CN106975100B - A kind of cerium oxide/mesoporous silicon nanocomposite material and its preparation method and application - Google Patents

A kind of cerium oxide/mesoporous silicon nanocomposite material and its preparation method and application Download PDF

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CN106975100B
CN106975100B CN201610027779.5A CN201610027779A CN106975100B CN 106975100 B CN106975100 B CN 106975100B CN 201610027779 A CN201610027779 A CN 201610027779A CN 106975100 B CN106975100 B CN 106975100B
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cerium oxide
mesoporous silicon
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CN106975100A (en
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凌代舜
吴海滨
高建青
李方园
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Zhejiang University ZJU
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Abstract

本发明涉及一种氧化铈/介孔硅的纳米复合材料，包含配体转换的氧化铈纳米晶和氨基修饰的介孔硅纳米粒子，配体转换的氧化铈纳米晶修饰于氨基修饰的介孔硅纳米粒子的表面；配体转换的氧化铈纳米晶与氨基修饰的介孔硅纳米粒子的质量比为1～20；配体转换的氧化铈纳米晶利用2‑溴代异丁酸进行配体转换。本发明还涉及氧化铈/介孔硅的纳米复合材料的制备方法及其在创伤愈合或组织修复中的应用。该复合材料能够平衡创面的活性氧自由基水平，降低炎症水平，利用纳米桥联效应发挥黏合作用；而且制备反应体系温和，条件可控，所制备的材料均具有良好的生物相容性，具有良好的临床转化可能性。

The invention relates to a cerium oxide/mesoporous silicon nanocomposite material, comprising ligand-converted cerium oxide nanocrystals and amino-modified mesoporous silicon nanoparticles, and the ligand-converted cerium oxide nanocrystals are modified with amino-modified mesopores The surface of silicon nanoparticles; the mass ratio of ligand-converted cerium oxide nanocrystals to amino-modified mesoporous silicon nanoparticles is 1 to 20; the ligand-converted cerium oxide nanocrystals are liganded by 2-bromoisobutyric acid convert. The invention also relates to a preparation method of the cerium oxide/mesoporous silicon nanocomposite material and its application in wound healing or tissue repair. The composite material can balance the level of active oxygen free radicals on the wound surface, reduce the level of inflammation, and utilize the nano-bridging effect to exert adhesion; and the preparation reaction system is mild and the conditions are controllable, the prepared materials have good biocompatibility, and have Good clinical translation potential.

Description

A kind of nanocomposite and its preparation method and application of cerium oxide/mesoporous silicon
Technical field
The present invention relates to cerium oxide/mesoporous silicon field of composite material preparation, and in particular to a kind of cerium oxide/mesoporous silicon is received Nano composite material and its preparation method and application.
Background technique
Chronic refractory skin trauma brings pain to patient, while bringing heavy burden to health system.By There is very high disability rate and lethality in chronic refractory sexual trauma, need to develop new treatment means and make up existing therapies means Deficiency.According to statistics, only in the chronic refractory trauma patient in the U.S. just about 6,500,000, it is used for chronic refractory sexual trauma every year Cost just more than 25,000,000,000 dollars, and it is contemplated that, with obesity, the disease incidence of diabetes is higher and higher, this number It will also continue to increase.
To the afunction of various molecular cells signal necessary to proper wound agglutination or to be interfered be shape At the basic reason of chronic refractory sexual trauma.In addition, the microorganisms intrusion surface of a wound in external environment also results in chronic inflammation Disease reaction, is more unfavorable for the healing of the surface of a wound.It has been reported that chronic inflammatory reaction is certain related to the generation of tumour presence Property.Other than chronic refractory sexual trauma, promote by liver, kidney, lung, the healing of the internal organ such as heart wound caused by operation and organ The recovery of function is also to work as previous more intractable difficult medical problem.For by liver, kidney, lung, the internal organ such as heart are caused by operation Wound, operation stitching and polymer bonding agent are common at present and effective treatment means.But for liver, lung etc. For soft connective tissue, operation stitching will cause certain organ injury.Polymer bonding agent is also because control intracorporal polymerization Or the condition of cross-linking reaction is excessively complicated and acts on the reasons such as limited in wet vivo environment and limits its scope of application.
