Compound detergent for radionuclide contaminated skin and use method of compound detergent

Abstract

The invention belongs to the technical field of radionuclide removal, and provides a compound detergent for skin contaminated by radionuclide and a use method of the compound detergent. The compound detergent comprises a compound complexing agent and a film forming solution; the composite complexing agent comprises sodium alginate, chitosan, a chelating agent and a PBS (Phosphate Buffer Solution); the chelating agent is prepared from 1-hydroxyethylidene-1, 1-diphosphonic acid, diethylene triamine pentaacetic acid and carboxymethyl chitosan. The compound detergent is used for nuclide removal experiments on uranium, cesium, strontium, cobalt and cerium elements on guinea pig skin, the removal effect is 90% or above, and the nuclide removal effect is good. The compound detergent disclosed by the invention is small in volume and convenient to carry; wastewater is not generated in the nuclide removal process, and waste materials generated after use are small in size and relatively convenient to treat. Compared with hydrogel which is widely studied at present, the skin nuclide cleaning process is faster, the cleaning speed is high, a film can be formed within 1.5 min, and nuclides contaminated on the skin can be removed.

Description

Technical Field

[0001] The present invention relates to the technical field of removing radionuclides, and particularly to a compound decontaminant for radioactive nuclide-contaminated skin and a method for using the same. Background Art

[0002] In recent years, nuclear energy has been widely used in power generation, scientific research, etc., providing a lot of convenience for life and scientific research. However, the danger caused by nuclear leakage has always lingered. In particular, people engaged in various nuclear-related activities may suffer injuries such as cuts, explosion injuries, and burns, exposing the skin to radionuclides. Although intact skin provides an effective barrier to prevent most substances from entering the human body. However, skin wounds are the most direct way for contaminated nuclides to enter the human body, allowing the nuclides on the skin to enter the systemic circulation through the wounds and transfer to tissues such as blood, liver, and kidneys, resulting in internal organs being irradiated and causing systemic damage. Therefore, skin wounds contaminated with radionuclides should seek medical attention in a timely manner. After accidents occur in nuclear power plants, spent fuel treatment, nuclear wastewater, etc., in addition to the most important uranium element, fission produces various radionuclides such as 137 Cs, 134 Cs, 90 Sr, 144 Ce, 60 Co contaminating the skin, especially wounds, can easily cause radioactive and chemical toxicity damage to the skin and the human internal environment.

[0003] According to research, actinides such as uranium can penetrate the wound skin and enter the human body 30 minutes after contamination, causing more serious harm. It is very necessary to quickly remove the nuclides contaminated on the skin in a short time. 137 Cesium is one of the metal cesium isotopes, with extremely strong radioactivity and often used as a radiation source. Its rays can cause the chromosomes in the human body to break or distort, inducing mutations and mutations in the DNA of cells. Rinsing radioactive nuclide-contaminated wounds with a large amount of normal saline or 1% DTPA solution can maximize the inhibition of the binding of nuclides to the human body surface. For rare earth elements, plutonium, and super plutonium contamination, the commonly used decontaminant is 1% diethylenetriaminepentaacetic acid (DTPA) (pH value of 3 - 5) or dilute hydrochloric acid solution (pH value of 1). For uranium contamination, 1.4% sodium bicarbonate solution is a commonly used decontamination agent. For unknown radioactive nuclide contamination, 5% ethylenediaminetetraacetic acid (EDTA) or DTPA solution can be used for treatment. However, the radioactive wastewater generated by these liquid decontaminants can cause secondary radioactive contamination, and the liquid decontaminants are highly dependent on water. Most of the existing decontaminants cannot be used at the nuclear nuclide contamination site.

[0004] Sodium alginate is a natural polysaccharide compound extracted from seaweeds. It is easily soluble in water and prone to swelling in warm water. After the sodium ions therein undergo ion exchange with divalent calcium ions, guluronic acid groups accumulate to form a cross-linked network structure, enabling the rapid formation of a hydrogel. However, the hydrogel structure of sodium alginate is loose and has poor tensile strength. Chitosan is prepared by deacetylating chitin to remove more than 50% of the acetyl groups. It is the only basic polysaccharide among natural polysaccharides. There are a large number of primary amino groups on the chitosan molecular chain, and a large number of carboxyl groups on the sodium alginate molecular chain. Under electrostatic force, a polyelectrolyte membrane can be formed through the attraction of positive and negative charges.

[0005] Therefore, it is extremely urgent to develop a new and efficient decontamination membrane for radioactive skin wounds that can be applied to the site of radionuclide contamination. Summary of the Invention

[0006] The purpose of the present invention is to provide a compound decontaminant for radioactive nuclide-contaminated skin and its usage method to overcome the deficiencies of the prior art, which can achieve the cleaning of radioactive nuclide-contaminated skin in water-scarce environments such as nuclear battlefields and submarines.

