CN106563154A - Mesoporous copper calcium silicate, preparation method and applications thereof - Google Patents

Mesoporous copper calcium silicate, preparation method and applications thereof Download PDF

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Publication number
CN106563154A
CN106563154A CN201610693751.5A CN201610693751A CN106563154A CN 106563154 A CN106563154 A CN 106563154A CN 201610693751 A CN201610693751 A CN 201610693751A CN 106563154 A CN106563154 A CN 106563154A
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preparation
calcium
copper
mesoporous
acidic catalyst
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牛云飞
申晓军
蒋熙
郭列平
纪方
丁徐铭
吴祥
苏佳灿
何大为
魏强
王春玲
张东华
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Second Military Medical University SMMU
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • A61L24/0031Hydrogels or hydrocolloids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • A61L24/0015Medicaments; Biocides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • A61L24/0042Materials resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/046Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/04Materials for stopping bleeding

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Surgery (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The present invention discloses mesoporous copper calcium silicate, a preparation method and applications thereof. The preparation method comprises: (1) in the mixture of P123 and water, adding an acidic catalyst, uniformly mixing, adding a soluble calcium salt and a soluble copper salt, adding TEOS to the solution in a dropwise manner, stirring until white turbidity is generated in the solution, and continuously stirring to obtain a sol-gel white emulsion; and (2) aging the white emulsion obtained in the step (1), carrying out suction filtration to remove the upper layer liquid, drying the precipitate, and sintering to obtain the mesoporous copper calcium silicate. According to the present invention, with the application of the prepared mesoporous copper calcium silicate as the antibacterial bleeding-stopping material, the advantages of rapid and strong bleeding stopping, continuous antibacterial property, good biocompatibility and degradability in vivo are provided; and the preparation is easy.

Description

A kind of mesoporous calcium copper silicate and its preparation method and application
Technical field
The present invention relates to Material Field, more particularly to a kind of mesoporous calcium copper silicate and its preparation method and application.
Background technology
Bleeding is always the much-talked-about topic of the concerns such as medical circle, army's event horizon, no matter in daily life or on battlefield, loses blood Ubiquitous, especially uncontrollable massive haemorrhage has become the one of the main reasons of human death.And can be at injured scene Or go to and give wounded's traumatic bleeding on the road of hospital and fast and effeciently controlled, will have huge to improving wounded's survival rate Big meaning.Even if the wounded can support at Medical Devices and obtain medical treatment, but uncontrollable bleeding is still to threaten the wounded Life and the principal element for causing complication.Research shows that the wounded are between treatment most preferably, if energy from a hour for being subject to create The condition of the injury that the wounded are made in this section of Best Times is controlled, then more than 80% wounded's life can access treatment.
Meanwhile, the bleeding that surgical operation is widely present seriously injures the life of patient with oozing of blood.In the abundant internal organs of blood supply, Particularly many vascular internal organs (spleen and liver) cannot avoid bleeding in operation.It is reported that, in traumatic Died Patients, It is to cause main causes of death to lose blood, and there are about 27% is to just arrive to emergency ward death, has 49% death occurred in 48 hours. In the world, the 30-40% that the trauma patient lost blood accounts for sum is died from every year, wherein reaching before medical treatment mechanism Death account for 33-56%.Surface of a wound bleeding in operation be due to caused by local factor or systemic factor, the former by artery, Vein and capillary hemorrhage are caused, caused by the latter then occurs for dysfunction of platelet or blood coagulation system.In addition with because mixed Caused by conjunction factor dysfunction or blood coagulation system occur.Therefore, it is topically effective to patient and quickly to stop blooding be to control as soon as possible Lose blood and reduce the optimal strategy of mortality.
Through unremitting exploratory development, various countries scientist successfully have developed various hemostatic materials, including gelfoam, fibre Fibrillarin glue, oxycellulose, shitosan, a-cyanoacrylate, porous zeolite etc..But, these common styptic convection current The blood surface of a wound acts primarily as anastalsis, and function and therapeutic effect are more single, and the function such as anti-anti-inflammation is not good.Many styptics can be Wound secretion is absorbed, causes secretion contaminated wound, and form new wound secretion contaminated wound, so as to cause complication. Therefore, the focus of current styptic R and D is this kind of novel local of multifunctional material except the feature with common styptic Outside, also with antibacterial and inflammation-diminishing function.
