CN101797392A - Palladium-103 and iodine-125 composite sealed seed source, source core and source core preparation method - Google Patents

Palladium-103 and iodine-125 composite sealed seed source, source core and source core preparation method Download PDF

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CN101797392A
CN101797392A CN201010104700A CN201010104700A CN101797392A CN 101797392 A CN101797392 A CN 101797392A CN 201010104700 A CN201010104700 A CN 201010104700A CN 201010104700 A CN201010104700 A CN 201010104700A CN 101797392 A CN101797392 A CN 101797392A
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palladium
silver
iodine
support rod
hydrazine
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CN101797392B (en
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高惠波
李忠勇
张文辉
韩连革
尹卫
陈大明
刘卓
王巍
邓雪松
金小海
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ATOM HIGH TECH Co Ltd
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China Institute of Atomic of Energy
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Abstract

The invention belongs to the technical field of medical preparations containing radioactive substances, and particularly relates to a palladium-103 and iodine-125 composite sealed seed source, a source core and a source core preparation method. The source core is a composite film which is formed by covering a layer of palladium-103 and iodine-125 on a carrier, and the composite sealing seed source is prepared by welding the source core in a titanium tube or a titanium alloy tube. The preparation method of the palladium-103 and iodine-125 composite sealed seed source core comprises the following steps: inoculating nano palladium seed crystals: immersing a carrier rod into a chloroform solution of palladium acetate, and then immersing into an alkaline ammonia solution of hydrazine; (2) electroless plating of palladium-103 and silver: putting the carrier rod into a mixed solution consisting of palladium chloride, silver nitrate, ethylene diamine tetraacetic acid, ammonium hydroxide and hydrazine, and uniformly covering a layer of palladium-103 and silver on the surface of the carrier; (3) chemical adsorption of iodine-125: putting the carrier rod into a mixed solution of sodium bromide or potassium bromide, sodium iodide or potassium iodide, sodium hydroxide or potassium hydroxide and potassium ferricyanide.

Description

Palladium-103 and iodine-125 compound seal seed source, source core and source core preparation method
Technical field
The invention belongs to the medicinal preparation technical field that contains radioactive substance, be specifically related to a kind of palladium-103 and iodine-125 compound seal seed source, source core and source core preparation method.
Background technology
Implanting treatment between tissue is with radioactive seed source implantation tumour tissue, utilizes the seed irridiation injury kill tumor cell that radiates of core in a steady stream, reaches the purpose of treatment tumor and alleviation disease.Implant treatment between tissue and be used for the treatment of various entity tumors, as carcinoma of prostate, breast carcinoma, hepatocarcinoma, pulmonary carcinoma, the brain cancer, ovarian cancer etc., obtained, outer radiotherapy is identical even better therapeutic effect with surgical operation.Implant treatment between tissue and be divided into temporary implantation and permanent implanted, temporary implantation is meant radioactive seed source implantation tumour position, takes out after treatment a period of time; And permanent implanted being meant no longer taken out radioactive seed source implantation tumour position.Implant the common employing of treatment between permanent tissue and be prepared into the seed source than short and the lower radionuclide of ray energy, as iodine-125 seed source and palladium-103 seed source by the half-life.
The iodine-125 half-life is 59.6 days, and the gamma-rays average energy is 28keV, and the predose rate is 9cGy/h, is applicable to treatment good differentiation, the tumor that increasess slowly; Palladium-103 half-life is 16.96 days, and the gamma-rays average energy is 23keV, and the predose rate is 20cGy/h, is applicable to that the treatment differentiation is relatively poor, breeds tumor rapidly.Many documents have been made report extensively and profoundly to the curative effect that iodine-125 and palladium-103 are used for the treatment of treatment of solid tumors such as carcinoma of prostate, for example Ling et al. uses linear quaternary model to compare the curative effect of iodine-125 and palladium-103 on the radiobiological basis of theory, conclusion is: on the basis of clinical practice dosage, iodine-125 is preponderated in the slower tumor of treatment propagation, and palladium-103 pair kills and to breed rapidly that the tumor cell effect is better than iodine-125.And for example the animal experiment study of Nag et al. shows: the carcinoma of palladium-103 treatment differentiation difference is more effective.Therefore based on above-mentioned and other some achievements in research, iodine-125 is commonly used to treat early stage tumor, and is used for the treatment of the middle and advanced stage tumor palladium-103 more.
Treatment is that radioactivity palladium-103 is fixed in silver is excellent with palladium-103 sealed seed source, is welded in to make in titanium or the titanium alloy tube.The method that the radioactivity iodine-125 is fixed on the silver-colored rod adopts galvanoplastic and chemiadsorption usually.Galvanoplastic require shortcomings such as high, production cycle length owing to complex process, instrument and equipment, be difficult to apply.Comparatively speaking, chemiadsorption technology, equipment are simple, with short production cycle, are easy to use in large-scale production.For example United States Patent (USP) 4323055 discloses a kind of chemiadsorption, and this method is that the silver rod was handled 1.5 hours with the hydrochloric acid mixed solution of sodium chlorite and 6mol/L, makes silver-colored excellent surface oxidation, chlorination, obtains the silver rod of surface coverage silver nitride precipitation; Again with itself and iodine [ 125I] change sodium solution and under the condition of pH=10, carried out ion-exchange reactions 18 hours, make silver nitride precipitation be converted into iodine [ 125I] change silver precipitation.In this method, sodium chlorite is not conventional reagent, is difficult to buying on the market; And produce the chlorine that penetrating odor is arranged in a large number in the course of reaction, environment is polluted.
