CN104199077B - A kind of preparation method of three-dimensional radiation discoloration gel gauge - Google Patents

A kind of preparation method of three-dimensional radiation discoloration gel gauge Download PDF

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CN104199077B
CN104199077B CN201410397195.8A CN201410397195A CN104199077B CN 104199077 B CN104199077 B CN 104199077B CN 201410397195 A CN201410397195 A CN 201410397195A CN 104199077 B CN104199077 B CN 104199077B
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gel
solution
class compound
gauge
radiation
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CN104199077A (en
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蒋波
孙鹏
傅玉川
黄玮
胡娟
郝娜
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Sichuan University
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Sichuan University
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Abstract

The invention discloses a kind of preparation method of three-dimensional radiation discoloration gel gauge, radiating color changing system and the gel carrier system of tissue equivalent, the vesica that diacetylene class compound is made is prepared from as radiating color changing system, gel carrier by the high-molecular organic material of tissue equivalent;Including preparing diacetylene class compound nano vesica and using chemical crosslink technique, again freeze method or condensation method prepares radiating color changing gel gauge using injection method or membrane process.Each infinitesimal of inventive gel can occur corresponding color change with the difference of absorbed dose of radiation, visually just can determine whether 3-dimensional dose distribution substantially;After carrying out Dose calibration to gel, scanning survey its absorbance is that can determine that 3-dimensional dose is distributed;Diffusion effect, radiation aftereffect, the problem of forming ability difference that existing gel gauge is present effectively are overcome, there is accurate measurement precipitous dosage distribution dosage field 3-dimensional dose to be distributed;Prepare simple, easy analysis, sensitivity high, stable performance is conducive to promoting the use of.

Description

A kind of preparation method of three-dimensional radiation discoloration gel gauge
Technical field
It is solidifying the invention belongs to Radiation Chemistry of Polymer and the application field of nuclear technology, more particularly to a kind of discoloration of three-dimensional radiation The preparation method of jelly gauge.
Background technology
Carrier of the gel gauge using gel media as spatial dosage information, is uniformly distributed radiosensitive compound, When receiving ionizing radiation, there is radiation chemical reaction in compound, the chemical yield of product is the function of absorbed dose of radiation.By surveying Measure gel physicochemical characteristics change caused by the chemical yield or product of product, you can Reducing and absorption dosage.With other Routing Dosimeter is compared, and gel gauge once can just measure the dosage of any point in target area, and not exclusively face dosage or Certain dose point.Gel gauge has spatial resolution higher, accuracy of dose and tissue equivalent's property, can realize thering is precipitous dose The 3-dimensional dose distribution measuring of amount distribution dosage field.
Current gel gauge, is broadly divided into two categories below:Fricke gels gauge and polymer gel dosimeter. Fricke gel gauge is that the components such as ferrous salt are distributed in the solid gel dosimeter constituted in gel, with Fricke liquid The advantage of dosimeter.Problem is to receive inorganic ions Fe after ionising radiation2+And Fe3+Still may proceed to be spread in gel, cause agent Amount image blur, it is impossible to which accurate measurement dosage is distributed.Polymer gel dosimeter is uniform by acrylic acid or acrylamide monomers It is dispersed in gel and is prepared from, monomer occurs radiation polymerization and cross-linking reaction after acceptable dose.But oxygen effect (is quenched irradiation During the free radical that produces and suppress polymerisation), radiation aftereffect cause measurement deviation be this kind of aggretion type dosimeter without The problem that method is avoided.And this two gellikes dosimeter forming ability is poor, it is necessary to maintain form with container, reduce dosimeter Tissue equivalent's property, therefore existing gel dose meter systems be not well positioned to meet radiating medical, scientific experiment and radiation plus The requirement of 3-dimensional dose distribution measuring during work.
The content of the invention
The purpose of the embodiment of the present invention is to provide the preparation method that a kind of three-dimensional radiation changes colour gel gauge, it is intended to solved The deficiency of diffusion effect, radiation aftereffect, forming ability difference that certainly existing gel gauge is present etc., it is impossible to which accurate measurement has The problem of precipitous dosage distribution dosage field 3-dimensional dose distribution.
