Alg-cu fe solution and preparation method and use thereof

Abstract

The embodiment of the application provides an Alg-CuFe solution, a preparation method and application thereof, wherein the Alg-CuFe solution comprises the following raw materials: a CuFe solution and a sodium alginate solution with a volume ratio of 1:1; the CuFe solution comprises CuFe nanoparticles and water, the mass concentration of the CuFe nanoparticles in the CuFe solution is 2 mg / mL; the sodium alginate solution comprises sodium alginate and water, the mass concentration of the sodium alginate in the sodium alginate solution is 1.8-2.4%; the Alg-CuFe solution has the beneficial effects of high-efficiency excretion of cesium ions and cesium radiation protection; and is suitable for the technical field of nanomaterials.

Description

Technical Field

[0001] This application relates to the technical field of nanomaterials, specifically to an Alg-CuFe solution, its preparation method, and its uses. Background Technology

[0002] Nuclear contamination accidents and the discharge of radioactive nuclear wastewater have caused serious damage to the ecological environment. The radioactive wastewater contains the radionuclide cesium (Cesium). 137 Cs、 134 Cesium (Cs) is one of the main radioactive elements causing long-term environmental pollution. Once released into the environment, due to its high water solubility and mobility, cesium can enter the human body through multiple pathways, including water, air, soil, and the food chain. Ingested cesium ions are excreted into the intestines via blood circulation and can be reabsorbed into the blood, bones, and soft tissues. Long-term internal irradiation can lead to severe organ damage and even cancer. The toxic mechanisms of radionuclides mainly include chemical toxicity and radiotoxicity. Cesium's chemical properties are very similar to potassium, and it competitively absorbs cesium, causing osmotic pressure disturbances and generating large amounts of reactive oxygen species (ROS), further exacerbating cellular damage. Therefore, the treatment of internal radionuclide contamination not only requires promoting the excretion of radionuclides to prevent them from entering tissues but also clearing excess ROS to reduce radiation damage. Therefore, developing novel "highly effective excretion-promoting + radiation protection" synergistic therapeutic drugs is of great significance for the treatment of internal radionuclide contamination.

[0003] To address the aforementioned issues, a method for preparing and applying magnetic Prussian blue particles has been proposed. This method involves adding an aqueous solution of ferric salt and ferricyanide to ethylene glycol in the presence of polyethylene glycol, acetate, and anionic surfactant, followed by a closed reaction at 180-200°C. This yields magnetic Prussian blue particles, a highly selective and biocompatible cesium adsorbent, which are then used for the adsorption of cesium ions in blood. Another method for preparing and applying a water-soluble Prussian blue / parotide composite material has been proposed. This method involves placing palladium, sodium alginate, and water in a three-necked flask and stirring vigorously to obtain a dispersed suspension. The suspension is then mixed with water-soluble Prussian blue and subjected to a hydrothermal reaction in a polytetrafluoroethylene (PTFE) liner. After standing, centrifugation, and drying, the water-soluble Prussian blue / parotide composite material is obtained and added as an additive to feed. As a feed additive to promote excretion, it can significantly reduce cesium ion levels in freshwater fish by approximately 15-24%.

[0004] In summary, recent studies have focused on the role of Prussian blue in promoting cesium excretion, but not on reducing radiation damage. Summary of the Invention

[0005] To solve one of the above technical defects, the application provides an Alg-CuFe solution, a preparation method and application thereof.

[0006] According to a first aspect of the application, an Alg-CuFe solution is provided, comprising the following raw materials: a CuFe solution and a sodium alginate solution in a volume ratio of 1:1; the CuFe solution comprises CuFe nanoparticles and water, and the mass concentration of the CuFe nanoparticles in the CuFe solution is 2 mg / mL; the sodium alginate solution comprises sodium alginate and water, and the mass concentration of the sodium alginate in the sodium alginate solution is 1.8-2.4%.

[0007] Preferably, the mass percentage of copper in the CuFe nanoparticles is 16-18.2%, and the mass percentage of iron is 7.7-9.3%.

[0008] More preferably, the particle size of the CuFe nanoparticles is 60-100 nm, and the hydration particle size of the CuFe nanoparticles is 75-120 nm.

[0009] Preferably, the CuFe nanoparticles comprise the following raw materials in a molar ratio: potassium ferricyanide: citric acid: copper salt = 0.04:10:0.06; the concentration of the potassium ferricyanide is 2.8-3.2 mM, the concentration of the citric acid is 230-260 mM, and the concentration of the copper salt is 2.8-3.2 mM.

[0010] Preferably, the citric acid is anhydrous citric acid or monohydrate citric acid.

[0011] Preferably, the copper salt is Cu(CH3COO)2·H2O.

