of 500r/min, stir 24h, then naturally cool to room temperature, re-use revolve steam evaporimeter revolve steaming, mixedThing A; 2., taking carrene as cleaning agent, use Rotary Evaporators mixture A is revolved to steaming; 3., repeating step, obtain the graphene oxide of chloride one 2. for 4 times;
The quality of the graphene oxide described in step 1 and the volume ratio of DMF are 0.05g:1mL;
The quality of the graphene oxide described in step 1 and the volume ratio of thionyl chloride are 0.02g:1mL;
Two, the graphene oxide that amino group is contained on preparation surface: in the graphene oxide of chloride, add carrene,Be ultrasonic processing 30min under 320W at ultrasonic power, then add 1,3-propane diamine with the rate of addition of 15/min, thenBe condensing reflux reaction 24h under 40 DEG C and the mixing speed condition that is 550r/min in temperature, then naturally cool to room temperature,Re-use revolve steam evaporimeter revolve steaming, obtain mixture B; Again respectively taking methyl alcohol, deionized water and absolute ethyl alcohol as cleaningAgent, distinguishes centrifuge washing 6 times to mixture B, then is freeze drying 48h at-53 DEG C in temperature, obtains spongy product;Re-use mortar spongy product is ground to and there is no macroscopic particle, obtain the graphite oxide that amino group is contained on surfaceAlkene;
The quality of the graphene oxide of the chloride described in step 2 and the volume ratio of carrene are 0.003g:1mL;
The volume ratio of the quality of the graphene oxide of the chloride described in step 2 and 1,3-propane diamine is 0.02g:1mL;
Three, chemical graft: 1., graphene oxide that amino group is contained in 25mg surface is distributed to the anhydrous second of 200mLIn alcohol, be then the ultrasonic processing of 280W 30min at ultrasonic power, the graphene oxide that obtains containing amino group in surface is moltenLiquid; Again 2.5g oxidized regenerated cellulose is immersed in the graphene oxide solution that contains amino group in surface, then ultrasonicPower is ultrasonic processing 30min under 320W, and then uses oscillator oscillation treatment 24h, then by oxidized regenerated celluloseThe graphene oxide solution that contains amino group from surface, take out, obtain the oxidized regenerated cellulose after grafting; 2., will connectOxidized regenerated cellulose after branch is immersed in deionized water, is ultrasonic processing 30min under 240W at ultrasonic power; 3.,Repeating step three 2. 5 times, then the oxidized regenerated cellulose after grafting is taken out from deionized water, then be-53 DEG C in temperatureLower vacuum freeze drying 24h, obtains graphene oxide graft modification regenerated oxycellulose as styptic material;
In graphene oxide graft modification regenerated oxycellulose as styptic material described in step 3, amino group is contained on surfaceGraphene oxide and the mass ratio of oxidized regenerated cellulose be 0.55:100;
In oxidized regenerated cellulose described in step 3, carboxyl-content is 17.36%;
Oxidation regeneration fiber described in step 3 is to exist with form of fabric.
The described graphene oxide of this test is, with Hummers method, Graphene is carried out to oxidation processes, then through washing, dryDry, grinding, obtain oxidation product; Again oxidation product is joined in DMF, ultrasonic processing, then makeRemove DMF with Rotary Evaporators, obtain graphene oxide.
Bleeding stopping period is measured: slowly inject after amobarbital sodium solution anesthetized animal, by its central authorities by 40mg/kg dosage veinArteria auricularis region preserved skin, sterilization, cut skin along arteria auricularis direction, and blunt separation goes out arteria auricularis, vein and nerve, then usesScalpel transversely cutting artery sticks in wound surface and uses by 1 layer of test material or control sample immediately after blood is gushed outPull and push dynamometer applies the pressure of 3N, observes hemostasis situation every 10s, until finally record bleeding stopping period after hemostasis completely.Test result is as follows: using the bleeding stopping period of the fabric of the oxidized regenerated cellulose of carboxyl-content 17.36% is 130s, usesThe bleeding stopping period of the test one graphene oxide graft modification regenerated oxycellulose as styptic material obtaining is 120s.