The embodiment of the present invention is achieved in that a kind of preparation method of three-dimensional radiation discoloration gel gauge, the three-dimensional The preparation method of radiating color changing gel gauge includes the gel carrier system of radiating color changing system and tissue equivalent, diacetylene class The vesica that compound is made is prepared from as radiating color changing system, gel carrier by the high-molecular organic material of tissue equivalent; Specifically include following steps:
Step one, diacetylene class compound nano vesica is prepared using injection method, and diacetylene class compound has been dissolved in 0.3%~2% solution is configured in machine solvent, by above-mentioned solution according to volume ratio 1:4~1:50 implantation temperatures are higher than organic Simultaneously high temperature bath is ultrasonic in the deionized water of solvent boiling point, stands to room temperature and is put into refrigerator 4 DEG C of refrigeration, 6 hours fourths derived above Two acetylenic compound nano vesicle solutions;
Step 2, radiating color changing gel gauge is prepared using chemical crosslink technique, by acrylamide and N, N- di-2-ethylhexylphosphine oxide (acrylamide is 10 with N,N methylene bis acrylamide mass ratio to acrylamide:1~20:1) diacetylene class compound is added (acrylamide is 1 with vesicle solution mass ratio to vesicle solution:10~2:10), after ultrasonic dissolution heating water bath to 50~60 DEG C, Ammonium persulfate aqueous solution (catalyst) is added to be uniformly mixed, keeping temperature is until acrylamide monomer polymerization crosslinking completes shape Into radiating color changing gel.
Further, diacetylene class compound nano vesica is prepared in step one to be specifically included using membrane process: The dissolving of diacetylene class compound is configured to 0.3%~2% solution in organic solvent, above-mentioned solution is added into round bottom burns In bottle, after the method solvent evaporated of rotary evaporation, drag forms one layer of film of homogeneous transparent, is added in flask Deionized water (deionized water volume is 4~50 times of the diacetylene class compound solution volume in addition round-bottomed flask), 50~ 80 DEG C of high temperature bath 30 minutes transparent or semitransparent emulsion derived above of ultrasound, it is to be cooled to after room temperature, solution is placed 4 DEG C of refrigeration, 6 hours diacetylene class compound nano vesicle solutions derived above in refrigerator.
Further, in step 2, preparing radiating color changing gel gauge can also be specifically included using method is frozen again:Claim Take a certain amount of polyvinyl alcohol to be placed in container, add appropriate water, be heated with stirring to 90 DEG C of polyethylene dissolving alcohol and be configured to matter Amount fraction is 15%~20% polyvinyl alcohol water solution, in standing 1 hour removing bubble at 60 DEG C;Polyvinyl alcohol is water-soluble Liquid and diacetylene class compound vesicle solution by volume 1:1~2:After 1 is well mixed, cryogenic freezing and normal temperature unfreezing repeatedly, Until polyvinyl alcohol molecule crosslinks the radiating color changing gel to form solid phase.
Further, in step 2, preparing radiating color changing gel gauge can also be specifically included using condensation method:Will Agarose or gelatin be added to the water be heated to more than 90 DEG C make its dissolving be configured to 5%~10% solution, with diacetylene class Compound vesicle solution by volume 1:1~1:2 uniform mixing, are cooled to room temperature and allow gel sets to form radiating color changing gel.
Further, during the preparation method of three-dimensional radiation discoloration gel gauge prepares radiating color changing gel process, pass through Increase diacetylene class compound vesicle solution concentration or add glucose, sucrose to improve change colour response of the gel to irradiation dose Sensitivity, or diacetylene class compound vesicle solution concentration is reduced to reduce discoloration response sensitivity of the gel to irradiation dose, Response of the extension gel to irradiation dose is interval.
Further, diacetylene class compound be the carbon diacetylenic acids of 10,12- 25, the carbon diacetylenic acids of 10,12- 23,10, Diine -1- the alcohol of 12- 25,10,12- pentacosane diacetylenic acids methyl esters, the carbon diacetylenic acids of 10,12- 27,10,12- 29 Carbon diacetylenic acid, the carbon diacetylenic acids of 5,7- 16, the carbon diacetylenic acids of 2,4- 15, the carbon diacetylenic acids of 2,4- 17, the carbon diacetylenic acids of 2,4- 19, Any one in the carbon diacetylenic acids of 2,4- 21.