[0012] According to a second aspect of the application, a preparation method of the Alg-CuFe solution is provided, comprising the following steps:

[0013] S10, preparing CuFe nanoparticles:

[0014] S101, dissolving potassium ferricyanide and half of the citric acid in 20 ml of water, heating to 60°C and stirring at a speed of 800-1200 rpm until completely dissolved to obtain solution A;

[0015] S102, dissolving the copper salt and the other half of the citric acid in 20 ml of water, vortexing to completely dissolve to obtain solution B;

[0016] S103, adding solution B into solution A at a rate of 1.8-2.2 mL / min, the adding time is 5-30 min, the adding process is treated with constant temperature of 60℃, and stirring at a rate of 800-1200 rpm, after the adding is completed, continue to stir, to obtain solution C;

[0017] S104, stirring solution C at a rate of 800-1200 rpm and cooling to room temperature for 20-60 min;

[0018] S105, then obtaining CuFe nanoparticles by first centrifugation, resuspension, detergent washing, second centrifugation, and drying;

[0019] S20, preparing a CuFe solution: dissolving CuFe nanoparticles in water to obtain a CuFe solution;

[0020] S30, preparing a sodium alginate solution: dissolving sodium alginate in water to obtain a sodium alginate solution;

[0021] S40, blending CuFe solution and sodium alginate solution in equal volume and stirring at a rate of 500-800 rpm for 6-12 hours to obtain an Alg-CuFe solution.

[0022] Preferably, the first centrifugation and the second centrifugation in step S105 are both: centrifugation treatment at a rate of 9000-15000 rpm for 8-10 min, the centrifugation temperature is 25℃-30℃; the drying in step S105 specifically includes: vacuum drying treatment at a temperature of 40℃-60℃ overnight or for 12 hours.

[0023] Preferably, the detergent in step S105 includes: ethanol and ultrapure water in a volume ratio of 1:1.

[0024] According to a third aspect of the embodiments of the present application, there is provided an application of the Alg-CuFe solution in cesium detoxification.

[0025] The CuFe nanoparticles in the Alg-CuFe solution provided in the embodiments of the present application replace the iron in Prussian blue (PB) by the transition metal Cu to form Prussian blue analogs (PBAs), and the PBAs can also treat the seawater contaminated by the radionuclide cesium because the PBAs have a similar chemical structure to the PB. Meanwhile, the Alg-CuFe solution provided in the embodiments of the present application can not only efficiently promote the excretion of cesium ions, but also can remove the active oxygen induced by the radionuclide cesium because the PBAs have multiple anti-oxidative enzyme activities, thereby reducing the radiation damage induced by the internal pollution of the radionuclide cesium. The radiation protection of cesium is realized while the cesium ions are efficiently promoted to be excreted. BRIEF DESCRIPTION OF DRAWINGS

[0026] The accompanying drawings, which are included to provide a further understanding of the present application and are incorporated in and constitute a part of this application, illustrate embodiments of the present application and serve to explain the principles of the present application, and do not limit the present application in any manner. In the drawings:

[0027] Figure 1 A structural schematic diagram of the CuFe nanoparticles provided in the embodiments of the present application;

[0028] Figure 2 A transmission electron microscope characterization result diagram of the CuFe nanoparticles provided in Embodiment One of the present application;

[0029] Figure 3 A scanning electron microscope characterization result diagram of the CuFe nanoparticles provided in Embodiment One of the present application;

[0030] Figure 4 An XRD characterization result diagram of the CuFe nanoparticles provided in Embodiment One of the present application;

[0031] Figure 5 An infrared spectrometer characterization result diagram of the CuFe nanoparticles provided in Embodiment One of the present application;

[0032] Figure 6 A dynamic light scattering instrument characterization result diagram of the CuFe nanoparticles provided in Embodiment One of the present application;

[0033] Figure 7 An ESR characterization result diagram of the CuFe nanoparticles provided in Embodiment One of the present application;

[0034] Figure 8 An XPS instrument characterization result diagram of the CuFe nanoparticles provided in Embodiment One of the present application;

[0035] Figure 9The CuFe nanoparticle provided for Comparative Example 1 of the present application is characterized by transmission electron microscopy, and the result is shown in the figure;

[0036] Figure 10 The CuFe nanoparticle provided for Comparative Example 2 of the present application is characterized by transmission electron microscopy, and the result is shown in the figure;

[0037] Figure 11 The Prussian blue or Prussian blue analog provided for Reference Example 1 to Reference Example 4 of the present application is characterized by transmission electron microscopy, and the result is shown in the figure;

[0038] Figure 12 The difference in cesium ion adsorption capacity of Prussian blue or Prussian blue analogs provided for the examples and reference examples of the present application is shown in the result figure;