[0007] To achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0008] The present invention provides a compound decontaminant for radioactive nuclide-contaminated skin. The compound decontaminant comprises a composite complexing agent and a film-forming solution; the composite complexing agent comprises sodium alginate, chitosan, a chelating agent, and a PBS solution; the chelating agent comprises hydroxyethylidene diphosphonic acid, diethylenetriamine pentaacetic acid, and carboxymethyl chitosan.

[0009] Preferably, the mass ratio of sodium alginate, chitosan, and the chelating agent is 2.5 - 3.5:2.5 - 3.5:5 - 8; the mass fraction of sodium alginate in the composite complexing agent is 2.5 - 3.5%.

[0010] Preferably, the mass ratio of hydroxyethylidene diphosphonic acid, diethylenetriamine pentaacetic acid, and carboxymethyl chitosan is 1 - 2:3.5 - 4.5:0.5 - 1.5.

[0011] Preferably, the concentration of the PBS solution is 0.008 - 0.012 mol / L, and the pH value is 6.5 - 7.5.

[0012] Preferably, the preparation method of the composite complexing agent is: mixing sodium alginate, chitosan, hydroxyethylidene diphosphonic acid, diethylenetriamine pentaacetic acid, carboxymethyl chitosan, and the PBS solution to obtain the composite complexing agent. The mixing is carried out at a rotation speed of 1200 - 1400 r / min for 10 - 15 h.

[0013] Preferably, the film-forming solution is an aqueous calcium chloride solution with a mass concentration of 9-11%.

[0014] The present invention also provides a method for using the compound decontaminant for radioactive nuclide-contaminated skin. Apply the complexing agent on the skin, cover the complexing agent with a gauze impregnated with the film-forming solution, and then remove the formed compound decontamination film.

[0015] Preferably, the application amount of the complexing agent on the skin is 0.15-0.25 mL / 3-5 cm 2 .

[0016] Preferably, the covering time is 1.3-1.5 min.

[0017] Preferably, the skin is intact skin or wounded skin.

[0018] The beneficial effects of the present invention include:

[0019] 1) The combined use of multiple chelating agents in the present invention has a better nuclide scavenging effect than a single chelating agent. A chelating agent composed of hydroxyethylidene diphosphonic acid, diethylenetriaminepentaacetic acid, and carboxymethyl chitosan is loaded on a sodium alginate and chitosan polyelectrolyte membrane to obtain a compound decontaminant that can quickly form a film for use at the nuclear explosion site and in nuclear contamination sites in water-scarce environments such as submarines.

[0020] 2) The compound decontaminant of the present invention was used in a nuclide scavenging experiment on guinea pig skin for uranium, cesium, strontium, cobalt, and cerium elements. The results show that the scavenging effect is above 90%, and the compound decontaminant has a good nuclide scavenging effect. The compound decontaminant of the present invention is small in volume and convenient to carry; no wastewater is generated during the nuclide scavenging process, and no secondary pollution of wastewater is brought; the waste generated after use is small in volume and relatively convenient to handle.

[0021] 3) Compared with the widely studied hydrogel type at present, the compound decontaminant of the present invention is fast in the process of skin nuclide scavenging. Only need to apply the complexing agent on the skin, and then cover it with a gauze infiltrated with the film-forming solution, and a film can be formed in 1.5 min to complete the scavenging of the nuclide contaminated on the skin. Description of the Drawings

[0022] Figure 1 Is the uranium element removal rate of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and physiological saline on intact skin;

[0023] Figure 2 Is the amount of uranium element collected on intact skin by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2;

[0024] Figure 3The cesium element clearance rates of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline on intact skin;

[0025] Figure 4 The amounts of cesium element collected by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 on intact skin;

[0026] Figure 5 The uranium element clearance rates of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline on wounded skin;

[0027] Figure 6 The amounts of uranium element collected by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 on wounded skin;

[0028] Figure 7 The amounts of uranium element detected in the whole blood of guinea pigs in the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, the normal saline group, and the model group;

[0029] Figure 8 The cesium element clearance rates of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline on wounded skin;

[0030] Figure 9 The amounts of cesium element collected by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 on wounded skin;

[0031] Figure 10 The amounts of cesium element detected in the whole blood of guinea pigs in the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, the normal saline group, and the model group;

[0032] Figure 11 The strontium element clearance rates of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline on wounded skin;

[0033] Figure 12 The amounts of strontium element collected by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 on wounded skin;

[0034] Figure 13 The amounts of strontium element detected in the whole blood of guinea pigs in the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, the normal saline group, and the model group;

