阅读说明：本技术 铁钨复合氧化物纳米晶团簇的制备方法及其应用 (The preparation method and applications of ferrotungsten composite oxide nano-crystal cluster ) 是由 徐祖顺 刘豪杰 喻春涵 于 2019-07-31 设计创作，主要内容包括：本发明提供了铁钨复合氧化物纳米晶团簇的制备方法及其应用,该方法包括：(1)以水溶性的三价铁盐和二价铁盐为原料,以水溶性阴离子有机物为表面活性剂,以去离子水为溶剂,加入碱源,采用化学共沉淀法制备水溶性的四氧化三铁纳米粒子；(2)以水溶性钨盐为原料,以水溶性聚合物为表面活性剂,以多元醇为溶剂,采用热分解法制备水溶性的氧化钨纳米粒子；(3)取四氧化三铁纳米粒子、氧化钨纳米粒子和聚乙烯亚胺在去离子水中进行自组装反应,得铁钨复合氧化物纳米晶团簇。本发明纳米晶团簇在水相中低温合成,方法简单,成本低廉,所合成纳米晶团簇具有较好的MR/CT成像增强效果。(The present invention provides the preparation method and applications of ferrotungsten composite oxide nano-crystal cluster, this method comprises: (1) is using water-soluble trivalent iron salt and divalent iron salt as raw material, using water soluble anion organic matter as surfactant, using deionized water as solvent, alkali source is added, water-soluble ferriferrous oxide nano-particle is prepared using chemical coprecipitation；(2) using water-soluble tungsten salt as raw material, using water-soluble polymer as surfactant, using polyalcohol as solvent, water-soluble tungsten oxide nanometer particle is prepared using thermal decomposition method；(3) it takes ferriferrous oxide nano-particle, tungsten oxide nanometer particle and polyethyleneimine to carry out self-assembling reaction in deionized water, obtains ferrotungsten composite oxide nano-crystal cluster.The nanocrystalline cluster of present invention low temperature in water phase synthesizes, and method is simple, and low in cost, synthesized nanocrystalline cluster has preferable MR/CT image enhancement effect.)

1. the preparation method of ferrotungsten composite oxide nano-crystal cluster, characterized in that include:

(1) using water-soluble trivalent iron salt and divalent iron salt as raw material, using water soluble anion organic matter as surfactant, with Deionized water is solvent, and alkali source is added, prepares water-soluble ferriferrous oxide nano-particle using chemical coprecipitation；

(2) using water-soluble tungsten salt as raw material, using water-soluble polymer as surfactant, using polyalcohol as solvent, using heat point Solution prepares water-soluble tungsten oxide nanometer particle；

(3) ferriferrous oxide nano-particle, tungsten oxide nanometer particle and polyethyleneimine is taken to carry out self assembly in deionized water Reaction, obtains ferrotungsten composite oxide nano-crystal cluster.

2. the preparation method of ferrotungsten composite oxide nano-crystal cluster as described in claim 1, it is characterized in that:

Step (1) specifically:

Raw material, surfactant and alkali source are added in solvent, it is 11~12 that alkali source, which is used to control reaction solution pH,；In oxygen free condition Under, 1~3h is stirred to react at a temperature of 40~80 DEG C；Through Magnetic Isolation, washing, disperse products therefrom in deionized water.

3. the preparation method of ferrotungsten composite oxide nano-crystal cluster as described in claim 1, it is characterized in that:

In step (1), the molar ratio of ferro element is 1.06:1 in trivalent iron salt and divalent iron salt, water soluble anion organic matter and The molar ratio of iron ion is 1:(3~10), iron ion includes ferrous ion and ferric ion.

4. the preparation method of ferrotungsten composite oxide nano-crystal cluster as described in claim 1, it is characterized in that:

The water soluble anion organic matter is sodium citrate, sodium tartrate, disodium ethylene diamine tetraacetate, ethylenediamine tetra-acetic acid Sodium, citric acid, tartaric acid or ethylenediamine tetra-acetic acid.

5. the preparation method of ferrotungsten composite oxide nano-crystal cluster as described in claim 1, it is characterized in that:

Step (2) specifically:

Tungsten salt and surfactant are added in solvent, under anaerobic, 20~60min is reacted at a temperature of 160~180 DEG C； It is centrifuged, washed again after being cooled to room temperature, dispersed products therefrom in deionized water.

6. the preparation method of ferrotungsten composite oxide nano-crystal cluster as described in claim 1, it is characterized in that:

The dosage of the water-soluble polymer is the 1%~8% of tungsten salt quality.

