CN115212342B - Kaolin composite hemostatic material and preparation method thereof - Google Patents

Kaolin composite hemostatic material and preparation method thereof Download PDF

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CN115212342B
CN115212342B CN202210794453.0A CN202210794453A CN115212342B CN 115212342 B CN115212342 B CN 115212342B CN 202210794453 A CN202210794453 A CN 202210794453A CN 115212342 B CN115212342 B CN 115212342B
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kaol
alpha
kaolin
hemostatic material
calcining
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CN115212342A (en
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杨华明
陈东华
郑琪颖
章霞
刘云扬
曹泽亮
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Long Yan Kaolinclay Co ltd
China University of Geosciences
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Long Yan Kaolinclay Co ltd
China University of Geosciences
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/0047—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L24/0052—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material with an inorganic matrix
    • A61L24/0068—Inorganic materials not covered by groups A61L24/0057 or A61L24/0063
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001—Use of materials characterised by their function or physical properties
    • A61L24/0015—Medicaments; Biocides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/62—Encapsulated active agents, e.g. emulsified droplets
    • A61L2300/624—Nanocapsules
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/04—Materials for stopping bleeding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention discloses a kaolin composite hemostatic materialThe preparation method. The invention relates to a kaolin composite hemostatic material, which takes kaolin as a carrier and is loaded with alpha-Fe 2 O 3 And is doped with Ce. The preparation method comprises mechanically mixing kaolin, polymeric hydroxyl iron ion solution and Ce salt solution; calcining at a certain temperature to obtain high-biocompatibility hemostatic material alpha-Fe 2 O 3 Kaol. The invention loads alpha-Fe 2 O 3 Simultaneously, ce is doped to improve the hemostatic effect of the kaolin composite hemostatic material, and the prepared Ce-alpha-Fe 2 O 3 The Kaol composite hemostatic material has no obvious cytotoxicity, no hemolysis, good biocompatibility, high safety performance and antibacterial effect; the preparation method disclosed by the invention is simple in steps, easy to operate and beneficial to large-scale production.

Description

Kaolin composite hemostatic material and preparation method thereof
Technical Field
The invention relates to the technical field of hemostatic materials, in particular to a kaolin composite hemostatic material and a preparation method thereof.
Background
The wound first-aid hemostatic materials on the market at present are mainly divided into biological derivative materials, chemical synthetic polymers, powder inorganic matters and the like, but the biological derivative materials are poor in stability and high in price, and the preparation process of the chemical synthetic polymers is complex. Inorganic materials such as natural clays have been reported to have excellent hemostatic efficacy. Compared with zeolite-based and montmorillonite-based hemostatic materials, the kaolinite-based hemostatic material can absorb water rapidly, does not release heat and does not cause thermal damage to wound tissues, and in addition, the unique lamellar structure and surface groups of the kaolinite are beneficial to functional loading of nano particles. However, the reported commercial hemostatic materials have the defects of single component and lack of functions, and restrict the development and application of high-performance hemostatic products.
Disclosure of Invention
The invention aims at providing a kaolin composite hemostatic material with high biocompatibility and good hemostatic effect and a preparation method thereof, aiming at the defects of the prior art.
The invention relates to a kaolin composite hemostatic material, which takes kaolin as a carrier and is loaded with alpha-Fe 2 O 3 And is doped with Ce.
Further, the kaolin is composed of platy kaolinite and tubular halloysite.
Further, the alpha-Fe 2 O 3 The load rate is 50-70%.
A preparation method of a kaolin composite hemostatic material comprises the following steps:
s1: mechanically mixing kaolin, a polymeric hydroxyl iron ion solution and a Ce salt solution;
s2: calcining at a certain temperature to obtain high-biocompatibility hemostatic material Ce-alpha-Fe 2 O 3 /Kaol。
Further, calcining at 500-600deg.C.
Further, the mixture was calcined at 550 ℃.