Further, organic solvent is any one in acetone, ethanol, methyl alcohol, chloroform, ethyl acetate.
The preparation method of the three-dimensional radiation discoloration gel gauge that the present invention is provided, using some diacetylene class compounds Parents characteristic (strand one end is hydrophilic, other end oleophylic), assembles them into nanometer dosage vesica to solve diacetylene class chemical combination Thing and the compatibility of gel rubber system, are successfully used for 3-dimensional dose distribution measuring by such electrochromic substance.Additionally, of the invention three Dimension radiating color changing gel gauge overcomes the existing gel gauge such as diffusion effect, radiation aftereffect, forming ability difference not Foot, is with a wide range of applications in radiating medical, scientific experiment and radiation industry.
The invention has the advantages that:
1. made by the present invention three-dimensional radiation discoloration gel gauge, to X-ray, γ in 2-1000Gy dosage ranges The ionising radiations such as ray, electron beam, proton beam have good dose response linear, in radiating medical, scientific experiment and radiation Had broad application prospects in industry;
2nd, the three-dimensional radiation discoloration gel gauge made by the present invention is placed in radiation field and irradiates, and each infinitesimal of gel can be with Absorbed dose of radiation difference and there is corresponding color change, visually just can determine whether substantially 3-dimensional dose distribution;Gel is carried out After Dose calibration, scanning survey its absorbance is that can determine that 3-dimensional dose is distributed;
3. made by the present invention three-dimensional radiation discoloration gel gauge, effectively overcome diffusion effect, radiation aftereffect, The deficiency of the existing gel gauge such as forming ability difference, can accurately measure the 3-dimensional dose point with precipitous dosage distribution dosage field Cloth;
4. the present invention has the features such as simple preparation, easy analysis, sensitivity high, stable performance, is conducive to promoting the use of.
Brief description of the drawings
Fig. 1 is the preparation method flow chart of three-dimensional radiation discoloration gel gauge provided in an embodiment of the present invention;
Fig. 2 is certain formula high sensitivity radiating color changing gel gauge provided in an embodiment of the present invention in absworption peak Net optical density-dose response relation the schematic diagram at (680nm) place;
Fig. 3 is certain formula muting sensitivity radiating color changing gel gauge provided in an embodiment of the present invention in absworption peak Net optical density-dose response relation the schematic diagram at (680nm) place;
Fig. 4 a, Fig. 4 b are respectively cylindrical gel dosimeters provided in an embodiment of the present invention by 1cm × 1cm square field spokes Top view and sectional view according to after.
Fig. 5 is the unit not measured in the same time after three-dimensional radiation discoloration gel gauge provided in an embodiment of the present invention is irradiated The net optical density schematic diagram of thickness;
Fig. 6 is 0.5 hour and 96 after circular gel piece provided in an embodiment of the present invention is irradiated by 1cm × 1cm square fields The net optical density distribution schematic diagram of radial direction of hour.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
Below in conjunction with the accompanying drawings and specific embodiment is further described to application principle of the invention.
As shown in figure 1, the preparation method of the three-dimensional radiation discoloration gel gauge of the embodiment of the present invention is comprised the following steps:
S101:Diacetylene class compound nano vesica is prepared using injection method or membrane process;
S102:Using chemical crosslink technique, jelly method or condensation method prepare radiating color changing gel gauge again.
In step S101, the preparation method of diacetylene class compound nano vesica includes:
Diacetylene class compound nano vesica is prepared using injection method or membrane process;
Injection method:The dissolving of diacetylene class compound is configured to 0.3%~2% solution in organic solvent, will be above-mentioned Solution is according to volume ratio 1:4~1:Simultaneously high temperature bath is ultrasonic higher than in the deionized water of organic solvent boiling point for 50 implantation temperatures, quiet Put to room temperature and be put into refrigerator 4 DEG C of refrigeration, 6 hours diacetylene class compound nano vesicle solutions derived above;
Membrane process:The dissolving of diacetylene class compound is configured to 0.3%~2% solution in organic solvent, will be above-mentioned Solution is added in round-bottomed flask, after the method solvent evaporated of rotary evaporation, drag one layer of homogeneous transparent of formation Film, to deionized water is added in flask, (deionized water volume is to add the diacetylene class compound solution body in round-bottomed flask Long-pending 4~50 times), 50~80 DEG C of high temperature bath 30 minutes transparent or semitransparent emulsion derived above of ultrasound are to be cooled to arrive After room temperature, solution is placed on 4 DEG C of refrigeration, 6 hours diacetylene class compound nano vesicle solutions derived above in refrigerator.