7. the preparation method of ferrotungsten composite oxide nano-crystal cluster as described in claim 1, it is characterized in that:

The water-soluble polymer is polyethylene glycol, polyvinyl alcohol, polyethyleneimine or polyacrylic acid.

8. the preparation method of ferrotungsten composite oxide nano-crystal cluster as described in claim 1, it is characterized in that:

Step (3) specifically:

Ferriferrous oxide nano-particle, tungsten oxide nanometer particle and polyethyleneimine is taken to be dissolved in deionized water, in inert environments, 3~5h is reacted at room temperature, is centrifuged to obtain ferrotungsten composite oxide nano-crystal cluster.

9. the preparation method of ferrotungsten composite oxide nano-crystal cluster as described in claim 1, it is characterized in that:

In step (3), the molar ratio of taken ferriferrous oxide nano-particle and tungsten oxide nanometer particle is (0.3~3): 1, poly- second The dosage of alkene imines is the 3%~15% of ferriferrous oxide nano-particle and tungsten oxide nanometer mass particle sum.

10. ferrotungsten composite oxide nano-crystal cluster prepared by any one of claim 1~9 is used to make MRI/CT bimodal The application of image-forming contrast medium.

Technical field

The present invention relates to material science and biomedicine technical field, specially ferrotungsten composite oxide nano-crystal cluster Preparation method and applications.

Background technique

Nanocomposite, especially functional nano compound particle Recent study are extensive.To wherein have magnetic Inorganic material (such as Fe₃O₄, γ-Fe₂O₃, Ni, Co and the oxide of Mn etc.) and various with functional nano material with other The composite nanoparticle that (such as environment-responsive, catalysis, bio-imaging, treatment etc.) combines preparation, due to the function of its multiplicity Property, it is widely used in biological medicine (as carried medicine, protein, gene, cell separation, MRI, CT, optics contrast imaging) and industry Using fields such as (catalysis, sewage treatments etc.), good effect is achieved, thus its research potential is huge.

Summary of the invention

The object of the present invention is to provide the preparation method and applications of ferrotungsten composite oxide nano-crystal cluster.

The preparation method of ferrotungsten composite oxide nano-crystal cluster provided by the invention, comprising:

(1) using water-soluble trivalent iron salt and divalent iron salt as raw material, using water soluble anion organic matter as surface-active Agent is added alkali source, prepares water-soluble ferriferrous oxide nano-particle using chemical coprecipitation using deionized water as solvent；

It should be noted that referred to trivalent iron salt and divalent iron salt is all made of water soluble salt；

(2) it using water-soluble tungsten salt as raw material, using water-soluble polymer as surfactant, using polyalcohol as solvent, uses Thermal decomposition method prepares water-soluble tungsten oxide nanometer particle；

(3) ferriferrous oxide nano-particle, tungsten oxide nanometer particle and polyethyleneimine is taken to carry out in deionized water certainly Group reaction cartridge, obtains ferrotungsten composite oxide nano-crystal cluster.

The ferriferrous oxide nano-particle that step (1) obtains is the ferroso-ferric oxide after the modification of water soluble anion organic matter Nanoparticle, in water phase, negative electrical charge is presented in the nanoparticle surface after the modification.The tungsten oxide nanometer grain that step (2) obtains Son be it is water-soluble polymers decorated after tungsten oxide nanometer particle, in water phase, the nanoparticle surface after the modification is equally in Existing negative electrical charge.And positive charge is presented in polyethyleneimine in water phase, is acted on by electrostatic interaction and macromolecular chain winding, then can make Ferriferrous oxide nano-particle and tungsten oxide nanometer particle form nanometer crystal druse, to successfully synthesize stable ferrotungsten combined oxidation The nanocrystalline cluster of object.

Further, step (1) specifically:

Raw material, surfactant and alkali source are added in solvent, it is 11~12 that alkali source, which is used to control reaction solution pH,；In anaerobic Under the conditions of, 1~3h is stirred to react at a temperature of 40~80 DEG C；Through Magnetic Isolation, washing, deionized water is dispersed by products therefrom In.

In step (1), the molar ratio of ferro element is 1.06:1 in trivalent iron salt and divalent iron salt, and water soluble anion is organic The molar ratio of object and iron ion is 1:(3~10), iron ion includes ferrous ion and ferric ion.

Further, divalent iron salt is preferably Iron dichloride tetrahydrate, green vitriol or ferrous citrate.

Further, trivalent iron salt is preferably ferric chloride hexahydrate, iron sulfate heptahydrate or ironic citrate.