The feature that moistens for certain internal organs softnesses and lead to many external internal factors of chronic refractory sexual trauma, Nearest some basic research and preclinical study show that nanoparticle has in terms of promoting wound healing caused by a variety of causes There are huge potentiality.A drop silicon nano is molten at room temperature for the research achievement discovery of Ludwik Leibler et al. Liquid can generate quickly strong adhesive effect between two blocks of individual hydrogels.In animal skin wound and internal organ operation wound Ludwik Leibler et al.'s the experimental results showed that, nano-particle solution consistent with result on the hydrogel on model It can accelerate the healing of wound by a kind of so-called nanometer bridge effect.
But existing research the result shows that, due to lack glutathione, the endogenic antioxidant such as vitamin E so that It is one of the reason of diabetes and age ageing etc. form chronic refractory sexual trauma that the raised reactive oxygen species of site of injury, which cannot be neutralized,. Therefore, the healing for only accelerating wound by nanometer bridge effect in the prior art, does not balance site of injury with antioxidant Reactive oxygen species, the effect of accelerating wound healing is unobvious.
Summary of the invention
The purpose of the present invention is overcoming defect in the prior art, a kind of nano combined material of cerium oxide/mesoporous silicon is provided Material and its preparation method and application.
Technical solution provided by the invention is as follows:
A kind of nanocomposite of cerium oxide/mesoporous silicon, the cerium oxide nanocrystal and amido modified comprising ligand conversion Nanometer particle, the cerium oxide nanocrystal of the described ligand conversion modifies in amido modified nanometer particle Surface；The mass ratio of cerium oxide nanocrystal that ligand is converted and amido modified nanometer particle is 1~20；Described The cerium oxide nanocrystal of ligand conversion carries out ligand conversion using 2- bromo acid.
The nanocomposite of above-mentioned cerium oxide/mesoporous silicon provided by the invention can balance the active oxygen radical of the surface of a wound Level reduces level of inflammation, and plays adhesive effect using nanometer bridge effect.Firstly, nanometer particle has nanometer Bridge effect can promote wound healing；Secondly, cerium oxide nanocrystal can balance the raised reactive oxygen species of site of injury, in turn Reactive oxygen species are reduced to act on the oxidative damage of the cell membrane of periwound environment and protein, will neutralization activity oxygen cluster oxygen It is nanocrystalline for wound repair to change cerium, can make up for it the deficiency of endogenous antioxidant.In order to by cerium oxide nanocrystal with stabilization The form of covalent bond be connected to nanometer particle surface, ligand is carried out to cerium oxide nanocrystal first with 2- bromo acid Conversion, then nanometer particle surface is carried out amido modified, be conducive between the two compound, finally make two kinds of materials Performance is further promoted after compound.
Preferably, the partial size for the cerium oxide nanocrystal that the ligand is converted is 1~10nm, described is amido modified The partial size of nanometer particle is 5~500nm.Cerium oxide nanocrystal and the affiliated particle size range of nanometer particle, are convenient for Cerium oxide nanocrystal is uniform must to modify the composite material for obtaining pattern in the surface of nanometer particle and haveing excellent performance.
The present invention also provides a kind of preparation methods of the nanocomposite of cerium oxide/mesoporous silicon, include the following steps:
1) cerous acetate hydrate and oleyl amine are added in dimethylbenzene, 3~6h is reacted at 85 DEG C~95 DEG C, aging is sunk It forms sediment, obtains cerium oxide nanocrystal；
2) to cerium oxide nanocrystal obtained in step 1), ligand conversion is carried out using 2- bromo acid, obtains ligand The cerium oxide nanocrystal of conversion；
3) hexadecyltrimethylammonium chloride and triethanolamine be then dissolved in water, react 0.5 at 90 DEG C~100 DEG C~ 5h, continuously adds ethyl orthosilicate and 3- aminopropyl triethoxysilane reacts 0.5~5h, is centrifuged, and washing obtains amido modified Mesoporous silicon dioxide nano particle；
4) cerium oxide nanocrystal of ligand conversion and amido modified nanometer particle are added in ethyl alcohol, 45 DEG C~55 DEG C at react 8~15h, obtain cerium oxide/mesoporous silicon nanocomposite.
Using above-mentioned preparation method, cerium oxide/mesoporous silicon nanocomposite can be prepared, which can Active oxygen radical by the cerium oxide nanocrystal balance surface of a wound is horizontal, reduces level of inflammation, and can utilize nanometer grain The nanometer bridge effect of son plays adhesive effect, and therefore, the advantage of two kinds of materials mutually assists, so that cerium oxide/mesoporous silicon The performance of nanocomposite further gets a promotion.
