CN103432598B - Preparation method of nano rear earth doped gadolinium oxide bi-modal contrast medium - Google Patents
Preparation method of nano rear earth doped gadolinium oxide bi-modal contrast medium Download PDFInfo
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- CN103432598B CN103432598B CN201310400737.8A CN201310400737A CN103432598B CN 103432598 B CN103432598 B CN 103432598B CN 201310400737 A CN201310400737 A CN 201310400737A CN 103432598 B CN103432598 B CN 103432598B
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Abstract
The invention discloses a preparation method of a nano rear earth doped gadolinium oxide bi-modal contrast medium. According to the method, target materials and ions of a rear earth solution react under high energy of lasers by changing different rear earth ion solutions, thereby preparing nano rear earth doped gadolinium oxide bi-modal contrast medium particles and meanwhile achieving zeugmatography and fluorescence imaging. According to the preparation method, nano materials are doped by changing different reaction liquids through an ablation method by utilizing lasers in a liquid phase environment. According to the method, the operation is simple, the cost is low, moreover severe operation environment requirements do not exist, products can be prepared under a normal-temperature normal-pressure condition, and the prepared nano particles show favorable zeugmatography and fluorescence imaging.
Description
Technical field
The present invention relates to the medical domain of bimodal contrast agent, refer in particular to the preparation method of a kind of nano rare earth doping Gadolinia. bimodal contrast agent.
Background technology
Known in the industry, NMR (Nuclear Magnetic Resonance)-imaging is one of the most frequently used diagnostic method of present medical science, because it has high resolution, and good contrast in tissue, and various anatomical details can be provided exactly, so more and more come into one's own now.The use of contrast agent, can carry out Enhanced Imaging effect by the relaxation diagram picture changing water proton, the normal organ in human body and the water morphology of diseased organ have very big-difference, by using contrast agent, better can show diversity, realize the diagnosis to pathological tissues.And gadolinium ion has 7 unpaired electrons due to skin, be considered to best positive contrast agent material.A lot of research now concentrates on research Gadolinia. nano material as NMR contrast agent, although NMR (Nuclear Magnetic Resonance)-imaging has high spatial resolution and good imaging depth, also has the problem of insufficient sensitivity.Therefore can in conjunction with optical imagery, such as fluorescence imaging, again because rear-earth-doped luminescence has high stability and long luminescence lifetime, so rear-earth-doped oxidation gadolinium nano material has important researching value and wide application prospect.We call bimodal imaging syncaryon nuclear magnetic resonance and fluorescence imaging.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of safe and reliable method can preparing nano rare earth doping Gadolinia. bimodal contrast agent is fast provided.
For achieving the above object, technical scheme provided by the present invention is: a kind of preparation method of nano rare earth doping Gadolinia. bimodal contrast agent, comprises the following steps:
1) Gadolinia. target is placed in reaction vessel, then in reaction vessel, injects rare-earth ion solution, rare-earth ion solution submergence Gadolinia. target;
2) light path of regulating impulse laser beam, makes laser beam after completely reflecting mirror and condenser lens, focus on the contact surface of Gadolinia. target and rare-earth ion solution successively, and contact surface produces plasma plume;
3) unbalanced pulse laser, carries out pulse laser ablation reaction in liquid environment under the effect of laser;
4) react after 30 ~ 60 minutes, close pulse laser, then take out reacted rare-earth ion solution, and drying, separation are carried out to it, finally obtain required nano rare earth doping Gadolinia. bimodal contrast agent.
Step 4) in adopt the rare-earth ion solution product of deionized water repeatedly after clean dry, to realize being separated, again the product after being separated is dried afterwards, just can obtain required nano rare earth doping Gadolinia. bimodal contrast agent.
Step 1) described in rare-earth ion solution be one or more combination in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutecium rare-earth ion solution.
Described rare-earth ion solution is chlorination or nitric acid thing, and concentration is 1mmol/L-10mmol/L.
Step 1) described in the upper surface of rare-earth ion solution exceed Gadolinia. target upper surface 5-10mm.
Step 1) described in the purity of Gadolinia. target be 99%-99.999%, thickness is 3-5mm, and its surface is through polishing process.
The shape of described Gadolinia. target is circular or square.
The frequency of described pulse laser is 1 ~ 10Hz.
Described reaction vessel is glass container or plastic containers.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
1, the present invention utilizes pulse laser ablation technology to make nano rare earth doping Gadolinia. bimodal contrast agent (graininess) in rare-earth ion solution, the method is simple to operate, with low cost, and there is no harsh operating environment requirement, the preparation of product can be realized under normal temperature and pressure conditions;
2, the preparation method of nano rare earth doping Gadolinia. bimodal contrast agent provided by the invention, be utilize pulse laser ablation technology in rare-earth ion solution environment, realized the fluorescent emission of different wave length by the concentration and kind changing rare-earth ion solution easily;
3, the nano rare earth doping Gadolinia. bimodal contrast agent that prepared by the present invention can not only affect the relaxation rate of water proton effectively, has magnetic resonance imaging ability, and under the exciting of the light of certain wavelength, can send fluorescence, realize bimodal imaging.
