CN104383588B - A kind of preparation method of SWCN graft modification regenerated oxycellulose as styptic material - Google Patents
A kind of preparation method of SWCN graft modification regenerated oxycellulose as styptic material Download PDFInfo
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Abstract
A preparation method for SWCN graft modification regenerated oxycellulose as styptic material, it relates to a kind of preparation method of hemostatic material. The object of the invention is to solve existing using the material modified original form that can not ensure oxidized regenerated cellulose that exists as hemostatic material of oxidized regenerated cellulose, in use can to the mammal skin of contact position and other body cells produce excitants and anthemorrhagic performance promotes the little problem of amplitude. Prepared by the SWCN that a kind of SWCN graft modification regenerated oxycellulose as styptic material contains amino group by surface and oxidized regenerated cellulose; Preparation method: one, the SWCN of preparation chloride; Two, the SWCN that amino group is contained on preparation surface; Three, chemical graft. Material bleeding stopping period prepared by the present invention has reduced by 4.6%～18.5%. The present invention can obtain a kind of SWCN graft modification regenerated oxycellulose as styptic material and preparation method thereof.
Description
Technical field
The present invention relates to a kind of preparation method of hemostatic material.
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 contactAfter blood, can adsorb a large amount of erythrocytes, then the acid carboxyl in oxidized regenerated cellulose structure can cause haemolysis,Erythrocyte dissolves, breaks, and discharges hemoglobin. Meanwhile, owing to containing ferric ion in hemoglobin, oxidationRegenerated 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,The hemostasis of oxidized regenerated cellulose is a series of Biochemical Engineering, and carboxyl quantity in material structure hasLimit, therefore causes the anthemorrhagic speed of oxidized regenerated cellulose material relatively slow, causes such material cannot be applicable to artery etc.The massive haemorrhage situation at position.
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 and existingly exist and can not ensure as hemostatic material so that oxidized regenerated cellulose is material modifiedOriginal form of oxidized regenerated cellulose, in use can produce the mammal skin of contact position and other body cellsExcitant and anthemorrhagic performance promote the little problem of amplitude, and a kind of SWCN graft modification oxidized regenerated cellulose is providedThe preparation method of hemostatic material.
The single wall carbon that a kind of SWCN graft modification regenerated oxycellulose as styptic material contains amino group by surfacePrepared by nanotube and oxidized regenerated cellulose; The SWCN that amino group is contained on described surface and oxidation regeneration fibreThe mass ratio of tieing up plain filament yarn fabric is (0.05～2): 100.
A preparation method for SWCN graft modification regenerated oxycellulose as styptic material, specifically according to the following stepsComplete:
One, the SWCN of preparation chloride: 1., carboxylated SWCN is joined to N, N-dimethyl methylIn acid amides, then be ultrasonic processing 15min～60min under 160W～400W at ultrasonic power, then add thionyl chloride, in temperatureDegree is to stir 16h～48h under 60 DEG C～100 DEG C and the mixing speed condition that is 300r/min～750r/min, then naturally cools toRoom temperature, re-use revolve steam evaporimeter revolve steaming, obtain mixture A; 2., taking carrene as cleaning agent, use rotationEvaporimeter revolves steaming to mixture A; 3., repeating step one 2. 4 times～6 times, obtain the SWCN of chloride;
The quality of carboxylated SWCN described in step 1 and the volume ratio of DMF are (0.004g～0.05g):1mL；
The quality of carboxylated SWCN described in step 1 and the volume ratio of thionyl chloride are(0.007g～0.03g):1mL；
Two, the SWCN that amino group is contained on preparation surface: add dichloromethane in the SWCN of chlorideAlkane, is ultrasonic processing 10min～45min under 200W～400W at ultrasonic power, then with 10/min～25 droplet/min'sRate of addition adds 1,3-propane diamine, then is the condition that 35 DEG C～60 DEG C and mixing speed are 350r/min～800r/min in temperatureLower condensing reflux reaction 8h～32h, then naturally cool to room temperature, re-uses to revolve and steams evaporimeter and revolve steaming, obtains mixtureB; 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,Be freeze drying 24h～60h at-70 DEG C～-40 DEG C in temperature again, obtain the SWCN that amino group is contained on surface;