[0039] Figure 13 The effect of Prussian blue or Prussian blue analogs provided for Example 1, Reference Example 1, and Reference Example 4 of the present application on the viability of HUVEC cells is shown in the result figure;

[0040] Figure 14 The effect of CuFe nanoparticles provided for Example 1 of the present application on the removal of reactive oxygen species is shown in the figure;

[0041] Figure 15 The results of the anti-oxidative damage of CuFe nanoparticles provided for Example 1 of the present application at the cellular level are shown in the figure;

[0042] Figure 16 The results of the efficiency of Alg-CuFe solution provided for Example 1 of the present application in different treatment groups for cesium mobilization are shown in the figure;

[0043] Figure 17 The pathological picture of H&E staining of the gastrointestinal tract by Alg-CuFe solution provided for Example 1 of the present application under a microscope is shown in the figure. DETAILED DESCRIPTION

[0044] In order to make the technical solutions and advantages of the embodiments of the present application clearer, the exemplary embodiments of the present application are further described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all the embodiments. It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict.

[0045] To solve the above problems, the Alg-CuFe solution provided in the embodiments of the present application includes the following raw materials: CuFe solution and sodium alginate solution in a volume ratio of 1:1; the CuFe solution includes CuFe nanoparticles and water, and the mass concentration of the CuFe nanoparticles in the CuFe solution is 2 mg / mL; the sodium alginate solution includes sodium alginate and water, and the mass concentration of the sodium alginate in the sodium alginate solution is 1.8-2.4%.

[0046] Further, the CuFe nanoparticles include the following raw materials in a molar ratio: potassium ferricyanide: citric acid: copper salt = 0.04:10:0.06; the concentration of the potassium ferricyanide is 2.8-3.2 mM, the concentration of the citric acid is 230-260 mM, and the concentration of the copper salt is 2.8-3.2 mM.

[0047] Figure 1 A structural schematic diagram of the CuFe nanoparticles provided in the embodiments of the present application is shown in FIG. 1. Figure 1 Specifically, the CuFe nanoparticles are Prussian blue analogs Cu3[Fe(CN)6]2.

[0048] The CuFe nanoparticles in the Alg-CuFe solution provided in the embodiments of the present application replace the iron in Prussian blue (PB) with transition metal Cu to form Prussian blue analogs (PBAs). Since the PBAs have a similar chemical structure to the PB, the PBAs can also be used to treat seawater contaminated with the radionuclide cesium. Meanwhile, the Alg-CuFe solution provided in the embodiments of the present application can not only efficiently promote the excretion of cesium ions, but also can remove the active oxygen induced by the radionuclide cesium due to the multiple anti-oxidative enzyme activities of the PBAs, thereby reducing the radiation damage induced by the internal pollution of the radionuclide cesium. The Alg-CuFe solution provided in the embodiments of the present application can achieve efficient promotion of the excretion of cesium ions while performing cesium radiation protection.

[0049] Further, the citric acid is anhydrous citric acid or monohydrate citric acid.

[0050] Further, the copper salt is Cu(CH3COO)2·H2O.

[0051] Further, the mass percentage of the copper element in the CuFe nanoparticles is 16%-18.2%, and the mass percentage of the iron element is 7.7%-9.3%.

[0052] Further, the CuFe nanoparticles have a particle size of 60-100 nm; and the CuFe nanoparticles have a hydrated particle size of 75-120 nm. The CuFe nanoparticles prepared in the present application have a particle size of 60-100 nm, which makes the prepared CuFe nanoparticles have good biocompatibility, improves the use effect, and reduces the toxic effect on cells.

[0053] Embodiment One

[0054] The present application provides a preparation method of an Alg-CuFe solution, which comprises the following steps:

[0055] S10, preparing CuFe nanoparticles:

[0056] S101, dissolving 0.04 mmol of potassium ferricyanide and 5 mmol of citric acid in 20 ml of water, heating to 60°C and stirring at a speed of 800-1200 rpm until completely dissolved to obtain solution A;

[0057] S102, dissolving 0.06 mmol of Cu(CH3COO)2·H2O and 5 mmol of citric acid in 20 ml of water, vortexing to completely dissolve to obtain solution B;

[0058] S103, adding solution B to solution A at a rate of 2 mL / min, the adding time is 10 min, and the solution color gradually changes to yellow during the adding process; after the adding is completed, continue to stir for 5 min to obtain solution C;

[0059] S104, stirring solution C at a speed of 800-1200 rpm and cooling to room temperature for 30 min;

[0060] S105, then obtaining CuFe nanoparticles by first centrifugation, resuspension, detergent washing, second centrifugation, and drying;

[0061] S20, preparing a CuFe solution: dissolving CuFe nanoparticles in water to obtain a CuFe solution with a concentration of 2 mg / mL;

[0062] S30, preparing a sodium alginate solution: dissolving sodium alginate in water to obtain a sodium alginate solution with a mass concentration of 2%;

[0063] S40, blending the CuFe solution and the sodium alginate solution in equal volumes and stirring at a speed of 500-800 rpm for 6-12 hours to obtain an Alg-CuFe solution.

