CN103110964A - Dual-mode contrast medium with fluorescence and magnetic resonance imaging and preparation method thereof - Google Patents
Dual-mode contrast medium with fluorescence and magnetic resonance imaging and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a dual-mode contrast medium with fluorescence and magnetic resonance imaging and a preparation method thereof. The dual-mode contrast medium is provided with a core-shell type structure comprising an inner core and an outer shell. The preparation method comprises the steps of: adding copper salts, indium salts and lauryl mercaptan to a reactor which is filled with a non-polar organic solvent, and reacting to obtain a uniform CuInS2 colloidal solution; adding a precursor solution of zinc and a precursor solution of manganese, and reacting to obtain a quantum-dot colloidal solution with the CuInS2/Zn1-xMnxS core-shell structure; adding an extracting agent for extracting obtained quantum dots to obtain the CuInS2/Zn1-xMnxS quantum dots with the core-shell structure, and dispersing in the non-polar organic solvent; and adding mercaptan acid, and carrying out ligand exchange, thereby obtaining the dual-mode contrast medium. The preparation method of the dual-mode contrast medium, provided by the invention, has the advantages of simplicity in operation, mild reaction and less pollution; and the dual-mode contrast medium does not contain toxic element cadium. The prepared dual-mode contrast medium has dual functions of fluorescence and magnetic resonance imaging and can be used for medical imaging diagnosis.
Description
Technical field
The present invention relates to the diagnosis imaging field.More specifically, relate to design and synthetic a kind of double mode contrast agent and preparation method thereof, can operate this contrast agent obtains chemical-biological activities in live organism high-resolution nuclear magnetic resonance (MRI) and optical imagery.
Background technology
Along with the development of Medical Technology, comprise that the imaging tool such as nuclear magnetic resonance, computed tomography (CT), positron emission computerized tomography (PET), fluorescence imaging are widely used in medical diagnosis.The multi-mode imaging system that above-mentioned several modes is combined also has been used in the medical diagnosis research of cancer, heart disease and gene therapy.MRI can provide high-resolution three-dimension to dissect or structural information, and fluorescence can carry out process visualization on cellular level.Therefore, utilize the complementarity of dissecting resolution and detection sensitivity, the MRI technology is combined with optical technology, caused that in recent years people pay close attention to greatly.Compare with independent imaging, mixed model has obvious superiority, has increased the accuracy of diagnosis.
At present, the method for the double mode contrast agent of common preparation fluorescence and nuclear magnetic resonance has two kinds.A kind of method is with paramagnetic ion and quantum dot combination, as document J. Am. Chem. Soc. 2005,127,1656 report with Mn
2+Be entrained in cadmiumsulfide quantum dot, coat outside one deck zinc sulfide shell.The magneto-optic nano-contrast agent that this method is prepared has stability preferably, but can not solve due to Mn
2+Doping and keep simultaneously the problem of quantum dot high quantum production rate, and directly with Mn
2+Be entrained in the lattice of quantum dot and can cut down fluorescent effect.In addition, cadmium content point may make the lattice collapse in biotic environment, cause the release of cadmium ion, makes them have high toxicity and potential contamination hazard, has limited its application aspect biological.Another kind method is with silicon layer coated magnetic core and fluorogen or paramagnetic ion is modified the silicon layer that coats fluorescent core, is that core, silicon dioxide are the nanoparticle contrast agent of shell as the Chinese patent CN 102614532 disclosed parcel fluorescent dyes of A and magnetic Nano ferroso-ferric oxide; But silicon layer coats and makes the process of synthetic contrast agent more complicated, and has increased the size of particle.From biological angle, the granule of large particle diameter is not suitable for the application in biology, and the granule of large particle diameter is easily identified and removed by macrophage.In addition, the easy photobleaching of fluorescent dye and lose fluorescence, less stable.
Summary of the invention
Purpose of the present invention is intended to be to provide a kind of double mode contrast agent with fluorescence and nuclear magnetic resonance and preparation method thereof, solves the low magnetic of double mode contrast agent Henan rate, high toxicity, low fluorescence quantum yield and the photobleaching problem of the fluorescence of existing technology and nuclear magnetic resonance.Concrete scheme is as follows:
A kind of double mode contrast agent with fluorescence and nuclear magnetic resonance, described double mode contrast agent has the hud typed structure that comprises kernel and shell, and described kernel is the CuInS with fluorescence imaging
2The optical probe of quantum dot, described shell are the nuclear-magnetism probes of zinc sulfide shell of divalent manganesetion of having adulterated, and the surface of described shell is the hydrophilic organic ligand.