Test two: below a kind of preparation method of graphene oxide graft modification regenerated oxycellulose as styptic material specifically pressesStep completes:
One, the graphene oxide of preparation chloride: 1., graphene oxide is joined in DMF, thenBeing ultrasonic processing 30min under 400W at ultrasonic power, then adding thionyl chloride, is that 70 DEG C and mixing speed are in temperatureUnder the condition of 550r/min, stir 32h, then naturally cool to room temperature, re-use revolve steam evaporimeter revolve steaming, mixedThing A; 2., taking carrene as cleaning agent, use Rotary Evaporators mixture A is revolved to steaming; 3., repeating step, obtain the graphene oxide of chloride one 2. for 5 times;
The quality of the graphene oxide described in step 1 and the volume ratio of DMF are 0.025g:1mL;
The quality of the graphene oxide described in step 1 and the volume ratio of thionyl chloride are 0.015g:1mL;
Two, the graphene oxide that amino group is contained on preparation surface: in the graphene oxide of chloride, add carrene,Be ultrasonic processing 25min under 400W at ultrasonic power, then add 1,3-propane diamine with the rate of addition of 10/min, thenBe condensing reflux reaction 32h under 37 DEG C and the mixing speed condition that is 700r/min in temperature, then naturally cool to room temperature,Re-use revolve steam evaporimeter revolve steaming, obtain mixture B; Again respectively taking methyl alcohol, deionized water and absolute ethyl alcohol as cleaningAgent, distinguishes centrifuge washing 7 times to mixture B, then is freeze drying 56h at-53 DEG C in temperature, obtains spongy product;Re-use mortar spongy product is ground to and there is no macroscopic particle, obtain the graphite oxide that amino group is contained on surfaceAlkene;
The quality of the graphene oxide of the chloride described in step 2 and the volume ratio of carrene are 0.004g:1mL;
The volume ratio of the quality of the graphene oxide of the chloride described in step 2 and 1,3-propane diamine is 0.017g:1mL;
Three, chemical graft: 1., graphene oxide that amino group is contained in 50mg surface is distributed in 200mL water,Then be the ultrasonic processing of 320W 45min at ultrasonic power, obtain the graphene oxide solution that contains amino group in surface; Again2.5g oxidized regenerated cellulose is immersed in the graphene oxide solution that contains amino group in surface, then at ultrasonic power isUltrasonic processing 30min under 400W, and then use oscillator oscillation treatment 2h, then oxidized regenerated cellulose is contained from surfaceHave in the graphene oxide solution of amino group and take out, obtain the oxidized regenerated cellulose after grafting; 2., by the oxygen after graftingChanging regenerated cellulose and be immersed in deionized water, is ultrasonic processing 40min under 320W at ultrasonic power; 3., repeating stepThree 2. 3 times, then the oxidized regenerated cellulose after grafting is taken out from deionized water, then be that at-53 DEG C, vacuum is cold in temperatureThe dry 72h of freeze-drying, obtains graphene oxide graft modification regenerated oxycellulose as styptic material;
In graphene oxide graft modification regenerated oxycellulose as styptic material described in step 3, amino group is contained on surfaceGraphene oxide and the mass ratio of oxidized regenerated cellulose be 1.29:100;
In oxidized regenerated cellulose described in step 3, carboxyl-content is 17.36%;
Oxidation regeneration fiber described in step 3 is to exist with form of fabric.
The described graphene oxide of this test is, with Hummers method, Graphene is carried out to oxidation processes, then through washing, dryDry, grinding, obtain oxidation product; Again oxidation product is joined in DMF, ultrasonic processing, then makeRemove DMF with Rotary Evaporators, obtain graphene oxide.
Bleeding stopping period is measured: slowly inject after amobarbital sodium solution anesthetized animal, by its central authorities by 40mg/kg dosage veinArteria auricularis region preserved skin, sterilization, cut skin along arteria auricularis direction, and blunt separation goes out arteria auricularis, vein and nerve, then usesScalpel transversely cutting artery sticks in wound surface and uses by 1 layer of test material or control sample immediately after blood is gushed outPull and push dynamometer applies the pressure of 3N, observes hemostasis situation every 10s, until finally record bleeding stopping period after hemostasis completely.Test result is as follows: using the bleeding stopping period of the fabric of the oxidized regenerated cellulose of carboxyl-content 17.36% is 130s, usesThe bleeding stopping period of the test two graphene oxide graft modification regenerated oxycellulose as styptic material that obtain is 116s.