[0064] Since the preparation method provided in the present application includes the same raw materials as the above-mentioned Alg-CuFe solution, it can be considered to have the same effect as the above-mentioned Alg-CuFe solution, and will not be described here.

[0065] The performance of the CuFe nanoparticles prepared in Example 1 of the present application was determined: the Alg-CuFe nanoparticles prepared in Example 1 of the present application were characterized by transmission electron microscopy, scanning electron microscopy, XRD, infrared spectrometer, dynamic light scattering instrument, ICP-OES instrument, ESR, and XPS instrument, respectively.

[0066] Figure 2 The characterization results of the CuFe nanoparticles provided in Example 1 of the present application by transmission electron microscopy are shown in FIG. 1. Figure 3 The characterization results of the CuFe nanoparticles provided in Example 1 of the present application by scanning electron microscopy are shown in FIG. 2. Figure 2 And Figure 3 As shown in FIGS. 1 and 2, the particle size of the CuFe nanoparticles is between 60-100 nm.

[0067] Figure 4 The characterization results of the CuFe nanoparticles provided in Example 1 of the present application by XRD are shown in FIG. 3. Figure 4 As shown in FIG. 3, the peaks of the CuFe nanoparticles are consistent with the standard pattern of face-centered cubic PB NPs (JCPDS No. 73-0687), and no other impurities are detected.

[0068] Figure 5 The characterization results of the CuFe nanoparticles provided in Example 1 of the present application by infrared spectrometer are shown in FIG. 4. Figure 5 As shown in FIG. 4, the range of 2000-2200 cm-1 corresponds to the vibration peak of v(M1-C≡N-M2). The other two characteristic peaks in the range of 490-600 cm-1 belong to the vibration absorption peaks of Fe-C≡N and C≡N-m2. -1 -1

[0069] As can be seen from the above, Figures 2 to 5 the CuFe nanoparticles prepared in Example 1 of the present application are nanometer cubic particles.

[0070] Figure 6 The characterization results of the CuFe nanoparticles provided in Example 1 of the present application by dynamic light scattering instrument are shown in FIG. 5. Figure 6 As shown in FIG. 5, the hydration particle size of the CuFe nanoparticles is 75-120 nm.

[0071] Quantitative analysis by ICP-OES instrument showed that the mass percentage of copper element in the CuFe nanoparticles prepared in Example 1 of the present application was 18.2%, and the mass percentage of iron element was 9.3%. ​​

[0072] Figure 7 The ESR characterization result graph of the CuFe nanoparticles provided by the embodiment one of the application is shown in Figure 2, and the CuFe nanoparticles prepared by the embodiment one of the application show characteristic paramagnetic peaks, indicating that there are defect sites in the crystal structure of CuFe. Figure 7

[0073] The XPS characterization result graph of the CuFe nanoparticles provided by the embodiment one of the application is shown in Figure 3, and according to the XPS result, the chemical composition of the CuFe nanoparticles is Cu3[Fe(CN)6]2, indicating that there is a [Fe(CN)6] missing linker in the crystal structure of CuFe. Figure 8 Figure 8

[0074] Further, the first centrifugation and the second centrifugation in the step S105 are both: centrifugation treatment at a rate of 10000 rpm for 10 min, and the centrifugation temperature is 25-30°C; the drying in the step S105 specifically includes: vacuum drying treatment at a temperature of 40°C overnight.

[0075] Further, the detergent in the step S105 includes: 20 ml of ethanol and 20 ml of ultrapure water.

[0076] Specifically, the molecular weight of sodium alginate is 222.

[0077] More specifically, the constant temperature treatment in the step S103 is water bath or oil bath heating. The water bath or oil bath heating is more uniform, and can meet the use requirement of constant temperature.

[0078] More specifically, the total volume of the mixed CuFe solution and sodium alginate solution is 5-10 mL.

[0079] Comparative Example One

[0080] The difference between the method for preparing the Alg-CuFe solution in the comparative example one and the above-mentioned embodiment one is that the stirring rate in the step S103 is 600 rpm. The rest of the reaction conditions are the same as those in the embodiment one.

[0081] The CuFe nanoparticles prepared in the comparative example one are characterized by using a transmission electron microscope, Figure 9 The transmission electron microscope characterization result graph of the CuFe nanoparticles provided by the comparative example one of the application is shown in Figure 4, and when the stirring rate in the step S103 is slowed down, the morphology of the CuFe nanoparticles becomes irregular, and presents irregular shapes as shown in Figure 4. Figure 9 Figure 9

[0082] Comparative Example Two ​​​​

[0083] The method for preparing the Alg-CuFe solution in Comparative Example Two is different from that in Example One in that the stirring in step S103 is at a rate of 500 rpm. The rest of the reaction conditions are the same as in Example One.