Preferably, the mass ratio of cerous acetate hydrate and oleyl amine is 1:7~9 in the step 1).
Preferably, hexadecyltrimethylammonium chloride, triethanolamine, ethyl orthosilicate and 3- ammonia in the step 3) The feed ratio of propyl-triethoxysilicane are as follows: 1.5~2.5g:0.03~0.05g:1.4~1.6ml:0.14~0.16ml.
Preferably, ligand is converted in the step 4) cerium oxide nanocrystal and amido modified nanometer grain The mass ratio of son is 1~20.By regulating and controlling mass ratio between the two, control in cerium oxide/mesoporous silicon nanocomposite The content of the cerium oxide nanocrystal of ligand conversion, so that the cerium oxide nanocrystal of ligand conversion is easy to modify in amido modified Jie Hole silicon nano surface, convenient for the regulation of pattern and the modification of cerium oxide nanocrystal.
Preferably, ligand conversion refers in the step 2), by cerium oxide nanocrystal obtained in step 1), 2- bromine The in the mixed solvent for being added sequentially to chloroform and N-N dimethylformamide for isobutyric acid and citric acid stirs 20~30h.Ligand Conversion is in order to which cerium oxide nanocrystal is connected to nanometer particle surface in the form of stable covalent bond.
Preferably, the mass ratio of the 2- bromo acid and cerium oxide nanocrystal are as follows: 20~60.
The present invention also provides a kind of application of the nanocomposite of cerium oxide/mesoporous silicon in wound healing.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) cerium oxide/mesoporous silicon novel nanocomposite materials can balance the active oxygen radical level of the surface of a wound, reduce scorching Disease is horizontal, plays the mechanism such as adhesive effect using nanometer bridge effect and promotes acute and chronic wound healing and tissue repair.
(2) it is mild that the present invention relates to reaction systems, and condition is controllable, and prepared material all has good bio-compatible Property, there is good clinical conversion possibility.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of the cerium oxide nanocrystal of the ligand conversion in embodiment 1；
Fig. 2 is the transmission electron microscope photo of the cerium oxide nanocrystal of the ligand conversion in embodiment 1；
Fig. 3 is the transmission electron microscope photo of the amido modified nanometer particle in embodiment 1；
Fig. 4 is the transmission electron microscope photo of cerium oxide/mesoporous silicon nanocomposite in embodiment 1；
Fig. 5 is the scanning transmission electron microscope photo of cerium oxide/mesoporous silicon nanocomposite in embodiment 1；
Fig. 6 is the distribution diagram of element of cerium oxide/mesoporous silicon nanocomposite in embodiment 1；
Fig. 7 is the MTS cell activity quantitative analysis results of cerium oxide/mesoporous silicon nanocomposite in application examples Figure；
Fig. 8 is that the different materials in the present invention handle SD rat trauma model Healing Rate, and wherein MSN-ceria is oxidation Cerium/mesoporous silicon nanocomposite, MSN are nanometer particle, and Control is blank test；
Fig. 9 is the picture of the processing SD rat trauma model of the different materials in the present invention, and wherein MSN-ceria is oxidation Cerium/mesoporous silicon nanocomposite, MSN are nanometer particle, and Control is blank test.
Specific embodiment
Cerium oxide of the present invention/nanometer composite material system is elaborated below with reference to specific embodiment and attached drawing Application standby and its in promotion wound healing.
Embodiment 1
(1) synthesis of cerium oxide nanocrystal and ligand conversion: 0.4g cerous acetate hydrate and 3.2g oleyl amine are added to It in 15ml dimethylbenzene, is stirred at room temperature 4 hours, hastens to rise to 90 degrees Celsius with the heating of 2 centigrade per minutes；By 1ml deionization Water injection is into reaction system, and aging three hours, acetone precipitation, centrifugation obtained cerium oxide nanocrystal.The oxidation that synthesis is obtained Cerium is nanocrystalline, 0.5g 2- bromo acid and 0.05g citric acid are added sequentially to 7.5ml chloroform and 7.5ml N, N- dimethyl The in the mixed solvent of formamide stirs 24 hours to obtain the final product.