[0035] Figure 14The cobalt element clearance rates of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline on the wound skin;

[0036] Figure 15 The amounts of cobalt element collected by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 on the wound skin;

[0037] Figure 16 The amounts of cobalt element detected in the whole blood of guinea pigs in the groups of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, the normal saline group, and the model group;

[0038] Figure 17 The cerium element clearance rates of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline on the wound skin;

[0039] Figure 18 The amounts of cerium element collected by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 on the wound skin. Detailed implementation manners

[0040] The present invention provides a compound decontaminant for radioactive nuclide contaminated skin. The compound decontaminant comprises a composite complexing agent and a film-forming solution; the composite complexing agent comprises sodium alginate, chitosan, a chelating agent, and a PBS solution; the chelating agent comprises hydroxyethylidene diphosphonic acid, diethylenetriaminepentaacetic acid, and carboxymethyl chitosan.

[0041] In the present invention, the mass ratio of sodium alginate, chitosan, and the chelating agent is preferably 2.5 - 3.5:2.5 - 3.5:5 - 8, more preferably 2.7 - 3.2:2.7 - 3.2:5.5 - 7.5, and even more preferably 2.9 - 3.0:2.9 - 3.0:6 - 7; the mass fraction of sodium alginate in the composite complexing agent is preferably 2.5 - 3.5%, more preferably 2.7 - 3.2%, and even more preferably 2.9 - 3.0%.

[0042] In the present invention, the mass ratio of hydroxyethylidene diphosphonic acid, diethylenetriaminepentaacetic acid, and carboxymethyl chitosan is preferably 1 - 2:3.5 - 4.5:0.5 - 1.5, more preferably 1.2 - 1.8:3.7 - 4.2:0.7 - 1.3, and even more preferably 1.5 - 1.6:3.9 - 4.0:0.9 - 1.0.

[0043] In the present invention, the concentration of the PBS solution is preferably 0.008 - 0.012 mol / L, more preferably 0.009 - 0.011 mol / L, and even more preferably 0.01 mol / L; the pH value is preferably 6.5 - 7.5, and more preferably 7.

[0044] In the present invention, the preparation method of the composite complexing agent is preferably as follows: sodium alginate, chitosan, hydroxyethylidene diphosphonic acid, diethylenetriamine pentaacetic acid, carboxymethyl chitosan and PBS solution are mixed to obtain the composite complexing agent. The mixing is preferably carried out at a rotation speed of 1200 - 1400 r / min, more preferably 1250 - 1350 r / min, and even more preferably 1300 r / min; the mixing time is preferably 10 - 15 h, more preferably 11 - 14 h, and even more preferably 12 - 13 h.

[0045] In the present invention, the PBS solution is preferably the 1xPBS solution of Thermo Fisher Scientific. After the preparation of the composite complexing agent is completed, it is preferably stored at 4°C.

[0046] In the present invention, the film-forming solution is preferably an aqueous calcium chloride solution, and the mass concentration of the aqueous calcium chloride solution is preferably 9 - 11%, more preferably 10%.

[0047] In the present invention, the aqueous calcium chloride solution is a clear and transparent solution and is preferably stored at 4°C.

[0048] The present invention also provides a method for using the compound decontaminant for radioactive nuclide-contaminated skin. The composite complexing agent is applied to the skin, and a gauze impregnated with the film-forming solution is covered on the composite complexing agent, and then the formed compound decontamination film is removed.

[0049] In the present invention, the application amount of the composite complexing agent on the skin is preferably 0.15 - 0.25 mL / 3 - 5 cm 2 , more preferably 0.18 - 0.22 mL / 3 - 5 cm 2 , even more preferably 0.2 mL / 4 cm 2 .

[0050] In the present invention, the covering time is preferably 1.3 - 1.5 min.

[0051] In the present invention, the skin is preferably intact skin or wounded skin.

[0052] In the present invention, the gauze impregnated with the film-forming solution is a gauze completely soaked with the film-forming solution, and the gauze is preferably medical gauze.

[0053] The technical solutions provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the protection scope of the present invention.

[0054] In the examples, the PBS solution is the 1xPBS solution of Thermo Fisher Scientific.

[0055] Example 1 (Compound film)

[0056] The preparation method of the compound decontaminant is as follows: Mix 1.5 g of sodium alginate, 1.5 g of chitosan, 0.75 g of hydroxyethane diphosphonic acid, 2 g of diethylenetriamine pentaacetic acid, 0.5 g of carboxymethyl chitosan and 43.75 g of PBS solution (concentration 0.01 mol / L, pH value 7) at a rotation speed of 1300 r / min for 13 h to obtain a composite complexing agent. Add 10 g of calcium chloride to 90 g of water and stir until the solution is clear and transparent to obtain a film-forming solution.

