WO2018090406A1

WO2018090406A1 - Method for removing cesium ion in blood

Info

Publication number: WO2018090406A1
Application number: PCT/CN2016/108647
Authority: WO
Inventors: 华道本; 钱骏
Original assignee: 苏州大学
Priority date: 2016-11-16
Filing date: 2016-12-06
Publication date: 2018-05-24
Also published as: CN106730994B; CN106730994A

Abstract

A method for removing cesium ions in blood belongs to the field of blood purification and nuclear medicine emergency. The method comprises the following steps: in the presence of polyethylene glycol, an acetate salt and an anionic surfactant, adding a trivalent ferric salt and an aqueous ferricyanide solution into ethylene glycol, and performing a closed reaction at a temperature of 180-200℃, so as to obtain magnetic Prussian Blue particles; dispersing the magnetic Prussian Blue particles in blood; and after adsorption equilibrium, separating from blood the magnetic Prussian Blue particles that have adsorbed cesium ions. The adsorbent having high selectivity and biocompatibility prepared by the method can be used for adsorbing cesium ions in blood. The method is characterized by being efficient and rapid. Cesium ions in blood can be more accurately measured using ICP-MS.

Description

Method for removing strontium ions in blood

Technical field

The invention relates to the field of blood purification and nuclear medicine emergency, in particular to a method for removing barium ions in blood.

Background technique

In 2011, the accident at the Fukushima nuclear power plant caused a large amount of radioactive waste leakage, especially the leakage and pollution of ¹³⁷ Cs. As a main component of radioactive waste liquid, ¹³⁷ Cs has a long half-life (30 years), high volatility, high activity and high solubility, and it is easy to migrate in the environment. Helium ions can enter the human body through the food chain, causing teratogenic, carcinogenic, mutagenic effects, etc., endangering human health. Moreover, the metabolic half-life of strontium ions in humans takes at least 70 days. Therefore, it is of great strategic significance to study the effective removal of barium ions in human blood.

At present, the method for removing barium ions in an aqueous solution is usually to disperse the adsorbent in a water body, and after the adsorption is balanced, the adsorbent is separated. The choice of adsorbents is mainly concentrated in crown ethers, calixarene and composite materials. The method for promoting the excretion of cesium ions by the organism usually involves the introduction of the stimulating drug into the living body by feeding, and after a few days, the action of removing strontium ions in the living body is achieved, and the selection of the stimulating drug is mainly concentrated in the Prussian blue and the alginate. In matter.

However, there has been no effective method for removing strontium ions in the blood to date. This is due to the complex blood environment, which contains various types of blood cells, enzymes, ions, etc., which have high requirements on the biocompatibility, dispersibility, cesium ion selectivity and adsorption efficiency of the materials. Due to these limitations, the materials and methods currently used for the removal of barium ions in aqueous solutions are not suitable for the removal of barium ions in the blood. In addition, although the drug-releasing drug has a high removal rate of strontium ions in the living body, it takes a long time (it takes several days to several weeks), and it is not as efficient and rapid as to directly carry out blood adsorption to remove the strontium ions therein.

The prior art generally uses a flame atomic absorption spectrophotometer to measure strontium ions in blood. The instrument can only detect cesium ions in the ppm level. When the concentration of cerium ions in the sample to be tested is lower, the flame atomic absorption spectrophotometer reaches Not required for testing.

Summary of the invention

In order to solve the above technical problems, an object of the present invention is to provide a method for removing barium ions in blood, which is prepared with a highly selective, highly dispersible and biocompatible adsorbent and used in blood. The adsorption of the cesium ion is efficient and rapid. At the same time, it provides a method for measuring the cesium ion concentration in the blood by using ICP-MS, which can more accurately determine the strontium ions in the blood.

A method of removing strontium ions in blood according to the present invention comprises the following steps:

(1) Water-soluble ferric salt and ferricyanide in the presence of polyethylene glycol, acetate and anionic surfactant The liquid is added to ethylene glycol, and the sealing reaction is carried out at 180-200 ° C to obtain magnetic Prussian blue particles;

(2) The magnetic Prussian blue particles obtained in the step (1) are dispersed in the blood, and after adsorption equilibrium, the magnetic Prussian blue particles to which the cerium ions are adsorbed are separated from the blood.