Treatment is that radioactivity palladium-103 is fixed in silver is excellent with palladium-103 sealed seed source, is welded in to make in titanium or the titanium alloy tube.The method that radioactivity palladium-103 is fixed on the silver-colored rod adopts galvanoplastic and electroless plating method usually.Galvanoplastic complex process, instrument and equipment require high, and the production cycle is long, is difficult to carry out large-scale production.And electroless plating method technology, equipment are simple, with short production cycle, are easy to apply.For example Chinese patent ZL01105243.0 discloses a kind of electroless plating method, and this method is to be main solution composition with Palladous chloride., ammonium chloride, ammonia, sodium hypophosphite, regulates pH=10,35 ℃ of following chemical platings 1 hour, makes silver-colored excellent surface coverage one deck palladium-103.The silver-colored rod of the surface coverage palladium-103 that obtains in this method is difficult to adsorb iodine-125 in the above, can only prepare palladium-103 seed source.
Mostly present research is single nucleic seed source implantation tumour of planting is treated.-103 two kinds of radioactive seed sources of iodine-125 and palladium can mix application.The half-life of palladium-103 is 16.96 days, and the dosage of release 50% has only 8.5 days, becomes " the line army " that attack tumor cell; 59.6 days iodine-125 half-life, the dosage of release 50% needs 30 days, just in time becomes palladium-103 " second echelon " afterwards.This imagination based on radiobiological effect also is applicable to tumor cell that differentiation differs from, that propagation is fast because of palladium-103, and iodine-125 is applicable to good differentiation, divides slower tumor cell, and both share and can more fully attack tumor cell.For example research such as Chen is thought, if in the iodine-125 seed source plantation treatment of using clinical survival dose, mix and implant palladium-103 seed source, will increase the lethality to tumor cell; On the other hand, if when using clinical survival dose plantation palladium-103 seed source treatment tumor, mix the iodine-125 seed source of implanting, will produce radiobiology so-called " cold spot " (reparation that is this scope inner cell survival or the inferior cell that causes death increases) so at the main position of iodine-125 seed source dose distribution, for the tumor rapidly of growing, " cold spot " effect is particularly evident.But, while plates palladium-103 on carrier and there is certain difficulty in iodine-125, if while depositing Pd-103 and iodine-125 on carrier, because two kinds of nucleic chemical property are widely different, the deposition of palladium-103 need adopt Reducing agent, and the deposition of iodine-125 needs oxidant, and the two can not be present in simultaneously with in a kind of solution; If on carrier, plate earlier palladium-103, because palladic chemical property is stable, deposition iodine-125 above being difficult in; If plate iodine-125 earlier, there is NH in iodine-125 with the form deposition of AgI during owing to chemical palladium-plating 4OH can cause a large amount of losses of AgI.Based on above reason, the research of having reported at present only limits to palladium-103 seed source and iodine-125 seed source implantation tumour tissue respectively, does not have still that palladium-103 and iodine-125 are compound to be the seed source of one.
Summary of the invention
(1) goal of the invention
The object of the invention is to provide a kind of palladium-103 and iodine-125 compound seal seed source, source core and source core preparation method.
(2) technical scheme
For achieving the above object, the invention provides following technical scheme:
The source core in a kind of palladium-103 and iodine-125 compound seal seed source, with can as the metal of X ray label or nonmetal be carrier, cover one deck radiosiotope thin film on this carrier, key is: described radiosiotope thin film is the laminated film of palladium-103 and iodine-125.Described metallic carrier is made by wherein a kind of of silver, copper, nickel, palladium, gold or the alloy that contains this metal, and described non-metal carrier is made by resin, plastics.Described support shapes can be bar-shaped or round shaped grain shape.Described support rod specification is diameter 0.1~2.0mm, length 1.0~10.0mm.
Make the source core sealing in above-mentioned palladium-103 and iodine-125 compound seal seed source in a kind of palladium-103 and iodine-125 compound seal seed source in titanium pipe or titanium alloy tube.
A kind of above-mentioned palladium-103 and iodine-125 compound seal seed method of core in a steady stream for preparing comprises the steps:
(1) inoculation of nanometer palladium crystal seed:
(a) support rod is immersed in the chloroformic solution of 0.1~5mol/L palladium 3~20 minutes, take out the back air blow drying, wherein palladium can be with the Palladous nitrate. or the palladium acetylacetonate replacement of same concentrations;
(b) support rod is immersed in the alkaline ammonia solution of hydrazine 3~20 minutes, the concentration of hydrazine is 0.5~10mol/L in this solution, and the concentration of ammonia is 0.1~5mol/L, and it is dry under 80~160 ℃ of temperature to take out the back;
(c) repeat (a) and (b) step 3~10 times.
This step can be replaced by following steps:
(a) carrier is immersed in the tin chloride solution of 0.01~0.1mol/L 1~10 minute;
(b) carrier is immersed in the palladium chloride solution of 1~5mmol/L 1~10 minute, wherein Palladous chloride. can be with replacements such as the Palladous nitrate. of same concentrations, palladium, palladium acetylacetonates;
(c) repeat (a) and (b) step 5~10 times.