Test three: below a kind of preparation method of graphene oxide graft modification regenerated oxycellulose as styptic material specifically pressesStep completes:
One, the graphene oxide of preparation chloride: 1., graphene oxide is joined in DMF, thenBeing ultrasonic processing 15min under 400W at ultrasonic power, then adding thionyl chloride, is that 65 DEG C and mixing speed are in temperatureUnder the condition of 600r/min, stir 48h, then naturally cool to room temperature, re-use revolve steam evaporimeter revolve steaming, mixedThing A; 2., taking carrene as cleaning agent, use Rotary Evaporators mixture A is revolved to steaming; 3., repeating step, obtain the graphene oxide of chloride one 2. for 3 times;
The quality of the graphene oxide described in step 1 and the volume ratio of DMF are 0.004g:1mL;
The quality of the graphene oxide described in step 1 and the volume ratio of thionyl chloride are 0.008g:1mL;
Two, the graphene oxide that amino group is contained on preparation surface: in the graphene oxide of chloride, add carrene,Be ultrasonic processing 25min under 400W at ultrasonic power, then add 1,3-propane diamine with the rate of addition of 20/min, thenBe condensing reflux reaction 32h under 45 DEG C and the mixing speed condition that is 750r/min in temperature, then naturally cool to room temperature,Re-use revolve steam evaporimeter revolve steaming, obtain mixture B; Again respectively taking methyl alcohol, deionized water and absolute ethyl alcohol as cleaningAgent, distinguishes centrifuge washing 8 times to mixture B, then is freeze drying 48h at-53 DEG C in temperature, obtains spongy product;Re-use mortar spongy product is ground to and there is no macroscopic particle, obtain the graphite oxide that amino group is contained on surfaceAlkene;
The quality of the graphene oxide of the chloride described in step 2 and the volume ratio of carrene are 0.005g:1mL;
The volume ratio of the quality of the graphene oxide of the chloride described in step 2 and 1,3-propane diamine is 0.0125g:1mL;
Three, chemical graft: 1., graphene oxide that amino group is contained in 50mg surface is distributed in 500mL water,Then be the ultrasonic processing of 240W 30min at ultrasonic power, obtain the graphene oxide solution that contains amino group in surface; Again2.5g oxidized regenerated cellulose is immersed in the graphene oxide solution that contains amino group in surface, then at ultrasonic power isUltrasonic processing 30min under 320W, and then use oscillator oscillation treatment 8h, then oxidized regenerated cellulose is contained from surfaceHave in the graphene oxide solution of amino group and take out, obtain the oxidized regenerated cellulose after grafting; 2., by the oxygen after graftingChanging regenerated cellulose and be immersed in deionized water, is ultrasonic processing 40min under 280W at ultrasonic power; 3., repeating stepThree 2. 3 times, then the oxidized regenerated cellulose after grafting is taken out from deionized water, then be that at-53 DEG C, vacuum is cold in temperatureThe dry 72h of freeze-drying, obtains graphene oxide graft modification regenerated oxycellulose as styptic material;
In graphene oxide graft modification regenerated oxycellulose as styptic material described in step 3, amino group is contained on surfaceGraphene oxide and the mass ratio of oxidized regenerated cellulose be 1.77:100;
In oxidized regenerated cellulose described in step 3, carboxyl-content is 17.36%;
Oxidation regeneration fiber described in step 3 is to exist with form of fabric.
The described graphene oxide of this test is, with Hummers method, Graphene is carried out to oxidation processes, then through washing, dryDry, grinding, obtain oxidation product; Again oxidation product is joined in DMF, ultrasonic processing, then makeRemove DMF with Rotary Evaporators, obtain graphene oxide.
Bleeding stopping period is measured: slowly inject after amobarbital sodium solution anesthetized animal, by its central authorities by 40mg/kg dosage veinArteria auricularis region preserved skin, sterilization, cut skin along arteria auricularis direction, and blunt separation goes out arteria auricularis, vein and nerve, then usesScalpel transversely cutting artery sticks in wound surface and uses by 1 layer of test material or control sample immediately after blood is gushed outPull and push dynamometer applies the pressure of 3N, observes hemostasis situation every 10s, until finally record bleeding stopping period after hemostasis completely.Test result is as follows: using the bleeding stopping period of the fabric of the oxidized regenerated cellulose of carboxyl-content 17.36% is 130s, usesThe bleeding stopping period of the test three graphene oxide graft modification regenerated oxycellulose as styptic material that obtain is 109s.