Further, in the step (1), the ferric salt is first dissolved in the reducing agent, then the polyethylene glycol, the acetate and the anionic surfactant are added, and finally the aqueous solution of ferricyanide is added, and after mixing, The stainless steel reaction vessel with the polytetrafluoroethylene liner is sealed at 180-200 ° C for 6-10 h, and after cooling, washing and drying, the magnetic Prussian blue is obtained;

Further, in the step (1), after the acid is added to the reaction system, the reaction is sealed at 180 to 200 °C. The acid is one or more of concentrated hydrochloric acid, acetic acid and sulfuric acid. The role of the acid is to maintain the ferric ion on the surface of the ferroferric oxide obtained by the reduction reaction, so that the ferric ion reacts with the reduced ferrocyanide ion to form Prussian blue, and the Prussian blue is combined with the ferroferric oxide. close.

Further, in the step (1), the acetate is one or more of sodium acetate, potassium acetate and ammonium acetate.

Further, in the step (1), the anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate and sodium lauryl sulfate.

Further, in the step (1), the molecular weight of the polyethylene glycol is 2000-3000 g/mol, and the polyethylene glycol can improve the dispersibility and biocompatibility of the nanoparticles.

Further, the acetate and the anionic surfactant have an electrostatic stabilizing effect, can prevent agglomeration and sedimentation of the nanoparticles, and achieve better dispersion of the nanoparticles.

Further, in the step (1), the ferric salt is one or more of ferric chloride, iron nitrate and iron sulfate.

Further, in the step (1), the ferricyanide is potassium ferricyanide and/or sodium ferricyanide.

Further, in the step (1), the molar ratio of the ferric salt to the ferricyanide is 2:1 to 4:1.

Further, in the step (1), the mass ratio of the polyethylene glycol, the acetate salt and the anionic surfactant is 1-2:7-9:7-9.

Further, in the step (1), the molar ratio of the acetate to the ferric salt is 1:1 to 1:2.

Further, in the step (2), the magnetic Prussian blue is separated from the blood by a magnet.

Further, after the step (2), the method further comprises the step (3): soaking the blood treated with the magnetic Prussian blue particles in concentrated nitric acid for 5-12 hours, adding hydrogen peroxide, and sealing and heating to 120-130 ° C for treatment 2.5- 4h, then the concentration of strontium ions in the blood was measured.

Further, the volume ratio of blood, concentrated nitric acid and hydrogen peroxide is 1-2:3-5:1-2.

Further, the treatment of blood at 120-130 ° C under confined conditions using concentrated nitric acid and hydrogen peroxide can sufficiently digest the organic matter in the blood while preventing the volatilization of the cesium at a high temperature.

Further, after filtration, the step (3) is determined by inductively coupled plasma high resolution mass spectrometry (ICP-MS). The concentration of barium ions in the treated blood.

The principle of the present invention for preparing magnetic Prussian blue is as follows:

The preparation of magnetic Prussian blue by one-pot method is realized by simultaneously reducing trivalent iron salt and ferricyanide at high temperature of ethylene glycol. The one-pot method has the advantage of being economical and efficient. The addition of polyethylene glycol can increase the dispersibility and product and biocompatibility of the nanoparticles of the reactants in the reaction system. Acetate and anionic surfactants have an electrostatic stabilizing effect, which can prevent agglomeration and sedimentation of nanoparticles and achieve better dispersion of nanoparticles. The acid is a ferric ion added to the surface of the ferroferric oxide which can be maintained by the reduction reaction, so that the ferric ion reacts with the reduced ferrocyanide ion to form Prussian blue, and the Prussian blue is combined with the ferroferric oxide. close.

With the above solution, the present invention has at least the following advantages:

In the process of preparing the adsorbent, polyethylene glycol, acetate and anionic surfactant are used, which not only improves the biocompatibility of the product, but also prevents the sedimentation of the reactants and improves the dispersibility of the product; Maintaining the ferric ion on the surface of the ferroferric oxide obtained by the reduction reaction, and reacting with the ferrocyanide ion obtained by the reduction to form Prussian blue, so that the Prussian blue is more closely combined with the ferroferric oxide; the present invention has a biological phase Capacitive adsorbent, which is directly used for blood adsorption, has the characteristics of high efficiency and rapidity; before the detection of helium ions in the blood, the blood is pretreated, and under the constant temperature and closed conditions, the organic matter in the blood is fully digested, and the air is sealed. The condition can prevent the volatilization of the liquid at high temperature to volatilize, provides high pressure for the whole reaction, and prevents the volatilization loss of the cesium at a high temperature, and is convenient for obtaining more accurate test results; the present invention uses ICP-MS to measure the lower concentration of cesium ions.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the state of magnetic Prussian blue prepared in the present invention in the presence of water and a magnet.