The inoculation that silver-colored rod is carried out nanometer palladium crystal seed helps initiation reaction when chemical plating, makes palladium-103 and silver be deposited on the surface of silver rod fast, uniformly.
(2) chemical plating of palladium-103 and silver: support rod is placed the mixed solution of forming by Palladous chloride., silver nitrate, disodiumedetate, ammonium hydroxide, hydrazine, wherein contain palladium-103 in the palladium chloride solution, regulating pH value is 6~12, stirring reaction is 0.5~5 hour under 25~100 ℃ of condition of water bath heating, makes carrier surface evenly cover one deck palladium-103 and silver.
Palladous chloride. concentration is 1~50mmol/L in this step, and this concentration hour can not guarantee palladium-103 at the excellent surperficial uniform distribution of silver very much, influences the uniformity that single seed source dosage field distributes, and the palladium layer is blocked up when too big, the ray that too much absorption palladium-103 is emitted; Silver nitrate concentration is 0.5~25mmol/L, and the chemisorbed that this concentration hour can't provide enough silver to be used for iodine-125 very much can increase seed source itself emits ray to palladium-103 and iodine-125 self-absorption when too big; Disodiumedetate concentration is 0.1~0.5mol/L, and it act as chelating agent and regulates silver and palladic current potential, makes silver and palladium to be deposited on simultaneously on the support rod; Ammonium hydroxide concentration is 1~10mol/L, and it act as is to regulate silver and palladic current potential as chelating agent, simultaneously also as the pH value regulator; Hydrazine concentration is 5~50mmol/L, and this concentration hour can reduce very much reaction rate and reduce the utilization rate of palladium-103, easily causes plating bath to decompose when too big.PH value all in 6~12 scopes, can add proper amount of sodium hydroxide as required pH value is regulated generally speaking in the solution in solution.Carrier surface area is 1~10cm with the liquor capacity ratio in this step 2/ mL.Wherein Palladous chloride. can replace with Palladous nitrate., palladium or the palladium acetylacetonate of same concentrations, and disodiumedetate can replace with ethylenediaminetetraacetic acid.
The chemical plating of palladium in this step-103 and silver can have following three kinds of modes:
(I) support rod is placed the mixed solution of forming by the hydrazine of the ammonium hydroxide of the disodiumedetate of the silver nitrate of the Palladous chloride. of 1~50mmol/L, 0.5~25mmol/L, 0.1~0.5mol/L, 1~10mol/L, 5~50mmol/L carry out the chemical plating of palladium and silver simultaneously.Take this chemical plating mode, palladium and silver are that to be mixed into one deck equally distributed in the plated film.
(II) earlier support rod is placed the mixed solution preplating palladium of forming by the hydrazine of the ammonium hydroxide of the disodiumedetate of the Palladous chloride. of 1~50mmol/L, 0.1~0.5mol/L, 1~10mol/L, 5~50mmol/L, and then in mixed solution, add silver nitrate, the concentration that makes silver nitrate is 0.5~25mmol/L, carries out the chemical plating of palladium and silver.Take this chemical plating mode, plated film is divided into two-layer, and internal layer is the palladium layer, and skin is the mixed layer of palladium and silver
(III) elder generation places support rod by the Palladous chloride. of 1~50mmol/L, the disodiumedetate of 0.1~0.5mol/L, the ammonium hydroxide of 1~10mol/L, the mixed solution that the hydrazine of 5~50mmol/L is formed and carries out palladic chemical plating, take out then, place by the silver nitrate of 0.5~25mmol/L, the disodiumedetate of 0.1~0.5mol/L, the ammonium hydroxide of 1~10mol/L, the mixed solution that the hydrazine of 5~50mmol/L is formed and carry out silver-colored chemical plating.Take this chemical plating mode, plated film is divided into two-layer, and internal layer is the palladium layer, and skin is a silver layer.
This step can be replaced by following steps: support rod is placed the mixed solution of being made up of the sodium hypophosphite of the ammonium hydroxide of the ammonium chloride of the silver nitrate of the Palladous chloride. of 1~30mmol/L, 0.5~25mmol/L, 0.3~3mol/L, 0.2~2mol/L, 0.05~0.4mol/L, wherein contain palladium-103 in the palladium chloride solution, regulating pH value is 6~12, stirring reaction is 0.5~5 hour under 25~90 ℃ of condition of water bath heating, and carrier surface area is 1~10cm with the liquor capacity ratio 2/ mL.Wherein Palladous chloride. can replace with Palladous nitrate., palladium or the palladium acetylacetonate of same concentrations, and disodiumedetate can replace with ethylenediaminetetraacetic acid.
The solution pH value is general all in 6~12 scopes in this step, if the solution that disposes not in this scope, can use acetic acid or sodium hydroxide that pH value is adjusted to 6~12.
In addition, step (1) and (2) can independently be used to prepare the source core of palladium-103 sealed seed source.