Claims (8)
1. a graphene oxide graft modification regenerated oxycellulose as styptic material, is characterized in that a kind of graphene oxide connectsPrepared by graphene oxide and oxidized regenerated cellulose that the modified oxidized regenerated cellulose hemostatic material of branch contains amino group by surface; The graphene oxide that amino group is contained on described surface and the mass ratio of oxidized regenerated cellulose are (0.01～3): 100;
In described oxidized regenerated cellulose, carboxyl-content is 16%～24%; Described oxidized regenerated cellulose is with short silk, longThe form of silk or fabric exists;
The preparation method of the graphene oxide that amino group is contained on described surface completes according to the following steps:
One, the graphene oxide of preparation chloride: 1., graphene oxide is joined in DMF, thenUltrasonic power is ultrasonic processing 15min～60min under 160W～400W, then adds thionyl chloride, is 60 DEG C～100 DEG C in temperatureWith under the mixing speed condition that is 300r/min～750r/min, stir 16h～48h, then naturally cool to room temperature, re-use and revolve steamingEvaporimeter revolves steaming, obtains mixture A; 2., taking carrene as cleaning agent, use Rotary Evaporators to mixture ARevolve steaming; 3., repeating step one 2. 2 times～6 times, obtain the graphene oxide of chloride;
The quality of the graphene oxide described in step 1 and the volume ratio of DMF are(0.004g～0.05g):1mL；
The quality of the graphene oxide described in step 1 and the volume ratio of thionyl chloride are (0.007g～0.03g): 1mL;
Two, the graphene oxide that amino group is contained on preparation surface: in the graphene oxide of chloride, add carrene,Be ultrasonic processing 10min～45min under 200W～400W at ultrasonic power, then with the dropping speed of 10/min～25 droplet/minDegree adds 1,3-propane diamine, then is condensation under 35 DEG C～60 DEG C and the mixing speed condition that is 350r/min～800r/min in temperatureBack flow reaction 8h～32h, then naturally cool to room temperature, re-uses to revolve and steams evaporimeter and revolve steaming, obtains mixture B; Divide again, taking methyl alcohol, deionized water and absolute ethyl alcohol as cleaning agent, mixture B is not distinguished to centrifuge washing 3 times～8 times, then in temperatureFor freeze drying 24h～60h at-70 DEG C～-40 DEG C, obtain spongy product; Re-using mortar is ground to spongy product notThere is macroscopic particle, obtain the graphene oxide that amino group is contained on surface;
The quality of the graphene oxide of the chloride described in step 2 and the volume ratio of carrene are(0.002g～0.005g):1mL；
The volume ratio of the quality of the graphene oxide of the chloride described in step 2 and 1,3-propane diamine is(0.0125g～0.033g):1mL。
2. a preparation method for graphene oxide graft modification regenerated oxycellulose as styptic material, is characterized in that a kind of oxygenThe preparation method of functionalized graphene graft modification regenerated oxycellulose as styptic material specifically completes according to the following steps:
One, the graphene oxide of preparation chloride: 1., graphene oxide is joined in DMF, thenUltrasonic power is ultrasonic processing 15min～60min under 160W～400W, then adds thionyl chloride, is 60 DEG C～100 DEG C in temperatureWith under the mixing speed condition that is 300r/min～750r/min, stir 16h～48h, then naturally cool to room temperature, re-use and revolve steamingEvaporimeter revolves steaming, obtains mixture A; 2., taking carrene as cleaning agent, use Rotary Evaporators to mixture ARevolve steaming; 3., repeating step one 2. 2 times～6 times, obtain the graphene oxide of chloride;
The quality of the graphene oxide described in step 1 and the volume ratio of DMF are(0.004g～0.05g):1mL；
The quality of the graphene oxide described in step 1 and the volume ratio of thionyl chloride are (0.007g～0.03g): 1mL;
Two, the graphene oxide that amino group is contained on preparation surface: in the graphene oxide of chloride, add carrene,Be ultrasonic processing 10min～45min under 200W～400W at ultrasonic power, then with the dropping speed of 10/min～25 droplet/minDegree adds 1,3-propane diamine, then is condensation under 35 DEG C～60 DEG C and the mixing speed condition that is 350r/min～800r/min in temperatureBack flow reaction 8h～32h, then naturally cool to room temperature, re-uses to revolve and steams evaporimeter and revolve steaming, obtains mixture B; Divide again, taking methyl alcohol, deionized water and absolute ethyl alcohol as cleaning agent, mixture B is not distinguished to centrifuge washing 3 times～8 times, then in temperatureFor freeze drying 24h～60h at-70 DEG C～-40 DEG C, obtain spongy product; Re-using mortar is ground to spongy product notThere is macroscopic particle, obtain the graphene oxide that amino group is contained on surface;