X-ray diffraction is carried out to the cerium oxide nanocrystal of obtained ligand conversion, as shown in Fig. 1；And ligand is turned The cerium oxide nanocrystal changed carries out morphology characterization with transmission electron microscope, as shown in Figure 2.
(2) synthesis of amido modified mesoporous silicon dioxide nano particle: by 2g hexadecyltrimethylammonium chloride and 0.02g triethanolamine is added in 20ml deionized water, and stirring is warming up to 95 degrees Celsius, and ethyl orthosilicate 1.5ml and 150 is added μ L 3- aminopropyl triethoxysilane is stirred to react 0.5~1h.Template is washed away by centrifugation and 1wt% sodium chloride methanol solution Amido modified mesoporous silicon dioxide nano particle can be obtained in agent.
Transmission electron microscope morphology characterization, such as Fig. 3 are carried out to the amido modified nanometer particle being prepared It is shown.
(3) synthesis of cerium oxide/mesoporous silicon nanocomposite: the concentration that 5ml ligand is converted is 0.6mM cerium oxide The ethanol solution of the 0.5mg/ml of nanocrystalline ethanol solution and 1ml amido modified mesoporous silicon dioxide nano particle is taken the photograph 45 Family name's degree, which reacts 12 hours, can be obtained cerium oxide/mesoporous silicon nanocomposite.It is multiple to cerium oxide/mesoporous silicon nanometer is obtained Condensation material carries out transmission electron microscope and scanning transmission electron microscope, and acquired results are as shown in Figures 4 and 5, cerium oxide/mesoporous The diameter of the nanocomposite of silicon is 50~60nm；In addition elemental analysis has also been carried out, as shown in Figure 6, it is known that the ball of grey Refer to that mesoporous silicon, white point refer to cerium oxide.
Embodiment 2
(1) 0.4g cerous acetate hydrate and 3.6g oleyl amine the synthesis of cerium oxide nanocrystal and ligand conversion: are added to two It in toluene, is stirred at room temperature 6 hours, hastens to rise to 95 degrees Celsius with the heating of 2 centigrade per minutes；1ml deionized water is injected Into the reaction system of inert gas shielding, aging three hours, acetone precipitation, centrifugation obtained cerium oxide nanocrystal.It will synthesize To oxidation be that nanocrystalline, 0.5g 2- bromo acid and 0.05g citric acid are added sequentially to 7.5ml chloroform and 7.5ml N, The in the mixed solvent of dinethylformamide stirs 24 hours to obtain the final product.
(2) synthesis of amido modified mesoporous silicon dioxide nano particle: by 2.4g hexadecyltrimethylammonium chloride and 0.05g triethanolamine is added in 20ml deionized water, and stirring is warming up to 95 degrees Celsius, and ethyl orthosilicate 1.4ml and 160 is added μ L 3- aminopropyl triethoxysilane is stirred to react.Washing away template by centrifugation and 1wt% sodium chloride methanol solution can obtain To amido modified mesoporous silicon dioxide nano particle.
(3) synthesis of cerium oxide/mesoporous silicon nanocomposite: the concentration that 8ml ligand is converted is 0.6mM cerium oxide The 0.5mg/ml of nanocrystalline ethanol solution and 1ml amido modified mesoporous silicon dioxide nano particle 50 is taken the photograph in ethanol system Family name's degree, which reacts 12 hours, can be obtained cerium oxide/mesoporous silicon nanocomposite.
Embodiment 3
(1) 0.4g cerous acetate hydrate and 2.8g oleyl amine the synthesis of cerium oxide nanocrystal and ligand conversion: are added to two It in toluene, is stirred at room temperature 3 hours, hastens to rise to 88 degrees Celsius with the heating of 2 centigrade per minutes；1ml deionized water is injected Into the reaction system of inert gas shielding, aging three hours, acetone precipitation, centrifugation obtained cerium oxide nanocrystal.It will synthesize To oxidation be that nanocrystalline, 0.5g 2- bromo acid and 0.05g citric acid are added sequentially to 7.5ml chloroform and 7.5ml N, The in the mixed solvent of dinethylformamide stirs 24 hours to obtain the final product.
