CN103110964B - 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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- CN103110964B CN103110964B CN201310061587.2A CN201310061587A CN103110964B CN 103110964 B CN103110964 B CN 103110964B CN 201310061587 A CN201310061587 A CN 201310061587A CN 103110964 B CN103110964 B CN 103110964B
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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 diagnosis imaging field.More specifically, relate to design and synthesize a kind of dual-mode contrast medium and preparation method thereof, high-resolution nuclear magnetic resonance (MRI) and optical imagery that this contrast agent obtains chemical-biological activities in live organism can be operated.
Background technology
Along with the development of Medical Technology, comprise the imaging tool such as nuclear magnetic resonance, computed tomography (CT), positron emission computerized tomography (PET), fluorescence imaging and be widely used in medical diagnosis.The multi-mode imaging system combined by above-mentioned several modes has also 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 a cellular level.Therefore, utilize the complementarity of dissecting resolution and detection sensitivity, MRI technology is combined with optical technology, causes people in recent years and pay close attention to greatly.Compare with independent imaging, mixed model has obvious superiority, adds the accuracy of diagnosis.
At present, the common method preparing the dual-mode contrast medium of fluorescence and nuclear magnetic resonance has two kinds.One method is combined paramagnetic ion and quantum dot, as document J. Am. Chem. Soc. 2005,127,1656 report by Mn
2+be entrained in cadmiumsulfide quantum dot, outside coated one deck zinc sulfide shell.The magneto-optic nano-contrast agent that this method is prepared has good stability, but can not solve due to Mn
2+doping and keep the problem of quantum dot high quantum production rate, and directly by Mn simultaneously
2+be entrained in the lattice of quantum dot and can cut down fluorescent effect.In addition, cadmium content point may make lattice collapse in biotic environment, causes the release of cadmium ion, makes them have high toxicity and potential contamination hazard, limits its application in biological.Another kind method is that the parcel fluorescent dye disclosed in Chinese patent CN 102614532 A and magnetic nano ferroferric oxide are core, silicon dioxide is the nanoparticle contrast agent of shell with silicon layer coated magnetic core and fluorogen or silicon layer paramagnetic ion being modified coated fluorescent core; But the coated process of synthesizing contrast agent that makes of silicon layer is more complicated, and adds the size of particle.From biological angle, the granule of Large stone is not suitable for the application in biology, and the granule of Large stone is easily removed by macrophage identification.In addition, the easy photobleaching of fluorescent dye and lose fluorescence, less stable.
Summary of the invention
Object of the present invention is intended to be to provide and a kind ofly has dual-mode contrast medium of fluorescence and nuclear magnetic resonance and preparation method thereof, solves the dual-mode contrast medium low magnetic Henan rate of the fluorescence of existing technology and nuclear magnetic resonance, high toxicity, low Poison quantum yield and photobleaching problem.Concrete scheme is as follows:
Have a dual-mode contrast medium for fluorescence and nuclear magnetic resonance, described dual-mode contrast medium has the coreshell type structure comprising kernel and shell, and described kernel is the CuInS with fluorescence imaging
2the optical probe of quantum dot, described shell is the nuclear-magnetism probe of the zinc sulfide shell being doped with divalent manganesetion, and the surface of described shell is hydrophilic organic ligand.
Described CuInS
2quantum dot is Chalkopyrite, sphalerite or wurtzite structure, and particle diameter is 2 ~ 5nm.
The described zinc sulfide shell being doped with divalent manganesetion 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 dual-mode contrast medium, comprises the steps:
1) mantoquita, indium salt and lauryl mercaptan are added be equipped with in non-polar organic solvent reactor, then pass into noble gas and discharge air in described reactor, react 1 ~ 30 minute at 180 ~ 250 DEG C, obtain uniform CuInS
2colloid solution;
2) to the CuInS that step 1) obtains
2add the precursor solution of zinc and the precursor solution of manganese in colloid solution, afterwards, add the precursor solution of sulfur, react 1 ~ 30 minute at 180 ~ 250 DEG C, obtain CuInS
2/ Zn
1-xmn
xthe quantum dot colloid solution of S nucleocapsid structure;
3) to step 2) the quantum dot colloid solution that obtains adds extractant, extracts the quantum dot obtained, then adds polar solvent, and sedimentation, centrifugal, cleaning, vacuum drying, obtain nucleocapsid structure CuInS
2/ Zn
1-xmn
xs quantum dot, is dispersed in non-polar organic solvent;
4) solution obtained to step 3) adds mercaptan acid, carries out ligand exchange, obtains described dual-mode contrast medium;
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 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 and is dissolved in by zinc stearate, zinc acetate, xanthic acid zinc a kind of or their mixture the colloid solution that octadecylene and/or oleic acid obtains; The precursor solution of described manganese comprises and is dissolved in by a kind of in manganese acetate, manganese stearate, manganese chloride or their mixture the colloid solution that octadecylene and/or oleic acid obtains; The precursor solution of described sulfur is dissolved in the colloid solution that trioctylphosphine phosphorus/oleyl amine obtains for sulfur powder.