[0084] The CuFe nanoparticles prepared in Comparative Example Two were characterized using a transmission electron microscope, Figure 10 The characterization results of the CuFe nanoparticles prepared in Comparative Example Two using a transmission electron microscope are shown in FIG. 2. As shown in FIG. 2, the particle size of the CuFe nanoparticles is larger when the stirring rate in step S103 is slower. Figure 10

[0085] From the above Comparative Examples One and Two, it can be seen that the stirring rate of 800 rpm in step S103 of the present application has the best effect, and the CuFe nanoparticles have a regular morphology and a particle size of 60-100 nm.

[0086] The present application also provides other Prussian blue or Prussian blue analogues. Examples One to Four were prepared in accordance with the following Reference Examples One to Four, respectively: FeFe nanoparticles, NiFe nanoparticles, CoFe nanoparticles, and MnFe nanoparticles. The specific preparation conditions of each of the Reference Examples are different from the preparation conditions of Example One, as shown in Table 1 below, and the rest of the reaction conditions are the same as in Example One.

[0087] Table 1

[0088]

[0089] The Prussian blue or Prussian blue analogues prepared in Reference Examples One to Four were characterized using a transmission electron microscope, Figure 11 The characterization results of the Prussian blue or Prussian blue analogues prepared in Reference Examples One to Four using a transmission electron microscope are shown in FIG. 3. As shown in FIG. 3, the particle size of the Prussian blue or Prussian blue analogues prepared in Reference Examples One to Four is also 60-120 nm, and the hydrated particle size is 75-140 nm. In addition, the FeFe nanoparticles prepared in Reference Example One were characterized using XRD, dynamic light scattering, and ESR, and the characterization results are shown in FIGs. 4, Figure 11 Figure 4 Figure 5 Figure 7

[0090] The differences in the adsorption capacity of the Prussian blue or Prussian blue analogues prepared in Reference Examples One to Four for cesium ions and the effects on cell viability were observed.

[0091] Experiment One: Difference in the adsorption capacity of cesium ions between Example One and each of the Reference Examples

[0092] ​​​​​The adsorption effect of Prussian blue or Prussian blue analogues prepared in Example 1 and various reference examples on cesium was determined as follows: Appropriate amounts of Prussian blue or Prussian blue analogue nanoparticles were weighed into water to prepare a stock solution with a concentration of 2 mg / ml, and ultrasonicated to ensure complete dispersion. Then, appropriate amounts of cesium ion solution and the stock solution were added to water, with a total volume of 1 ml, where the cesium ion concentration and the stock solution concentration were 100 μg / ml and 500 μg / ml, respectively. The solution was then placed in a metal bath and shaken at 37°C and 500 rpm for 1 h, 2 h, 6 h, and 12 h. Afterward, the supernatant was collected by centrifugation at 15000 rpm, filtered through a 0.22 μm filter, and diluted 1000 times with deionized water. Finally, the concentration of cesium ions in the sample was determined by ICP-MS.

[0093] Figure 12 This is a graph showing the differences in the adsorption capacity of Prussian blue or Prussian blue analogues for cesium ions prepared in the embodiments and reference examples of this application. Figure 12 As shown, the adsorption capacity of the mother liquor prepared with Prussian blue or Prussian blue analogues for cesium ions varies. Within the same reaction time, MnFe nanoparticles showed the best adsorption effect for cesium ions, reaching 140 mg / g, followed by CuFe nanoparticles, CoFe nanoparticles, NiFe nanoparticles, and FeFe nanoparticles. This demonstrates that by replacing the divalent metal Fe in FeFe nanoparticles with other transition metals during the composition optimization process, the adsorption capacity of Prussian blue analogues for cesium ions can be significantly improved.

[0094] Experiment 2: Effects of Example 1, Reference Example 1, and Reference Example 4 on Cell Viability

[0095] The effect of Prussian blue or Prussian blue analog nanoparticles prepared in Example 1 and various reference examples on cell viability was determined as follows:

[0096] 1) Cell Culture

[0097] HUVEC cells were cultured in DMEM or 1640 liquid medium containing 10% fetal bovine serum and placed in a cell culture incubator at 37°C and 5% CO2.