detailed description

The specific embodiments of the present invention are further described in detail below with reference to the drawings and embodiments. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

Example 1

The _{_{FeCl 3 · 6H 2 O (1.0g}} , 3.7mmol) was dissolved in 40mL of ethylene glycol, followed by addition of polyethylene glycol _{(0.1g, M n = 2000g /} mol), sodium acetate (0.8g, 9.7mmol) And sodium dodecyl sulfate (0.8 g, 2.3 mmol), then 5 mL of K ₃ [Fe(CN) ₆ ]·3H ₂ O (0.4 g, 1.0 mmol) aqueous solution was added to the above mixture, stirring was continued until the system was homogeneous. Finally, concentrated hydrochloric acid (0.6 mL, 37.5 wt%) was added. The mixture was then transferred to a stainless steel reaction vessel of a Teflon liner and heated to 180 ° C for 6 hours. Then, it was cooled to room temperature, washed once with ethanol, then once with water, and finally once with ethanol, and dried under vacuum to constant weight to obtain a magnetic Prussian blue adsorbent. As shown in Fig. 1, Fig. 1(A) is a diagram showing the dispersion state of magnetic Prussian blue nanoparticles in water. In water, the adsorbent dispersion has a uniform blue-green color, indicating that the obtained magnetic Prussian blue nanoparticles have good dispersion. Figure 1 (B) is a state diagram of magnetic Prussian blue nanoparticles in a bottle after a magnet is applied to one side of the bottle. It can be seen that the Prussian blue nanoparticles are concentrated on the side of the applied magnet, indicating the magnetic properties prepared by the present invention. Prussian blue nanoparticles have good magnetic properties.

The magnetic Prussian blue nanoparticles of different concentrations (0-40 μg/mL) were exposed to blood for 8 hours and then subjected to blood routine test. The results are shown in Table 1. The results showed that the magnetic Prussian blue nanoparticles had no significant effect on blood, and the method was prepared. The adsorbent has good biocompatibility and can therefore be used for the removal of barium ions in the blood.

Table 1 blood routine test results

The adsorbent prepared above was dispersed in blood, and after adsorption equilibrium, the adsorbent was aspirated from the blood by a magnet, and 1 mL of blood was taken before and after adsorption using the adsorbent, and the cesium ion concentrations of the two were measured.

Place 1 mL of blood in a Teflon inner tank, add 3 mL of concentrated HNO _{3 to it} overnight, add 1 mL of H ₂ O ₂ , cover the inner lid, tighten the stainless steel jacket, and put in a constant temperature of 120 ° C. The oven was cooled for 2.5 h and then the temperature inside the chamber was naturally cooled to room temperature. The treated blood was diluted, filtered through a 200 nm filter, and the concentration of strontium ions in the treated blood was measured by an inductively coupled plasma high resolution mass spectrometer (ICP-MS).

Table 2 shows the removal of barium ions in the blood by different adsorbents at different initial concentrations. As shown in Table 2, the adsorption efficiency of magnetic Prussian blue nanoparticles can reach 53.5 after 1 hour contact time at different concentrations of barium ions. Above 100%, when the cesium ion concentration is 168.4 ppb, the partition coefficient can also reach 36000 mL/g or more.

Table 2 Removal of strontium ions in blood by adsorbents at different initial concentrations

In Table 2, c ₀ represents the initial concentration of barium ions in the blood before adsorption, c _e represents the final concentration of barium ions in the blood after adsorption, V represents the volume of blood, m represents the amount of adsorbent, K _d represents the partition coefficient, AE Indicates adsorption efficiency.

Example 2

The _{_{Fe (NO 3) 3 · 9H}} 2 O (1.0g, 2.5mmol) was dissolved in 40mL of ethylene glycol and polyethylene glycol were added _{(0.1 g, M n = 2000g} / mol), sodium acetate (0.8g , 9.7 mmol) and sodium dodecyl sulfate (0.8 g, 2.3 mmol), then 5 mL of an aqueous solution of K ₃ [Fe(CN) ₆ ]·3H ₂ O (0.4 g, 1.0 mmol) was added to the above mixture. Stir until the system is homogeneous, and finally add sulfuric acid (0.6 mL, 5 mol/L). The mixture was then transferred to a stainless steel reaction vessel in a Teflon liner and heated to 200 ° C for 6 hours. Then, it was cooled to room temperature, washed once with ethanol, then once with water, and finally once with ethanol, and dried under vacuum to constant weight to obtain a magnetic Prussian blue adsorbent.