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, be respectively with mantoquita, indium salt and lauryl mercaptan be copper, the presoma of indium and sulfur, wherein, lauryl mercaptan both provided sulfur source, again can as the surface ligand of quantum dot, avoid quantum dot reunion.Under nitrogen protection, high―temperature nuclei quantum dot.Again as core, add the precursor solution of zinc and manganese, the zinc sulfide shell of such additive Mn is just coated on outside the quantum dot of above synthesis.
Hud typed CuInS prepared by the present invention
2/ Zn
1-xmn
xs nanoparticle contrast agent, has stronger relaxation ability, can be used for nuclear magnetic resonance, have fluorescent emission character simultaneously, have 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, not containing toxic element cadmium, pollute little.Obtained contrast agent had both had the stable fluorescent emission of 600 ~ 800nm, had the luminescence feature in penetrator, had again the nuclear magnetic resonance feature of good relaxed rate simultaneously, achieved the difunctional of fluorescence and nuclear magnetic resonance.Can be used for medical imaging diagnosis.
Accompanying drawing explanation
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 contrast agent 1/T in aqueous
1relative to the rectilinear of manganese concentration matching; The slope of figure cathetus is longitudinal flux Henan rate r
1, R is relative coefficient.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, but only for the invention will be further described, can not limiting the scope of the invention be interpreted as.To the other changes and modifications that those skilled in the art makes when not deviating from the present invention's spirit and protection domain, be still included within scope.
Embodiment 1
Step 1): the precursor solution preparing zinc and manganese, that is, ((0.506 g), joins in the octadecylene of 5 mL, ultrasonic 30 minutes for the zinc stearate of 0.006 g) He 0.8 mmol to take 0.01 mmol manganese stearate.Prepare the precursor solution of sulfur, that is, (0.026 g) is dissolved in (volume ratio 1:1, totally 2 mL) in three pungent phosphorus and oleyl amine forms colloid solution to take the sulfur powder of 0.8 mmol.
Step 2): ((0.029 g) is added in the octadecylene of 8 mL, then adds the lauryl mercaptan of 1 mL, and lower 80 DEG C of vacuum stirs 1 hour for the indium acetate of 0.019 g) He 0.1 mmol to take the Hydro-Giene (Water Science). of 0.1 mmol.Be filled with nitrogen, be heated to 230 DEG C, react 25 minutes, stop reaction, natural cooling, obtains uniform CuInS
2colloid solution.
Step 3): precursor solution step 1) obtained adds step 2) CuInS that obtains
2colloid solution, evacuation three times, finally, is filled with nitrogen repeatedly, is warmed up to 210 DEG C, and the precursor solution injecting sulfur with 0.5 mL per minute, reacts 40 minutes, obtain CuInS
2/ Zn
1-xmn
xthe quantum dot colloid solution of S nucleocapsid structure.
Step 4): add chloroform/methanol mixed extractant about 12 mL that volume ratio is 1:1 in the quantum dot colloid solution that step 3) obtains, extraction quantum dot, add acetone centrifugal, be dispersed in normal hexane, add acetone more centrifugal, such iterative cycles 3 times, obtain the quantum dot with NMR (Nuclear Magnetic Resonance) imaging and optical imagery, namely target product dual-mode contrast medium, is kept in chloroform.
Fig. 1 is the fluorescence spectrum figure of the core that obtains of embodiment 1 and core-shell structure nanometer particle (target product dual-mode contrast medium), fluorescence spectrum display CuInS
2the coated Zn of core
1-xmn
xafter S shell, fluorescence intensity obviously strengthens.
Fig. 2 is the XRD figure of core and core-shell structure nanometer particle, is all shown as yellow copper structure.The diffraction maximum of core-shell structure nanometer particle offsets slightly towards wide-angle, does not occur the diffraction maximum of zinc sulfide and Manganese monosulfide., shows Zn
1-xmn
xs shell is coated to CuInS
2on core, define 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 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 preparing zinc and manganese, that is, ((0.506 g) joins in the octadecylene of 5 mL the zinc stearate of 0.063 g) He 0.8 mmol, ultrasonic 30 minutes to take the manganese stearate of 0.1 mmol.Prepare the precursor solution of sulfur, that is, (0.026 g) is dissolved in 2 mL trioctylphosphine phosphorus that volume ratio is 1:1 and oleyl amine and forms colloid solution the sulfur powder of 0.8 mmol.
Step 2): repeat the step 2 in embodiment 1) ~ step 4), obtain the quantum dot of the nucleocapsid structure of different additive Mn, namely target product dual-mode contrast medium, is kept in chloroform.
Embodiment 3
Step 1): the precursor solution preparing zinc and manganese, that is, ((0.506 g) joins in the octadecylene of 5 mL the zinc stearate of 0.125 g) He 0.8 mmol, ultrasonic 30 minutes to take the manganese stearate of 0.2 mmol.Prepare the precursor solution of sulfur, that is, (0.026 g) is dissolved in (volume ratio 1:1, totally 2 mL) in trioctylphosphine phosphorus and oleyl amine forms colloid solution to take the sulfur powder of 0.8 mmol.