Described CuInS
2Quantum dot is Chalkopyrite, sphalerite or wurtzite structure, and particle diameter is 2～5nm.
The zinc sulfide shell of the described divalent manganesetion that adulterated refers to Zn
1-xMn
xS, wherein, x=0.01～0.40, reasonable is 0.08～0.20.
The shell thickness of described shell is 1～4nm, and reasonable is 2～3nm.
Described hydrophilic organic ligand is the polyacrylic acid that TGA, mercaptopropionic acid, dimercaptosuccinic acid, reduction octyl sulfate or lauryl amine are modified.
The preparation method of above-mentioned double mode contrast agent comprises the steps:
1) mantoquita, indium salt and lauryl mercaptan are added be equipped with in the non-polar organic solvent reactor, then pass into noble gas and discharge air in described reactor, reacted under 180～250 ℃ 1～30 minute, obtain uniform CuInS
2Colloid solution;
2) CuInS that obtains to step 1)
2Add the precursor solution of zinc and the precursor solution of manganese in colloid solution, afterwards, add the precursor solution of sulfur, reacted under 180～250 ℃ 1～30 minute, obtain CuInS
2/ Zn
1-xMn
xThe quantum dot colloid solution of S nucleocapsid structure;
3) to step 2) resulting quantum dot colloid solution adds extractant, extracts resulting quantum dot, then adds polar solvent, and sedimentation, centrifugal, cleaning, vacuum drying obtain nucleocapsid structure CuInS
2/ Zn
1-xMn
xThe S quantum dot is dispersed in non-polar organic solvent;
4) add mercaptan acid to the resulting solution of step 3), carry out ligand exchange, obtain described double mode contrast agent;
In step 1), the mol ratio of mantoquita, indium salt and lauryl mercaptan is 1:1:20～1:1:50; The volume ratio of lauryl mercaptan and non-polar organic solvent is 1:5～1:10;
Step 2) in, the mol ratio of the precursor solution of the precursor solution of zinc, the precursor solution of manganese and sulfur is 0.99:0.01:1～0.6:0.4:1;
In step 4), the mol ratio of mercaptan acid and zinc precursor liquid solution is 1:1.
Described mantoquita comprises a kind of in Hydro-Giene (Water Science)., Copper diiodide, Cu-lyt., copper chloride, copper acetate, cuprous acetate or their mixture; Described indium salt comprises a kind of in indium iodide, indium chloride, indium acetate or their mixture; Described non-polar organic solvent comprises a kind of in octadecylene, octadecane, paraffin, diphenyl ether, dioctyl ether or their mixture.
The precursor solution of described zinc comprises by a kind of of zinc stearate, zinc acetate, xanthic acid zinc or their mixture and is dissolved in octadecylene and/or the resulting colloid solution of oleic acid; The precursor solution of described manganese comprises by a kind of in manganese acetate, manganese stearate, manganese chloride or their mixture and is dissolved in octadecylene and/or the resulting colloid solution of oleic acid; The precursor solution of described sulfur is that the sulfur powder is dissolved in the resulting colloid solution of trioctylphosphine phosphorus/oleyl amine.
Described extractant comprises the mixed solution of petroleum ether, normal hexane or chloroform and methanol, and wherein the volume ratio of petroleum ether, normal hexane or chloroform and methanol is 1:1; Described polar solvent comprises acetone, methanol, ethanol; Described non-polar solven comprises chloroform, normal hexane, toluene.
Described mercaptan acid comprises a kind of in TGA, mercaptopropionic acid, dimercaptosuccinic acid or their mixture.
The technical solution adopted in the present invention is the presoma take mantoquita, indium salt and lauryl mercaptan as copper, indium and sulfur respectively, and wherein, lauryl mercaptan both provided the sulfur source, can be used as again the surface ligand of quantum dot, avoided quantum dot reunion.Under nitrogen protection, high temperature synthesizes quantum dot.As core, add the precursor solution of zinc and manganese again, the zinc sulfide shell of manganese doping just is coated on outside above synthetic quantum dot like this.
The hud typed CuInS of the present invention's preparation
2/ Zn
1-xMn
xThe S nanoparticle contrast agent has stronger relaxation ability, can be used for nuclear magnetic resonance, has simultaneously fluorescent emission character, has difunctional.