Accompanying drawing explanation
Fig. 1 prepares schematic diagram in embodiment 1.
Fig. 2 a is the low power transmission electron microscope photo figure of the nano rare earth doping Gadolinia. bimodal contrast agent of gained in embodiment 1.
Fig. 2 b is the high power transmission electron microscope photo figure of the nano rare earth doping Gadolinia. bimodal contrast agent of gained in embodiment 1.
Fig. 3 is the X-ray diffraction analysis collection of illustrative plates of nano rare earth doping Gadolinia. bimodal contrast agent in embodiment 1.
Fig. 4 a is the T1 weighted graph of nano rare earth doping Gadolinia. bimodal contrast agent in embodiment 1.
Fig. 4 b is the magnetic Henan rate figure of nano rare earth doping Gadolinia. bimodal contrast agent in embodiment 1.
Fig. 5 a is the excitation spectrum of nano rare earth doping Gadolinia. bimodal contrast agent in embodiment 1.
Fig. 5 b is the emission spectra of nano rare earth doping Gadolinia. bimodal contrast agent in embodiment 1.
Fig. 6 is the cell survival rate figure in embodiment 1 under the nano rare earth doping Gadolinia. bimodal contrast agent of variable concentrations is cultivated.
Detailed description of the invention
Below in conjunction with multiple specific embodiment, the invention will be further described.
Embodiment 1
As shown in Figure 1, the preparation method of the nano rare earth doping Gadolinia. bimodal contrast agent described in the present embodiment, adopts laser instrument 1 (to adopt Nd:YAG pulse laser, optical maser wavelength 532nm, pulsewidth 10ns, energy is 100mJ), total reflective mirror 2, condenser lens 3, Gadolinia. target 4 (Gd
2o
3), reaction vessel 5, rare-earth ion solution, wherein, the pulse laser frequency of described laser instrument 1 is 1 ~ 10Hz, and selects 10Hz in the present embodiment; The surface of described Gadolinia. target 4 is through polishing process, and its purity is 99%-99.999%, and thickness is 3-5mm, shape is circular or square, and in the present embodiment, the shape of this Gadolinia. target 4 is specially circle, its purity is 99.999%, and diameter is 10mm, thick 5mm; Described reaction vessel 5 can be glass container or plastic containers, and selects glass container in the present embodiment; Described rare-earth ion solution can lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, one or more combination in lutecium rare-earth ion solution, be specially chlorination or nitric acid thing, its concentration is 1mmol/L-10mmol/L, and selects concentration to be the Europium chloride (EuCl of 5mmol/L in the present embodiment
3) solion.
Be below the detailed process of preparation method described in the present embodiment:
1) Gadolinia. target 4 is placed in reaction vessel 5, then in reaction vessel 5, inject the Europium chloride solion of 5mmol/L, make Europium chloride solion submergence Gadolinia. target 4, and make the upper surface of Europium chloride solion exceed Gadolinia. target 4 upper surface 5-10mm, be specially 5mm in the present embodiment;
2) regulate the light path of the pulsed laser beam of laser instrument 1, make laser beam after completely reflecting mirror 2 and condenser lens 3, focus on Gadolinia. target 4 and the contact surface of Europium chloride solion successively, make contact surface produce plasma plume;
3) unbalanced pulse laser, carries out pulse laser ablation reaction in liquid environment under the effect of laser;
4) course of reaction continued after 30 ~ 60 minutes, be specially 30 minutes in the present embodiment, close pulse laser, then take out reacted Europium chloride solion, and drying is carried out to it, obtain powder, finally repeatedly clean with deionized water, to realize being separated, again the product after separation is dried afterwards, just can obtain required nano rare earth doping Gadolinia. bimodal contrast agent (Gd
2o
3: Eu
3+, graininess).
In addition, in this enforcement also to the nano rare earth of above-mentioned gained doping Gadolinia. bimodal contrast agent Gd
2o
3: Eu
3+carry out tem study, X-ray diffraction analysis test:
Transmission electron microscope photo as shown in figures 2 a and 2b, as seen from the figure, nano rare earth doping Gadolinia. bimodal contrast agent Gd
2o
3: Eu
3+the diameter of granule is about 10nm.
X-ray diffraction analysis collection of illustrative plates as shown in Figure 3, according to test result, can confirm that the nano material obtained is gadolinium sesquioxide (Gd
2o
3), the gadolinium sesquioxide that corresponding PDF card base is single-phase: JCPDS 42-1465 is monocline.
Nano rare earth doping Gadolinia. bimodal contrast agent Gd
2o
3: Eu
3+external imaging effect specifically as shown in Figs. 4a and 4b, Fig. 4 a is nano rare earth doping Gadolinia. bimodal contrast agent Gd
2o
3: Eu
3+t1 weighted graph, Fig. 4 b is nano rare earth doping Gadolinia. bimodal contrast agent Gd
2o
3: Eu
3+magnetic Henan rate figure.