Further, the concentration of the polymeric hydroxyl iron ion solution is 0.4mol/L, and the mass-volume ratio of the kaolin to the polymeric hydroxyl iron ion solution is 1:50g/mL.
Further, in step S1, ce (NO 3 ) 3 A solution.
Further, the Ce (NO 3 ) 3 The concentration of the solution was 0.12mol/L.
The invention loads alpha-Fe 2 O 3 Simultaneously, ce is doped to improve the hemostatic effect of the kaolin composite hemostatic material, and the prepared Ce-alpha-Fe 2 O 3 The Kaol composite hemostatic material has no obvious cytotoxicity, no hemolysis, good biocompatibility, high safety performance and antibacterial effectEffects; the preparation method disclosed by the invention is simple in steps, easy to operate and beneficial to large-scale production.
The invention also utilizes the feature of the morphology structure (figure 1) of the tubular halloysite and the flaky kaolinite doped with each other to lead the alpha-Fe to be 2 O 3 The high-efficiency nano particles are loaded on the surface of the kaolin, the surface of the platy kaolinite is negatively charged, and the high-efficiency nano particles have rich surface hydroxyl and interlayer pore canal structures, so that the high-efficiency nano particles are beneficial to the high-efficiency loading of the functional nano particles; halloysite has enough physical and mechanical strength to ensure the integrity, while halloysite with tubular shape has good biocompatibility, and proper surface microstructure and biochemical characteristics promote cell adhesion, proliferation and differentiation, so that the halloysite and the halloysite are mutually doped to load alpha-Fe 2 O 3 The loading rate of the porous ceramic material can reach 50-70%, and on the premise of guaranteeing the hemostatic performance of kaolin, the cellular safety and biocompatibility of the mineral material are improved, so that the porous ceramic material can be applied to the hemostatic field and hemostatic products with social and economic significance are developed.
Drawings
FIG. 1 is a morphology of platy kaolinite, tubular halloysite, and kaolin;
FIG. 2 shows the alpha-Fe prepared in examples 1-5 of the present invention 2 O 3 Kaol composite hemostatic material and alpha-Fe 2 O 3 Is a graph of cytotoxicity test results;
FIG. 3 shows the alpha-Fe prepared in examples 1-5 of the present invention 2 O 3 Kaol composite hemostatic material and alpha-Fe 2 O 3 Is a hemolysis test result of (a);
FIG. 4 is a graph showing the results of in vitro procoagulant tests for kaolin and various iron oxide/Kaol composite hemostatic materials;
FIG. 5 shows Ce- α -Fe prepared in examples 7-9 2 O 3 Kaol composite hemostatic material, raw ore, alpha-Fe prepared in example 6 2 O 3 Test results of in vitro bleeding time of Kaol and control group;
FIG. 6 shows the results of hemolysis test of platy kaolinite, tubular halloysite and kaolin.
Detailed Description
The following are specific embodiments of the present invention and the technical solutions of the present invention will be further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
The term "kaolin" in the present specification has the formula Al 2 O 3 ·2SiO 2 ·2H 2 O, in some forms, the kaolin comprises about 45.31% silica, about 37.21% alumina, and about 14.1% water.
The kaolin in the examples in this specification is a standard product of the division of Kaolinite, the origin is Fujian Longyan, and it was found to contain halloysite and kaolinite by quantitative analysis of mineralogy by X-ray diffraction (XRD), and it was found that the halloysite contained was tubular and the kaolinite was flaky by Scanning Electron Microscope (SEM) analysis of FIG. 1.
Preparation of Kaolin
A preparation stage of a kaolin raw material, the method comprising the steps of: crushing the kaolin crude ore into powder by using a crusher, uniformly mixing the crude ore by using a nine-grid ore dressing method, and bagging the middle part of the nine-grid ore. The mineral material was further ground using a three-head grinder to prepare a synthetic sample.
Preparation of polymeric hydroxy ferric ion solution
FeCl is taken 3 ·6H 2 O and NaOH were formulated as a polymeric ferric hydroxide solution at a concentration of 0.4 mol/L.