(2) synthesis of amido modified mesoporous silicon dioxide nano particle: by 2g hexadecyltrimethylammonium chloride and 0.04g triethanolamine is added in 20ml deionized water, and stirring is warming up to 95 degrees Celsius, and ethyl orthosilicate 1.4ml and 160 is added μ L 3- aminopropyl triethoxysilane is stirred to react.Template is washed away by centrifugation and 1wt% sodium chloride methanol solution Obtain amido modified mesoporous silicon dioxide nano particle.
(3) synthesis of cerium oxide/mesoporous silicon nanocomposite: the concentration that 4ml ligand is converted is 0.6mM cerium oxide The 0.5mg/ml of nanocrystalline ethanol solution and 1ml amido modified mesoporous silicon dioxide nano particle 60 is taken the photograph in ethanol system Family name's degree, which reacts 12 hours, can be obtained cerium oxide/mesoporous silicon nanocomposite.
Application examples
Cerium oxide/mesoporous silicon nanocomposite promotes skin wound healing for SD rat
Biocompatibility in vitro evaluation: various concentration nanometer is investigated in selection human skin fibroblasts strain (HSF) The biocompatibility in vitro of material and cerium oxide/mesoporous silicon nanocomposite.MTS cell activity quantitative analysis results are as schemed Shown in 7, various concentration group cell survival rate 80% or more, shows nanometer material (MSN) and cerium oxide/mesoporous silicon Nanocomposite (MSN-ceria) all have good biocompatibility in vitro.
The foundation and interpretation of result of skin trauma model: according to the dosage of 4ml/kg by 10wt% chloraldurate to SD Rats by intraperitoneal injection anesthesia, rejects back hair, the wound of the full skin thickness of standardized 2 centimeter lengths at back.Rat is random It is divided into 3 groups, every group 5.3 groups of rat back site of injury give blank (control), 50 μ L 10mg/ml nanometer grains respectively Sub- water dispersion solution (MSN), 50 μ L 10mg/ml cerium oxide/mesoporous silicon nanocomposite water dispersion solution (MSN- ceria).Each group wound length recovery situation is recorded at the specified time point.The reparation rate of wound is as shown in figure 8, Fig. 9 is rat Back wound was first day and photo on the 9th.
Technical solution of the present invention and beneficial effect is described in detail in embodiment described above, it should be understood that with Upper described is only specific embodiments of the present invention, be not intended to restrict the invention, all to be done in spirit of the invention Any modification, supplement and equivalent replacement etc., should all be included in the protection scope of the present invention.

Claims (8)

1.一种氧化铈/介孔硅的纳米复合材料，其特征在于，由配体转换的氧化铈纳米晶和氨基修饰的介孔硅纳米粒子组成，所述的配体转换的氧化铈纳米晶修饰于氨基修饰的介孔硅纳米粒子的表面；配体转换的氧化铈纳米晶与氨基修饰的介孔硅纳米粒子的质量比为1～20；所述的配体转换的氧化铈纳米晶利用2-溴代异丁酸进行配体转换。1. a nanocomposite material of cerium oxide/mesoporous silicon, is characterized in that, the mesoporous silicon nanoparticle of cerium oxide nanocrystal of ligand conversion and amino modification is made up of, the cerium oxide nanocrystal of described ligand conversion Modified on the surface of amino-modified mesoporous silicon nanoparticles; the mass ratio of ligand-converted cerium oxide nanocrystals to amino-modified mesoporous silicon nanoparticles is 1 to 20; the ligand-converted cerium oxide nanocrystals utilize 2-Bromoisobutyric acid for ligand switching. 2.根据权利要求1所述的氧化铈/介孔硅的纳米复合材料，其特征在于，所述的配体转换的氧化铈纳米晶的粒径为1～10nm，所述的氨基修饰的介孔硅纳米粒子的粒径为5～500nm。