[0098] 2) Cell viability assay

[0099] In a 96-well plate, the inoculation density is 5 × 10⁻⁶ per well. 3HUVEC cells were cultured for 24 h at 37℃ in a constant temperature incubator with 5% CO2. Experimental groups were set up by adding different concentrations of FeFe nanoparticles, CuFe nanoparticles and MnFe nanoparticles, respectively, for co-culturing, with concentrations of 50, 100, 200 and 300 μg / mL, and three replicate wells for each concentration. A control group was set up without adding Prussian blue or Prussian blue analogue nanoparticles. The 96-well plate was placed in a constant temperature incubator at 37℃ with 5% CO2 for further incubation for 24 h. After the incubation, the supernatant was removed, and fresh culture medium containing CCK-8 (V / V = 1 / 1) was added. The plate was placed in the incubator for 4 h, and the absorbance OD at 450 nm was detected by an enzyme labeler.

[0100] Figure 13 Fig. 1 is a graph showing the effect of Prussian blue or Prussian blue analogue prepared in Embodiment One, Reference Example One and Reference Example Four on the activity of HUVEC cells, as shown in the following table. Figure 13 As shown in Fig. 1, the cell activity of HUVEC cells in the experimental groups was greater than 90% in different concentrations of FeFe nanoparticles and CuFe nanoparticles, indicating that FeFe nanoparticles and CuFe nanoparticles had no toxicity to HUVEC cells, while MnFe nanoparticles had a greater impact on the activity of HUVEC cells.

[0101] Based on the above-mentioned Experimental One and Experimental Two, the CuFe nanoparticles prepared in Embodiment One not only have a high adsorption capacity for cesium ions, but also have no toxicity to HUVEC cells, and are relatively safe.

[0102] The present application also provides Experimental Three to Experimental Six to prove that 1, the CuFe nanoparticles prepared in the present application have a strong active oxygen scavenging capacity; 2, the CuFe nanoparticles can effectively reduce the radiation damage caused by the radionuclide cesium, expand the function of the chelating agent, make up for the deficiency of medical Prussian blue, and provide a new idea for developing a radioactive cesium internal contamination drug; 3, the Alg-CuFe solution prepared in the present application has a higher cesium chelating effect and can organize the deposition of cesium in tissues and organs.

[0103] Experimental Three: Determination of the scavenging effect of CuFe nanoparticles prepared in Embodiment One on active oxygen

[0104] H2O2 scavenging activity determination: CuFe nanoparticles were mixed with 0.1-100 mM H2O2 of different concentrations and incubated at 30℃ for 1 min. After the incubation, the residual H2O2 was detected by horseradish peroxidase-3,3',5,5'-tetramethylbenzidine (HRP-TMB) cascade reaction, and the consumption of H2O2 was determined, and the determination results are shown in Fig. 2(a). Figure 14

[0105] ​The scavenging activity of O2 ·- was measured by using nitro blue tetrazolium (NBT) total superoxide dismutase assay kit. Then EPR spectrum measurement was performed to evaluate the scavenging ability of CuFe nanoparticles on reactive oxygen species. EPR spectrum measurement: reaction mixture containing 0.1 M BMPO, CuFe nanoparticles, 1 mM xanthine and 0.1 U / mL xanthine oxidase (XOD) was prepared. Xan / XOD generated O2 ·- , and the ability of CuFe nanoparticles cubic to scavenge O2 ·- was tested. ESR spectrum was taken two minutes after the introduction of XOD to start the generation of superoxide, in order to evaluate the scavenging effect of CuFe nanoparticles on O2 ·- , as shown in Figure 14 (b)、 Figure 14 (c).

[0106] To evaluate the scavenging ability of CuFe nanoparticles on hydroxyl radical (·OH), reaction mixture containing 0.1 M BMPO, CuFe nanoparticles, 0.02 mM Fe 2+ and 100 mM H2O2 was prepared. Fe 2+ and H2O2 reacted to generate ·OH, and the ability of CuFe nanoparticles cubic to scavenge ·OH was tested. ESR spectrum was used to evaluate the scavenging effect of CuFe on ·OH two minutes after the introduction of H2O2 to start the generation of ·OH, as shown in Figure 14 (d).

[0107] Figure 14 Figures showing the scavenging effect of CuFe nanoparticles on reactive oxygen species provided in Example One of the present application, Figure 14 (a) is a result graph of the scavenging rate of CuFe nanoparticles on hydrogen peroxide, Figure 14 (b) and Figure 14 (c) are respectively result graphs of CuFe nanoparticles on superoxide anion, Figure 14 (d) is a scavenging effect of CuFe nanoparticles on hydroxyl radical, as shown in Figure 15 , CuFe nanoparticles at different concentrations all have good H2O2, O2 ·- , ·OH scavenging ability.