Ce(NO 3 ) 3 Preparation of the solution
Taking Ce (NO) 3 ) 3 ·6H 2 O is prepared to obtain Ce (NO) with the concentration of 0.12mol/L 3 ) 3 A solution.
Different load ratios alpha-Fe 2 O 3 Preparation of Kaol composite product (examples 1-6)
Example 1:
the present example provides alpha-Fe 2 O 3 alpha-Fe with content of 50.41% 2 O 3 /Kaol 1 The preparation method of the composite hemostatic material comprises the following steps: 5g of Gao Baite sample and 250mL of polymeric hydroxyl iron ion solution are mixed, the pH of the system is adjusted to about 3 by 5mol/L NaOH solution, and after stirring for 5 hours at 60 ℃,8000rpm is used for separationAnd (3) washing for 3 times, and drying to obtain the FeOOH/Kaol kaolin compound. Grinding FeOOH/Kaol kaolin compound, calcining (calcining at 250deg.C for 1h, calcining at 350deg.C for 1h, and calcining at 550deg.C for 4 h) to obtain alpha-Fe 2 O 3 alpha-Fe with content of 50.41% 2 O 3 /Kaol 1 A composite hemostatic material.
Example 2:
the present example provides alpha-Fe 2 O 3 alpha-Fe with content of 34.52% 2 O 3 /Kaol 2 The preparation method of the composite hemostatic material comprises the following steps: 10g of Gao Baite sample and 250mL of polymeric hydroxyl iron ion solution are mixed, the pH of the system is adjusted to about 3 by using 5mol/L NaOH solution, the system is stirred for 5 hours at the temperature of 60 ℃, and the mixture is centrifuged at 8000rpm, washed for 3 times and dried to obtain the FeOOH/Kaol kaolin compound. Grinding FeOOH/Kaol kaolin compound, calcining (calcining at 250deg.C for 1h, calcining at 350deg.C for 1h, and calcining at 550deg.C for 4 h) to obtain alpha-Fe 2 O 3 alpha-Fe with content of 34.52% 2 O 3 /Kaol 2 A composite hemostatic material.
Example 3:
the present example provides alpha-Fe 2 O 3 alpha-Fe with content of 22.29% 2 O 3 /Kaol 4 The preparation method of the composite hemostatic material comprises the following steps: 20g of Gao Baite sample and 250mL of polymeric hydroxyl iron ion solution are mixed, the pH of the system is adjusted to about 3 by using 5mol/L NaOH solution, the system is stirred for 5 hours at the temperature of 60 ℃, and the mixture is centrifuged at 8000rpm, washed for 3 times and dried to obtain the FeOOH/Kaol kaolin compound. Grinding FeOOH/Kaol kaolin compound, calcining (calcining at 250deg.C for 1h, calcining at 350deg.C for 1h, and calcining at 550deg.C for 4 h) to obtain alpha-Fe 2 O 3 alpha-Fe with content of 22.29% 2 O 3 /Kaol 4 A composite hemostatic material.
Example 4:
the present example provides alpha-Fe 2 O 3 alpha-Fe with 6.26% content 2 O 3 /Kaol 8 The preparation method of the composite hemostatic material comprises the following steps: 40g Gao Baite sample and 25Mixing 0mL of polymeric hydroxyl iron ion solution, regulating the pH of the system to about 3 by using 5mol/L NaOH solution, stirring for 5 hours at the temperature of 60 ℃, centrifuging at 8000rpm, washing for 3 times, and drying to obtain the FeOOH/Kaol kaolin compound. Grinding FeOOH/Kaol kaolin compound, calcining (calcining at 250deg.C for 1h, calcining at 350deg.C for 1h, and calcining at 550deg.C for 4 h) to obtain alpha-Fe 2 O 3 alpha-Fe with 6.26% content 2 O 3 /Kaol 8 A composite hemostatic material.
