CN102423503A - Preparation method of high-efficiency silicon oxide hemostasis material - Google Patents
Preparation method of high-efficiency silicon oxide hemostasis material Download PDFInfo
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- CN102423503A CN102423503A CN2011104423105A CN201110442310A CN102423503A CN 102423503 A CN102423503 A CN 102423503A CN 2011104423105 A CN2011104423105 A CN 2011104423105A CN 201110442310 A CN201110442310 A CN 201110442310A CN 102423503 A CN102423503 A CN 102423503A
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Abstract
The invention relates to a high-efficiency silicon oxide hemostasis material. The hemostasis material is prepared from silicon oxide adsorbing a large number of calcium ions and materials activating blood plasma. The invention has the advantages of moderate reaction conditions, convenient and feasible operation process, and low cost and easy acquisition of raw materials; and the prepared hemostasis material product has an excellent hemostasis effect. By using silicon oxide as the hemostasis material, the biocompatibility of the hemostasis material can be obviously improved, thereby showing the good prospect of the silicon oxide hemostasis material in the in-vivo application; because of the specific pore properties, the mesoporous silicon oxide material can adsorb antibiotic, analgesic and the like, thereby being beneficial to the treatment of wounds; and the material provided by the invention can be used for hemostasis in different medical situations, and can be prepared into wound plasters, transfusion plasters, self-adhesive dressings, cores of tablets and capsules, operation kits, first-aid kits and the like when being combined with other medical materials and medical appliances.
Description
Technical field
The invention belongs to field of biomedical materials, specifically, is a kind of method for preparing of high-efficiency titanium dioxide silicon hemostatic material.
Technical background
Emergency haemostatic is an emerging research field in the world.Emergency haemostatic is primarily aimed at the outer damaging the spleen and stomach emergency that The blood streamed down and develops.The emergency as aorta is bled just can be controlled in (3 minutes) in a short period of time, for further medical treatment tries to gain time precious to one.Francis X.Hursey was not intended to find that zeolite molecular sieve has good anastalsis and applied for patent in 1989 the eighties in 20 century.At the beginning of 2002; Z-Medica company sets up; The novel hemostatic material of special Development and Production commodity Quikclot by name; This material be synthetic zeolite (A type zeolite, LTA structure) with 75% for the composite type zeolite hemostatic material that substrate and 25% clay mix as binding agent, use zeolite molecular sieve material to obtain the drugs approved by FDA listing at present as the novel hemostatic material Quikclot of main body; No matter in laboratory (especially in the field operations battlefield) still in practice, its haemostatic effect and improve survival rate two aspects and all be superior to traditional hemostatic material.Because the Quikclot hemostatic material has the thermal discharge height, can burn to wound tissue.Thereby exploitation has the low hemostatic material of good haemostatic effect side effect simultaneously, is the consistent target of research worker.
We have developed a series of molecular sieve hemostatic material on this basis, and (number of patent application is respectively 200810063282.4; 200810122044.6; 200810122045.0,200910095272.3,200910095273.8 etc.); But because aluminium element has very big harm to nervous system and immune system, thereby limited this type hemostatic material in the intravital application of people.But there is not this type problem in earth silicon material, thereby the haemostatic effect of raising silica material seems very necessary.Chinese patent CN100345597C disclosed mesopore molecular sieve hemostatic material and preparation method thereof; But they just stress simple mesoporous material (main component is silicon dioxide and other oxides); But owing to there is not the processing through other, haemostatic effect is relatively poor relatively.