[0108] Experiment Four: The effect of CuFe nanoparticles prepared in Example One of the present application on oxidative stress cell model was determined

[0109] HUVEC cells were inoculated in 96-well plates, 5×10 3Cells were seeded in 96-well plates at 5 x 104cells per well and cultured for 24 h. The culture medium was then replaced with fresh medium containing 1 mM H2O2and 50-100 μg / mL CuFe nanoparticles. After 24 h of incubation, cell viability was detected using a CCK-8 kit.

[0110] Anti-radiation damage experiment: L02 cells were seeded in 96-well plates at 5 x 104cells per well and cultured for 24 h. The cells were then incubated in medium containing 10-20 μg / mL CuFe nanoparticles for 4 h, and then irradiated with an 8 Gy dose of x-ray irradiation equipment. The irradiated cells were incubated for 24 h, and cell viability was detected using a CCK-8 kit. 3

[0111] Figure 15 The anti-oxidative damage results of the CuFe nanoparticles provided in Example One of the present application at the cellular level are shown in FIGS. Figure 15 (a). Compared with the blank control group, 1 mM H2O2treatment for 24 h significantly increased cell toxicity. However, with the help of CuFe nanoparticles, the cell survival rate was increased by about 25%-40%. In addition, using DCFH-DA as a fluorescent probe, the intracellular ROS level was evaluated, as shown in FIG. Figure 16 (b). Compared with the control group, the fluorescence intensity was significantly reduced in the presence of CuFe nanoparticles, indicating that CuFe had an effective active oxygen scavenging effect. In addition, under X-ray irradiation, the introduction of CuFe can improve the survival rate of cells. The above results collectively indicate that CuFe nanoparticles not only can effectively eliminate ROS, but also can reduce oxidative stress damage, thereby protecting cells from the damaging effects of ionizing radiation.

[0112] Experiment Five: The Cs-removal promotion of the Alg-CuFe solution provided in Example One of the present application in different treatment groups

[0113] Selection and culture of experimental animals: Female balb / c mice were randomly divided into 3 groups, 6 mice in each group. Two groups were experimental groups, and one group was a control group. The three groups were all injected with a cesium ion solution with a concentration of 100 ug / kg by gavage. After 20 min, the mice in the two experimental groups were injected with 20 mg / kg of Alg-FeFe solution or 20 mg / kg of Alg-CuFe solution in PBS solution by gavage. The control group mice were injected with pure PBS solution. The mice were normally fed and during the feeding period, the feces and urine of the mice were collected by metabolic cages at 1 h, 2 h, 4 h, 6 h, 12 h, 24 h, 48 h, 72 h, and 96 h. After that, the feces, urine, and various organs and blood were transferred to conical bottles, 3 ml of hydrochloric acid and 1 ml of nitric acid were added for digestion overnight. The next day, the digestion was further digested and the acid was chased using a digestion table. The obtained solution was diluted to 15 ml by weighing method, and filtered using a 220 nm water system filter head. The cesium concentration was determined by ICP-MS.​

[0114] Figure 16 The results of the efficiency of the Alg-CuFe solution provided by the embodiment one of the present application on cesium excretion in different treatment groups are shown in the following figure: Figure 17 As shown in the figure, compared with the PBS control group and the Alg-FeFe Prussian blue group, the Cs content excreted through feces in the Alg-CuFe group is higher, which confirms the adsorption of Alg-CuFe in the intestinal tract. The Alg-CuFe promotes the rapid excretion of Cs, especially in the time intervals of 1-2 hours, 2-4 hours and 4-6 hours, the excretion rates of Cs are 18.6%, 17.8% and 12.3% respectively, while the fecal excretion rates of the Alg-FeFe Prussian blue group in the corresponding time intervals are lower, only 13.4%, 7.6% and 1.69% respectively. In addition, compared with the Alg-FeFe Prussian blue group, the cumulative fecal excretion rate and the total excretion rate of the Alg-CuFe group are higher. In addition, the Cs contents in the heart, liver, spleen, lung, kidney and muscle of the Alg-CuFe group treatment group are 26.2 ng / g, 12.52 ng / g, 20.4 ng / g, 20.4 ng / g, 39.65 ng / g and 45.59 ng / g respectively, which are lower than the corresponding values of the Alg-FeFe Prussian blue treatment group.

[0115] Experiment six: the effect of the Alg-CuFe solution provided by the embodiment one of the present application on the structural changes of organs and tissues such as gastrointestinal tract after cesium excretion treatment

[0116] Taking the Alg-CuFe solution prepared in the embodiment one as an example, after the cesium excretion experiment in experiment five is completed, the heart, liver, spleen, lung, kidney, stomach and duodenum of the mouse are taken out, fixed with 4% paraformaldehyde solution, embedded with paraffin, sliced, H&E stained and subjected to pathological analysis under a microscope.

[0117] Figure 17 The pathological figures of H&E staining of gastrointestinal tract under a microscope for the Alg-CuFe solution provided by the embodiment one of the present application are shown in the following figure: ​ As shown in the figure, the H&E staining results of the gastrointestinal tract are all normal histomorphology.