[0057] Evenly apply 0.2 mL of the composite complexing agent to the back skin of a guinea pig (2 cm × 2 cm) to fully combine the toxicant with the chelating agent in the composite complexing agent; cover the skin of the guinea pig coated with the composite complexing agent with a medical gauze fully soaked in the film-forming solution. After 1.5 min, the composite complexing agent forms a film. Peel off the compound film contaminated with radionuclides from the surface of the guinea pig skin, and then wait for 5 min, and then take the skin and blood.

[0058] Example 2 (Compound film)

[0059] The preparation method of the compound decontaminant is as follows: Mix 1.35 g of sodium alginate, 1.35 g of chitosan, 0.6 g of hydroxyethane diphosphonic acid, 2.85 g of diethylenetriamine pentaacetic acid, 0.35 g of carboxymethyl chitosan and 43.5 g of PBS solution (concentration 0.009 mol / L, pH value 7) at a rotation speed of 1250 r / min for 12 h to obtain a composite complexing agent. Add 9.5 g of calcium chloride to 90.5 g of water and stir until the solution is clear and transparent to obtain a film-forming solution.

[0060] Evenly apply 0.18 mL of the composite complexing agent to the back skin of a guinea pig (2 cm × 2 cm) to fully combine the toxicant with the chelating agent in the composite complexing agent; cover the skin of the guinea pig coated with the composite complexing agent with a medical gauze fully soaked in the film-forming solution. After 1.3 min, the composite complexing agent forms a film. Peel off the compound film contaminated with radionuclides from the surface of the guinea pig skin.

[0061] Example 3 (Compound film)

[0062] The preparation method of the compound decontaminant is as follows: Mix 1.6 g of sodium alginate, 1.6 g of chitosan, 0.9 g of hydroxyethane diphosphonic acid, 2.1 g of diethylenetriamine pentaacetic acid, 0.65 g of carboxymethyl chitosan and 43.15 g of PBS solution (concentration 0.011 mol / L, pH value 7) at a rotation speed of 1350 r / min for 14 h to obtain a composite complexing agent. Add 10.5 g of calcium chloride to 89.5 g of water and stir until the solution is clear and transparent to obtain a film-forming solution.

[0063] Apply 0.22 mL of the composite complexing agent evenly to the back skin (2 cm × 2 cm) of guinea pigs, so that the chelating agent in the toxicant and the composite complexing agent are fully combined; cover the skin of the guinea pigs coated with the composite complexing agent with a medical gauze fully soaked in the film-forming solution. After 1.5 min, the composite complexing agent forms a film, and then peel off the compound film contaminated with radionuclides from the surface of the guinea pig skin.

[0064] Control Example 1 (matrix film)

[0065] Mix 1.5 g of sodium alginate, 1.5 g of chitosan and 47 mL of PBS solution (concentration: 0.01 mol / L, pH value: 7) to obtain a matrix solution.

[0066] After the poisoned guinea pigs are left standing for 5 min, apply 0.2 mL of the matrix solution to the skin surface of the guinea pigs with an area of 2 cm × 2 cm. After waiting for 1.5 min, remove the matrix decontamination film (matrix film), and then wait for another 5 min, and then take the skin and blood.

[0067] Control Example 2 (1% DTPA film)

[0068] Mix 1.5 g of sodium alginate, 1.5 g of chitosan, 0.5 g of diethylenetriaminepentaacetic acid and 46.5 mL of PBS solution to obtain a 1% DTPA solution.

[0069] After the poisoned guinea pigs are left standing for 5 min, apply 0.2 mL of the 1% DTPA solution to the skin surface of the guinea pigs with an area of 2 cm × 2 cm. After waiting for 1.5 min, remove the 1% DTPA decontamination film (1% DTPA film), and then wait for another 5 min, and then take the skin and blood.

[0070] The complete skin (non-wound contamination) test, wound skin test were carried out on the compound decontaminant of Example 1, the matrix solution of Comparative Example 1, and the 1% DTPA solution of Comparative Example 2. The contaminating agents for the complete skin test were uranyl nitrate solution with a concentration of 1 g / L and cesium chloride solution with a concentration of 1 g / L respectively, and the wound skin test used uranyl nitrate solution with a concentration of 1 g / L, cesium chloride solution with a concentration of 1 g / L, strontium chloride solution with a concentration of 1 g / L, cobalt chloride solution with a concentration of 1 g / L, and cerium nitrate solution with a concentration of 1 g / L respectively; the contaminating agents were stored at 4°C. Each of the above 7 test groups (each contaminating agent on the complete skin and wound skin corresponded to a group of experiments) contained 5 subgroups (model group, normal saline group, matrix film group, 1% DTPA group, and compound film group); 6 guinea pigs were used for parallel tests in each subgroup. ICP-MS was used to detect the content of radionuclides in the skin, whole blood, and decontamination film. When processing the data, the mean value of the skin residue in the model group was taken as the total amount of radionuclides in this batch of tests. First, the mean value of the radionuclide residue in the model group was calculated. The difference between the skin residue in each treatment group (normal saline group, matrix film group, 1% DTPA group, and compound film group) and the mean value of the radionuclide residue in the model group was calculated, and then divided by the mean value of the radionuclide residue in the model group. This ratio was the clearance rate of the radionuclide. The formula for the radionuclide clearance rate is:

