CN100345597C - Hemostatic material of new type pore-borne molecular sieve and preparation method - Google Patents
Hemostatic material of new type pore-borne molecular sieve and preparation method Download PDFInfo
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- CN100345597C CN100345597C CNB2005100268389A CN200510026838A CN100345597C CN 100345597 C CN100345597 C CN 100345597C CN B2005100268389 A CNB2005100268389 A CN B2005100268389A CN 200510026838 A CN200510026838 A CN 200510026838A CN 100345597 C CN100345597 C CN 100345597C
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Abstract
The present invention belongs to the field of biomedical material technology, particularly to a hemostatic material of a mesoporous molecular sieve and a preparation method thereof. With the utilization of the self-assembly property and the template action of surfactant, the mesoporous molecular sieve with high efficient hemostatic function is synthesized through sol-gel process by the present invention. The novel hemostatic material has homogeneous and adjustable nanometer pores (1 to 30 nm), high specific surface area (100 to 1000 m<2>/g) and large pore volume (0.3 to 1.5cm<3>/g); simultaneously, the mesoscopic structure (cube, hexagon, layer, vesicle, etc.) and the macroscopic pattern (film, fiber, monolithic, powder, etc.) of the hemostatic material are controllable, and the compositon (silicon dioxide, calcium oxide, aluminum oxide, etc.) of the hemostatic material is adjustable. Thereby, the present invention can be used for hemostasis in different medical occasions; by combining with other medical materials and medical equipment, the hemostatic material can be made into woundplaster, fluid infusion plaster, self adhesive dressing, the core material of tablets and capsules, operating instrument sets, first-aid kits, etc.; simultaneously, with the utilization of the characteristics of the mesopores of the hemostatic material, antibiotics and analgesic can be absorbed, and thereby, better therapeutic effect can be obtained.
Description
Technical field
The invention belongs to technical field of biomedical materials, be specifically related to a class and have mesopore molecular sieve hemostatic material of different mesoscopic structures, composition, pattern etc. and preparation method thereof.
Technical background
Mobil company research worker in 1992 are utilized the self assembly and the template action of surfactant, successfully synthesize the basic ordered mesoporous molecular sieve material of M41S series silicon oxide (aluminum) that the first in the world aperture is evenly adjustable, specific surface area is bigger.With MCM-41 and SBA-15 is that the meso pore silicon oxide material of representative has caused people's extensive interest, deepens continuously and expands for the research of mesoporous material.Because mesoporous material has high surface area and pore volume, the aperture that homogeneous is adjustable, the meso-hole structure (as aperture, dimension, duct connected mode etc.) that high-sequential is easy to modulation, the surface group that enriches and be easy to design, and regulatable macro morphology (as film, fiber, ball, monocrystalline etc.), thereby shown unique development potentiality in fields such as catalysis, absorption, Separation of Proteins, biosensor and microelectronics.
Obviously, mesoporous material has the physicochemical properties of a series of excellences, but how to explore its further practical application, and this problem will directly restrict further developing of this novel nano functional material of mesoporous material.Before mesopore molecular sieve is synthesized, it has been found that zeolite eka-silicon (aluminum) hydrochlorate micro porous molecular sieve material after dehydration, sterilization, can become a kind of powerful absorbent, and selectivity absorbs multiple gases and liquid, but the also moisture in the absorbing blood.The eighties in 20th century, Francis X.Hursey has been not intended to find that zeolite molecular sieve has good anastalsis and has applied for patent in 1989.At the beginning of 2002, Z-Medica company sets up, the novel hemostatic material of special Development and Production commodity QuikClot by name.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 actual applications, its haemostatic effect and improve survival rate two aspects and all be better than traditional hemostatic material.Its hemostatic mechanism mainly is to depend on the extraordinary absorbability of molecular screen material, can blot the moisture in the wound outflow blood in the several seconds, and not absorb erythrocyte, platelet and other thrombins, thereby make thrombin concentrate and bring into play immediately anastalsis.QuikClot also discharges certain heat in the moisture in absorbing blood, make wound feel little fiber crops, not only the analgesia but also strengthened haemostatic effect.Because QuikClot does not possess physics and chemism, thereby can not cause any anaphylaxis, can not cause wound infection yet, uses as safe as a house.A research department of USN adopts pig femoral artery and two groups of animal models of losing blood of vein, as standard control, QuikClot has been done demonstration test with military tourniquet.The result shows that QuikClot group mortality rate is 0, and survival rate is 100%, all is being better than the standard control group aspect haemostatic effect and the raising survival rate two.U.S. army has all used QuikClot in Afghanistan and Irak military operation, it is very satisfied that effect is made us.The more important thing is that because easy to use, effect is far superior to tradition hemostasis series products, QuikClot is entering average family, and its market prospect is very bright.