The quality of the SWCN 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 SWCN 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 is obtained contains amino SWCN and be distributed in solvent, soAfter be the ultrasonic processing of 160W～400W 15min～50min at ultrasonic power, obtain surface and contain amino SWCNSolution; Again oxidized regenerated cellulose is immersed in to surface and contains in amino SWCN solution, then at ultrasonic power beUltrasonic processing 20min～40min under 240W～400W, and then use oscillator oscillation treatment 1h～24h, then will be oxidized againRaw cellulose contains amino SWCN solution and takes out from surface, obtains the oxidized regenerated cellulose after grafting; 2.,Oxidized regenerated cellulose after grafting is immersed in deionized water, is ultrasonic processing under 200W～320W at ultrasonic power20min～60min; 3., repeating step three 2. 2 times～5 times, then by the oxidized regenerated cellulose after grafting from deionized waterTake out, then be vacuum freeze drying 8h～96h at-70 DEG C～-20 DEG C in temperature, obtain SWCN graft modification oxidationRegenerated cellulose hemostatic material;
The quality that amino SWCN is contained on surface described in step 3 and the volume ratio of solvent are(0.1mg～1.0mg):1mL；
The quality of the oxidized regenerated cellulose described in step 3 and the surperficial volume that contains amino SWCN solutionThan being (0.003g～0.05g): 1mL;
In SWCN graft modification regenerated oxycellulose as styptic material described in step 3, amino is contained on surfaceThe mass ratio of SWCN and oxidized regenerated cellulose is (0.05～2): 100.
In step 3 of the present invention, utilize surface to contain amino group and the oxidized regenerated cellulose in amino SWCNCarboxyl reaction in structure generates amido link, thus by wall carbon nano tube chemical graft to oxidized regenerated cellulose.
Advantage of the present invention:
One, in step 3 of the present invention, utilize surface to contain amino group and the oxidation regeneration fiber in amino SWCNThe carboxyl reaction of element in structure generates amido link, thus by wall carbon nano tube chemical graft to oxidized regenerated cellulose, therebyObtain the hemostatic material of molecular structure stabilized, can also improve the anthemorrhagic performance of oxidized regenerated cellulose, while can not damage simultaneouslyHinder mechanical strength and the biological absorbable performance of oxidized regenerated cellulose;
Two, the SWCN graft modification regenerated oxycellulose as styptic material that uses the present invention to prepare stops blooding, onlyThe blood time has reduced by 4.6%～18.5%.
The present invention can obtain a kind of SWCN graft modification regenerated oxycellulose as styptic material and preparation method thereof.
Detailed description of the invention
Detailed description of the invention one: present embodiment is a kind of SWCN graft modification regenerated oxycellulose as styptic materialPrepared by the SWCN that contains amino group by surface and oxidized regenerated cellulose; Amino group is contained on described surfaceSWCN and the mass ratio of the filament yarn fabric of oxidized regenerated cellulose be (0.05～2): 100.
In present embodiment step 3, utilize surface to contain amino group and the oxidation regeneration fibre in amino SWCNTie up carboxyl reaction in plain structure and generate amido link, thus by wall carbon nano tube chemical graft to oxidized regenerated cellulose.
The advantage of present embodiment:
One, in present embodiment step 3, utilize surface to contain amino group and the oxidation regeneration in amino SWCNCarboxyl reaction in cellulosic structure generates amido link, thus by wall carbon nano tube chemical graft to oxidized regenerated cellulose,Thereby obtain the hemostatic material of molecular structure stabilized, can also improve the anthemorrhagic performance of oxidized regenerated cellulose simultaneously, while notCan damage mechanical strength and the biological absorbable performance of oxidized regenerated cellulose;
Two, the SWCN graft modification regenerated oxycellulose as styptic material that uses embodiment to prepare stops blooding,Bleeding stopping period has reduced by 4.6%～18.5%.
Present embodiment can obtain a kind of SWCN graft modification regenerated oxycellulose as styptic material and preparation side thereofMethod.
Detailed description of the invention two: the difference of present embodiment and detailed description of the invention one is: in described oxidation regeneration fiberCarboxyl-content is 16%～24%; Described oxidized regenerated cellulose is to exist with short silk, long filament or form of fabric. Other withDetailed description of the invention one is identical.