In step s 102, freeze method using chemical crosslink technique, again or condensation method prepares radiating color changing gel gauge and includes:
Chemical crosslink technique:By acrylamide and N,N methylene bis acrylamide (acrylamide and N, N- di-2-ethylhexylphosphine oxide third Acrylamide mass ratio is 10:1~20:1) diacetylene class compound vesicle solution (acrylamide and vesicle solution mass ratio are added It is 1:10~2:10), heating water bath, to 50~60 DEG C, adds ammonium persulfate aqueous solution (catalyst) stirring mixing after ultrasonic dissolution Uniformly, keeping temperature is until acrylamide monomer polymerization crosslinking completes to form radiating color changing gel;
Freeze method again:Weigh a certain amount of polyvinyl alcohol to be placed in container, add appropriate water, be heated with stirring to 90 DEG C of dissolvings Polyvinyl alcohol is configured to the polyvinyl alcohol water solution that mass fraction is 15%~20%, at 60 DEG C stand 1 hour with except degassing Bubble;By polyvinyl alcohol water solution and diacetylene class compound vesicle solution by volume 1:1~2:It is repeatedly low after 1 is well mixed Temperature freezing and normal temperature unfreezing, until polyvinyl alcohol molecule crosslinks the radiating color changing gel to form solid phase;
Condensation method:Agarose or gelatin are added to the water and are heated to more than 90 DEG C and its dissolving is configured to 5%~10% Solution, with diacetylene class compound vesicle solution by volume 1:1~1:2 uniform mixing, are cooled to room temperature and allow gel sets shape Into radiating color changing gel.
Radiating color changing gel process is prepared of the invention, can by increasing diacetylene class compound vesicle solution concentration Or add glucose, sucrose etc. to improve discoloration response sensitivity of the gel to irradiation dose, can also reduce diacetylene class chemical combination Thing vesicle solution concentration extends response area of the gel to irradiation dose to reduce discoloration response sensitivity of the gel to irradiation dose Between.
Operation principle of the invention:
The present invention is self-assembled into nano vesicle anti-from the diacetylene class compound monomer with parents' molecular structure After answering device, the radiating color changing gel developed for 3-dimensional dose distribution measuring is dispersed in the gel carrier of tissue equivalent Dosimeter, the design of nano vesicle effectively overcomes dosage image blur caused by monomer molecule diffusion, while polymeric chain is increased Length is limited in inside vesica and carries out, and reduces the influence of radiation aftereffect, and gel carrier prepared by the present invention has good group Knit equivalence and elastic strength, can arbitrarily plastotype and cutting, for 3-dimensional dose distribution measuring provides good spatial configuration, Therefore, the radiating color changing gel gauge compensate for the deficiency of existing gel gauge, be to be distributed dosage field with precipitous dosage 3-dimensional dose distribution measuring provide a kind of new method.
Three-dimensional radiation discoloration gel gauge is in 2-1000Gy dosage ranges to X-ray, gamma-rays, electron beam, matter The ionising radiations such as beamlet have good dose response linear, while it is poor to overcome diffusion effect, radiation aftereffect, forming ability Etc. the deficiency of existing gel gauge, it is with a wide range of applications in radiating medical, scientific experiment and radiation industry.