(3) chemisorbed of iodine-125: the potassium ferricyanide mixed solution of support rod being put into the sodium hydroxide of the sodium iodide of the sodium bromide of 0.05~1mol/L or potassium bromide, 1~10mmol/L or potassium iodide, 0.01~0.5mol/L or potassium hydroxide, 5~50mmol/L, wherein contain iodine-125 in sodium iodide or the liquor kalii iodide, regulating pH value is 6~12, and stirring reaction is 5~60 minutes under 25~60 ℃ of conditions.Wherein the concentration of sodium iodide or potassium iodide hour can not guarantee iodine-125 at the excellent surperficial uniform distribution of silver very much, influences the uniformity that single seed source dosage field distributes, and can reduce the utilization rate of iodine-125 when too big.Carrier surface area is 1~10cm with the liquor capacity ratio in this step 2/ mL.The solution pH value is general all in 6~12 scopes in this step, if the solution that disposes not in this scope, can use acetic acid or sodium hydroxide that pH value is adjusted to 6~12.
Source core structure according to the prepared sealed seed source of chemical plating mode (I) in the step (2) and this step is that palladium and iodine uniform mixing are one deck; Source core structure according to the prepared sealed seed source of chemical plating mode (II) in the step (2) and this step is two-layer, and wherein internal layer is a palladium, and skin is the mixed layer of palladium and iodine; Source core structure according to the prepared sealed seed source of chemical plating mode (III) in the step (2) and this step is two-layer, and wherein internal layer is a palladium, and skin is an iodine.
In addition, this step can independently be used to prepare the source core of iodine-125 sealed seed source, is more than 15 minutes the time when the response time of chemisorbed iodine-125, and the iodine-125 conversion ratio is higher than 97%.
(3) beneficial effect
Technical scheme provided by the invention has following advantage:
(I) can successfully be fixed in palladium-103 and iodine-125 on the carrier simultaneously, and carrier surface palladium-103 and iodine-125 are evenly distributed, densification, just can make both dose distribution all reach satisfied effect at whole tumor region, thereby utilize the characteristic of two kinds of nucleic more fully, learn from other's strong points to offset one's weaknesses, overcome and mix the shortcoming of implanting, obtain maximum lethal effect, obtain better therapeutic effect;
(II) reagent of Cai Yonging is conventional commercial reagent, and buying is convenient, and low price reduces production cost greatly;
(III) the utilization rate height of palladium-103 and iodine-125;
(IV) in course of reaction, do not have irritative gas to produce, do not cause environmental pollution, can guarantee working environment;
(V) the response time weak point has reduced the suffered radiation dose of operator.
The specific embodiment
The present invention will be further described according to specific embodiment below.
Embodiment one
Present embodiment is most preferred technical scheme, and used reagent is analytical pure.
The source core in a kind of palladium-103 and iodine-125 compound seal seed source, with can as the metal of X ray label or nonmetal be carrier, cover one deck radiosiotope thin film on this carrier, key is: described radiosiotope thin film is the laminated film of palladium-103 and iodine-125.Described metallic carrier is made by wherein a kind of of silver, copper, nickel, palladium, gold or the alloy that contains this metal, and described non-metal carrier is made by resin, plastics etc., and the carrier in the present embodiment is made from silver.Described support shapes can be bar-shaped or round shaped grain shape, and the carrier in the present embodiment is made bar-shaped.Described support rod specification is diameter 0.1~2.0mm, length 1.0~10.0mm.Preferred diameter 0.5mm in the present embodiment, the silver rod of length 3mm is as carrier.
A kind of palladium-103 and iodine-125 compound seal seed source adopt the method for laser soldering seal that the source core sealing in above-mentioned palladium-103 and iodine-125 compound seal seed source is made in titanium pipe or titanium alloy tube.
A kind of above-mentioned palladium-103 and iodine-125 compound seal seed method of core in a steady stream for preparing comprises the steps:
(1) inoculation of nanometer palladium crystal seed:
(a) silver rod is immersed in the chloroformic solution of 0.5mol/L palladium 15 minutes, take out the back air blow drying, wherein palladium can be with the Palladous nitrate. or the palladium acetylacetonate replacement of same concentrations;
(b) silver rod is immersed in the alkaline ammonia solution of hydrazine 15 minutes, the concentration of hydrazine is 2mol/L in this solution, and the concentration of ammonia is 0.2mol/L, and it is dry under 110 ℃ of temperature to take out the back;
(c) repeat (a) and (b) step 7 time, make silver-colored excellent surface coverage one deck nanometer palladium crystal seed.
(2) chemical plating of palladium-103 and silver: silver-colored rod is placed the mixed solution of forming by the hydrazine of the ammonium hydroxide of the disodiumedetate of the silver nitrate of the Palladous chloride. of 8mmol/L, 2mmol/L, 0.15mol/L, 5mol/L, 15mmol/L, wherein contain palladium-103 in the palladium chloride solution, its radioactivity can be regulated as required.Regulating pH value is 10, and the silver-colored rod of the coated with nanometre palladium crystal seed of (1) step preparation is put into plating bath, and carrier surface area is 8cm with the liquor capacity ratio 2/ mL, stirring reaction is 2 hours under 45 ℃ of condition of water bath heating, makes the composite membrane of surface coverage one deck palladium-103 and silver.Take out the silver rod, discard surperficial clear liquid, water cleaning silver rod three times, standby.Measure the radioactivity of mixed solution and supernatant respectively, calculate the adsorption efficiency of palladium-103 by following formula:
Radioactivity * 100% of the adsorption efficiency of palladium-103=(radioactivity of the radioactivity-supernatant of mixed solution)/mixed solution, the adsorption efficiency that obtains palladium-103 is 98%.