Because the absorption calcium ion earth silicon material behind the adsorption activation blood plasma again is similar with traditional zeolite molecular sieve, meet that blood can absorb rapidly, swelling, through effects such as physics, chemistry, biology promotion thrombin activation and stick platelet, promotion thrombosis.Simultaneously have more superior character in some aspects, can be used as novel hemostatic material to guarantee it.Because the absorption calcium ion earth silicon material behind the adsorption activation blood plasma again can discharge calcium ion; Thereby acceleration coagulation process; Simultaneously because earth silicon material activation coagulation process; Can produce more various activatory thrombin, and these thrombins can only keep active at silica containing inorganic surfaces in this case, be the thrombin proenzyme in can direct activation blood when this material touches blood; Thereby quicken coagulation process greatly, play the effect of quick-acting haemostatic powder.Utilize its mesoporous silicon oxide to have characteristics such as bigger aperture, pore volume simultaneously, adsorbable antibiotics or analgesic are to obtain better therapeutic.The biocompatibility of more main silicon dioxide hemostatic material is better, and side effect is low when being applied to human body.
Research shows that through silicon dioxide absorption calcium ion, adsorption activation blood plasma can improve the haemostatic effect of silicon dioxide greatly again.So far, do not see to have earth silicon material adsorbed calcium ion that adsorption activation blood plasma is to be used for the domestic and international patent document report of medical applications again.
Summary of the invention
The object of the invention to the weak point of prior art, proposes a kind of method for preparing that improves the earth silicon material haemostatic effect just.
In the method for preparing of a kind of high-efficiency titanium dioxide silicon hemostatic material that the present invention proposes, silicon dioxide has following characteristics: less than Powdered silicon dioxide and the mesoporous silicon oxide of 100um.Mesoporous silicon oxide among the present invention is self-assembly property and a template action of utilizing surfactant; Synthetic through sol-gel process; The present invention has simultaneously done corresponding improvement on this basis; Obtained the mesoporous material of a large amount of absorption calcium ions, and and then adsorption activation blood plasma, obtained having the mesoporous silicon oxide hemostatic material of efficient haemostatic effect.But silicon dioxide of the present invention is not limited to this, and every other granular size all is applicable to the present invention less than the Powdered silicon dioxide of 100um such as commercialization SiO 2 powder, column chromatography silicon dioxide.
Concrete technical scheme of the present invention is following:
The present invention is a kind of high-efficiency titanium dioxide silicon hemostatic material, and hemostatic material is that silicon dioxide has adsorbed a large amount of calcium ions, and adsorption activation the material of blood plasma.
Concrete steps of the present invention are following:
1) raw material of hemostatic material and the solution of calcium ions are carried out calcium ion absorption;
2) with the silicon dioxide adsorption activation blood plasma after the calcium ion absorption, vacuum drying, preservation then gets high-efficiency titanium dioxide silicon hemostatic material.
The raw material of hemostatic material of the present invention is a mesoporous silicon oxide; Mesoporous silicon oxide is synthetic through sol-gal process; Mesoporous material synthetic specific as follows: structure directing agent is dissolved in the deionized water that contains medium; Stirring obtains uniform solution, adds inorganic precursors TEOS then, continues to stir to obtain stable sols; With the colloidal sol that obtains hydro-thermal regular hour at a certain temperature, burin-in process; Cool to room temperature after-filtration, washing, drying then.Structure directing agent is removed in roasting at a certain temperature at last.The sintering temperature of the mesoporous silicon oxide after synthetic is 250 ℃～450 ℃, and roasting time is 3h～6h.
The raw material of hemostatic material of the present invention also can be the Powdered silicon dioxide less than 100um.
Powdered silicon dioxide less than 100um of the present invention is commercialization SiO 2 powder or column chromatography silicon dioxide.
Calcium ion concentration of the present invention is 0.1M～5M, and the calcium ion adsorption time is 1h～3h, and the adsorption temp of calcium ion is 10 ℃～100 ℃.
The earth silicon material after the calcium ion absorption of the present invention and the ratio of blood plasma are 1: 0.2～5; The ratio of the earth silicon material after amount of deionized water that adds during blood plasma absorption and the calcium ion absorption is 1:; 1～6; The adsorption activation time is 10～30min, and the vacuum drying temperature is 20 ℃～38 ℃.