[0071] Clearance rate = (mean value of the model group - residue of the treatment group) / mean value of the model group × 100%

[0072] Animal model establishment: One day before the experiment, the hair on the back of the guinea pig was shaved, depilatory cream was applied, and it was infiltrated for 10 min. The depilatory cream was wiped off with a gauze, and the area was scrubbed 3 times with deionized water to ensure no residue of the depilatory cream remained. After raising for 12 h, the guinea pig was anesthetized with sodium pentobarbital. A 2 cm × 2 cm area on the back skin was marked and recorded as the target area. A cross incision was made in the target area with a surgical blade, damaging the fascia layer. 20 μL of the contaminating agent was evenly applied to the wound for contamination.

[0073] Model group: After the contaminated guinea pigs were left standing for 11.5 min, skin and blood were taken. Normal saline group: After the contaminated guinea pigs were left standing for 5 min, the target area was rinsed with 10 mL of normal saline and then left standing for 6.5 min, and then skin and blood were taken. Comparative Example 1 was the matrix film group, Comparative Example 2 was the 1% DTPA film group, and Example 1 was the compound film group.

[0074] Method for taking blood: The anesthetized guinea pig was placed with its abdomen facing up. The place where the heart beat was obvious was felt with fingers between the 4th and 5th intercostals of the guinea pig, and then the syringe was inserted at a 45° angle to draw blood from the heart and placed in a centrifuge tube with sodium citrate anticoagulant.

[0075] Method for taking skin: The guinea pig was decapitated and then the back skin was cut off with scissors and placed in a centrifuge tube.

[0076] Nitration treatment: Add guinea pig skin and whole blood samples to concentrated nitric acid (mass fraction 68%) at a mass ratio of 1:5. First, pre-digest at room temperature for 30 min, and then heat for nitration in a water bath at 98 °C for 2 h. Add the decontamination film samples to concentrated nitric acid (mass fraction 68%) at a mass ratio of 1:10. First, pre-digest overnight at room temperature, and then heat for nitration in a water bath at 98 °C for 2 h. Cool the nitrated samples to room temperature in a fume hood. Store the well-nitrated samples in a refrigerator at 4 °C.

[0077] ICP-MS detection of nitrated samples

[0078] Take 0.3 mL of the nitrated skin sample and dilute it to 6 mL with deionized water, and detect it with an ICP-MS instrument; take 0.5 mL of the nitrated whole blood sample and dilute it to 5 mL with deionized water, and detect it with an ICP-MS instrument; take 0.2 mL of the nitrated decontamination film sample and dilute it to 7 mL with deionized water, and detect it with an ICP-MS instrument.

[0079] The ICP-MS instrument conditions for detecting the contents of uranium, cesium, strontium, cobalt, and cerium elements in guinea pig skin, whole blood, and decontamination film are as follows: RF power: 1550 W, RF matching: 1.8 V, sampling depth: 10 mm, nebulizer: concentric nebulizer MicroMist, plasma flow rate: 15 L / min, acquisition mode: TRA, Omega deflection voltage: 105 V, Omega lens voltage: 13.6 V, element detection: 115 In, 133 Cs, 209 Bi, 238 U, 88 Sr, 59 Co, 133 Cs, 144 Ce; integration time: 1.0 s.

[0080] Intact skin test

[0081] Uranium element scavenging test

[0082] The uranium element scavenging rates of the compound film in Example 1, the matrix film in Comparative Example 1, the 1% DTPA film in Comparative Example 2, and normal saline on intact skin are as Figure 1 shown; the amounts of uranium elements collected by the compound film in Example 1, the matrix film in Comparative Example 1, and the 1% DTPA film in Comparative Example 2 on intact skin are as Figure 2 shown. From Figure 1It can be seen that the removal rate of uranium by the compound film is 95.4±0.2%, the removal rate of uranium by the normal saline group is 48.6±0.3%, the removal rate of uranium by the matrix film is 88.1±0.3%, and the removal rate of uranium by the 1% DTPA film is 88.8±0.3%. The removal rate of uranium in the compound film group is significantly higher than that in the normal saline group, matrix film group, and 1% DTPA group (P<0.001). From Figure 2 It can be seen that the amount of uranium collected in the compound film group is much higher than that in the matrix film group and 1% DTPA film group (P<0.001). In summary, it shows that the compound decontamination film has a good removal effect on uranium on intact skin.