For the hemostatic material of internal hemostasis, if without good biocompatibility, wound tissue can produce to material Repel, or cause inflammatory reaction, necrosis can be caused when serious, or even can life-threatening.Therefore a kind of hemostatic material only Courage and uprightness can be strong again, and hemostasis efficiency is high again, and biocompatibility is also the threshold that it must pass through, and otherwise the material is in clinical application Can have a greatly reduced quality.The wound that hemostatic material is applied, it is interior to internal organs, the also bleeding of deep position including outward to body surface.Material exists After completing hemostasis, can mix with blood, form thrombus, it is difficult to clear out of in vivo, to avoid the carrying out of second operation, reduce The pain of the wounded, material degradation in vivo is also a kind of hard requirement.If material can not in a short time obtain fast degradation, And be excluded in vitro by some modes, or absorbed by human body, can not only cause immune response, and bacterium infection can be increased Possibility.
The content of the invention
The technical problem to be solved is that to overcome existing hemostatic material haemostatic effect single, it is impossible to effectively Antibacterial, preparation cost is high, poor biocompatibility, it is difficult to the defect such as degraded in vivo, and provide a kind of mesoporous calcium copper silicate and its Preparation method and application.Mesoporous calcium copper silicate of the invention obtained as antimicrobial form hemostatic material, can quickly potent hemostasis, persistently Antibacterial, good biocompatibility can degrade in vivo, prepare easy.
The present invention solves by the following technical programs above-mentioned technical problem.
The invention provides a kind of preparation method of mesoporous calcium copper silicate, it is comprised the following steps:
(1) in the mixture of P123 and water, add acidic catalyst to be well mixed, be subsequently adding soluble calcium salt and can Dissolubility mantoquita, TEOS is dropped in solution, is stirred to solution and is occurred after white opacity, continues to stir, and obtains collosol and gel white Color emulsion;
(2) the white emulsion described in step (1) is aged, suction filtration removes supernatant liquid, drying precipitate is burnt Knot, obtains final product mesoporous calcium copper silicate.
In step (1), the polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer that the P123 is known in the art Thing (EO20PO70EO20), is purchased from Aldrich-sigma Reagent Companies.
In step (1), described water is water commonly used in the art, generally deionized water.
The temperature of the addition acidic catalyst described in step (1) is preferably 25~55 DEG C, is more preferably 50 DEG C.
In step (1), the concentration of described acidic catalyst is preferably 1~4mol/L, is more preferably 2mol/L.
In step (1), described acidic catalyst is preferably one kind in hydrochloric acid, nitric acid, sulfuric acid and citric acid or many Kind.
In step (1), described soluble calcium salt can be solubility calcium various soluble in water commonly used in the art Salt, the present invention is preferably one or more in calcium chloride, calcium nitrate, calcium monohydrogen phosphate, calcium acetate, calcium bromide and calcirm-fluoride.
In step (1), described soluble copper salt can be soluble copper various soluble in water commonly used in the art Salt, the present invention is preferably one or more in copper chloride, copper nitrate, copper acetate, copper bromide, copper fluoride.
In step (1), described P123 and the mass ratio of described water are preferably 1: (5~9), described P123 and institute The mass volume ratio of the acidic catalyst stated is preferably 1g: (22~40) mL, the quality of described P123 and described TEOS Volume ratio is preferably 1g: (1.5~4) mL, described P123 and described soluble calcium salt, soluble copper salt mass ratio compared with It is goodly 1: (1.1~3.8): (1.1~3.8).
In step (1), the TEOS is tetraethyl orthosilicate commonly used in the art.The speed of described dropwise addition is preferable Ground is 5 drop/min~25 drops/min.
In step (1), the time that described continuation is stirred is preferably 5~7 hours.
In step (2), described drying means and condition is the conventional method in this area and condition.The temperature of described drying Preferably 60~100 DEG C of degree.
In step (2), the method and condition of the sintering are the conventional method in this area and condition.The temperature of described sintering Preferably 450~720 DEG C of degree;The time of described sintering is preferably 5~10 hours.