Detailed description of the invention three: the difference of present embodiment and detailed description of the invention one or two is: ammonia is contained on described surfaceThe preparation method of the SWCN of base group specifically completes according to the following steps: one, the single wall carbon of preparation chlorideNanotube: 1., carboxylated SWCN is joined in DMF, then at ultrasonic power beUltrasonic processing 15min～60min under 160W～400W, then add thionyl chloride, be 60 DEG C～100 DEG C and stir speed in temperatureUnder the condition of degree for 300r/min～750r/min, stir 16h～48h, then naturally cool to room temperature, re-use and revolve steaming evaporimeterRevolve steaming, obtain mixture A; 2., taking carrene as cleaning agent, use Rotary Evaporators mixture A is carried outRevolve steaming; 3., repeating step one 2. 4 times～6 times, obtain the SWCN of chloride;
The quality of carboxylated SWCN described in step 1 and the volume ratio of DMF are(0.004g～0.05g):1mL；
The quality of carboxylated SWCN described in step 1 and the volume ratio of thionyl chloride are(0.007g～0.03g):1mL；
Two, the SWCN that amino group is contained on preparation surface: add dichloromethane in the SWCN of chlorideAlkane, is ultrasonic processing 10min～45min under 200W～400W at ultrasonic power, then with 10/min～25 droplet/min'sRate of addition adds 1,3-propane diamine, then is the condition that 35 DEG C～60 DEG C and mixing speed are 350r/min～800r/min in temperatureLower condensing reflux reaction 8h～32h, then naturally cool to room temperature, re-uses to revolve and steams evaporimeter and revolve steaming, obtains mixtureB; 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,Be freeze drying 24h～60h at-70 DEG C～-40 DEG C in temperature again, obtain the SWCN that amino group is contained on surface;
The quality of the SWCN 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 SWCN of the chloride described in step 2 and 1,3-propane diamine is(0.0125g～0.033g): 1mL. Other are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is a kind of SWCN graft modification regenerated oxycellulose as styptic materialPreparation method specifically complete according to the following steps:
One, the SWCN of preparation chloride: 1., carboxylated SWCN is joined to N, N-dimethyl methylIn acid amides, then be ultrasonic processing 15min～60min under 160W～400W at ultrasonic power, then add thionyl chloride, in temperatureDegree is to stir 16h～48h under 60 DEG C～100 DEG C and the mixing speed condition that is 300r/min～750r/min, then naturally cools toRoom temperature, re-use revolve steam evaporimeter revolve steaming, obtain mixture A; 2., taking carrene as cleaning agent, use rotationEvaporimeter revolves steaming to mixture A; 3., repeating step one 2. 4 times～6 times, obtain the SWCN of chloride;
The quality of carboxylated SWCN described in step 1 and the volume ratio of DMF are(0.004g～0.05g):1mL；
The quality of carboxylated SWCN described in step 1 and the volume ratio of thionyl chloride are(0.007g～0.03g):1mL；
Two, the SWCN that amino group is contained on preparation surface: add dichloromethane in the SWCN of chlorideAlkane, is ultrasonic processing 10min～45min under 200W～400W at ultrasonic power, then with 10/min～25 droplet/min'sRate of addition adds 1,3-propane diamine, then is the condition that 35 DEG C～60 DEG C and mixing speed are 350r/min～800r/min in temperatureLower condensing reflux reaction 8h～32h, then naturally cool to room temperature, re-uses to revolve and steams evaporimeter and revolve steaming, obtains mixtureB; 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,Be freeze drying 24h～60h at-70 DEG C～-40 DEG C in temperature again, obtain the SWCN that amino group is contained on surface;
The quality of the SWCN 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 SWCN 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 is obtained contains amino SWCN and be distributed in solvent, soAfter be the ultrasonic processing of 160W～400W 15min～50min at ultrasonic power, obtain surface and contain amino SWCNSolution; Again oxidized regenerated cellulose is immersed in to surface and contains in amino SWCN solution, then at ultrasonic power beUltrasonic processing 20min～40min under 240W～400W, and then use oscillator oscillation treatment 1h～24h, then will be oxidized againRaw cellulose contains amino SWCN solution and takes out from surface, obtains the oxidized regenerated cellulose after grafting; 2.,Oxidized regenerated cellulose after grafting is immersed in deionized water, is ultrasonic processing under 200W～320W at ultrasonic power20min～60min; 3., repeating step three 2. 2 times～5 times, then by the oxidized regenerated cellulose after grafting from deionized waterTake out, then be vacuum freeze drying 8h～96h at-70 DEG C～-20 DEG C in temperature, obtain SWCN graft modification oxidationRegenerated cellulose hemostatic material;
The quality that amino SWCN is contained on surface described in step 3 and the volume ratio of solvent are(0.1mg～1.0mg):1mL；
The quality of the oxidized regenerated cellulose described in step 3 and the surperficial volume that contains amino SWCN solutionThan being (0.003g～0.05g): 1mL;
In SWCN graft modification regenerated oxycellulose as styptic material described in step 3, amino is contained on surfaceThe mass ratio of SWCN and oxidized regenerated cellulose is (0.05～2): 100.