[0083] The present invention also detected the content of uranium in whole blood and found that it was lower than the lower limit of quantification, indicating that the amount of uranium entering the blood through intact skin is extremely small. By estimating the blood concentration through the lower limit of quantification, the concentration in whole blood of the intact skin group is 1.6407 ng / g.

[0084] Cesium removal test

[0085] The removal rates of cesium by the compound film in Example 1, the matrix film in Comparative Example 1, the 1% DTPA film in Comparative Example 2, and normal saline on intact skin are as Figure 3 shown; the amounts of cesium collected by the compound film in Example 1, the matrix film in Comparative Example 1, and the 1% DTPA film in Comparative Example 2 on intact skin are as Figure 4 shown. From Figure 3 It can be seen that the removal rate of cesium by the compound film is 96.6±0.5%, the removal rate of cesium by the normal saline group is 84.2±0.4%, the removal rate of cesium by the matrix film is 91.8±0.4%, and the removal rate of cesium by the 1% DTPA film is 93.8±0.6%. The removal rate of cesium in the compound film group is significantly higher than that in the normal saline group, matrix film group, and 1% DTPA group (P<0.001). From Figure 4 It can be seen that the amount of cesium collected in the compound film group is much higher than that in the matrix film group and 1% DTPA film group (P<0.001). In summary, it shows that the compound decontamination film has a significantly better removal effect on cesium on intact skin than other treatment groups.

[0086] By detecting the residual amount of cesium in whole blood by ICP-MS, it was found that the detection results were all lower than the lower limit of quantification. Therefore, the amount of cesium entering the blood in the intact skin group is extremely small. By estimating the content of cesium in whole blood through the lower limit of quantification, the cesium concentration is 1.5558 ng / g.

[0087] Wound skin test

[0088] Uranium removal test

[0089] The uranium element clearance rates of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline on the wound skin are as Figure 5 shown; the amounts of uranium element collected by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 on the wound skin are as Figure 6 shown. It can be seen from Figure 5 that the clearance rate of the compound film for uranium element is 92.2±0.5%, the clearance rate of the normal saline group for uranium element is 46.9±0.6%, the clearance rate of the matrix film for uranium element is 83.5±0.5%, and the clearance rate of the 1% DTPA film for uranium element is 89.9±0.8%. The clearance rate of the compound film group for uranium element is significantly higher than that of the normal saline group, the matrix film group, and the 1% DTPA group (P<0.001). It can be seen from Figure 6 that the amount of uranium element collected by the compound film group is much higher than that of the matrix film group and the 1% DTPA film group (P<0.001). It shows that the compound decontamination film has a good clearance effect on uranium element on the wound skin.

[0090] The amounts of uranium element detected in the whole blood of guinea pigs by the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, the normal saline group, and the model group are as Figure 7 shown. It can be seen from Figure 7 that the amount of uranium element entering the blood is less, and the concentration of uranium element in the whole blood is the highest in the model group, which is 7.8022±1.5336 ng / g, and the content of uranium element entering the blood in the compound film group is the least, which is 3.6521±1.0876 ng / g. The concentrations of uranium element in the whole blood of each treatment group are lower than that of the model group, indicating that the components of the compound decontamination film do not promote the entry of uranium element into the blood.

[0091] Cesium element clearance test

[0092] The cesium element clearance rates of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline on the wound skin are as Figure 8 shown; the amounts of cesium element collected by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 on the wound skin are as Figure 9 shown. It can be seen from Figure 8 that the clearance rate of the compound film for cesium element is 90.4±1.2%, the clearance rate of the normal saline group for cesium element is 79.1±1.2%, the clearance rate of the matrix film for cesium element is 87.8±0.6%, and the clearance rate of the 1% DTPA film for cesium element is 88.2±1.3%. The clearance rate of the compound film group for cesium element is significantly higher than that of the normal saline group, the matrix film group, and the 1% DTPA group (P<0.001). It can be seen from Figure 9It can be seen that the amount of cesium collected in the compound film group is much higher than that in the matrix film group and the 1% DTPA film group (P<0.001). In summary, it shows that the compound decontamination film has a significantly better effect on removing cesium from the wound skin than other treatment groups.