Example 5:
the present example provides alpha-Fe 2 O 3 alpha-Fe with content of 7.45% 2 O 3 /Kaol 10 The preparation method of the composite hemostatic material comprises the following steps: 50g of Gao Baite sample and 250mL of polymeric hydroxyl iron ion solution are mixed, the pH of the system is adjusted to about 3 by using 5mol/L NaOH solution, the system is stirred for 5 hours at the temperature of 60 ℃, and the mixture is centrifuged at 8000rpm, washed for 3 times and dried to obtain the FeOOH/Kaol kaolin compound. Grinding FeOOH/Kaol kaolin compound, calcining (calcining at 250deg.C for 1h, calcining at 350deg.C for 1h, and calcining at 550deg.C for 4 h) to obtain alpha-Fe 2 O 3 alpha-Fe with content of 7.45% 2 O 3 /Kaol 10 A composite hemostatic material.
Example 6:
the present example provides alpha-Fe 2 O 3 alpha-Fe with content of 62.19% 2 O 3 The preparation method of the Kaol composite hemostatic material comprises the following steps: 30g of Gao Baite sample and 1500mL of polymeric hydroxyl iron ion solution are mixed, the pH of the system is adjusted to about 3 by using 5mol/L NaOH solution, the system is stirred for 5 hours at the temperature of 60 ℃, and then centrifugal separation and washing are carried out for 3 times at 8000rpm, and drying are carried out, thus obtaining the FeOOH/Kaol kaolin composite. Grinding FeOOH/Kaol kaolin compound, calcining (calcining at 250deg.C for 1h, calcining at 350deg.C for 1h, and calcining at 550deg.C for 4 h) to obtain alpha-Fe 2 O 3 alpha-Fe with content of 62.19% 2 O 3 Kaol composite hemostatic material.
For the alpha-Fe prepared in examples 1-5 2 O 3 /Kaol 1 、α-Fe 2 O 3 /Kaol 2 、α-Fe 2 O 3 /Kaol 4 、α-Fe 2 O 3 /Kaol 8 、α-Fe 2 O 3 /Kaol 10 Composite hemostatic material and alpha-Fe 2 O 3 Cytotoxicity test (FIG. 2) and hemolysis test (FIG. 3) were performed, and the results showed that alpha-Fe 2 O 3 Has higher cell activity and lower hemolysis, and the load rate is more than 50 percent of alpha-Fe 2 O 3 Kaol, biocompatibility was better than other loading rates.
Ce-α-Fe 2 O 3 Preparation of Kaol composite hemostatic material
Example 7:
the present example provides Ce-alpha-Fe 2 O 3 The preparation method of the Kaol composite hemostatic material comprises the following steps: 5g of kaolin and 250mL of polymeric ferric hydroxide ion solution were mixed and stirred, and 20mL of Ce (NO 3 ) 3 And (3) dropwise adding the solution into the mixed solution, regulating the pH of the system to about 3 by using a 5mol/L NaOH solution, stirring for 5 hours at the temperature of 60 ℃, centrifuging at 8000rpm, washing for 3 times, and drying to obtain the Ce-FeOOH/Kaol compound. Grinding and calcining (calcining at 250deg.C for 1h, calcining at 350deg.C for 1h, and calcining at 550deg.C for 4 h) the Ce-alpha-Fe compound to obtain 2 O 3 Kaol composite hemostatic material. And for Ce-alpha-Fe 2 O 3 The composition of the Kaol composite hemostatic material was analyzed by X-ray fluorescence spectroscopy (XRF) (Table 1).
TABLE 1 Ce-alpha-Fe 2 O 3 Analysis of oxide content in Kaol composite hemostatic Material
Composition of the components Content (wt%)
Fe 2 O 3 41.54
SiO 2 41.29
Al 2 O 3 15.07
K 2 O 1.37
CeO 2 0.0566
Table 1 shows that Ce-alpha-Fe 2 O 3 Fe in Kaol 2 O 3 Is 41.54% loaded and is successfully doped with a small amount of Ce.