Place 0.5 mL of blood in a Teflon inner tank, add 3.5 mL of concentrated HNO _{3 to it} overnight, add 1 mL of H ₂ O ₂ , cover the inner lid, tighten the stainless steel jacket, and place at 125 ° C. In a constant temperature drying oven for 3 h, then the temperature inside the chamber was naturally cooled to room temperature. The treated blood was diluted, filtered through a 200 nm filter, and the concentration of strontium ions in the treated blood was measured by an inductively coupled plasma high resolution mass spectrometer (ICP-MS).

Example 3

The _{_{Fe (SO 4) 3 · 5H}} 2 O (1.5g, 3.0mmol) was dissolved in 40mL of ethylene glycol, followed by addition of polyethylene glycol _{(0.1g, M n = 2000g /} mol), sodium acetate (0.8g , 9.7 mmol) and sodium dodecylbenzene sulfonate (0.8 g, 2.3 mmol), then 5 mL of an aqueous solution of Na ₃ [Fe(CN) ₆ ]·H ₂ O (0.4 g, 1.3 mmol) was added to the above mixture. Stirring was continued until the system was homogeneous, and finally sulfuric acid (0.6 mL, 5 mol/L) was added. The mixture was then transferred to a stainless steel reaction vessel in a Teflon liner and heated to 185 ° C for 6 hours. Then, it was cooled to room temperature, washed once with ethanol, then once with water, and finally once with ethanol, and dried under vacuum to constant weight to obtain a magnetic Prussian blue adsorbent.

Place 0.5 mL of blood in a Teflon inner tank, add 3 mL of concentrated HNO _{3 to} soak overnight, add 1.5 mL of H ₂ O ₂ , cover the inner lid, tighten the stainless steel jacket, and place at 130 ° C. In a constant temperature drying oven for 2.5 h, then the temperature inside the chamber was naturally cooled to room temperature. The treated blood was diluted, filtered through a 200 nm filter, and the concentration of strontium ions in the treated blood was measured by an inductively coupled plasma high resolution mass spectrometer (ICP-MS).

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. It should be noted that those skilled in the art can make some improvements without departing from the technical principles of the present invention. And modifications and variations are also considered to be within the scope of the invention.

Claims

A method for removing strontium ions in blood, comprising the steps of:

(1) In the presence of polyethylene glycol, acetate and anionic surfactant, the ferric salt and ferricyanide aqueous solution are added to ethylene glycol, and the sealing reaction is carried out at 180-200 ° C to obtain magnetic properties. Prussian blue granules;

(2) The magnetic Prussian blue particles obtained in the step (1) are dispersed in the blood, and after adsorption equilibrium, the magnetic Prussian blue particles to which the cerium ions are adsorbed are separated from the blood.
The method of removing strontium ions in blood according to claim 1, wherein in the step (1), the sealing reaction is carried out in the presence of an acid.
The method for removing strontium ions in blood according to claim 2, wherein the acid is one or more of concentrated hydrochloric acid, acetic acid and sulfuric acid.
The method for removing strontium ions in blood according to claim 1, wherein in the step (1), the acetate is one or more of sodium acetate, potassium acetate and ammonium acetate.
The method for removing barium ions in blood according to claim 1, wherein in the step (1), the anionic surfactant is sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and One or more of sodium lauryl sulfate.
The method for removing strontium ions in blood according to claim 1, wherein in the step (1), the ferric salt is one or more of ferric chloride, ferric nitrate and ferric sulphate. .
The method for removing strontium ions in blood according to claim 1, wherein in the step (1), the ferricyanide is potassium ferricyanide and/or sodium ferricyanide.
The method for removing strontium ions in blood according to any one of claims 1, 6, and 7, wherein the molar ratio of the ferric salt to the ferricyanide is from 2:1 to 4:1.
The method for removing strontium ions in blood according to claim 1, wherein in the step (1), the mass ratio of the polyethylene glycol, the acetate salt and the anionic surfactant is 1-2:7. -9:7-9.
The method for removing strontium ions in blood according to claim 1, wherein in the step (1), the molar ratio of the acetate to the ferric salt is 1:1 to 1:2.
The method for removing strontium ions in blood according to claim 1, further comprising the step (3) after the step (2): soaking the blood treated with the magnetic Prussian blue particles in concentrated nitric acid, adding peroxidation Hydrogen was sealed and heated to 120-130 ° C, and then the concentration of barium ions in the blood was measured.
The method of detecting strontium ions in blood according to claim 11, wherein the volume ratio of said blood, concentrated nitric acid and hydrogen peroxide is 1-2: 3-5: 1-2.