It is of the invention to concretely comprise the following steps:
Three-dimensional radiation discoloration gel gauge of the invention is made up of two systems:Radiating color changing system and tissue equivalent Gel carrier system, the vesica that diacetylene class compound is made is had as radiating color changing system, gel carrier by tissue equivalent Machine macromolecular material is prepared from, and the preparation method of three-dimensional radiation discoloration gel gauge is comprised the following steps:
1st, the preparation of diacetylene class compound nano vesica:
Injection method can be respectively adopted and membrane process prepares diacetylene class compound nano vesica, comprise the following steps that:
Injection method:The dissolving of diacetylene class compound is configured to 0.3%~2% solution in organic solvent, will be above-mentioned Solution is according to volume ratio 1:4~1:Simultaneously high temperature bath is ultrasonic higher than in the deionized water of organic solvent boiling point for 50 implantation temperatures, quiet Put to room temperature and be put into refrigerator 4 DEG C of refrigeration, 6 hours diacetylene class compound nano vesicle solutions derived above;
Membrane process:The dissolving of diacetylene class compound is configured to 0.3%~2% solution in organic solvent, will be above-mentioned Solution is added in round-bottomed flask, after the method solvent evaporated of rotary evaporation, drag one layer of homogeneous transparent of formation Film, to deionized water is added in flask, (deionized water volume is to add the diacetylene class compound solution body in round-bottomed flask Long-pending 4~50 times), 50~80 DEG C of high temperature bath 30 minutes transparent or semitransparent emulsion derived above of ultrasound are to be cooled to arrive After room temperature, solution is placed on 4 DEG C of refrigeration, 6 hours diacetylene class compound nano vesicle solutions derived above in refrigerator.
2nd, prepared by radiating color changing gel:
Multiple polymers can be fabricated to gel carrier, mainly have three kinds of preparation methods according to polymer type:
Chemical crosslink technique:By acrylamide and N,N methylene bis acrylamide (acrylamide and N, N- di-2-ethylhexylphosphine oxide third Acrylamide mass ratio is 10:1~20:1) diacetylene class compound vesicle solution (acrylamide and vesicle solution mass ratio are added It is 1:10~2:10), heating water bath, to 50~60 DEG C, adds ammonium persulfate aqueous solution (catalyst) stirring mixing after ultrasonic dissolution Uniformly, keeping temperature is until acrylamide monomer polymerization crosslinking completes to form radiating color changing gel;
Freeze method again:Weigh a certain amount of polyvinyl alcohol to be placed in container, add appropriate water, be heated with stirring to 90 DEG C of dissolvings Polyvinyl alcohol is configured to the polyvinyl alcohol water solution that mass fraction is 15%~20%, at 60 DEG C stand 1 hour with except degassing Bubble;By polyvinyl alcohol water solution and diacetylene class compound vesicle solution by volume 1:1~2:It is repeatedly low after 1 is well mixed Temperature freezing and normal temperature unfreezing, until polyvinyl alcohol molecule crosslinks the radiating color changing gel to form solid phase;
Condensation method:Agarose or gelatin are added to the water and are heated to more than 90 DEG C and its dissolving is configured to 5%~10% Solution, with diacetylene class compound vesicle solution by volume 1:1~1:2 uniform mixing, are cooled to room temperature and allow gel sets shape Into radiating color changing gel.
3rd, three-dimensional radiation discoloration gel gauge adjustment of sensitivity:
In radiating color changing gel process being prepared using the above method, can be dense by increasing diacetylene class compound vesicle solution Degree adds glucose, sucrose etc. to improve discoloration response sensitivity of the gel to irradiation dose, can also reduce diacetylene class Compound vesicle solution concentration extends response of the gel to irradiation dose to reduce discoloration response sensitivity of the gel to irradiation dose It is interval.
Wherein, diacetylene class compound is the carbon diacetylenic acids (10,12- of 10,12- 25 Pentacosadiynoicacid), the carbon diacetylenic acids (10,12-Tricosadiynoicacid) of 10,12- 23,10,12- bis- 15 diine -1- alcohol (10,12-Pentacosadiyn-1-ol), 10,12- pentacosane diacetylenic acids methyl esters (Methyl-10, 12-pentacosadiynoate), the carbon diacetylenic acids of 10,12- 27 (10,12-heptacosadiynoic acid), 10, The carbon diacetylenic acids of 12- 29 (10,12-nonacosadiynoic acid), the carbon diacetylenic acid (5,7- of 5,7- 16 Hexadecadiynoic acid), the carbon diacetylenic acids of 2,4- 15 (2,4-pentadecadiynoic acid), the carbon of 2,4- 17 Diacetylenic acid (2,4-heptadecadiynoic acid), the carbon diacetylenic acids of 2,4- 19 (2,4-nonadecadiynoic acid), Any one in the carbon diacetylenic acids of 2,4- 21 (2,4-heneicosadiynoic acid);
Organic solvent is any one in acetone, ethanol, methyl alcohol, chloroform, ethyl acetate.