[0093] The amounts of cesium detected in the whole blood of guinea pigs for the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, the normal saline group, and the model group are as Figure 10 shown. It can be Figure 10 seen that the amount of cesium entering the blood is less, and the concentration of cesium in the whole blood is the highest in the model group, which is 13.5083±2.5939 ng / g, and the lowest in the compound film group, which is 7.9719±0.9494 ng / g. The concentrations of cesium in the whole blood of each treatment group are lower than that in the model group, indicating that the components of the compound decontamination film do not promote the entry of cesium into the blood.

[0094] Strontium removal test

[0095] The removal rates of strontium on the wound skin for the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline are as Figure 11 shown; the amounts of strontium collected on the wound skin for the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 are as Figure 12 shown. It can be Figure 11 seen that the removal rate of strontium by the compound film is 92.0±0.9%, the removal rate of strontium by the normal saline group is 61.6±4.9%, the removal rate of strontium by the matrix film is 78.4±1.3%, and the removal rate of strontium by the 1% DTPA film is 85.9±2.0%. The removal rate of strontium by the compound film group is significantly higher than that of the normal saline group, the matrix film group, and the 1% DTPA group (P<0.001). It can be Figure 12 seen that the amount of strontium collected in the compound film group is significantly higher than that in the matrix film group and the 1% DTPA film group (P<0.001). It shows that the compound film has a significantly better effect on removing strontium from the wound skin than other treatment groups.

[0096] The amounts of strontium detected in the whole blood of guinea pigs for the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, the normal saline group, and the model group are as Figure 13 shown. The strontium concentrations in the whole blood of the model group and the normal saline group are similar, which are 70.5221±17.2058 ng / g and 72.7873±18.8796 ng / g respectively, and the concentration in the compound film group is the lowest, which is 29.3304±10.4097 ng / g. The concentrations of strontium in the whole blood of each treatment group are lower than that in the model group, indicating that the components of the decontamination film do not promote the entry of strontium into the blood.

[0097] Cobalt removal test

[0098] The cobalt element clearance rates of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline on the wound skin are as Figure 14 shown; the amounts of cobalt element collected by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 on the wound skin are as Figure 15 shown. From Figure 14 it can be seen that the cobalt element clearance rate of the compound film is 92.8 ± 0.5%, the cobalt element clearance rate of the normal saline group is 60.7 ± 3.5%, the cobalt element clearance rate of the matrix film is 77.8 ± 1.9%, and the cobalt element clearance rate of the 1% DTPA film is 83.7 ± 2.5%. The cobalt element clearance rate of the compound film group is significantly higher than that of the normal saline group, the matrix film group, and the 1% DTPA group (P < 0.001). From Figure 15 it can be seen that the amount of cobalt element collected by the compound film group is significantly higher than that of the matrix film group and the 1% DTPA film group (P < 0.001). It shows that the cobalt element clearance effect of the compound film on the wound skin is significantly better than that of other treatment groups.

[0099] The amounts of cobalt element detected in the whole blood of guinea pigs by the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, the normal saline group, and the model group are as Figure 16 shown. The cobalt element concentration in the whole blood of the model group is the highest, which is 22.0106 ± 6.7986 ng / g, and the concentration of the compound film group is the lowest, which is 9.0321 ± 2.9447 ng / g. The cobalt element concentrations in the whole blood of each treatment group are lower than that of the compound film group, indicating that the decontamination film components do not promote the entry of cobalt element into the blood.

[0100] Cerium element clearance test

[0101] The cerium element clearance rates of the compound film of Example 1, the matrix film of Comparative Example 1, the 1% DTPA film of Comparative Example 2, and normal saline on the wound skin are as Figure 17 shown; the amounts of cerium element collected by the compound film of Example 1, the matrix film of Comparative Example 1, and the 1% DTPA film of Comparative Example 2 on the wound skin are as Figure 18 shown. From Figure 17 it can be seen that the cerium element clearance rate of the compound film is 92.8 ± 0.8%, the cerium element clearance rate of the normal saline group is 70.6 ± 1.2%, the cerium element clearance rate of the matrix film is 85.1 ± 1.3%, and the cerium element clearance rate of the 1% DTPA film is 88.0 ± 1.2%. The cerium element clearance rate of the compound film group is significantly higher than that of the normal saline group, the matrix film group, and the 1% DTPA group (P < 0.001). From Figure 18It can be seen that the amount of cerium element collected in the compound film group was significantly higher than that in the matrix film and 1% DTPA film groups (P<0.001). This indicates that the compound film has a significantly better scavenging effect on cerium element on the wound skin than other treatment groups.

[0102] By detecting the content of cerium element in whole blood by ICP-MS, it was found that the detection results were all lower than the lower limit of quantification. Using the lower limit of quantification to estimate the concentration of cerium element in whole blood, the concentration of cerium element was 1.5059 ng / g.