The mixed solution that silver-colored rod can be placed the Palladous chloride., silver nitrate, disodiumedetate, ammonium hydroxide, hydrazine of respective concentration to form in this step carries out the chemical plating of palladium and silver simultaneously.Also can earlier silver-colored rod be placed the mixed solution preplating palladium of forming by Palladous chloride., disodiumedetate, ammonium hydroxide, the hydrazine of respective concentration, and then in mixed solution, add silver nitrate, the concentration that makes silver nitrate is above-mentioned respective concentration, carries out the chemical plating of palladium and silver.Can also place the mixed solution of forming by Palladous chloride., disodiumedetate, ammonium hydroxide, the hydrazine of respective concentration to carry out palladic chemical plating silver-colored rod earlier, take out then, place the mixed solution of forming by silver nitrate, disodiumedetate, ammonium hydroxide, the hydrazine of respective concentration to carry out the chemical plating of silver.
In this step wherein Palladous chloride. can replace with the Palladous nitrate. of same concentrations, palladium or palladium acetylacetonate, disodiumedetate can replace with ethylenediaminetetraacetic acid.
(3) chemisorbed of iodine-125: the potassium ferricyanide mixed solution of silver-colored rod being put into the sodium hydroxide of the sodium iodide of the sodium bromide of 0.2mol/L or potassium bromide, 5mmol/L or potassium iodide, 0.05mol/L or potassium hydroxide, 25mmol/L, wherein contain iodine-125 in sodium iodide or the liquor kalii iodide, its radioactivity can be regulated as required.Regulating pH value is 10, and the surface coverage palladium-103 of second step preparation and the silver-colored rod of silver composite membrane are put into solution, and carrier surface area is 8cm with the liquor capacity ratio 2/ mL, stirring reaction is 15 minutes under 25 ℃ of condition of water bath heating, takes out the silver rod, discards surperficial clear liquid, water, acetone cleaning silver rod surface three times.Measure the radioactivity of mixed solution and supernatant respectively, calculate adsorption efficiency by following formula:
Radioactivity * 100% of the adsorption efficiency of iodine-125=(radioactivity of the radioactivity-supernatant of mixed solution)/mixed solution, the adsorption efficiency that obtains iodine-125 is 99%.
Embodiment two
Other guide is constant, is with the difference part of embodiment one:
A kind of above-mentioned palladium-103 and iodine-125 compound seal seed method of core in a steady stream for preparing comprises the steps:
(1) inoculation of nanometer palladium crystal seed:
(a) silver rod is immersed in the chloroformic solution of 0.1mol/L palladium 20 minutes, take out the back air blow drying, wherein palladium can be with the Palladous nitrate. or the palladium acetylacetonate replacement of same concentrations;
(b) silver rod is immersed in the alkaline ammonia solution of hydrazine 20 minutes, the concentration of hydrazine is 0.5mol/L in this solution, and the concentration of ammonia is 0.1mol/L, and it is dry under 80 ℃ of temperature to take out the back;
(c) repeat (a) and (b) step 10 time, make silver-colored excellent surface coverage one deck nanometer palladium crystal seed.
(2) chemical plating of palladium-103 and silver: silver-colored rod is placed the mixed solution of forming by the hydrazine of the ammonium hydroxide of the disodiumedetate of the silver nitrate of the Palladous chloride. of 1mmol/L, 0.5mmol/L, 0.1mol/L, 1mol/L, 5mmol/L, regulating pH value is 6, the silver-colored rod of the coated with nanometre palladium crystal seed of (1) step preparation is put into plating bath, and carrier surface area is 1cm with the liquor capacity ratio 2/ mL, stirring reaction is 0.5 hour under 100 ℃ of condition of water bath heating, makes the composite membrane of surface coverage one deck palladium-103 and silver.Take out the silver rod, discard surperficial clear liquid, water cleaning silver rod three times, standby.Calculating palladium-103 adsorption efficiency by embodiment 1 method is 96%.
(3) chemisorbed of iodine-125: the potassium ferricyanide mixed solution of silver-colored rod being put into the sodium hydroxide of the sodium iodide of the sodium bromide of 0.05mol/L or potassium bromide, 1mmol/L or potassium iodide, 0.01mol/L or potassium hydroxide, 5mmol/L, pH value is 6, the surface coverage palladium-103 of second step preparation and the silver-colored rod of silver composite membrane are put into solution, and carrier surface area is 1cm with the liquor capacity ratio 2/ mL, stirring reaction is 60 minutes under 45 ℃ of conditions, takes out the silver rod, discards surperficial clear liquid, water, acetone cleaning silver rod surface each three times.Calculating the iodine-125 adsorption efficiency by embodiment 1 method is 97%.
Embodiment three
Other guide is constant, is with the difference part of embodiment one:
A kind of above-mentioned palladium-103 and iodine-125 compound seal seed method of core in a steady stream for preparing comprises the steps:
(1) inoculation of nanometer palladium crystal seed:
(a) silver rod is immersed in the chloroformic solution of 5mol/L palladium 3 minutes, take out the back air blow drying, wherein palladium can be with the Palladous nitrate. or the palladium acetylacetonate replacement of same concentrations;
(b) silver rod is immersed in the alkaline ammonia solution of hydrazine 3 minutes, the concentration of hydrazine is 10mol/L in this solution, and the concentration of ammonia is 5mol/L, and it is dry under 160 ℃ of temperature to take out the back;
(c) repeat (a) and (b) step 3 time, make silver-colored excellent surface coverage one deck nanometer palladium crystal seed.