Specific embodiment of the invention:
Embodiment 1:
80mg10, the carbon diacetylenic acids of 12- 25 are formed into solution in being dissolved in 10ml acetone, above-mentioned solution is injected into 80ml Temperature is in 70 DEG C of deionized water and keeping temperature water bath sonicator, stands to room temperature and is put into 4 DEG C of refrigerator and refrigerates more than 6 hours Obtain the carbon diacetylenic acid nano vesicle solution of 10,12- 25;
By 12g acrylamides, 0.8gN, N- methylene-bisacrylamides and 0.8g glucose add 80ml10,12- 20 Five carbon diacetylenic acid vesicle solutions, heating water bath adds 12ml ammonium persulfate aqueous solution (concentration to 50~60 DEG C after ultrasonic dissolution 0.01g/ml) it is uniformly mixed, keeping temperature is until acrylamide monomer polymerization crosslinking completes to form high sensitivity radiation change Color gel gauge.
Embodiment 2:
80mg10, the carbon diacetylenic acids of 12- 23 are formed solution, above-mentioned solution is added into circle in being dissolved in 10ml ethanol In the flask of bottom, after the method solvent evaporated of rotary evaporation, drag forms one layer of film of homogeneous transparent, in flask 40ml deionized waters are added, transparent or semitransparent emulsion is obtained after high temperature (80 DEG C) water bath sonicator, it is to be cooled to after room temperature, Solution is placed on 4 DEG C of refrigeration, the 6 hours carbon diacetylenic acid nano vesicle solution of 10,12- derived above 23 in refrigerator;
Agarose is completely dissolved by being heated to more than 90 DEG C in 3.2g agaroses addition 40ml water, by agarose solution With diacetylene class compound vesicle solution by volume 1:1 uniform mixing, is cooled to room temperature and allows gel sets to form high sensitivity Radiating color changing gel gauge.
Embodiment 3:
13mg10, the carbon diacetylenic acids of 12- 25 are formed into solution in being dissolved in 2ml methyl alcohol, above-mentioned solution is injected into 80ml Temperature is in 70 DEG C of deionized water and keeping temperature water bath sonicator, stands to room temperature and is put into 4 DEG C of refrigerator and refrigerates more than 6 hours Obtain the carbon diacetylenic acid nano vesicle solution of 10,12- 25;
12g acrylamides and 0.8gN, N- methylene-bisacrylamide are added into the carbon diacetylenic acid capsules of 80ml10,12- 25 Bubble solution, heating water bath adds 12ml ammonium persulfate aqueous solutions (concentration 0.01g/ml) stirrings to 50~60 DEG C after ultrasonic dissolution Well mixed, keeping temperature is until acrylamide monomer polymerization crosslinking completes to form muting sensitivity radiating color changing gel gauge.
Embodiment 4:
28mg10, the diine -1- alcohol of 12- 25 are formed solution, above-mentioned solution is added into circle in being dissolved in 4ml chloroforms In the flask of bottom, after the method solvent evaporated of rotary evaporation, drag forms one layer of film of homogeneous transparent, in flask 80ml deionized waters are added, transparent or semitransparent emulsion is obtained after high temperature (80 DEG C) water bath sonicator, it is to be cooled to after room temperature, Solution is placed on 4 DEG C of refrigeration, the 6 hours diine -1- alcohol nano vesicle solution of 10,12- derived above 25 in refrigerator;
Gelatin is completely dissolved by being heated to more than 90 DEG C in 8.8g gelatin addition 80ml water, by aqueous gelatin solution and fourth two Acetylene compound vesicle solution by volume 1:1 uniform mixing, is cooled to room temperature and allows gel sets to form muting sensitivity radiation change Color gel gauge.
Embodiment 5:
21mg10, the carbon diacetylenic acids of 12- 27 are formed into solution in being dissolved in 3ml ethanol, above-mentioned solution is injected into 40ml Temperature is in 70 DEG C of deionized water and keeping temperature water bath sonicator, stands to room temperature and is put into 4 DEG C of refrigerator and refrigerates more than 6 hours Obtain the carbon diacetylenic acid nano vesicle solution of 10,12- 27;
Weigh 12g polyvinyl alcohol to be placed in flask, add 80ml deionized waters, be heated with stirring to 90 DEG C of polyethylene dissolvings Alcohol, obtains the limpid transparent aqueous solution, in standing 1 hour to remove bubble at 60 DEG C, by 80ml polyvinyl alcohol water solutions with After the carbon diacetylenic acid vesicle solution of 40ml10,12- 27 is well mixed, freezed 20 hours in -20 DEG C, then placed at normal temperatures It is 1 circulation to thaw within 4 hours, and 4 circulations are carried out altogether, and polyvinyl alcohol molecule crosslinks the radiation change to form satisfactory mechanical property Color gel gauge.