In present embodiment step 3, utilize surface to contain amino group and the oxidation regeneration fibre in amino SWCNTie up carboxyl reaction in plain structure and generate amido link, thus by wall carbon nano tube chemical graft to oxidized regenerated cellulose.
The advantage of present embodiment:
One, in present embodiment step 3, utilize surface to contain amino group and the oxidation regeneration in amino SWCNCarboxyl reaction in cellulosic structure generates amido link, thus by wall carbon nano tube chemical graft to oxidized regenerated cellulose,Thereby obtain the hemostatic material of molecular structure stabilized, can also improve the anthemorrhagic performance of oxidized regenerated cellulose simultaneously, while notCan damage mechanical strength and the biological absorbable performance of oxidized regenerated cellulose;
Two, the SWCN graft modification regenerated oxycellulose as styptic material that uses embodiment to prepare stops blooding,Bleeding stopping period has reduced by 4.6%～18.5%.
Present embodiment can obtain a kind of SWCN graft modification regenerated oxycellulose as styptic material and preparation side thereofMethod.
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 are identical with detailed description of the invention four.
Detailed description of the invention six: the difference of present embodiment and detailed description of the invention four or five is: the oxygen described in step 3Changing carboxyl-content in regenerated fiber is 16%～24%. Other are identical with detailed description of the invention four or five.
Detailed description of the invention seven: the difference of present embodiment and detailed description of the invention four to six is: the oxygen described in step 3Changing regenerated fiber is to exist with short silk, long filament or form of fabric. Other are identical with detailed description of the invention four to six.
Detailed description of the invention eight: the difference of present embodiment and detailed description of the invention four to seven is: the table described in step 3The quality that face contains amino SWCN and the volume ratio of solvent are (0.1mg～0.5mg): 1mL. Other are with concrete realExecute mode four to seven identical.
Detailed description of the invention nine: the difference of present embodiment and detailed description of the invention four to eight is: the oxygen described in step 3The quality of changing regenerated cellulose with the surperficial volume ratio that contains amino SWCN solution is(0.003g～0.01g): 1mL. Other are identical with detailed description of the invention four to eight.
Detailed description of the invention ten: the difference of present embodiment and detailed description of the invention four to nine is: the list described in step 3In wall carbon nano tube graft modification regenerated oxycellulose as styptic material, surface is contained amino SWCN and is oxidizedRaw cellulosic mass ratio is (0.2～1.5): 100. Other are identical with detailed description of the invention four to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of preparation method of SWCN graft modification regenerated oxycellulose as styptic material specifically by withLower step completes:
One, the SWCN of preparation chloride: 1., carboxylated SWCN is joined to N, N-dimethyl methylIn acid amides, then be ultrasonic processing 30min under 400W at ultrasonic power, then add thionyl chloride, be 70 DEG C and stir in temperatureThe speed of mixing is to stir 32h under the condition of 500r/min, then naturally cools to room temperature, re-use to revolve to steam evaporimeter and revolve steaming,Obtain mixture A; 2., taking carrene as cleaning agent, use Rotary Evaporators mixture A is revolved to steaming; 3.,Repeating step one 2. 6 times, obtains the SWCN of chloride;
The quality of carboxylated SWCN described in step 1 and the volume ratio of DMF are0.05g:1mL；
The quality of carboxylated SWCN described in step 1 and the volume ratio of thionyl chloride are 0.02g:1mL;
Two, amino SWCN is contained on preparation surface: in the SWCN 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 surface and contains ammoniaThe SWCN of base group;
The quality of the SWCN 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 SWCN of the chloride described in step 2 and 1,3-propane diamine is 0.02g:1mL;
Three, chemical graft: 1., amino SWCN is contained in 30mg surface be distributed to 200mL mass fractionBe, in 50% ethanolic solution, to be then the ultrasonic processing of 240W 30min at ultrasonic power, obtain surface and contain amino listWall carbon nano tube solution; Again 2.5g oxidized regenerated cellulose is immersed in to surface and contains in amino SWCN solution,Be ultrasonic processing 30min under 280W at ultrasonic power again, and then use oscillator oscillation treatment 24h, then will be oxidized againRaw cellulose contains amino SWCN solution and takes out from surface, obtains the oxidized regenerated cellulose after grafting; 2.,Oxidized regenerated cellulose after grafting is immersed in deionized water, is ultrasonic processing 30min under 200W at ultrasonic power;3., repeating step three 2. 3 times, then the oxidized regenerated cellulose after grafting is taken out from deionized water, then is-53 DEG C in temperatureLower vacuum freeze drying 72h, obtains SWCN graft modification regenerated oxycellulose as styptic material;
In SWCN graft modification regenerated oxycellulose as styptic material described in step 3, amino is contained on surfaceThe mass ratio of SWCN and oxidized regenerated cellulose is 0.31:100;
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.