The present invention has following advantage:
1, reaction condition is gentle, easy to operation, and low in raw material cost is easy to get; The hemostatic material product haemostatic effect that obtains is fabulous;
2, through using silicon dioxide, can obviously improve the biocompatibility of hemostatic material, represent the good prospect of using in vivo of silicon dioxide hemostatic material as hemostatic material;
3, the distinctive porous of Metaporous silicon dioxide material; Can adsorb antibiotics and analgesic etc.; Help the treatment of wound; Material of the present invention can be used for the hemostasis of different medical applications, with other medical materials, medical apparatus and instruments combination, can be made into adhesive bandage, infusion patch, sticking dressing, tablet and capsule core material, operation bag, first-aid kit etc.
Description of drawings
Fig. 1 is the blood coagulation design sketch of the blood coagulation material of FDU-12 Metaporous silicon dioxide material among the present invention;
It is the transmission electron microscope picture of the synthetic mesoporous FDU-12 Metaporous silicon dioxide material of structure directing agent water that Fig. 2 serves as reasons with F127;
It is the SAXS collection of illustrative plates of the synthetic mesoporous FDU-12 Metaporous silicon dioxide material of structure directing agent water that Fig. 3 serves as reasons with F127;
Fig. 4 is the external blood coagulation design sketch of commercialization silicon dioxide and column chromatography earth silicon material.
The specific embodiment
The invention is further illustrated by the following examples:
1.0g EO106PO70EO106 (F127), 1.2g trimethylbenzene and 2.5g KCl are dissolved in the HCl solution that 100ml concentration is 2M, and stirring adds 4.32g TEOS after half an hour, and mixture is strong agitation 24h under 14 ℃ of conditions.Mixed solution is transferred in the water heating kettle at 120 ℃ of hydro-thermal 24h.Filtration washing obtains product after 60 ℃ of dryings then, again in 350 ℃ of following roasting 6h.Promptly obtain the mesoporous FDU-12 material of three-dimensional cubic phase after the cooling room temperature.Its blood coagulation effect is relatively poor, sees the close oblique line of Fig. 1, and error line is obtained by three groups of experimental datas.The FDU-12 material has good order mesoporous structure, sees the TEM of Fig. 2 FDU-12, and the SAXS figure of FDU-12 material sees Fig. 3.
The CaCl2 solution mixed at room temperature of 2.0g FDU-12 material and 40ml 5M is stirred 3h, filter then, deionized water wash 5 times obtains adsorbing the mesoporous material of calcium ion after 60 ℃ of dryings.Its blood coagulation effect is relatively poor, sees the closeer oblique line of Fig. 1.
The FDU-12 material that 1.0g is adsorbed calcium ion mixes with the 3ml deionized water, adds the porcine blood plasma of 1ml then respectively.Mix, stir 15min, 25 ℃ of vacuum dryings then obtain the Metaporous silicon dioxide material of adsorption activation blood plasma, and its blood coagulation effect is very good, sees that Fig. 1 dredges oblique line.
Embodiment 4
Commercialization earth silicon material, column chromatography silicon dioxide (100 orders～200 orders) with 2.0g stirs 3h with the CaCl2 solution mixed at room temperature of 40ml 5M respectively; Filter then; Obtain adsorbing the earth silicon material of calcium ion behind the deionized water wash 5 times, 60 ℃ of dryings.Its blood coagulation effect is relatively poor sees the real block diagram of Fig. 4.
The commercialization SiO 2 powder and the column chromatography earth silicon material that respectively 1.0g are adsorbed calcium ion mix with the 1ml deionized water, add the porcine blood plasma of 1ml then respectively.Mix, stir 15min, 25 ℃ of vacuum dryings then obtain the earth silicon material of adsorption activation blood plasma, and its blood coagulation effect is very good, sees the empty block diagram of Fig. 4.