The hud typed CuInS of preparation provided by the invention
2/ Zn
1-xMn
xS nanoparticle contrast agent method is simple to operate, reaction temperature and, do not contain poisonous element cadmium, pollute little.The contrast agent that makes had both had the stable fluorescent emission of 600～800nm, and the luminescence feature in penetrator is arranged, and the nuclear magnetic resonance characteristics of good relaxed rate are arranged again simultaneously, had realized the difunctional of fluorescence and nuclear magnetic resonance.Can be used for the medical imaging diagnosis.
Description of drawings
Fig. 1 is the core-shell structure nanometer particle contrast agent fluorescence spectrum figure of embodiment 1;
Fig. 2 is the core-shell structure nanometer particle contrast agent X-ray diffractogram of embodiment 1;
Fig. 3 is the core-shell structure nanometer particle contrast agent transmission electron microscope photo of embodiment 1;
Fig. 4 is the photo of variable concentrations nucleocapsid structure contrast agent nuclear magnetic resonance, NMR;
Fig. 5 is the optical photograph of water soluble contrast material;
Fig. 6 is the 1/T of contrast agent in aqueous solution
1Rectilinear with respect to the match of manganese concentration; The slope of figure cathetus is longitudinal flux Henan rate r
1, R is relative coefficient.
The specific embodiment
Below by embodiment, the present invention is specifically described, but only for the invention will be further described, can not be interpreted as limiting the scope of the invention.To those skilled in the art in the situation that do not deviate from the other changes and modifications that the present invention spirit and protection domain are made, within still being included in protection domain of the present invention.
Embodiment 1
Step 1): the precursor solution of preparation zinc and manganese, that is, take the zinc stearate (0.506 g) of 0.01 mmol manganese stearate (0.006 g) and 0.8 mmol, join in the octadecylene of 5 mL ultrasonic 30 minutes.The precursor solution of preparation sulfur, that is, the sulfur powder (0.026 g) that takes 0.8 mmol is dissolved in (volume ratio 1:1, totally 2 mL) formation colloid solution in three hot phosphorus and oleyl amine.
Step 2): take the Hydro-Giene (Water Science). (0.019 g) of 0.1 mmol and the indium acetate (0.029 g) of 0.1 mmol and be added in the octadecylene of 8 mL, then add the lauryl mercaptan of 1 mL, the lower 80 ℃ of stirrings of vacuum 1 hour.Be filled with nitrogen, be heated to 230 ℃, reacted 25 minutes, stop reaction, natural cooling obtains uniform CuInS
2Colloid solution.
Step 3): the precursor solution that step 1) is obtained adds step 2) resulting CuInS
2Colloid solution, evacuation is three times repeatedly, and is last, is filled with nitrogen, is warmed up to 210 ℃, and the precursor solution with 0.5 mL injection sulfur per minute reacted 40 minutes, obtained CuInS
2/ Zn
1-xMn
xThe quantum dot colloid solution of S nucleocapsid structure.
Step 4): adding volume ratio in the quantum dot colloid solution that step 3) obtains is about 12 mL of chloroform/methanol mixed extractant of 1:1, the extraction quantum dot, add acetone centrifugal, be dispersed in normal hexane, add acetone centrifugal, iterative cycles is 3 times so again, obtains having the quantum dot of NMR (Nuclear Magnetic Resonance) imaging and optical imagery, be the double mode contrast agent of target product, be kept in chloroform.
Fig. 1 is the fluorescence spectrum figure of the resulting core of embodiment 1 and core-shell structure nanometer particle (the double mode contrast agent of target product), and fluorescence spectrum shows CuInS
2Core coats Zn
1-xMn
xAfter the S shell, fluorescence intensity obviously strengthens.
Fig. 2 is the XRD figure of core and core-shell structure nanometer particle, all is shown as yellow copper structure.The diffraction maximum of core-shell structure nanometer particle the diffraction maximum of zinc sulfide and Manganese monosulfide. do not occur slightly to the wide-angle skew, shows Zn
1-xMn
xThe S shell is coated to CuInS
2On core, formed nucleocapsid structure.
Fig. 3 is transmission electron microscope (TEM) photo of core-shell structure nanometer particle, and A is the transmission electron microscope photo of core, and B is the nucleocapsid structure transmission electron microscope photo, and scale is 10 nm.TEM shows: this core-shell structure nanometer particle has good monodispersity.CuInS
2The size of core is about 3.4 nm, the CuInS of nucleocapsid structure
2/ Zn
1-xMn
xThe size of S nanoparticle is about 5.5 nm.