Further, water soluble anion organic matter be preferably sodium citrate, sodium tartrate, disodium ethylene diamine tetraacetate, Sodium ethylene diamine tetracetate, citric acid, tartaric acid or ethylenediamine tetra-acetic acid.

Further, alkali source is preferably ammonium hydroxide, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate liquor or potassium carbonate Solution.The effect of alkali source is to adjust the pH value of reaction solution in the present invention, so that reacting solution pH value control is 11~12.

Further, step (2) specifically:

Tungsten salt and surfactant are added in solvent, under anaerobic, react 20 at a temperature of 160~180 DEG C~ 60min；It is centrifuged, washed again after being cooled to room temperature, dispersed products therefrom in deionized water.

Further, the dosage of water-soluble polymer is the 1%~8% of tungsten salt quality.

Further, tungsten salt is preferably tungsten selenide, ammonium paratungstate, sodium tungstate, tungsten sulfide or tungsten chloride.

Further, water-soluble polymer is preferably polyethylene glycol, polyvinyl alcohol, polyethyleneimine or polyacrylic acid.

Further, polyalcohol is preferably benzyl alcohol, ethylene glycol or diethylene glycol.

Further, step (3) specifically:

Ferriferrous oxide nano-particle, tungsten oxide nanometer particle and polyethyleneimine is taken to be dissolved in deionized water, in inertia ring In border, 3~5h is reacted at room temperature, is centrifuged to obtain ferrotungsten composite oxide nano-crystal cluster.

Further, the molar ratio of taken ferriferrous oxide nano-particle and tungsten oxide nanometer particle is (0.3~3): 1, The dosage of polyethyleneimine is the 3%~15% of ferriferrous oxide nano-particle and tungsten oxide nanometer mass particle sum.

Above-mentioned prepared ferrotungsten composite oxide nano-crystal cluster, ferroso-ferric oxide impart the nanocrystalline cluster weighting Magnetic resonance imaging function, tungsten oxide nanometer particle assign the nanocrystalline cluster CT image enhancement effect, two kinds of imaging mode complementations, So that the nanocrystalline cluster has the dual imaging function of CT and MRI, it can be used as MRI/CT bimodal image-forming contrast medium.

The present invention is using nano ferriferrous oxide and nanometer tungsten oxide as basic material, using the success of electrostatic self-assembled method Prepare uniform particle diameter and the stable ferrotungsten composite oxide nano-crystal cluster of performance.Because nano ferriferrous oxide have compared with Good magnetic resonance imaging effect, nanometer tungsten oxide have stronger X-ray absorption effect, can be used as CT image-forming contrast medium, and two kinds Imaging mode carries out complementation, and there is preferable MR/CT image enhancement effect can effectively improve imaging diagnosis accuracy.

Compared to traditional high-temperature solvent thermal synthesis metal oxide nano-material, present invention low temperature in water phase is synthesized, Method is simple, low in cost, so the ferrotungsten composite oxide nano-crystal cluster of this research preparation has in medical imaging application field There is potential application value.

The nanocrystalline cluster synthesis condition is simple, and biocompatibility is good, and two kinds of imaging modes carry out complementation, has preferable MR/CT image enhancement effect can effectively improve imaging diagnosis accuracy, there is potential application in terms of medical imaging Value.

In short, compared to the prior art, the invention has the advantages that and the utility model has the advantages that

(1) preparation condition is simple, and cost of material is low, and the reaction time is short, is conducive to promote.

(2) as a kind of novel diagnosis and treatment reagent, there are good T2, CT contrasting effects.

(3) preparation compared with small particle nano particle blood halflife with higher, nanoparticle is stablized, low biology poison Property, the potential using value with higher in clinical diagnosis.

Detailed description of the invention

Fig. 1~2 are transmission electron microscope picture of the nanocrystalline cluster under different amplification prepared by embodiment 1；

Fig. 3 is the external T2MRI radiography figure of nanocrystalline cluster prepared by embodiment 1；

Fig. 4 is the external CT radiography figure of nanocrystalline cluster prepared by embodiment 1.

Specific embodiment

The present invention will be further explained with reference to the examples below, as described below, is only to preferable implementation of the invention Example, not limits the present invention, any person skilled in the art is possibly also with the disclosure above Technology contents be changed to the equivalent embodiment changed on an equal basis.Without departing from the concept of the present invention, according to the present invention Technical spirit to following embodiment made it is simple modification or equivalent variations, fall within the scope of protection of the present invention.

The following examples are a further detailed description of the invention.