[0118] The present application also provides an application of the Alg-CuFe solution in cesium detoxification.

[0119] In addition, the terms "first", "second" are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first", "second" can explicitly or implicitly include one or more of the features. In the description of the present application, the meaning of "multiple" is at least two, for example, two, three, etc., unless otherwise specifically limited.

[0120] While the preferred embodiments of the application have been described, additional variations and modifications can be made to the embodiments by those skilled in the art once they learn of the basic inventive concepts. Therefore, the appended claims are intended to encompass within their scope all such variations and modifications as are included within the spirit and scope of the application.

[0121] It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the application. Thus, it is intended that the present application cover the modifications and variations of this application provided they come within the scope of the appended claims and their equivalents.

Claims

1. Use of an Alg-CuFe solution for the preparation of a cesium detoxifying medicament, characterized in that, The Alg-CuFe solution comprises the following raw materials: CuFe solution and sodium alginate solution in a volume ratio of 1:1; The CuFe solution comprises CuFe nanoparticles and water, the mass concentration of the CuFe nanoparticles in the CuFe solution is 2 mg / mL; the particle size of the CuFe nanoparticles is 60-100 nm; the hydrated particle size of the CuFe nanoparticles is 75-120 nm; the CuFe nanoparticles are Prussian blue analog Cu3[Fe(CN)6]2; The sodium alginate solution comprises sodium alginate and water, the mass concentration of the sodium alginate in the sodium alginate solution is 1.8-2.4%.

2. Use of the Alg-CuFe solution according to claim 1 for the preparation of a cesium detoxifying medicament, characterized in that, The mass percentage of copper element in the CuFe nanoparticles is 16%-18.2%, and the mass percentage of iron element is 7.7%-9.3%.

3. Use of the Alg-CuFe solution according to claim 2 for the preparation of a cesium detoxifying medicament, characterized in that, The preparation of the CuFe nanoparticles comprises the following raw materials in a molar ratio: potassium ferricyanide: citric acid: copper salt = 0.04:10:0.06; The concentration of the potassium ferricyanide is 2.8-3.2 mM, the concentration of the citric acid is 230-260 mM, and the concentration of the copper salt is 2.8-3.2 mM.

4. Use of the Alg-CuFe solution according to claim 3 for the preparation of a cesium detoxifying medicament, characterized in that, The citric acid is anhydrous citric acid or monohydrate citric acid.

5. Use of the Alg-CuFe solution according to claim 3 for the preparation of a cesium detoxifying medicament, characterized in that, The copper salt is Cu(CH3COO)2·H2O.

6. Use of the Alg-CuFe solution according to any one of claims 1 to 5 for the preparation of a cesium detoxifying medicament, characterized in that, The preparation of the Alg-CuFe solution comprises the following steps: S10, preparing CuFe nanoparticles: S101, dissolving potassium ferricyanide and half of the citric acid in 20 ml of water, heating to 60°C and stirring at a speed of 800-1200 rpm until completely dissolved to obtain solution A; S102, dissolving the copper salt and the other half of the citric acid in 20 ml of water, vortexing to completely dissolve to obtain solution B; S103, adding solution B to solution A at a rate of 1.8-2.2 mL / min, the addition time is 5-30 min, and a constant temperature of 60°C is used during the addition process, and stirring is carried out at a speed of 800-1200 rpm, and after the addition is completed, the stirring is continued, to obtain solution C; S104, stirring solution C at a speed of 800-1200 rpm and cooling to room temperature for 20-60 min; S105, then obtaining CuFe nanoparticles by first centrifugation, resuspension, detergent washing, second centrifugation, and drying; S20, preparing a CuFe solution: dissolving CuFe nanoparticles in water to obtain a CuFe solution; S30, preparing a sodium alginate solution: dissolving sodium alginate in water to obtain a sodium alginate solution; S40, blending the CuFe solution and the sodium alginate solution in equal volumes and stirring at a speed of 500-800 rpm for 6-12 hours to obtain an Alg-CuFe solution.

7. Use of the Alg-CuFe solution of claim 6 in the preparation of a cesium detoxification drug, characterized in that, In the step S105, both the first centrifugation and the second centrifugation are: centrifuging at a speed of 9000-15000 rpm for 8-10 min, and the centrifugation temperature is 25°C-30°C; The drying in the step S105 specifically includes: vacuum drying treatment at a temperature of 40-60 DEG C overnight or for 12 hours.

8. Use of the Alg-CuFe solution according to claim 7 for the preparation of a cesium detoxifying medicament, characterized in that, The washing agent in the step S105 includes: ethanol and ultrapure water in a volume ratio of 1:1.

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