The quality of the graphene oxide of the chloride described in step 2 and the volume ratio of carrene are(0.002g～0.005g):1mL；
The volume ratio of the quality of the graphene oxide of the chloride described in step 2 and 1,3-propane diamine is(0.0125g～0.033g):1mL；
Three, chemical graft: 1., surface that step 2 the is obtained graphene oxide that contains amino group is distributed in solvent,Then be the ultrasonic processing of 160W～400W 15min～50min at ultrasonic power, obtain the oxidation stone that contains amino group in surfaceChina ink alkene solution; Oxidized regenerated cellulose is immersed in the graphene oxide solution that contains amino group in surface again, then ultrasonicPower is ultrasonic processing 20min～40min under 200W～400W, and then uses oscillator oscillation treatment 1h～24h, then willThe graphene oxide solution that oxidized regenerated cellulose contains amino group from surface, take out, obtain the oxidation regeneration fibre after graftingDimension element; 2. be, the oxidized regenerated cellulose after grafting is immersed in deionized water, under 200W～320W at ultrasonic powerUltrasonic processing 20min～60min; 3., repeating step three 2. 2 times～5 times, then by the oxidized regenerated cellulose after grafting from goingIn ionized water, take out, then be vacuum freeze drying 8h～96h at-70 DEG C～-20 DEG C in temperature, obtain graphene oxide graft modificationRegenerated oxycellulose as styptic material;
The quality of the graphene oxide that amino group is contained on the surface described in step 3 and the volume ratio of solvent are(0.1mg～1.0mg):1mL；
The volume of the graphene oxide solution that amino group is contained on the quality of the oxidized regenerated cellulose described in step 3 and surfaceThan being (0.002g～0.05g): 1mL;
In graphene oxide graft modification regenerated oxycellulose as styptic material described in step 3, amino group is contained on surfaceThe mass ratio of graphene oxide and oxidized regenerated cellulose is (0.01～3): 100.
3. the preparation side of a kind of graphene oxide graft modification regenerated oxycellulose as styptic material according to claim 2Method, is characterized in that the solvent described in step 3 is that water, absolute ethyl alcohol or mass fraction are 20%～80% ethanolic solution.
4. the preparation side of a kind of graphene oxide graft modification regenerated oxycellulose as styptic material according to claim 2Method, is characterized in that in the oxidized regenerated cellulose described in step 3, carboxyl-content is 16%～24%.
5. the preparation side of a kind of graphene oxide graft modification regenerated oxycellulose as styptic material according to claim 2Method, is characterized in that the oxidized regenerated cellulose described in step 3 is to exist with the form of short silk, long filament or fabric.
6. the preparation side of a kind of graphene oxide graft modification regenerated oxycellulose as styptic material according to claim 2Method, is characterized in that the quality of the graphene oxide that contains amino group in the surface described in step 3 and the volume ratio of solvent are(0.1mg～0.5mg):1mL。
7. the preparation side of a kind of graphene oxide graft modification regenerated oxycellulose as styptic material according to claim 2Method, is characterized in that the quality of the oxidized regenerated cellulose described in step 3 and the graphene oxide that amino group is contained on surfaceThe volume ratio of solution is (0.01g～0.05g): 1mL.
8. the preparation side of a kind of graphene oxide graft modification regenerated oxycellulose as styptic material according to claim 2Method, is characterized in that in the graphene oxide graft modification regenerated oxycellulose as styptic material described in step 3, surface is containedThe graphene oxide of amino group and the mass ratio of oxidized regenerated cellulose are (0.01～2): 100.
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