Embodiment 5
External blood coagulation experiment is carried out at 25 ℃, and the pig whole blood is in advance 25 ℃ of constant temperature water bath half an hour.During experiment in vitro, confirm the nature clotting time earlier, get the 0.2M CaCl of different volumes
2Solution adds the homothermic whole blood of 2ml then, makes the nature clotting time about 10min.The external blood coagulation experimental procedure of hemostatic material is following: the material of getting 0.1g joins in the centrifuge tube of 10ml, adds a certain amount of 0.2M CaCl then
2, add the homothermic whole blood of 2ml at last, begin simultaneously to clock, the time when whole blood solidifies is designated as clotting time.For commercialization earth silicon material and column chromatography earth silicon material, the quantity of material of being got is 0.2g.
Claims (7)
1. a high-efficiency titanium dioxide silicon hemostatic material is characterized in that, described hemostatic material is that silicon dioxide has adsorbed a large amount of calcium ions, and adsorption activation the material of blood plasma.
2. the method for preparing of a high-efficiency titanium dioxide silicon hemostatic material as claimed in claim 1 is characterized in that concrete steps are following:
1) raw material of hemostatic material and the solution of calcium ions are carried out calcium ion absorption;
2) with the silicon dioxide adsorption activation blood plasma after the calcium ion absorption, vacuum drying, preservation then gets high-efficiency titanium dioxide silicon hemostatic material.
3. the method for preparing of high-efficiency titanium dioxide silicon hemostatic material according to claim 2; It is characterized in that; The raw material of described hemostatic material is a mesoporous silicon oxide; Described mesoporous silicon oxide is synthetic through sol-gal process, and the sintering temperature of the mesoporous silicon oxide after synthesizing is 250 ℃～450 ℃, and roasting time is 3h～6h.
4. the method for preparing of high-efficiency titanium dioxide silicon hemostatic material according to claim 2 is characterized in that, the raw material of described hemostatic material is the Powdered silicon dioxide less than 100um.
5. the method for preparing of high-efficiency titanium dioxide silicon hemostatic material according to claim 4 is characterized in that, described Powdered silicon dioxide less than 100um is commercialization SiO 2 powder or column chromatography silicon dioxide.
6. according to the method for preparing of claim 2 or 3 or 5 described high-efficiency titanium dioxide silicon hemostatic materials, it is characterized in that described calcium ion concentration is 0.1M～5M, the calcium ion adsorption time is 1h～3h, and the adsorption temp of calcium ion is 10 ℃～100 ℃.
7. according to the method for preparing of claim 2 or 3 or 5 described high-efficiency titanium dioxide silicon hemostatic materials; It is characterized in that; The earth silicon material after the described calcium ion absorption and the ratio of blood plasma are 1: 0.2～5, and the ratio of the earth silicon material after amount of deionized water that adds during blood plasma absorption and the calcium ion absorption is 1:, 1～6; The adsorption activation time is 10～30min, and the vacuum drying temperature is 20 ℃～38 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018234A (en) * | 2014-06-04 | 2014-09-03 | 东华大学 | Preparation method of composite nanofiber membrane capable of quickly stopping bleeding |
| CN106913546A (en) * | 2015-12-28 | 2017-07-04 | 山东新时代药业有限公司 | A kind of Minodronic acid tablets of Fast Stripping and preparation method thereof |
| CN108379648A (en) * | 2018-03-03 | 2018-08-10 | 青岛大学 | A kind of preparation method of original position inductive formation fibrin ferment load regenerated oxycellulose as styptic material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018234A (en) * | 2014-06-04 | 2014-09-03 | 东华大学 | Preparation method of composite nanofiber membrane capable of quickly stopping bleeding |
| CN106913546A (en) * | 2015-12-28 | 2017-07-04 | 山东新时代药业有限公司 | A kind of Minodronic acid tablets of Fast Stripping and preparation method thereof |
| CN106913546B (en) * | 2015-12-28 | 2021-06-22 | 山东新时代药业有限公司 | Fast-dissolving minodronic acid tablet and preparation method thereof |
| CN108379648A (en) * | 2018-03-03 | 2018-08-10 | 青岛大学 | A kind of preparation method of original position inductive formation fibrin ferment load regenerated oxycellulose as styptic material |
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