Because mesopore silicon oxide (aluminum) molecular screen material is similar to traditional zeolite molecular sieve, chance blood (containing transudate) can absorb rapidly, swelling, promotes the thrombin activation and adheres to platelet through effects such as physics, chemistry, biologies, promotion thrombosis.Simultaneously, have more superior character in some aspects, can be to guarantee it as the research of novel hemostatic material.Because novel meso-porous molecular sieve material has very high surface area and pore volume, can reach 2000cm respectively
2/ g and 3.2cm
3/ g; Can adsorb more hydrone.Although its aperture is greater than traditional zeolite molecular sieve material, the molecular weight of thrombin is higher mostly.Therefore,, not only can accomplish only to absorb hydrone and do not absorb thrombin, reach the enrichment latter's purpose, more can accelerate the speed of adsorbed water molecule, reach the effect of quick-acting haemostatic powder by the adjustment aperture size.And, in meso pore silicon oxide material, add calcium ion and more help material performance Blood clotting.Mesoporous material also has the regulatable characteristics of macro morphology, and this point is for its absorption property of change, and further the molding use has great importance.In addition, can also utilize novel mesopore molecular sieve hemostatic material investigate different compositions, pattern (different powder granule sizes, film, sheet etc.), pore passage structure (cube, six sides, unordered) and pore size (structural agent such as 1～30nm) to micromolecular water, the intrinsic coagulation factor (as the Hageman factor, molecular weight 82,000) or the adsorption (as adsorbance and adsorption dynamics adsorption kinetics) that has the model protein of similar molecular weight and isoelectric point, IP with it.Utilize its mesoporous characteristics that have than large pore volume, aperture, can be used for adsorbing antibiotics or analgesic, to obtain better therapeutic.
Studies show that mesopore molecular sieve has hemostatic function efficiently, has better market prospect.So far, do not see to have mesoporous material is applied to blood coagulation material, treatment of wounds and creates reparation outward and mesoporous material and multi-form combinations such as medical bandage, adhesive of medical, be used for the domestic and international patent documentation report that outer wound is repaired.
Summary of the invention
The objective of the invention is to propose a kind of novel mesopore molecular sieve hemostatic material and preparation method thereof.
The novel mesopore molecular sieve hemostatic material that the present invention proposes utilizes the structure directing agent self assembly, prepares by typical sol-gel process; The main component of its composition is silicon dioxide and other oxide, and mol ratio is a silicon dioxide: other oxide is (50～100): (0～50).Have controlled mesoscopic structure (cube, six sides, stratiform, vesicle etc.), the pore-size distribution homogeneous is adjustable (1～30nm), specific surface 100～1000m
2/ g, pore volume 0.3～1.5cm
3/ g.Pattern is that granule (Powdered, bar-shaped, spherical, monocrystalline shape etc.), monolithic, thin film, fiber etc. are controlled.Other oxides can be aluminium oxide, calcium oxide, sodium oxide, magnesium oxide, zinc oxide, phosphorus pentoxide etc.
The preparation method of novel mesopore molecular sieve hemostatic material of the present invention comprises that water synthesizes and nonaqueous phase synthesizes two kinds, and concrete steps are as follows:
1) water is synthetic
A) earlier structure directing agent is dissolved in the deionized water that contains synthetic medium, under stirring, obtains uniform solution;
B) add inorganic precursors, continue stirring and obtain stable sols;
C), wear out, ageing handles with the gel hydro-thermal or the solvent thermal under ℃ temperature of room temperature～100 that obtain;
D) be cooled to room temperature then, filter, wash drying;
E) at last in 550 ℃～800 ℃ roasting temperatures, extraction, micro-wave digestion removes structure directing agent.
2) nonaqueous phase is synthetic
A) earlier structure directing agent is dissolved in the organic solvent that contains synthetic medium, under stirring, obtains uniform solution;
B) add inorganic precursors, continue stirring and obtain stable sols;
C) colloidal sol is poured in the vessel, solvent is fully volatilized;
D) after the gel intensive drying that obtains, in 550 ℃～800 ℃ roasting temperatures, extraction, micro-wave digestion removes structure directing agent.
In the said method, described in water is synthetic the temperature of step (a) and (b) be room temperature to 60 ℃; In the synthetic temperature of nonaqueous phase is room temperature.