(2) chemical plating of palladium-103 and silver: silver-colored rod is placed the mixed solution of forming by the hydrazine of the ammonium hydroxide of the disodiumedetate of the silver nitrate of the Palladous chloride. of 50mmol/L, 25mmol/L, 0.5mol/L, 10mol/L, 50mmol/L, regulating pH value is 12, the silver-colored rod of the coated with nanometre palladium crystal seed of (1) step preparation is put into plating bath, and carrier surface area is 1cm with the liquor capacity ratio 2/ mL, stirring reaction is 5 hours under 25 ℃ of condition of water bath heating, makes the composite membrane of surface coverage one deck palladium-103 and silver.Take out the silver rod, discard surperficial clear liquid, water cleaning silver rod three times, standby.Calculating palladium-103 adsorption efficiency by embodiment 1 method is 95%.
(3) chemisorbed of iodine-125: the potassium ferricyanide mixed solution of silver-colored rod being put into the sodium hydroxide of the sodium iodide of the sodium bromide of 1mol/L or potassium bromide, 10mmol/L or potassium iodide, 0.5mol/L or potassium hydroxide, 50mmol/L, pH value is 12, the surface coverage palladium-103 of second step preparation and the silver-colored rod of silver composite membrane are put into solution, and carrier surface area is 10cm with the liquor capacity ratio 2/ mL, stirring reaction is 5 minutes under 60 ℃ of conditions, takes out the silver rod, discards surperficial clear liquid, water, acetone cleaning silver rod surface each three times.Calculating the iodine-125 adsorption efficiency by embodiment 1 method is 98%.
Embodiment four
Other guide is constant, is with the difference of embodiment one, and the inoculation of nanometer palladium crystal seed is in the step (1):
(a) silver rod is immersed in the tin chloride solution of 0.1mol/L 1 minute;
(b) silver rod is immersed in the palladium chloride solution of 5mmol/L 1 minute, wherein Palladous chloride. can be with replacements such as the Palladous nitrate. of same concentrations, palladium, palladium acetylacetonates;
(c) repeat (a) and (b) step 5 time, make silver-colored excellent surface coverage one deck nanometer palladium crystal seed.
Embodiment five
Other guide is constant, is with the difference of embodiment one, and the inoculation of nanometer palladium crystal seed is in the step (1):
(a) silver rod is immersed in the tin chloride solution of 0.05mol/L 5 minutes;
(b) silver rod is immersed in the palladium chloride solution of 3mmol/L 5 minutes, wherein Palladous chloride. can be with replacements such as the Palladous nitrate. of same concentrations, palladium, palladium acetylacetonates;
(c) repeat (a) and (b) step 8 time, make silver-colored excellent surface coverage one deck nanometer palladium crystal seed.
Embodiment six
Other guide is constant, is with the difference of embodiment one, and the inoculation of nanometer palladium crystal seed is in the step (1):
(a) silver rod is immersed in the tin chloride solution of 0.01mol/L 10 minutes;
(b) silver rod is immersed in the palladium chloride solution of 1mmol/L 10 minutes, wherein Palladous chloride. can be with replacements such as the Palladous nitrate. of same concentrations, palladium, palladium acetylacetonates;
(c) repeat (a) and (b) step 10 time, make silver-colored excellent surface coverage one deck nanometer palladium crystal seed.
Embodiment seven
Other guide is constant, be with the difference of embodiment one, the chemical plating of palladium-103 and silver is in the step (2): silver-colored rod is placed the mixed solution of being made up of the sodium hypophosphite of the ammonium hydroxide of the ammonium chloride of the silver nitrate of the Palladous chloride. of 10mmol/L, 5mmol/L, 0.5mol/L, 2.5mol/L, 0.1mol/L, regulating pH value is 10, stirring reaction is 2 hours under 60 ℃ of condition of water bath heating, and wherein carrier surface area is 6cm with the liquor capacity ratio 2/ mL.Wherein Palladous chloride. can replace with Palladous nitrate., palladium or the palladium acetylacetonate of same concentrations, and disodiumedetate can replace with ethylenediaminetetraacetic acid.
Embodiment eight
Other guide is constant, be with the difference of embodiment one, the chemical plating of palladium-103 and silver is in the step (2): silver-colored rod is placed the mixed solution of being made up of the sodium hypophosphite of the ammonium hydroxide of the ammonium chloride of the silver nitrate of the Palladous chloride. of 1mmol/L, 0.5mmol/L, 0.2mol/L, 0.3mol/L, 0.05mol/L, regulating pH value is 6, stirring reaction is 5 hours under 25 ℃ of condition of water bath heating, and carrier surface area is 1cm with the liquor capacity ratio 2/ mL.Wherein Palladous chloride. can replace with Palladous nitrate., palladium or the palladium acetylacetonate of same concentrations, and disodiumedetate can replace with ethylenediaminetetraacetic acid.