Example 8:
the present example provides alpha-Fe 2 O 3 The preparation method of the Ce/Kaol-Aladin composite hemostatic material comprises the following steps: 5g of kaolinite (Kaol-Aladin; aladin, CAS: 1332-58-7) in sheet form and 250mL of the polymeric ferric hydroxide ion solution are mixed and stirred, 20mL of Ce (NO) 3 ) 3 And (3) dropwise adding the solution into the mixed solution, regulating the pH of the system to about 3 by using a 5mol/L NaOH solution, stirring for 5 hours at the temperature of 60 ℃, centrifuging at 8000rpm, washing for 3 times, and drying to obtain the Ce-FeOOH/Kaol-Aladin compound. Grinding and calcining (calcining at 250 ℃ for 1h, calcining at 350 ℃ for 1h, and calcining at 550 ℃ for 4 h) the Ce-FeOOH/Kaol-Aladin compound to obtain the Ce-alpha-Fe 2 O 3 Kaol-Aladin composite hemostatic material.
Example 9:
the present example provides Ce-alpha-Fe 2 O 3 The preparation method of the HNTs-Sigma composite hemostatic material comprises the following steps: 5g of tubular halloysite (HNTs-Sigma; sigma, CAS: 12298-43-0) and 250mL of the polymeric hydroxy ferric ion solution were mixed and stirred, followed by 20mL of Ce (NO) 3 ) 3 Solution drippingAnd (3) adding the mixture into a mixed solution, regulating the pH of the system to about 3 by using a 5mol/L NaOH solution, stirring for 5 hours at the temperature of 60 ℃, centrifuging at 8000rpm, washing for 3 times, and drying to obtain the Ce-FeOOH/HNTs-Sigma compound. Grinding and calcining (calcining at 250deg.C for 1h, calcining at 350deg.C for 1h, and calcining at 550deg.C for 4 h) the Ce-alpha-Fe compound 2 O 3 HNTs-Sigma composite hemostatic material.
Confirmation of Ce-alpha-Fe by in vitro bleeding time assay (FIG. 5) 2 O 3 Kaol-Aladin composite hemostatic material (example 8) and Ce-alpha-Fe 2 O 3 HNTs-Sigma composite hemostatic Material (example 9) and Ce-alpha-Fe 2 O 3 The hemostatic effect of the Kaol composite hemostatic material (example 7) was comparable to that of alpha-Fe 2 O 3 Kaol (example 6) has remarkable hemostatic effect, which shows that the hemostatic effect of the Ce-doped composite hemostatic material is remarkably improved.
α-Fe 2 O 3 /Kaol、Fe 3 O 4 /Kaol、γ-Fe 2 O 3 Preparation of Kaol, feOOH/Kaol composite hemostatic material
α-Fe 2 O 3 /Kaol、Fe 3 O 4 /Kaol、γ-Fe 2 O 3 The preparation method of the composite hemostatic material of/Kaol, feOOH/Kaol comprises the following steps: mixing 5g of kaolin sample with 250mL of polymeric hydroxyl iron ion solution, regulating the pH of the system to about 3 by using 5mol/L NaOH solution, stirring for 5 hours at the temperature of 60 ℃, centrifuging at 8000rpm, washing for 3 times, and drying to obtain the FeOOH/Kaol compound. Grinding and calcining the FeOOH/Kaol compound (calcining at 250deg.C for 1h, at 350deg.C for 1h, and at 550deg.C for 4 h) to obtain alpha-Fe 2 O 3 Kaol composite hemostatic material. Calcining the prepared alpha-Fe 2 O 3 Kaol Complex at H 2 Calcining for 1h at 450 ℃ in Ar (volume ratio of 1:9) atmosphere to obtain Fe 3 O 4 Kaol. The obtained Fe 3 O 4 Calcining Kaol at 250deg.C in air atmosphere for 2 hr to obtain gamma-Fe 2 O 3 /Kaol。
Considering that different oxide types may have an effect on improving the hemostatic effect of kaolin byFor the prepared alpha-Fe 2 O 3 /Kaol、Fe 3 O 4 /Kaol、γ-Fe 2 O 3 Evaluation of the in vivo procoagulant assay of/Kaol, feOOH/Kaol (FIG. 4), shows that alpha-Fe 2 O 3 Kaol has more excellent procoagulant properties.