2. The cerium oxide/mesoporous silicon nanocomposite material according to claim 1, wherein the particle size of the ligand-converted cerium oxide nanocrystals is 1-10 nm, and the amino-modified mesoporous The particle size of the porous silicon nanoparticles is 5-500 nm. 3.一种如权利要求1或2所述的氧化铈/介孔硅的纳米复合材料的制备方法，其特征在于，包括如下步骤：3. a preparation method of the nanocomposite material of cerium oxide/mesoporous silicon as claimed in claim 1 or 2, is characterized in that, comprises the steps: 1)将醋酸铈水合物和油胺加入到二甲苯中，在85℃～95℃下反应3～6h，老化、沉淀，得到氧化铈纳米晶；1) adding cerium acetate hydrate and oleylamine into xylene, reacting at 85°C～95°C for 3～6 hours, aging and precipitation to obtain cerium oxide nanocrystals; 2)对步骤1)中得到的氧化铈纳米晶，利用2-溴代异丁酸进行配体转换，得到配体转换的氧化铈纳米晶；2) performing ligand conversion on the cerium oxide nanocrystals obtained in step 1) using 2-bromoisobutyric acid to obtain ligand-converted cerium oxide nanocrystals; 3)然后将十六烷基三甲基氯化铵和三乙醇胺溶于水，在90℃～100℃下反应0.5～5h，继续加入正硅酸乙酯和3-氨丙基三乙氧基硅烷反应0.5～5h，离心，洗涤，得到氨基修饰的介孔二氧化硅纳米粒子；3) Then dissolve cetyltrimethylammonium chloride and triethanolamine in water, react at 90℃～100℃ for 0.5～5h, and continue to add ethyl orthosilicate and 3-aminopropyltriethoxy Silane reaction for 0.5-5h, centrifugation and washing to obtain amino-modified mesoporous silica nanoparticles; 4)将配体转换的氧化铈纳米晶和氨基修饰的介孔硅纳米粒子加入到乙醇中，在45℃～55℃下反应8～15h，得到氧化铈/介孔硅的纳米复合材料。4) adding the ligand-converted cerium oxide nanocrystals and the amino-modified mesoporous silicon nanoparticles into ethanol, and reacting at 45°C to 55°C for 8 to 15 hours to obtain a cerium oxide/mesoporous silicon nanocomposite material. 4.根据权利要求3所述的氧化铈/介孔硅的纳米复合材料的制备方法，其特征在于，所述的步骤1)中醋酸铈水合物与油胺的质量比为1:7～9。4. the preparation method of the nanocomposite material of cerium oxide/mesoporous silicon according to claim 3, is characterized in that, in described step 1), the mass ratio of cerium acetate hydrate and oleylamine is 1:7～9 . 5.根据权利要求3所述的氧化铈/介孔硅的纳米复合材料的制备方法，其特征在于，所述的步骤3)中十六烷基三甲基氯化铵、三乙醇胺、正硅酸乙酯与3-氨丙基三乙氧基硅烷的投料比为：1.5～2.5g：0.03～0.05g：1.4～1.6ml：0.14～0.16ml。5. the preparation method of the nanocomposite material of cerium oxide/mesoporous silicon according to claim 3, is characterized in that, in described step 3), cetyl trimethyl ammonium chloride, triethanolamine, ortho-silicon The feeding ratio of ethyl acid to 3-aminopropyltriethoxysilane is: 1.5-2.5g: 0.03-0.05g: 1.4-1.6ml: 0.14-0.16ml. 6.根据权利要求3所述的氧化铈/介孔硅的纳米复合材料的制备方法，其特征在于，所述的步骤4)中配体转换的氧化铈纳米晶与氨基修饰的介孔硅纳米粒子的质量比为1～20。6. the preparation method of the nanocomposite material of cerium oxide/mesoporous silicon according to claim 3, is characterized in that, in described step 4), the cerium oxide nanocrystal of ligand conversion and the mesoporous silicon nanometer of amino modification The mass ratio of the particles is 1-20. 7.根据权利要求3所述的氧化铈/介孔硅的纳米复合材料的制备方法，其特征在于，所述的步骤2)中配体转换是指，将步骤1)中得到的氧化铈纳米晶、2-溴代异丁酸和柠檬酸依次加入到氯仿和N-N二甲基甲酰胺的混合溶剂中搅拌20～30h。7. the preparation method of the nanocomposite material of cerium oxide/mesoporous silicon according to claim 3, is characterized in that, in the described step 2), the ligand conversion refers to that the cerium oxide nanocomposites obtained in the step 1) are converted Crystalline, 2-bromoisobutyric acid and citric acid were successively added to the mixed solvent of chloroform and N-N dimethylformamide and stirred for 20-30 h. 8.一种如权利要求1或2所述的氧化铈/介孔硅的纳米复合材料在制备治疗创伤愈合药物中的应用。8. Application of the cerium oxide/mesoporous silicon nanocomposite material as claimed in claim 1 or 2 in the preparation of a medicine for treating wound healing.
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