Embodiment nine
Other guide is constant, be with the difference of embodiment one, the chemical plating of palladium-103 and silver is in the step (2): silver-colored rod is placed the mixed solution of being made up of the sodium hypophosphite of the ammonium hydroxide of the ammonium chloride of the silver nitrate of the Palladous chloride. of 30mmol/L, 20mmol/L, 2mol/L, 3mol/L, 0.4mol/L, regulating pH value is 12, stirring reaction is 0.5 hour under 100 ℃ of condition of water bath heating, and carrier surface area is 1~10cm with the liquor capacity ratio 2/ mL.Wherein Palladous chloride. can replace with Palladous nitrate., palladium or the palladium acetylacetonate of same concentrations, and disodiumedetate can replace with ethylenediaminetetraacetic acid.
Embodiment ten
The used reagent of present embodiment is analytical pure.
The source core in a kind of palladium-103 and iodine-125 compound seal seed source, with can as the metal of X ray label or nonmetal be carrier, cover one deck radiosiotope thin film on this carrier, key is: described radiosiotope thin film is the laminated film of palladium-103 and iodine-125.Described metallic carrier is made by wherein a kind of of silver, copper, nickel, palladium, gold or the alloy that contains this metal, and described non-metal carrier is by resin, plastics etc. SystemBecome, the carrier in the present embodiment is made from silver.Described support shapes can be bar-shaped or round shaped grain shape, and the carrier in the present embodiment is made bar-shaped.Described support rod specification is diameter 0.1~2.0mm, length 1.0~10.0mm.Preferred diameter 0.5mm in the present embodiment, the silver rod of length 3mm is as carrier.
A kind of palladium-103 and iodine-125 compound seal seed source adopt the method for laser soldering seal that the source core sealing in above-mentioned palladium-103 and iodine-125 compound seal seed source is made in titanium pipe or titanium alloy tube.
A kind of above-mentioned palladium-103 and iodine-125 compound seal seed method of core in a steady stream for preparing comprises the steps:
(1) chemical plating of palladium-103 and silver: silver-colored rod is placed the mixed solution of forming by the hydrazine of the ammonium hydroxide of the disodiumedetate of the silver nitrate of the Palladous chloride. of 8mmol/L, 2mmol/L, 0.15mol/L, 5mol/L, 15mmol/L, regulating pH value is 10, silver-colored rod is put into plating bath, and carrier surface area is 8cm with the liquor capacity ratio 2/ mL, stirring reaction is 5 hours under 45 ℃ of condition of water bath heating, makes the composite membrane of surface coverage one deck palladium-103 and silver.Take out the silver rod, discard surperficial clear liquid, water cleaning silver rod three times, standby.
The mixed solution that silver-colored rod can be placed the Palladous chloride., silver nitrate, disodiumedetate, ammonium hydroxide, hydrazine of respective concentration to form in this step carries out the chemical plating of palladium and silver simultaneously.Also can earlier silver-colored rod be placed the mixed solution preplating palladium of forming by Palladous chloride., disodiumedetate, ammonium hydroxide, the hydrazine of respective concentration, and then in mixed solution, add silver nitrate, the concentration that makes silver nitrate is above-mentioned respective concentration, carries out the chemical plating of palladium and silver.Can also place the mixed solution of forming by Palladous chloride., disodiumedetate, ammonium hydroxide, the hydrazine of respective concentration to carry out palladic chemical plating silver-colored rod earlier, take out then, place the mixed solution of forming by silver nitrate, disodiumedetate, ammonium hydroxide, the hydrazine of respective concentration to carry out the chemical plating of silver.
In this step wherein Palladous chloride. can replace with the Palladous nitrate. of same concentrations, palladium or palladium acetylacetonate, disodiumedetate can replace with ethylenediaminetetraacetic acid.
(2) chemisorbed of iodine-125: the potassium ferricyanide mixed solution of the silver-colored rod of preparation in the step (1) being put into the sodium hydroxide of the sodium iodide of the sodium bromide of 0.2mol/L or potassium bromide, 5mmol/L or potassium iodide, 0.05mol/L or potassium hydroxide, 25mmol/L, pH value is 10, the surface coverage palladium-103 of second step preparation and the silver-colored rod of silver composite membrane are put into solution, and carrier surface area is 8cm with the liquor capacity ratio 2/ mL, stirring reaction is 15 minutes under 25 ℃ of condition of water bath heating, takes out the silver rod, discards surperficial clear liquid, water, acetone cleaning silver rod surface three times.
Above content be in conjunction with preferred embodiment to specifying that the present invention did, can not assert that the specific embodiment of the present invention only limits to these explanations.Concerning the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deductions and conversion, all should be considered as belonging to protection scope of the present invention.

Claims (10)

1. the source core in palladium-103 and iodine-125 compound seal seed source covers one deck radiosiotope thin film on support rod, and it is characterized in that: described radiosiotope thin film is the laminated film that contains palladium-103 and iodine-125.
2. the source core in compound seal seed according to claim 1 source is characterized in that: described support rod is made by wherein a kind of of silver, copper, nickel, palladium, gold or the alloy that contains this metal.