In the said method, described surfactant is a nonionic surfactant, and (its molecular formula is EO as block copolymer
nPO
mEO
n, EO
nBO
mEO
n, EO
nBO
m) and Brij series (its molecular formula is C
mEO
n) or ionic surfactant (its molecular formula is C
nH
2n+1N (R)
3X, n=10～20, R=-CH
3, C
2H
5, X=Cl
-, Br
-) etc.
In the said method, described inorganic precursors comprises silicon source, calcium source, aluminum source or magnesium source etc.Wherein, the silicon source is ethyl orthosilicate (TEOS), methyl silicate (TMOS) or sodium silicate (Na
2SO
4), the calcium source is lime nitrate, calcium chloride etc., and the aluminum source is aluminum nitrate, aluminum chloride, and the magnesium source is magnesium nitrate, magnesium chloride etc.
In the said method, described synthetic medium is acidity or alkaline medium, and acid medium is that nonionic and ionic surfactant adopt during as structure directing agent jointly, and alkaline medium is that ionic surfactant adopts during as structure directing agent.
In the said method, described can the adding in synthetic and the inorganic salt (as potassium chloride, sodium chloride etc.) of structure directing agent similar mass and organic expander (as trimethylbenzene etc.).
The present invention has following advantage:
1, the reaction condition gentleness, easy to operation, raw material is cheap and easy to get.
2, (its molecular formula is EO to select commercialization ionic surfactant or nonionic block copolymer for use
nPO
mEO
n, EO
nBO
mEO
n, EO
nBO
m) and Brij series (its molecular formula is C
mEO
n) surfactant is structure directing agent, selecting organic ethyl orthosilicate or inorganic sodium silicate for use is the silicon source.Hydrophilic/hydrophobic volume ratio by the choice structure directed agents, control reaction temperature, adding inorganic salt, add means such as organic expander such as trimethylbenzene and control the mesoscopic structure of institute's synthesizing mesoporous silicon dioxide material (cube, six sides, etc.); Control the pore size (1～30nm) of mesoporous material by the hydro-thermal post-processing approach; By selecting synthetic system (as aqueous systems or ethanol system), means such as use inorganic salt prepare the mesoporous material (monolithic, ball, rod etc.) of different-shape.Use different sintering temperatures to remove the surfactant species fully and obtain the surface silanol group of variable concentrations.Utilize the meso-porous molecular sieve material that directly adds preparation different components such as calcium source or aluminum source when synthesizing.Select for use different forming agents with the molding of powder body mesoporous material or directly be coated on the medical bandage.
3, the distinctive porous of mesoporous material, more adsorbable antibiotics or 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 material, 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 for being the XRD spectra of the synthetic mesoporous silicon oxide molecular sieve hemostatic material of structure directing agent water by P123.
Fig. 2 is for being the transmission electron microscope picture of the synthetic mesoporous silicon oxide molecular sieve hemostatic material of structure directing agent water by P123.
Fig. 3 is for being the nitrogen adsorption-desorption curve and the pore distribution curve of the synthetic mesoporous silicon oxide molecular sieve hemostatic material of structure directing agent water by P123.Wherein, Fig. 2 (a) is nitrogen adsorption-desorption curve, and Fig. 2 (b) is a pore distribution curve.
Fig. 4 is mesoporous silicon oxide molecular sieve hemostatic material and the correlated Fibrinogen test result of other hemostatic materials that contains calcium oxide.Wherein, matched group is the situation of hemostatic material of no use; Experimental group is the situation with hemostatic material.
Fig. 5 is mesoporous silicon oxide molecular sieve hemostatic material and the correlated prothrombin time test result of other hemostatic materials that contains calcium oxide.Wherein, matched group is the situation of hemostatic material of no use; Experimental group is the situation with hemostatic material.
Fig. 6 is mesoporous silicon oxide molecular sieve hemostatic material and the correlated partial thromboplastin time test result of other hemostatic materials that contains calcium oxide.Wherein, matched group is the situation of hemostatic material of no use; Experimental group is the situation with hemostatic material.
The specific embodiment
The invention is further illustrated by the following examples.