In this test procedure three, utilize surface to contain amino group and the oxidized regenerated cellulose in amino SWCNCarboxyl reaction in structure generates amido link, thus by wall carbon nano tube chemical graft to oxidized regenerated cellulose.
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 SWCN graft modification regenerated oxycellulose as styptic material obtaining is 124s.
Test two: a kind of preparation method of SWCN graft modification regenerated oxycellulose as styptic material specifically by withLower step completes:
One, the SWCN of preparation chloride: 1., carboxylated SWCN is joined to N, N-dimethyl methylIn acid amides, then be ultrasonic processing 15min under 400W at ultrasonic power, then add thionyl chloride, be 75 DEG C and stir in temperatureThe speed of mixing is to stir 24h under the condition of 600r/min, then naturally cools to room temperature, re-use to revolve to steam evaporimeter and revolve steaming,Obtain mixture A; 2., taking carrene as cleaning agent, use Rotary Evaporators mixture A is revolved to steaming; 3.,Repeating step one 2. 3 times, obtains the SWCN of chloride;
The quality of carboxylated SWCN described in step 1 and the volume ratio of DMF are0.004g:1mL；
The quality of carboxylated SWCN described in step 1 and the volume ratio of thionyl chloride are 0.008g:1mL;
Two, amino SWCN is contained on preparation surface: in the SWCN 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 surface and contains ammoniaThe SWCN of base group;
The quality of the SWCN 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 SWCN of the chloride described in step 2 and 1,3-propane diamine is0.0125g:1mL；
Three, chemical graft: 1., amino SWCN is contained in 100mg surface be distributed in 200mL water, soAfter be the ultrasonic processing of 400W 50min at ultrasonic power, obtain surface and contain amino SWCN solution; Again by 2.5gOxidized regenerated cellulose is immersed in surface and contains in amino SWCN solution, then is super under 400W at ultrasonic powerSonication 40min, and then use oscillator oscillation treatment 16h, then oxidized regenerated cellulose is contained amino from surfaceIn SWCN solution, take out, obtain the oxidized regenerated cellulose after grafting; 2., by the oxidation regeneration fiber after graftingElement is immersed in deionized water, is ultrasonic processing 40min under 320W at ultrasonic power; 3., repeating step three 2. 3 times,Again the oxidized regenerated cellulose after grafting is taken out from deionized water, then is vacuum freeze drying 72h at-53 DEG C in temperature,Obtain SWCN graft modification regenerated oxycellulose as styptic material;
In SWCN graft modification regenerated oxycellulose as styptic material described in step 3, amino is contained on surfaceThe mass ratio of SWCN and oxidized regenerated cellulose is 1.45:100;
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.
In this test procedure three, utilize surface to contain amino group and the oxidized regenerated cellulose in amino SWCNCarboxyl reaction in structure generates amido link, thus by wall carbon nano tube chemical graft to oxidized regenerated cellulose.
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, usesTest two bleeding stopping period that obtain SWCN graft modification regenerated oxycellulose as styptic material are 106s.