Present invention also offers one kind mesoporous calcium copper silicate by obtained in above-mentioned preparation method, described mesoporous calcium copper silicate Mesoporous pore size be 3nm~15nm, preferably 10nm~15nm, it is a diameter of 5 μm~10 μm of described mesoporous calcium copper silicate, excellent Elect 7 μm~10 μm as.
Present invention also offers application of the above-mentioned mesoporous calcium copper silicate in hemostatic material is prepared.
Wherein, described hemostatic material is preferably used to prepare the hemostatic material of human epidermal, in-vivo tissue.
When hemostatic material is applied to, can be used alone or be combined with carrier material makes the mesoporous calcium copper silicate of the present invention With.
The mesoporous calcium copper silicate of the present invention as hemostatic material, using the high-specific surface area and high water absorbing capacity of meso-hole structure Characteristic, by calcium ion Coagulation test, quick-acting haemostatic powder are started.Additionally, copper ion serves antibacterial effect, it is to avoid infection.
The present invention mesoporous calcium copper silicate as antimicrobial form hemostatic material, can quickly potent hemostasis, sustained anti-microbial, biofacies Capacitive is good, can degrade in vivo, prepares easy.
On the basis of common sense in the field is met, above-mentioned each optimum condition can be combined, and obtain final product each preferable reality of the present invention Example.
Agents useful for same of the present invention and raw material are commercially available.
The present invention positive effect be:
(1) mesoporous calcium copper silicate of the invention is bar-shaped in length, a diameter of 5 μm~10 μm, its mesoporous pore size be 3nm~ 15nm, and mesoporous pore size is evenly distributed.
(2) the obtained mesoporous calcium copper silicate of the present invention is degradable, and bleeding stopping period is 30s-4min, good biocompatibility.
(3) mesoporous calcium copper silicate of the invention, for bleeding wound, during contact blood, is discharged few as hemostatic material Amount calcium ion, promotes blood clotting, reaches haemostatic effect;And formation condensation prevention glue after the moisture in blood can be absorbed, seal Stifled wound;After material water swelling simultaneously, certain pressure is formed to peripheral vessels and promotes hemostasis.Mesoporous material preparation technology It is simple, it is applied widely, can be used for various medical applications.
(4) mesoporous calcium copper silicate of the invention has quick potent hemostasis and effective antibacterial as antimicrobial form hemostatic material Double action, beneficial to Wound healing.
Description of the drawings
Fig. 1 is the digital photograph figure of mesoporous calcium copper silicate antimicrobial form hemostatic material.
Fig. 2 is the stereoscan photograph (a) and transmission electron microscope photo (b) of mesoporous calcium copper silicate antimicrobial form hemostatic material.
Fig. 3 is the nitrogen adsorption-desorption curve (a) and pore size distribution curve of mesoporous calcium copper silicate antimicrobial form hemostatic material (b)。
Fig. 4 stops blooding in vitro experimental result picture for mesoporous calcium copper silicate antimicrobial form hemostatic material:PT test results (a) and APTT Test result (b).
Fig. 5 is antibacterial effect figure of the mesoporous calcium copper silicate as antimicrobial form hemostatic material, is (a) blank control group, (b) is Mesoporous calcium copper silicate experimental group.
Fig. 6 is that mesoporous calcium copper silicate is used for new zealand white rabbit sensitization of skin experiment effect figure:Back wound (a), smear Mesoporous calcium copper silicate (b) is with after 4 weeks affected part situation (c).
Fig. 7 is the auricular vein hemostasis figure that mesoporous calcium copper silicate is used for new zealand white rabbit as antimicrobial form hemostatic material: Effect (b) after wound bleeding (a) and hemostasis.
Fig. 8 is the back hemostasis figure that mesoporous calcium copper silicate is used for new zealand white rabbit as antimicrobial form hemostatic material:Wound Effect (b) after bleeding (a) and hemostasis.
When Fig. 9 is the hemostasis that mesoporous calcium copper silicate is stopped blooding as the back that antimicrobial form hemostatic material is used for new zealand white rabbit Spoke-like figure:Commercially available hemostatic material Yunnan Baiyao (a) and mesoporous calcium copper silicate (b).