Hemolysis experiment:
preparation of 2% erythrocyte suspension: 1mL of fresh anticoagulated rabbit blood was centrifuged at 2500rpm for 5min, the supernatant was removed, washed 3 times with Phosphate Buffer (PBS), 500. Mu.L of the washed puree was taken into a 50mL centrifuge tube, and PBS was added to 50mL.
Hemolysis experiment: material solutions of kaolin, plate-like kaolinite, and tubular halloysite were prepared at respective concentrations of 0.125, 0.25, 0.5, 1.0, and 2.0mg/mL, respectively, in 3mL portions. 500. Mu.L of each concentration solution was mixed with 500. Mu.L of the prepared 2% erythrocyte suspension. Positive control group was set: 500 μl deionized water was mixed with 500 μl 2% erythrocyte suspension; negative control group: mu.L of PBS was mixed with 500. Mu.L of 2% erythrocyte suspension, 3 tubes of each group were aliquoted, the samples were incubated in a 37℃water bath for 1h, centrifuged at 2500rpm, and the supernatant was taken and its absorbance was measured with an enzyme-labeled instrument (414 nm).
Hemolysis ratio (%) = (sample absorption-negative control absorption)/(positive control absorption-negative control absorption) ×100%.
The lower the hemolysis, the higher the biocompatibility. The rate of hemolysis was less than 5%, and it was considered that hemolysis did not occur.
The hemolysis results of the cases are shown in FIG. 6, and from FIG. 6, it can be seen that the hemolysis rate of Kaol is lower than that of Kaol-Aladin and HNTs-Sigma, indicating that the biosafety of Kaol is higher.
In vitro procoagulant experiments:
100. Mu.L of anticoagulated whole blood was added dropwise to a 6-well plate, and 10. Mu.L of 0.2mol/LCaCl was added dropwise to the whole blood rapidly 2 The whole blood was recalcified with the solution, 10mg of material was added above the whole blood with a de-headed gum head dropper, and no material was added to the blank. The well plate was placed in a 37 ℃ water bath for co-incubation for 9min, after which 10mL deionized water was slowly added drop-wise around the drop of blood to avoid impacting the coagulated blood. After the dripping is finished, a proper amount of aqueous solution is quickly absorbed,1mL of the aqueous solution was centrifuged at 1000rpm, and the absorbance was measured by an enzyme-labeled instrument (540 nm).
10mg of each of the prepared kaolin and the prepared different iron oxide/Kaol composite hemostatic materials were weighed, and a group of blank control groups was prepared, each group being 3 replicates.
The in vitro procoagulant results of the case are shown in FIG. 4. As can be seen from FIG. 4, α -Fe 2 O 3 Kaol vs. Fe 3 O 4 /Kaol、γ-Fe 2 O 3 The absorbance of/Kaol, feOOH/Kaol is lower, indicating alpha-Fe 2 O 3 Kaol has more excellent procoagulant properties.
In vitro bleeding time assay:
weighing Kaol, ce-alpha-Fe 2 O 3 /Kaol-Aladdin、Ce-α-Fe 2 O 3 /HNTs-Sigma、α-Fe 2 O 3 /Kaol、Ce-α-Fe 2 O 3 10mg of Kaol composite hemostatic material is placed in a 2mL centrifuge tube, placed in a 37 ℃ water bath environment for preheating for 3 minutes, 200 mu L of New Zealand white rabbit anticoagulated whole blood is dripped into sample powder at the bottom of the tube, and then 10 mu L of 0.2mol/L CaCl is dripped into a mixed system rapidly 2 Solution calcified blood triggered clotting. The mixed system is rapidly placed into a 37 ℃ water bath environment for culture, the centrifuge tube is shaken every 15s, the flowing condition of blood in the tube is observed until the blood is coagulated, and the hemostatic time is recorded. 3 replicates were run for each material.