The invention has the advantages that:
1. made by the present invention three-dimensional radiation discoloration gel gauge, to X-ray, γ in 2-1000Gy dosage ranges The ionising radiations such as ray, electron beam, proton beam have good dose response linear, in radiating medical, scientific experiment and radiation Had broad application prospects in industry.
2nd, the three-dimensional radiation discoloration gel gauge made by the present invention is placed in radiation field and irradiates, and each infinitesimal of gel can be with Absorbed dose of radiation difference and there is corresponding color change, visually just can determine whether substantially 3-dimensional dose distribution.Gel is carried out After Dose calibration, scanning survey its absorbance is that can determine that 3-dimensional dose is distributed.
3. made by the present invention three-dimensional radiation discoloration gel gauge, effectively overcome diffusion effect, radiation aftereffect, The deficiency of the existing gel gauge such as forming ability difference, can accurately measure the 3-dimensional dose point with precipitous dosage distribution dosage field Cloth.
4. the present invention has the features such as simple preparation, easy analysis, sensitivity high, stable performance, is conducive to promoting the use of.
Application effect of the invention is described further by following performance test:
1. made by the present invention three-dimensional radiation discoloration gel gauge, to X-ray, γ in 2-1000Gy dosage ranges The ionising radiations such as ray, electron beam, proton beam have good dose response linear.
2. as a result as shown in Figure 2, dose of radiation is shown in the range of 2~100Gy, and high sensitivity radiating color changing gel is inhaled The net optical density for receiving peak is linear with absorbed dose of radiation.
3. as a result as shown in Figure 3, dose of radiation is shown in the range of 50~1000Gy, muting sensitivity radiating color changing gel The net optical density of absworption peak is linear with absorbed dose of radiation.
4. accompanying drawing 4a, Fig. 4 b are respectively the top views after cylindrical gel dosimeter is irradiated by 1cm × 1cm square fields And sectional view, clearly track has been internally formed in gel by the visible square shaped beam of sectional view, show the radiating color changing gel The measurable 3-dimensional dose distribution with precipitous dosage distribution dosage field of gauge.
5. the net optical density of the unit thickness such as Fig. 5 institutes not measured in the same time after the irradiation of three-dimensional radiation discoloration gel gauge Show;2 hours net optical density of inner gel increased 1.77% after irradiation, and 2 hours to the 48 hours net optical density of gel increase after irradiation 1.08%, have no that optical density increases in 48 hours to 168 hours, gel response tends towards stability;Test result shows the radiation The radiation aftereffect of discoloration gel gauge is far below polymer gel dosimeter.
6. the net optical density distribution of the radial direction of 0.5 hour and 96 hours after circular gel piece is irradiated by 1cm × 1cm square fields As shown in Figure 6.Gel is illuminated the optical density in region because radiation aftereffect is increased slightly, but optical density distribution curve halfwidth Position there is no transverse shifting in (± 5.6mm), show that radiating color changing gel also has no diffusion effect, agent in high dose gradient region Amount distribution imaging clearly.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.

Claims (7)

1. a kind of three-dimensional radiation changes colour the preparation method of gel gauge, it is characterised in that the three-dimensional radiation changes colour gel dose Meter includes the gel carrier system of radiating color changing system and tissue equivalent, and the vesica that diacetylene class compound is made becomes as radiation Color system, gel carrier is prepared from by the high-molecular organic material of tissue equivalent;Specifically include following steps:
Step one, diacetylene class compound nano vesica is prepared using injection method, diacetylene class compound is dissolved in organic molten 0.3%~2% solution is configured in agent, 0.3%~2% solution that will be prepared is according to volume ratio 1:4~1:50 implantation temperatures Higher than in the deionized water of organic solvent boiling point and high temperature bath ultrasound, stand to be put into after room temperature the refrigeration 6 hours of 4 DEG C of refrigerator with On obtain diacetylene class compound nano vesicle solution;
Step 2, radiating color changing gel gauge, acrylamide and N, N- methylene bisacrylamide acyl are prepared using chemical crosslink technique Amine mass ratio is 10:1~20:1;Add diacetylene class compound vesica molten acrylamide and N,N methylene bis acrylamide Liquid, acrylamide is 1 with vesicle solution mass ratio:10~2:10, heating water bath adds over cure to 50~60 DEG C after ultrasonic dissolution Sour aqueous ammonium is uniformly mixed, and keeping temperature is until acrylamide monomer polymerization crosslinking completes to form radiating color changing gel.