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality Among applying a scope.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or according to business Product specification is selected.
In following embodiments, the relative molecular mass of P123 used is 5800, is purchased from Aldrich-sigma reagents public Department.
Embodiment 1
A kind of preparation method of mesoporous calcium copper silicate, it comprises the steps:
(1) P123 of 4.0g is mixed with the water of 30mL, to solution clarification, addition 120mL concentration is at 50 DEG C 2mol/L hydrochloric acid stirring mixing 1h, be subsequently adding the calcium nitrate of 10.6g and the copper nitrate of 12.4g, by the TEOS of 9.12mL with The speed of 15 drop/min is dropped in solution, is stirred to solution and is occurred after white opacity, continues to stir 5 hours, obtains collosol and gel White emulsion;
(2) collosol and gel white emulsion be aged into 3 days at 25 DEG C, then suction filtration removing upper liquid, by sediment in It is dried at 80 DEG C, sinters 6 hours at 600 DEG C, obtains final product white powder.
The digital photograph of the mesoporous calcium copper silicate is as shown in Figure 1.
The stereoscan photograph and transmission electron microscope photo of the mesoporous calcium copper silicate is shown in respectively Fig. 2 (a), (b);It is obtained mesoporous Calcium copper silicate is in long bar-shaped, averagely about 30 μm, a diameter of 7~10 μm of length;The mesoporous pore size of the mesoporous calcium copper silicate is in 10nm ~15nm, pore-size distribution is homogeneous, there is higher specific surface area (618m2/ g, as shown in Figure 3).(wherein use porosity instrument (Tristar 3000, the U.S.) determines different relative pressure P/P under the continuous adsorption conditionses of 77K0Lower N2Isothermal adsorption-desorption is bent Line, the specific surface area of material is calculated by Brnauer-Emmett-Teller (BET) method, and average pore size and pore-size distribution are logical Cross the calculating of Barret-Joyer-Halenda (BJH) equivalent cylindricals model)
Embodiment 2~4
Embodiment 2~4 repeats the experimental procedure of embodiment 1, and difference is part Experiment condition, concrete such as table 1~2 It is shown.
Table 1 is obtained the reaction condition of collosol and gel white emulsion
Table 2 is obtained the reaction condition of white powder
Embodiment Baking temperature Sintering time Sintering temperature
2 70℃ 5 hours 450℃
3 80℃ 8 hours 720℃
4 100℃ 10 hours 600℃
The parameter index of mesoporous calcium copper silicate is with embodiment 1 obtained in embodiment 2~4.
Effect example 1
Prothrombin time (PT) and activated partial thromboplastin time (APTT) are determined:
Explain mesoporous calcium copper silicate antimicrobial form hemostatic material pair obtained in embodiment 1 by determining PT and APTT respectively Outward, the impact of intrinsic coagulation system.New blood takes from SD rats, and with 1: 9 volume ratio and the Chinese holly of 0.109mol/L Rafter acid sodium solution carries out mixing anti-freezing process, and the centrifugation under 3000 revs/min of rotating speed obtains Platelet poor blood in 15 minutes Slurry (PPP).The method of testing of PT is as follows:Pre-temperature rat plasma 0.1ml, PT reagent 0.2ml is distinguished at 37 DEG C, is added after pre-temperature Enter in the EP pipes containing detected materials, mix, record setting time.The method of testing of APTT is according to following steps:By 0.1mL APTT is added in the EP pipes containing detected materials, is mixed, and adds 0.1mL PPP, 37 DEG C of pre-temperatures to be incubated 5min, and 5min is managed after EP The CaCl of middle addition 0.1mL2Solution, records the setting time of blood plasma.Final result, with the setting time of blank control group as mark Accurate (being designated as 1), the relative scale of experiment with computing group.Experimental result is as shown in Figure 4.PT reflections are material exogenous blood coagulation systems The impact of system.As seen from the figure, the PT values of the mesoporous calcium copper silicate are relatively not added with the blank group of material and decrease, and this explanation is wherein deposited Ca2+There is the ability of activation extrinsic coagulation system, but with the increase of amount of samples, the range of decrease is not obvious.APTT reflections It is impact of the material to intrinsic coagulation system.It can be seen that compared with the blank group for being not added with material, the mesoporous silicic acid The APTT values of calcium copper are substantially reduced, and with the increase of amount of samples, reduction trend becomes apparent from.In a word, the mesoporous silicic acid Calcium copper product can activate exogenous and intrinsic coagulation system, active clotting mechanism.