Embodiment 2
Step 1): the precursor solution of preparation zinc and manganese namely, takes the manganese stearate (0.063 g) of 0.1 mmol and the zinc stearate (0.506 g) of 0.8 mmol and joins in the octadecylene of 5 mL, ultrasonic 30 minutes.The precursor solution of preparation sulfur, that is, the sulfur powder of 0.8 mmol (0.026 g) is dissolved in 2 mL trioctylphosphine phosphorus that volume ratio is 1:1 and oleyl amine and forms colloid solution.
Step 2): repeat the step 2 in embodiment 1)～step 4) obtains the quantum dot of the nucleocapsid structure of different manganese doping, and namely the double mode contrast agent of target product, be kept in chloroform.
Embodiment 3
Step 1): the precursor solution of preparation zinc and manganese namely, takes the manganese stearate (0.125 g) of 0.2 mmol and the zinc stearate (0.506 g) of 0.8 mmol and joins in the octadecylene of 5 mL, ultrasonic 30 minutes.The precursor solution of preparation sulfur, that is, the sulfur powder (0.026 g) that takes 0.8 mmol is dissolved in (volume ratio 1:1, totally 2 mL) formation colloid solution in trioctylphosphine phosphorus and oleyl amine.
Step 2): repeat the step 2 in embodiment 1)～step 4) obtains the quantum dot of the nucleocapsid structure of different manganese doping, and namely the double mode contrast agent of target product, be kept in chloroform.
Step 3): get the TGA of 40 μ L, the methanol of 0.5 mL, sodium hydroxide solution with 40% is regulated pH value to 12, the solution that obtains under agitation is added drop-wise to step 2) in the chloroformic solution of resulting quantum dot (0.2 mmol), stir one hour with the precipitation quantum dot, add again 5 mL deionized waters, stirred 20 minutes, standing.At last, layering occurs, remove the organic facies of bottom, add acetone at aqueous phase, centrifugal, remove unreacted TGA.It is in 7.4 PBS buffer solution that the water-soluble quantum dot that obtains is dispersed in pH.
Fig. 4 is the nuclear magnetic resonance picture of embodiment 3 resulting water miscible double mode contrast agent, and the concentration of corresponding manganese is respectively 0,0.015,0.028,0.039,0.054 mM.Clearly, along with the increase of manganese ion concentration, the signal of T1 weighted imaging is strengthening.
Fig. 5 is the fluorescent optics photo of water miscible double mode contrast agent, sends HONGGUANG clearly.
Fig. 6 is the 1/T of double mode contrast agent in aqueous solution
1Rectilinear with respect to the match of manganese concentration.Show that this contrast agent has higher magnetic Henan ability, its longitudinal flux Henan rate is 7.2 mM
-1S
-1, show that this contrast agent has the ability of nuclear magnetic resonance.
Claims (10)
1. the double mode contrast agent with fluorescence and nuclear magnetic resonance, is characterized in that, described double mode contrast agent has the hud typed structure that comprises kernel and shell, and described kernel is the CuInS with fluorescence imaging
2The optical probe of quantum dot, described shell are the nuclear-magnetism probes of zinc sulfide shell of divalent manganesetion of having adulterated, and the surface of described shell is the hydrophilic organic ligand.
2. double mode contrast agent according to claim 1, is characterized in that, described CuInS
2Quantum dot is Chalkopyrite, sphalerite or wurtzite structure, and particle diameter is 2～5nm.
3. double mode contrast agent according to claim 1, is characterized in that, the zinc sulfide shell of the described divalent manganesetion that adulterated refers to Zn
1-xMn
xS, wherein, x=0.01～0.40.
4. double mode contrast agent according to claim 1, is characterized in that, the shell thickness of described shell is 1～4nm, and reasonable is 2～3nm.
5. double mode contrast agent according to claim 1, is characterized in that, described hydrophilic organic ligand is the polyacrylic acid that TGA, mercaptopropionic acid, dimercaptosuccinic acid, reduction octyl sulfate or lauryl amine are modified.