3. claim 1 described palladium-103 and the iodine-125 compound seal seed preparation method of core in a steady stream comprises the steps:
(1) chemical plating of palladium-103 and silver: support rod is placed the mixed solution of forming by the hydrazine of the ammonium hydroxide of the disodiumedetate of the silver nitrate of the Palladous chloride. of 1~50mmol/L, 0.5~25mmol/L, 0.1~0.5mol/L, 1~10mol/L, 5~50mmol/L, wherein contain palladium-103 in the palladium chloride solution, regulating pH value is 6~12, and stirring reaction is 0.5~5 hour under 25~100 ℃ of condition of water bath heating;
(2) chemisorbed of iodine-125: the potassium ferricyanide mixed solution of support rod being put into the sodium hydroxide of the sodium iodide of the sodium bromide of 0.05~1mol/L or potassium bromide, 1~10mmol/L or potassium iodide, 0.01~0.5mol/L or potassium hydroxide, 5~50mmol/L, wherein contain iodine-125 in sodium iodide or the liquor kalii iodide, regulating pH value is 6~12, and stirring reaction is 5~60 minutes under 25~60 ℃ of conditions.
4. preparation method according to claim 3 is characterized in that: in the step (1) support rod placed the mixed solution of being made up of the hydrazine of the ammonium hydroxide of the disodiumedetate of the silver nitrate of the Palladous chloride. of 1~50mmol/L, 0.5~25mmol/L, 0.1~0.5mol/L, 1~10mol/L, 5~50mmol/L to carry out the chemical plating of palladium and silver simultaneously; Perhaps earlier support rod is placed the mixed solution preplating palladium of forming by the hydrazine of the ammonium hydroxide of the disodiumedetate of the Palladous chloride. of 1~50mmol/L, 0.1~0.5mol/L, 1~10mol/L, 5~50mmol/L, and then in mixed solution, add silver nitrate, the concentration that makes silver nitrate is 0.5~25mmol/L, carries out the chemical plating of palladium and silver; Perhaps earlier support rod is placed by the Palladous chloride. of 1~50mmol/L, the disodiumedetate of 0.1~0.5mol/L, the ammonium hydroxide of 1~10mol/L, the mixed solution that the hydrazine of 5~50mmol/L is formed and carry out palladic chemical plating, take out then, place by the silver nitrate of 0.5~25mmol/L, the disodiumedetate of 0.1~0.5mol/L, the ammonium hydroxide of 1~10mol/L, the mixed solution that the hydrazine of 5~50mmol/L is formed and carry out silver-colored chemical plating.
5. preparation method according to claim 3 is characterized in that: in step (1) and (2), the support rod surface area is 1~10cm with the liquor capacity ratio 2/ mL.
6. according to the described preparation method of claim 3 to 5, it is characterized in that, also comprise the step of the inoculation of nanometer palladium crystal seed in step (1) before:
(a) support rod is immersed in the chloroformic solution of 0.1~5mol/L palladium 3~20 minutes, take out the back air blow drying;
(b) support rod is immersed in the alkaline ammonia solution of hydrazine 3~20 minutes, the concentration of hydrazine is 0.5~10mol/L in this solution, and the concentration of ammonia is 0.1~5mol/L, and it is dry under 80~160 ℃ of temperature to take out the back;
(c) repeat (a) and (b) step 3~10 times.
7. according to the described preparation method of claim 3 to 5, it is characterized in that, also comprise the step of the inoculation of nanometer palladium crystal seed in step (1) before:
(a) support rod is immersed in the tin chloride solution of 0.01~0.1mol/L 1~10 minute;
(b) support rod is immersed in the palladium chloride solution of 1~5mmol/L 1~10 minute;
(c) repeat (a) and (b) step 5~10 times.
8. claim 1 described palladium-103 and the iodine-125 compound seal seed preparation method of core in a steady stream comprises the steps:
(1) chemical plating of palladium-103 and silver: support rod is placed the mixed solution of forming by the sodium hypophosphite of the ammonium hydroxide of the ammonium chloride of the silver nitrate of the Palladous chloride. of 1~30mmol/L, 0.5~25mmol/L, 0.3~3mol/L, 0.2~2mol/L, 0.05~0.4mol/L, wherein contain palladium-103 in the palladium chloride solution, regulating pH value is 6~12, and stirring reaction is 0.5~5 hour under 25~90 ℃ of condition of water bath heating;
(2) chemisorbed of iodine-125: the potassium ferricyanide mixed solution of support rod being put into the sodium hydroxide of the sodium iodide of the sodium bromide of 0.05~1mol/L or potassium bromide, 1~10mmol/L or potassium iodide, 0.01~0.5mol/L or potassium hydroxide, 5~50mmol/L, wherein contain iodine-125 in sodium iodide or the liquor kalii iodide, regulating pH value is 6~12, and stirring reaction is 5~60 minutes under 25~60 ℃ of conditions.
9. preparation method according to claim 8 is characterized in that, also comprises the step of the inoculation of nanometer palladium crystal seed before in step (1):
(a) support rod is immersed in the chloroformic solution of 0.1~5mol/L palladium 3~20 minutes, take out the back air blow drying;
(b) support rod is immersed in the alkaline ammonia solution of hydrazine 3~20 minutes, the concentration of hydrazine is 0.5~10mol/L in this solution, and the concentration of ammonia is 0.1~5mol/L, and it is dry under 80~160 ℃ of temperature to take out the back;
(c) repeat (a) and (b) step 3~10 times.
10. palladium-103 and iodine-125 compound seal seed source, sealing has the radioactivity source core in titanium pipe or titanium alloy tube, it is characterized in that: described radioactivity source core is the source core in palladium described in the claim 1-103 and iodine-125 compound seal seed source.
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CN112972708A (en) * 2021-02-22 2021-06-18 姜伟 Palladium-103 and iodine-125 composite sealed seed source, source core and source core preparation method

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