Step 2): repeat the step 2 in embodiment 1) ~ step 4), obtain the quantum dot of the nucleocapsid structure of different additive Mn, namely target product dual-mode contrast medium, is kept in chloroform.
Step 3): get the TGA of 40 μ L, the methanol of 0.5 mL, sodium hydroxide solution adjust ph with 40% is to 12, the solution obtained under agitation is added drop-wise to step 2) in the chloroformic solution of quantum dot (0.2 mmol) that obtains, stir one hour to precipitate quantum dot, add 5 mL deionized waters again, stir 20 minutes, leave standstill.Finally, there is layering, remove the organic facies of bottom, in aqueous phase, add acetone, centrifugal, remove unreacted TGA.The water-soluble quantum dot obtained being dispersed in pH is in the PBS buffer solution of 7.4.
Fig. 4 is the nuclear magnetic resonance picture of the water miscible dual-mode contrast medium that embodiment 3 obtains, and the concentration of corresponding manganese is 0,0.015 respectively, 0.028,0.039,0.054 mM.Clearly, along with the increase of manganese ion concentration, the signal of T1 weighted imaging is in enhancing.
Fig. 5 is the fluorescent optics photo of water miscible dual-mode contrast medium, sends HONGGUANG clearly.
Fig. 6 is dual-mode contrast medium 1/T in aqueous
1relative to the rectilinear of manganese concentration matching.Show that this contrast agent has higher magnetic Henan ability, its longitudinal flux Henan rate is 7.2 mM
-1s
-1, show the ability that this contrast agent has nuclear magnetic resonance.
Claims (5)
1. there is a preparation method for the dual-mode contrast medium of fluorescence and nuclear magnetic resonance, it is characterized in that, comprise the steps:
1) mantoquita, indium salt and lauryl mercaptan are added be equipped with in non-polar organic solvent reactor, then pass into noble gas and discharge air in described reactor, react 1 ~ 30 minute at 180 ~ 250 DEG C, obtain uniform CuInS
2colloid solution;
2) to step 1) CuInS that obtains
2add the precursor solution of zinc and the precursor solution of manganese in colloid solution, afterwards, add the precursor solution of sulfur, react 1 ~ 30 minute at 180 ~ 250 DEG C, obtain CuInS
2/ Zn
1-xmn
xthe quantum dot colloid solution of S nucleocapsid structure;
3) to step 2) the quantum dot colloid solution that obtains adds extractant, extracts the quantum dot obtained, then adds polar solvent, and sedimentation, centrifugal, cleaning, vacuum drying, obtain nucleocapsid structure CuInS
2/ Zn
1-xmn
xs quantum dot, is dispersed in non-polar organic solvent;
4) to step 3) solution that obtains adds mercaptan acid, and carry out ligand exchange, obtain described dual-mode contrast medium;
Step 1) in, 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;
Step 4) in, the mol ratio of the precursor solution of mercaptan acid and zinc is 1:1;
Described dual-mode contrast medium has the coreshell type structure comprising kernel and shell, and described kernel is the CuInS with fluorescence imaging
2the optical probe of quantum dot, described shell is the nuclear-magnetism probe of the zinc sulfide shell being doped with divalent manganesetion, and the surface of described shell is hydrophilic organic ligand;
Described CuInS
2quantum dot is Chalkopyrite, sphalerite or wurtzite structure, and particle diameter is 2 ~ 5nm;
The shell thickness of described shell is 1 ~ 4nm;
The described zinc sulfide shell being doped with divalent manganesetion refers to Zn
1-xmn
xs, wherein, x=0.01 ~ 0.40;
Described hydrophilic organic ligand is the polyacrylic acid that TGA, mercaptopropionic acid, dimercaptosuccinic acid, reduction octyl sulfate or lauryl amine are modified.
2. preparation method according to claim 1, 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.
3. preparation method according to claim 1, is characterized in that, the precursor solution of described zinc comprises and is dissolved in by zinc stearate, zinc acetate, xanthic acid zinc a kind of or their mixture the colloid solution that octadecylene and/or oleic acid obtains; The precursor solution of described manganese comprises and is dissolved in by a kind of in manganese acetate, manganese stearate, manganese chloride or their mixture the colloid solution that octadecylene and/or oleic acid obtains; The precursor solution of described sulfur is dissolved in the colloid solution that trioctylphosphine phosphorus/oleyl amine obtains for sulfur powder.
4. preparation method according to claim 1, 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.
5. preparation method according to claim 1, is characterized in that, described mercaptan acid comprises a kind of in TGA, mercaptopropionic acid, dimercaptosuccinic acid or their mixture.
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| 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 |
| CN105778917B (en) * | 2016-03-16 | 2017-12-01 | 深圳大学 | A kind of core-shell type nano luminescent material and preparation method thereof |
| 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 |
| KR101884380B1 (en) * | 2016-09-29 | 2018-08-01 | 동우 화인켐 주식회사 | Quantum dot dispersion, manufacturing method thereof, color filter and image display device manufactured using the same |
| 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 |
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