Claims (7)
1. a preparation method for SWCN graft modification regenerated oxycellulose as styptic material, is characterized in that oneThe preparation method of SWCN graft modification regenerated oxycellulose as styptic material specifically completes according to the following steps:
One, the SWCN of preparation chloride: 1., carboxylated SWCN is joined to N, N-dimethyl formylIn amine, then be ultrasonic processing 15min～60min under 160W～400W at ultrasonic power, then add thionyl chloride, in temperatureBe to stir 16h～48h under 60 DEG C～100 DEG C and the mixing speed condition that is 300r/min～750r/min, 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. 4 times～6 times, obtain the SWCN of chloride;
The quality of carboxylated SWCN described in step 1 and the volume ratio of DMF are(0.004g～0.05g):1mL；
The quality of carboxylated SWCN described in step 1 and the volume ratio of thionyl chloride are(0.007g～0.03g):1mL；
Two, the SWCN that amino group is contained on preparation surface: add dichloromethane in the SWCN of chlorideAlkane, is ultrasonic processing 10min～45min under 200W～400W at ultrasonic power, then dripping with 10/min～25 droplet/minAcceleration adds 1,3-propane diamine, then is under 35 DEG C～60 DEG C and the mixing speed condition that is 350r/min～800r/min in temperatureCondensing reflux 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, thenTemperature is freeze drying 24h～60h at-70 DEG C～-40 DEG C, obtains the SWCN that amino group is contained on surface;
The quality of the SWCN 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 SWCN 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 is obtained contains amino SWCN and be distributed in solvent, soAfter be the ultrasonic processing of 160W～400W 15min～50min at ultrasonic power, obtain surface and contain amino SWCNSolution; Again oxidized regenerated cellulose is immersed in to surface and contains in amino SWCN solution, then at ultrasonic power beUltrasonic processing 20min～40min under 240W～400W, and then use oscillator oscillation treatment 1h～24h, then will be oxidized againRaw cellulose contains amino SWCN solution and takes out from surface, obtains the oxidized regenerated cellulose after grafting; 2.,Oxidized regenerated cellulose after grafting is immersed in deionized water, is ultrasonic processing under 200W～320W at ultrasonic power20min～60min; 3., repeating step three 2. 2 times～5 times, then the oxidized regenerated cellulose after grafting is got from deionized waterGo out, then be vacuum freeze drying 8h～96h at-70 DEG C～-20 DEG C in temperature, obtain SWCN graft modification oxidation regenerationCellulose hemostatic material;
The quality that amino SWCN is contained on surface described in step 3 and the volume ratio of solvent are(0.1mg～1.0mg):1mL；
The quality of the oxidized regenerated cellulose described in step 3 and the surperficial volume ratio that contains amino SWCN solutionFor (0.003g～0.05g): 1mL;
In SWCN graft modification regenerated oxycellulose as styptic material described in step 3, amino list is contained on surfaceThe mass ratio of wall carbon nano tube and oxidized regenerated cellulose is (0.05～2): 100.
2. the preparation of a kind of SWCN graft modification regenerated oxycellulose as styptic material according to claim 1Method, is characterized in that the solvent described in step 3 is that water, absolute ethyl alcohol or mass fraction are 20%～80% ethanolic solution.
3. the preparation of a kind of SWCN graft modification regenerated oxycellulose as styptic material according to claim 1Method, is characterized in that in the oxidation regeneration fiber described in step 3, carboxyl-content is 16%～24%.
4. the preparation of a kind of SWCN graft modification regenerated oxycellulose as styptic material according to claim 1Method, is characterized in that the oxidation regeneration fiber described in step 3 is to exist with short silk, long filament or form of fabric.
5. the preparation of a kind of SWCN graft modification regenerated oxycellulose as styptic material according to claim 1Method, is characterized in that quality that amino SWCN is contained on the surface described in step 3 and the volume ratio of solvent are(0.1mg～0.5mg):1mL。
6. the preparation of a kind of SWCN graft modification regenerated oxycellulose as styptic material according to claim 1Method, the quality that it is characterized in that the oxidized regenerated cellulose described in step 3 contains amino SWCN with surfaceThe volume ratio of solution is (0.003g～0.01g): 1mL.
7. the preparation of a kind of SWCN graft modification regenerated oxycellulose as styptic material according to claim 1Method, is characterized in that surface in the SWCN graft modification regenerated oxycellulose as styptic material described in step 3The mass ratio that contains amino SWCN and oxidized regenerated cellulose is (0.2～1.5): 100.
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