The coagulating effectiveness of mesoporous calcium copper silicate is with embodiment 1 obtained in embodiment 2~4.
Effect example 2
Anti-microbial property is determined:
With Escherichia coli (E.coli, ATCC 8099) as experimental strain, using anti-microbial property of the sterilization experiment to material It is estimated.By the middle culture Escherichia coli of 24 hours, Jing PBS solutions diluted concentration to 10 in 37 DEG C of incubators4Cfu/ml, It is inoculated on solid medium, is then placed on cultivating in 37 DEG C of incubators after 12h, colony count is obtained on mesh number culture plate. Experimental result is implemented as shown in figure 5, it can be seen that all covered with Escherichia coli on the culture dish of blank control group Colibacillary bacterium colony on the mesoporous calcium copper silicate culture dish of example 1 seldom, can with mesh number, its antibiotic rate substantially 90% with On, with obvious antibacterial effect.Should test result indicate that, the copper in mesoporous calcium silicates copper product obtained by embodiment 1 from Son serves antibacterial effect.
Equally, the antibacterial effect of mesoporous calcium copper silicate obtained in embodiment 2~4 is with embodiment 1.
Effect example 3
Evaluation of its biocompatibility:
New zealand white rabbit 3 is taken, is fixed on autopsy table, after anaesthetizing to animal subject, by White Rabbit ridge The rabbit hair of vertebra both sides is shaved off, and with 70% alcohol disinfecting.Wound is caused beside vertebra with scalpel, and applies embodiment 1 to make The mesoporous calcium silicates copper powders for obtaining.Rabbit is put in cage, and is periodically fed with food until experiment terminates, changed apply daily With material, and periodically take pictures observation wound and surrounding skin sensitivity response situation are carried out to wound, as a result see accompanying drawing 6.Can by figure See, (Fig. 6 (c)) wound does not have swelling phenomenon after 4 weeks, without sensitivity response, and wound progressively heals, and shows the embodiment of the present invention Mesoporous calcium silicates copper product prepared by 1 has good biocompatibility.
Equally, mesoporous calcium copper silicate obtained in embodiment 2~4 also possesses good biocompatibility.
Effect example 4
Anthemorrhagic performance evaluation in vivo:
1. rabbit auricular vein hemostasis model
White Rabbit is placed on operating table, by the Nembutal sodium solution that left auricular vein injection concentration is 0.3%, and The rabbit hair on auris dextra ear face is shaved off, after Animal Anesthesia, with scalpel cross section wound is made at auris dextra vein, when wound is bled Afterwards, immediately sample spilt to go out in wound, and slight pressure is carried out using gauze, wound table is gently wiped away with gauze after the completion of hemostasis The material in face.The experimental result that Fig. 7 stops blooding for the auricular vein that the mesoporous calcium copper silicate of embodiment 1 is used for new zealand white rabbit Figure, it can be seen from figure 7 that when blood flow is controlled completely, mesoporous calcium silicates copper powders mix with blood, forms scab, Wound surface is closely adhered to, with haemostatic effect.
2. rabbit back hemostasis model
After anesthesia White Rabbit, the rabbit hair at back is removed." ten " font wound of a 5cm × 5cm is done with scalpel at back Mouthful, sample is spilt at bleeding immediately, and certain pressing is given by hospital gauze, after the completion of waiting to stop blooding, during record hemostasis Between, and wipe the sample of wound with gauze.Fig. 8 is used for the back of new zealand white rabbit for the mesoporous calcium copper silicate of embodiment 1 The experimental result picture of hemostasis, as can be seen from Figure 8, the big blood flow that "+" type wound causes stops completely, and sample has stopped blooding Cheng Hou, forms scab, and secure adhesion is in wound.Fig. 9 gives the mesoporous calcium copper silicate of embodiment 1 as antimicrobial form hemostatic material Expect the bleeding control time stopped blooding for the back of new zealand white rabbit, contrast finds, certain commercially available hemostatic material Yunnan Baiyao Bleeding stopping period needs about 100s, and the mesoporous calcium silicates copper powders of the embodiment of the present invention 1 needs shorter time (45s) can Stop blooding completely, haemostatic effect is preferable.