2. three-dimensional radiation as claimed in claim 1 changes colour the preparation method of gel gauge, it is characterised in that in step one Diacetylene class compound nano vesica is prepared to be specifically included using membrane process:Diacetylene class compound has been dissolved in 0.3%~2% solution is configured in machine solvent, the solution that will be configured to 0.3%~2% is added in round-bottomed flask, used After the method solvent evaporated of rotary evaporation, drag forms one layer of film of homogeneous transparent, to adding deionized water in flask, Deionized water volume is 4~50 times of the diacetylene class compound solution volume in addition round-bottomed flask, 50~80 DEG C of high-temperature water The ultrasonic 30 minutes transparent or semitransparent emulsion derived above of bath, it is to be cooled to after room temperature, solution is placed on 4 DEG C in refrigerator 6 hours diacetylene class compound nano vesicle solutions derived above of refrigeration.
3. three-dimensional radiation as claimed in claim 1 changes colour the preparation method of gel gauge, it is characterised in that in step 2 In, preparing radiating color changing gel gauge can also be specifically included using method is frozen again:Polyvinyl alcohol is weighed to be placed in container, plus Enter water, be heated with stirring to 90 DEG C of polyethylene dissolving alcohol and be configured to the polyvinyl alcohol water solution that mass fraction is 15%~20%, in Stand 1 hour to remove bubble at 60 DEG C;By polyvinyl alcohol water solution and diacetylene class compound vesicle solution by volume 1:1 ~2:After 1 is well mixed, cryogenic freezing and normal temperature unfreezing repeatedly, until polyvinyl alcohol molecule crosslinks the radiation to form solid phase Discoloration gel.
4. three-dimensional radiation as claimed in claim 1 changes colour the preparation method of gel gauge, it is characterised in that in step 2 In, preparing radiating color changing gel gauge can also be specifically included using condensation method:Agarose or gelatin are added to the water heating To more than 90 DEG C, dissolving is configured to 5%~10% solution, with diacetylene class compound vesicle solution by volume 1:1~1:2 Uniform mixing, is cooled to room temperature and allows gel sets to form radiating color changing gel.
5. three-dimensional radiation as claimed in claim 1 changes colour the preparation method of gel gauge, it is characterised in that the three-dimensional radiation The preparation method of discoloration gel gauge is prepared in radiating color changing gel process, by increasing diacetylene class compound vesicle solution Concentration adds glucose, sucrose to improve discoloration response sensitivity of the gel to irradiation dose, or reduces diacetylene class chemical combination Thing vesicle solution concentration extends response area of the gel to irradiation dose to reduce discoloration response sensitivity of the gel to irradiation dose Between.
6. three-dimensional radiation as claimed in claim 1 changes colour the preparation method of gel gauge, it is characterised in that diacetylene class Compound is the carbon diacetylenic acids of 10,12- 25, the carbon diacetylenic acids of 10,12- 23, the diine -1- alcohol of 10,12- 25,10,12- Pentacosane diacetylenic acid methyl esters, the carbon diacetylenic acids of 10,12- 27, the carbon diacetylenic acids of 10,12- 29, the carbon diines of 5,7- 16 In acid, the carbon diacetylenic acids of 2,4- 15, the carbon diacetylenic acids of 2,4- 17, the carbon diacetylenic acids of 2,4- 19, the carbon diacetylenic acids of 2,4- 21 Any one.
7. three-dimensional radiation as claimed in claim 1 changes colour the preparation method of gel gauge, it is characterised in that organic solvent is Any one in acetone, ethanol, methyl alcohol, chloroform, ethyl acetate.
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