[0103] Figures 1 to 18 Among them, *** is P<0.001.

[0104] Through the nuclide scavenging experiment, it was proved that the compound decontamination film prepared by the present invention has a good scavenging effect on a variety of nuclides on both the wound skin model and the intact skin model, and it is a broad-spectrum decontamination film. And by detecting the content of nuclides in the whole blood of each treatment group, it was shown that the components of the decontamination film do not promote the entry of nuclides into the blood, and the components of the decontamination film are very safe.

[0105] Film-forming time and breaking tensile strength test after film formation

[0106] In Examples 4 and Comparative Examples 3-26, the amounts of DTPA were all 0.4 g, the amounts of HEDP were all 0.15 g, the amounts of carboxymethyl chitosan were all 0.1 g, and the film-forming solutions were all clear and transparent solutions obtained by adding 10 g of calcium chloride to 90 mL of water. The differences lie in the ratios of sodium alginate, chitosan and PBS.

[0107] The film-forming time and breaking tensile strength of the complexing agents in Examples 4 and Comparative Examples 3-26 were tested, and the results are shown in Table 1.

[0108] Film-forming time determination method: Take 0.2 mL of the complexing agents in Examples 4 and Comparative Examples 3-26 and evenly apply them to a 2 cm×2 cm area on a glass plate, cover it with a gauze soaked in the film-forming solution, start timing, and stop timing when the decontamination film is formed and can be peeled off. Repeat the application 6 times, and take the average value of the film-forming time.

[0109] Breaking tensile strength test method: Prepare a decontamination film with an area of 3 cm×3 cm (thickness 0.5 mm) on a glass plate for the breaking tensile strength test of the decontamination film. Place the compound film on a tensile strength testing machine (purchased from Dongguan Huitai Machinery Co., Ltd., TM2101-T5), record the breaking tensile strength of the decontamination film, repeat 6 times, and take the average value of the results.

[0110] Table 1 Film-forming time and breaking tensile strength of decontamination films with different ratios of sodium alginate and chitosan

[0111]

[0112]

[0113] As can be seen from Table 1, by adopting the ratio of sodium alginate and chitosan of the present invention, the film-forming time of the composite complexing agent can be significantly shortened, and the breaking strength of the compound decontamination film can be improved.

[0114] The above are only the preferred embodiments of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A compound decontaminant for radioactive nuclide-contaminated skin, characterized in that, The compound decontaminant comprises a composite complexing agent and a film-forming solution; the composite complexing agent comprises sodium alginate, chitosan, a chelating agent and a PBS solution; the chelating agent comprises hydroxyethane diphosphonic acid, diethylenetriamine pentaacetic acid and carboxymethyl chitosan.

2. The compound decontaminant according to claim 1, wherein The mass ratio of the sodium alginate, chitosan and the chelating agent is 2.5-3.5:2.5-3.5:5-8; the mass fraction of sodium alginate in the composite complexing agent is 2.5-3.5%.

3. The compound detergent according to claim 1 or 2, characterized in that, The mass ratio of the hydroxyethane diphosphonic acid, diethylenetriamine pentaacetic acid and carboxymethyl chitosan is 1-2:3.5-4.5:0.5-1.

5.

4. The compound decontaminant according to claim 1, characterized in that, The concentration of the PBS solution is 0.008-0.012 mol / L, and the pH value is 6.5-7.

5.

5. The compound decontaminant according to claim 3, characterized in that, The preparation method of the composite complexing agent is: mixing sodium alginate, chitosan, hydroxyethane diphosphonic acid, diethylenetriamine pentaacetic acid, carboxymethyl chitosan and the PBS solution to obtain the composite complexing agent, and the mixing is carried out at a rotation speed of 1200-1400 r / min, and the mixing time is 10-15 h.

6. The compound decontaminant according to claim 1 or 5, characterized in that, The film-forming solution is an aqueous calcium chloride solution, and the mass concentration of the aqueous calcium chloride solution is 9-11%.

7. Method for using the compound decontaminant for radioactive nuclide-contaminated skin according to any one of claims 1 to 6, characterized in that, Apply the composite complexing agent on the skin, cover the composite complexing agent with a gauze impregnated with the film-forming solution, and remove the formed compound decontamination film.

8. The usage method according to claim 7, characterized in that, The application amount of the composite complexing agent on the skin is 0.15 - 0.25 mL / 3 - 5 cm 2 .

9. The method of use according to claim 7 or 8, characterized in that, The covering time is 1.3-1.5 min.

10. The usage method according to claim 9, characterized in that, The skin is intact skin or wound skin.

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