Equally, mesoporous calcium copper silicate obtained in embodiment 2~4 also possesses haemostatic effect good similarly to Example 1.

Claims (10)

1. a kind of preparation method of mesoporous calcium copper silicate, it is comprised the following steps:
(1) in the mixture of P123 and water, add acidic catalyst to be well mixed, be subsequently adding soluble calcium salt and solubility Mantoquita, TEOS is dropped in solution, is stirred to solution and is occurred after white opacity, continues to stir, and obtains collosol and gel white breast Turbid liquid;
(2) the white emulsion described in step (1) is aged, suction filtration removes supernatant liquid, drying precipitate is sintered, i.e., Obtain mesoporous calcium copper silicate.
2. preparation method as claimed in claim 1, it is characterised in that the temperature of the addition acidic catalyst described in step (1) Spend for 25~55 DEG C;
In step (1), the concentration of described acidic catalyst is preferably 1~4mol/L;Described acidic catalyst be hydrochloric acid, One or more in nitric acid, sulfuric acid and citric acid.
3. preparation method as claimed in claim 1, it is characterised in that in step (1), described soluble calcium salt is chlorination One or more in calcium, calcium nitrate, calcium monohydrogen phosphate, calcium acetate, calcium bromide and calcirm-fluoride;
In step (1), described soluble copper salt be the one kind in copper chloride, copper nitrate, copper acetate, copper bromide, copper fluoride or It is various.
4. preparation method as claimed in claim 1, it is characterised in that in step (1), the matter of described P123 and described water Amount is than being 1: (5~9), described P123 and the mass volume ratio of described acidic catalyst is 1g: (22~40) mL, described The mass volume ratio of P123 and described TEOS is 1g: (1.5~4) mL, described P123 and described soluble calcium salt, solvable Property mantoquita mass ratio be 1: (1.1~3.8): (1.1~3.8).
5. preparation method as claimed in claim 1, it is characterised in that in step (1), the speed of described dropwise addition be 5 drops/ Min~25 drop/min;
In step (1), the time that described continuation is stirred is 5~7 hours.
6. preparation method as claimed in claim 1, it is characterised in that in step (2), the temperature of described drying is 60~ 100℃。
7. preparation method as claimed in claim 1, it is characterised in that in step (2), the temperature of described sintering is 450~ 720℃;The time of described sintering is 5~10 hours.
8. a kind of calcium copper silicate mesoporous by obtained in the preparation method as described in any one in claim 1~7.
9. application of the mesoporous calcium copper silicate in hemostatic material is prepared as claimed in claim 8.
10. application as claimed in claim 9, it is characterised in that described hemostatic material is for preparing human epidermal, in vivo The hemostatic material of tissue.
CN201610693751.5A 2016-08-18 2016-08-18 Mesoporous copper calcium silicate, preparation method and applications thereof Pending CN106563154A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101716374A (en) * 2009-12-09 2010-06-02 华东理工大学 Mesoporous bone tissue reconstructing material, preparation method and application thereof
CN103721292A (en) * 2012-10-10 2014-04-16 中国科学院上海硅酸盐研究所 Novel multifunctional mesoporous glass bracket with biological activity as well as preparation method and purpose thereof
CN104548195A (en) * 2014-12-18 2015-04-29 华东理工大学 Mesoporous calcium magnesium silicate and polyetheretherketone composite, bone prosthesis as well as preparation method and application of composite

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101716374A (en) * 2009-12-09 2010-06-02 华东理工大学 Mesoporous bone tissue reconstructing material, preparation method and application thereof
CN103721292A (en) * 2012-10-10 2014-04-16 中国科学院上海硅酸盐研究所 Novel multifunctional mesoporous glass bracket with biological activity as well as preparation method and purpose thereof
CN104548195A (en) * 2014-12-18 2015-04-29 华东理工大学 Mesoporous calcium magnesium silicate and polyetheretherketone composite, bone prosthesis as well as preparation method and application of composite

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