6. the preparation method of the arbitrary described double mode contrast agent of claim 1 to 5, is characterized in that, comprises the steps:
1) mantoquita, indium salt and lauryl mercaptan are added be equipped with in the non-polar organic solvent reactor, then pass into noble gas and discharge air in described reactor, reacted under 180～250 ℃ 1～30 minute, obtain uniform CuInS
2Colloid solution;
2) CuInS that obtains to step 1)
2Add the precursor solution of zinc and the precursor solution of manganese in colloid solution, afterwards, add the precursor solution of sulfur, reacted under 180～250 ℃ 1～30 minute, obtain CuInS
2/ Zn
1-xMn
xThe quantum dot colloid solution of S nucleocapsid structure;
3) to step 2) resulting quantum dot colloid solution adds extractant, extracts resulting quantum dot, then adds polar solvent, and sedimentation, centrifugal, cleaning, vacuum drying obtain nucleocapsid structure CuInS
2/ Zn
1-xMn
xThe S quantum dot is dispersed in non-polar organic solvent;
4) add mercaptan acid to the resulting solution of step 3), carry out ligand exchange, obtain described double mode contrast agent;
In step 1), the mol ratio of mantoquita, indium salt and lauryl mercaptan is 1:1:20～1:1:50; The volume ratio of lauryl mercaptan and non-polar organic solvent is 1:5～1:10;
Step 2) in, the mol ratio of the precursor solution of the precursor solution of zinc, the precursor solution of manganese and sulfur is 0.99:0.01:1～0.6:0.4:1;
In step 4), the mol ratio of the precursor solution of mercaptan acid and zinc is 1:1.
7. preparation method according to claim 6, is characterized in that, described mantoquita comprises a kind of in Hydro-Giene (Water Science)., Copper diiodide, Cu-lyt., copper chloride, copper acetate, cuprous acetate or their mixture; Described indium salt comprises a kind of in indium iodide, indium chloride, indium acetate or their mixture; Described non-polar organic solvent comprises a kind of in octadecylene, octadecane, paraffin, diphenyl ether, dioctyl ether or their mixture.
8. preparation method according to claim 6, is characterized in that, the precursor solution of described zinc comprises by a kind of of zinc stearate, zinc acetate, xanthic acid zinc or their mixture and is dissolved in octadecylene and/or the resulting colloid solution of oleic acid; The precursor solution of described manganese comprises by a kind of in manganese acetate, manganese stearate, manganese chloride or their mixture and is dissolved in octadecylene and/or the resulting colloid solution of oleic acid; The precursor solution of described sulfur is that the sulfur powder is dissolved in the resulting colloid solution of trioctylphosphine phosphorus/oleyl amine.
9. preparation method according to claim 6, is characterized in that, described extractant comprises the mixed solution of petroleum ether, normal hexane or chloroform and methanol, and wherein the volume ratio of petroleum ether, normal hexane or chloroform and methanol is 1:1; Described polar solvent comprises acetone, methanol, ethanol; Described non-polar solven comprises chloroform, normal hexane, toluene.
10. preparation method according to claim 6, is characterized in that, described mercaptan acid comprises a kind of in TGA, mercaptopropionic acid, dimercaptosuccinic acid or their mixture.
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| CN104830324A (en) * | 2015-03-24 | 2015-08-12 | 吉林师范大学 | A preparing method of a double-light-emitting transition metal ion doped semiconductor quantum dot |
| CN105385436A (en) * | 2015-12-03 | 2016-03-09 | 东南大学 | Nontoxic diluted-magnetic quantum dot material with fluorescence and room temperature ferromagnetism, and preparation method thereof |
| CN105778917A (en) * | 2016-03-16 | 2016-07-20 | 深圳大学 | Core-shell nanometer luminous material and preparation method thereof |
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| CN104830324A (en) * | 2015-03-24 | 2015-08-12 | 吉林师范大学 | A preparing method of a double-light-emitting transition metal ion doped semiconductor quantum dot |
| CN105385436A (en) * | 2015-12-03 | 2016-03-09 | 东南大学 | Nontoxic diluted-magnetic quantum dot material with fluorescence and room temperature ferromagnetism, and preparation method thereof |
| CN105385436B (en) * | 2015-12-03 | 2017-06-23 | 东南大学 | A kind of nontoxic dilute coupled magnetic quantum dot material for having fluorescence and room-temperature ferromagnetic concurrently and preparation method thereof |
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| CN105907395A (en) * | 2016-04-16 | 2016-08-31 | 上海双洳生物科技有限公司 | A preparing method of an ultra small near infrared copper indium selenium quantum dot |
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| CN106833610A (en) * | 2017-01-20 | 2017-06-13 | 深圳天吉新创科技有限公司 | A kind of nuclear shell structure quantum point and preparation method thereof |
| CN106833610B (en) * | 2017-01-20 | 2020-04-10 | 深圳天吉新创科技有限公司 | Core-shell structure quantum dot and preparation method thereof |
| CN114806579A (en) * | 2021-01-27 | 2022-07-29 | 中国科学院化学研究所 | Near-infrared luminous magnetic quantum dot and preparation method and application thereof |
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