The results of the in vitro bleeding time of the case are shown in FIG. 5, and it can be seen from FIG. 5 that the comparative alpha-Fe 2 O 3 Kaol (example 6), ce-doped Ce-alpha-Fe 2 O 3 The bleeding time of the Kaol composite hemostatic material (example 7) was shortened, indicating that Ce doping can enhance the hemostatic effect of the composite hemostatic material.
In vivo hemostasis experiment:
female Kunming mice of 6 weeks of age were selected and randomly grouped by body weight, with 5 mice per group. Fixing the mouse, leaking the tail, cutting a 1cm wound on the tail vein of the mouse by using a surgical knife blade to enable the wound to bleed, immediately covering the wound by using hemostatic gauze after rapidly giving corresponding material powder after the incision, lightly pressing the hemostatic gauze to stop bleeding until the complete bleeding, recording the hemostatic time by using a timer, dipping the blood flowing out from the wound by using the gauze, and weighing to calculate the bleeding amount. The hemostatic time and the amount of bleeding in each case are shown in Table 2.
TABLE 2 Ce-alpha-Fe 2 O 3 Kaol composite hemostatic material bleeding time and amount
Case (B) Material Hemostatic time(s) Bleeding amount (mg)
Blank control group No material is added 179.8±36.6 132.7±75.9
Raw ore Kaol 153.2±33.7 104.8±50.5
Example 6 α-Fe 2 O 3 /Kaol 136±34.7 96.4±42.6
Example 7 Ce-α-Fe 2 O 3 /Kaol 112.6±23.4 84.81±40.4
Positive control group Yunnan Baiyao 136.6±40.9 53.1±32.5
Table 2 shows that alpha-Fe 2 O 3 Kaol doped Ce can effectively improve the hemostatic speed and reduce the bleeding amount.
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the foregoing examples are provided for the purpose of illustration only and are not intended to limit the scope of the invention, and that various modifications or additions and substitutions to the described specific embodiments may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the invention as defined in the accompanying claims. It should be understood by those skilled in the art that any modification, equivalent substitution, improvement, etc. made to the above embodiments according to the technical substance of the present invention should be included in the scope of protection of the present invention.

Claims (4)

1. A preparation method of a kaolin composite hemostatic material is characterized by comprising the following steps: the method comprises the following steps:
s1: mechanically mixing kaolin with a polymeric hydroxyl iron ion solution and a Ce salt solution;
s2: calcining at a certain temperature to obtain high-biocompatibility hemostatic material Ce-alpha-Fe 2 O 3 /Kaol；
The kaolin consists of platy kaolinite and tubular halloysite;
the specific operation is as follows: mixing and stirring kaolin and polymeric hydroxyl iron ion solution, and adding Ce (NO 3 ) 3 Dropwise adding the solution into the mixed solution, regulating the pH of the system to 3 by using a 5mol/L NaOH solution, stirring at 60 ℃ for 5h, centrifuging, washing and drying to obtain a Ce-FeOOH/Kaol compound; grinding the Ce-FeOOH/Kaol compound, calcining at 250 ℃ for 1h, at 350 ℃ for 1h, and at 550 ℃ for 4h to obtain Ce-alpha-Fe 2 O 3 Kaol composite hemostatic material.
2. The method of manufacturing according to claim 1, wherein: the concentration of the polymeric hydroxyl ferric ion solution is 0.4mol/L, and the mass volume ratio of the kaolin to the polymeric hydroxyl ferric ion solution is 1:50g/mL.
3. The method of manufacturing according to claim 1, wherein: the Ce (NO) 3 ) 3 The concentration of the solution was 0.12mol/L.
4. A kaolin composite hemostatic material prepared by the method of any one of claims 1-3.
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