2.08g (10mmol) TEOS is dissolved in 10g ethanol, adds 0.5g water and 0.4g 0.1M HCl in this solution, stir under the room temperature after 1 hour, behind the mix homogeneously again with contain 0.9g triblock copolymer surfactant P123 (EO
20PO
70EO
20), stirred 1 hour under the room temperature and the alcoholic solution mixing.Above-mentioned settled solution is transferred in the big culture dish, and (bone dry generally needs 1 day) behind the solution ethanol removed in volatilization naturally, obtains the softish thick film of water white transparency.With film from culture dish bottom separately after, add in the bottle of 100ml politef, add about 70ml water, hydrothermal treatment consists is 72 hours in 100 ℃ of baking ovens.Obtain the thick film of White-opalescent, sucking filtration separates, and after 500 ℃ of roastings of drying at room temperature were removed surfactant in 6 hours, just can obtain the pure silica mesopore molecular sieve bulk material of two dimension six side's phases (p6mm structure).Its blood coagulation is respond well.
At room temperature with 0.40g EO
39BO
47EO
39(B50-6600) be dissolved in the HCl solution of 30g 0.5mol/L, 2.08g TEOS is added in the gained settled solution, the mol ratio of each reactant is TEOS/EO
39BO
47EO
39/ HCl/H
2O=1: 0.0074: 6: 166.The reactant room temperature stirred after one day, and hydro-thermal is 1 day under 100 ℃ of conditions.The gained white depositions after filtration, after deionized water is given a baby a bath on the third day after its birth time, drying at room temperature.Template was removed in roasting in 6 hours under 550 ℃ of air atmospheres, and heating rate is controlled at 2 ℃/min, finally obtained the pure silica mesopore molecular sieve dusty material of three-dimensional cubic phase (Im3m structure).Its blood coagulation is respond well.
With 4.0g non-ionic surface active agent EO
20PO
70EO
20(P123), 1.4g lime nitrate (Ca (NO
3)
44H
2O), 6.7g ethyl orthosilicate (TEOS) is dissolved in the 60g ethanol, adds 1.0g 0.5M hydrochloric acid solution again, stirs 24h under the room temperature, pours in the culture dish, and the about 72h of ageing fully carries out hydrolysis-condensation reaction, forms gel, and gel is placed exsiccator.The gel piece that obtains after the drying in 700 ℃ of roasting 5h, can obtain the silicon oxide mesoporous molecular screen material that contains calcium oxide of two dimension six side's phases (p6mm structure) in Muffle furnace.Its blood coagulation is respond well.
At first utilize constant temperature water bath apparatus that the temperature of reaction system is controlled, in the time of 38 ℃ with the EO of 2.0g (0.4mmol)
20PO
70EO
20(P123), 2.2g (30mmol) KCl is dissolved in the 60g 2.0M HCl solution.The TEOS. that adds 4.2g (20mmol) under the vigorous stirring in this settled solution stirred after 8 minutes, kept reaction mixture sat one day under uniform temp, then with reactant transfer in water heating kettle, hydro-thermal is one day under 100 ℃ of conditions.Filtration is removed the inorganic salt that adds when synthesizing for three times in washing, and is dry under the room temperature.At last, 550 ℃ of roastings were removed organic formwork agent in 4 hours under air, obtained the bar-shaped meso-porous molecular sieve material of two dimension six side's phases (p6mm structure).Its blood coagulation is respond well.
Earlier with 2.0g EO
106PO
70EO
106(F127), 2.0g trimethylbenzene (TMB) and 5.0g KCl be dissolved in the HCl solution that 120ml concentration is 2M, 8.3gTEOS joined in this solution after stirring to clarify again, mixture is strong agitation 24h under～40 ℃ of temperature.Mixed solution is transferred in the water heating kettle hydro-thermal 72h at a certain temperature.Filtration washing, behind air drying, the product that obtains again in 550 ℃ of following roasting 6h, is cooled to and promptly obtains required three-dimensional cubic phase (Fm3m structure), large aperture (～12nm) meso-porous molecular sieve material after the room temperature.Its blood coagulation is respond well.
Embodiment 6
Earlier with 0.5g C
18EO
100(Brij700) be dissolved in the HCl solution of 50g 2M, after stirring to clarify again with an amount of TMB (0.2～1.0g) and 3.5g TEOS join in this solution, mixture is (4～40 ℃) strong agitation 24h at a certain temperature, transfers to then in the water heating kettle at 100 ℃ of following hydro-thermal 24h to 72h.Filtration washing, behind air drying, the product that obtains is again in 450～550 ℃ of following roasting 6h, is cooled to and promptly obtains required three-dimensional cubic phase (Im3m structure), small-bore (～3nm) meso-porous molecular sieve material after the room temperature.Its blood coagulation is respond well.
Embodiment 7
Under constant agitation, use 5mol/L H
2SO
4The pH value of regulating sodium silicate aqueous solution is about 10, adds cetyl trimethyl ammonium bromide (CTMAB) aqueous solution behind the 15min, and then stirs 30min, and the reactant mixture mole is composed as follows: SiO
2: 0.96Na
2O: 0.89H
2SO
4: 0.20CTMAB: 122H
2O transfers in the water heating kettle at 100 ℃ of following hydro-thermal 24h then to 72h filtration washing, behind air drying, the product that obtains again in 550 ℃ of following roasting 6h, is cooled to the mesoporous silicon oxide molecular sieve white powder material that promptly obtains required two dimension six side's phases (p6mm structure) after the room temperature.Its blood coagulation is respond well.
Claims (3)
1, a kind of mesopore molecular sieve is as the application of hemostatic material, and this mesopore molecular sieve utilizes the structure directing agent self assembly, prepares by typical sol-gel process; The main component of its composition is silicon dioxide and other oxide, and mol ratio is a silicon dioxide: other oxide is (50～100): (0～50); Other oxide here is aluminium oxide, calcium oxide, sodium oxide, magnesium oxide, zinc oxide or phosphorus pentoxide.
2, mesopore molecular sieve according to claim 1 is characterized in that as the application of hemostatic material this material has controlled mesoscopic structure, and the aperture is that 1～30nm distribution homogeneous is adjustable, and specific surface is 100～1000m
2/ g, pore volume are 0.3～1.5cm
3/ g.
3, mesopore molecular sieve according to claim 1 is characterized in that as the application of hemostatic material this material pattern is granule, monolithic, thin film, fiber.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7858123B2 (en) | 2005-04-04 | 2010-12-28 | The Regents Of The University Of California | Inorganic materials for hemostatic modulation and therapeutic wound healing |
| US9326995B2 (en) | 2005-04-04 | 2016-05-03 | The Regents Of The University Of California | Oxides for wound healing and body repair |
| CN1970090B (en) * | 2006-09-14 | 2015-11-25 | 华东理工大学 | Nanometer mesoporous silicon based xerogel hemostatic material and its preparation method and application |
| CN101883545B (en) * | 2007-12-06 | 2013-08-07 | 纳诺西斯有限公司 | Resorbable nanoenhanced hemostatic structures and bandage materials |
| CN101623513B (en) * | 2009-01-22 | 2013-04-17 | 中国科学院上海硅酸盐研究所 | One-step method for preparing mesoporous bioglass material |
| CN101991875B (en) * | 2010-10-29 | 2014-01-22 | 上海昊海生物科技股份有限公司 | Mesoporous bioactive glass and chitosan composite porous hemostatic material and preparation method thereof |
| CN102423503B (en) * | 2011-12-26 | 2014-04-09 | 浙江大学 | Preparation method of high-efficiency silicon oxide hemostasis material |
| US9861531B2 (en) * | 2013-06-18 | 2018-01-09 | Sanko Tekstil Isletmeleri Sanayi Ve Ticaret Anonim Sirketi | Multi-function emergency bandage |
| CN104474584B (en) * | 2014-11-24 | 2016-04-20 | 张家港保税区冠祥贸易有限公司 | A kind of preparation method of nano composite antibacterial dressing |
| CN106606799A (en) * | 2016-08-18 | 2017-05-03 | 中国人民解放军第二军医大学 | Porous starch composite material, and preparation method and applications thereof |
| CN108653791B (en) * | 2018-05-22 | 2021-06-08 | 山东景天堂药业有限公司 | Preparation method of silica medical dressing based on aerosol deposition |
| CN109172857A (en) * | 2018-09-10 | 2019-01-11 | 中国药科大学 | A kind of outer wound compound hemostatic material and preparation method thereof |
| CN113975454A (en) * | 2021-11-12 | 2022-01-28 | 延边大学 | Preparation and application of mesoporous silica/tannic acid composite hydrogel hemostatic material |
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| CN1554607A (en) * | 2003-12-22 | 2004-12-15 | 复旦大学 | Nano mesoporous and mesoporous-macroporous composite biological glass and its preparing method |
| CN1605562A (en) * | 2004-09-01 | 2005-04-13 | 复旦大学 | Macroporous sillca molecular sieve with ordered three-dimensional interconnected aperture wall and preparation method thereof |
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| CN1554607A (en) * | 2003-12-22 | 2004-12-15 | 复旦大学 | Nano mesoporous and mesoporous-macroporous composite biological glass and its preparing method |
| CN1605562A (en) * | 2004-09-01 | 2005-04-13 | 复旦大学 | Macroporous sillca molecular sieve with ordered three-dimensional interconnected aperture wall and preparation method thereof |
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