Fig. 5 a is nano rare earth doping Gadolinia. bimodal contrast agent Gd
2o
3: Eu
3+excitation spectrum, Fig. 5 b is nano rare earth doping Gadolinia. bimodal contrast agent Gd
2o
3: Eu
3+emission spectra, illustration is fluorescence imaging figure.
Fig. 6 is the nano rare earth doping Gadolinia. bimodal contrast agent Gd at variable concentrations
2o
3: Eu
3+cell survival rate figure under cultivating.
Embodiment 2
After Gadolinia. target 4 (purity is 99.999%, and diameter is 10mm, thick 5mm) is placed in reaction vessel 5 by the present embodiment as different from Example 1, in this reaction vessel 5, inject terbium chloride solion (TbCl
3), make terbium chloride solion submergence Gadolinia. target 4, and make the upper surface of terbium chloride solion higher than Gadolinia. target 4 upper surface 8mm; Regulate laser optical path afterwards, the pulsed laser beam that laser instrument 1 is launched through total reflective mirror 2 and by focal length be 500mm condenser lens 3 after, the laser focused on is radiated at the contact surface of Gadolinia. target 4 and terbium chloride solion, and contact surface produces plasma plume; Unbalanced pulse laser afterwards, laser frequency is selected 10Hz, carries out pulse laser ablation reaction, and course of reaction continued after 60 minutes, close pulse laser, then take out reacted terbium chloride solion, and drying is carried out to it, obtain powder, finally repeatedly clean with deionized water, to realize being separated, again the product after separation is dried afterwards, just can obtain required nano rare earth doping Gadolinia. bimodal contrast agent (Gd
2o
3: Tb
3+, graininess).
Embodiment 3
After Gadolinia. target 4 (purity is 99.999%, and diameter is 10mm, thick 5mm) is placed in reaction vessel 5 by the present embodiment as different from Example 1, in this reaction vessel 5, inject thulium chloride solion (TmCl
3), make thulium chloride solion submergence Gadolinia. target 4, and make the upper surface of thulium chloride solion higher than Gadolinia. target 4 upper surface 8mm; Regulate laser optical path afterwards, the pulsed laser beam that laser instrument 1 is launched through total reflective mirror 2 and by focal length be 500mm condenser lens 3 after, the laser focused on is radiated at the contact surface of Gadolinia. target 4 and thulium chloride solion, and contact surface produces plasma plume; Unbalanced pulse laser afterwards, laser frequency is selected 10Hz, carries out pulse laser ablation reaction, and course of reaction continued after 60 minutes, close pulse laser, then take out reacted thulium chloride solion, and drying is carried out to it, obtain powder, finally repeatedly clean with deionized water, to realize being separated, again the product after separation is dried afterwards, just can obtain required nano rare earth doping Gadolinia. bimodal contrast agent (Gd
2o
3: Tm
3+, graininess).
In sum, the present invention utilizes pulse laser to interact with the solid target being placed in liquid, plasma plume is produced in liquid-solid interface, the restriction that plasma plume is subject to liquid produces a High Temperature High Pressure district, condition that what this region was some chemical reactions provide is as the reaction between ablation thing, reaction etc. between ablation thing and liquid, in this process, produce Gadolinia. plasma plume and rare-earth ion solution in ionic reaction, and this plasma quenching time is very short, just produce nano rare earth doping Gadolinia. bimodal contrast agent particle.In addition, by converting different rare-earth ion solutions, the ion of target and earth solution can be made to react under the high-energy of laser, preparing nano rare earth doping Gadolinia. bimodal contrast agent particle, realizing NMR (Nuclear Magnetic Resonance)-imaging and fluorescence imaging simultaneously; The method is simple to operate, with low cost, and does not have harsh operating environment requirement, can realize the preparation of product, and the nano-particle prepared shows good NMR (Nuclear Magnetic Resonance)-imaging and fluorescence imaging, is worthy to be popularized under normal temperature and pressure conditions.
The examples of implementation of the above are only the preferred embodiment of the present invention, not limit practical range of the present invention with this, therefore the change that all shapes according to the present invention, principle are done, all should be encompassed in protection scope of the present invention.
Claims (8)
1. a preparation method for nano rare earth doping Gadolinia. bimodal contrast agent, is characterized in that, comprise the following steps:
1) Gadolinia. target (4) is placed in reaction vessel (5), then in reaction vessel (5), injects rare-earth ion solution, rare-earth ion solution submergence Gadolinia. target (4);
2) light path of the pulsed laser beam of laser instrument (1) is regulated, make laser beam after completely reflecting mirror (2) and condenser lens (3), focus on the contact surface of Gadolinia. target (4) and rare-earth ion solution successively, contact surface produces plasma plume;
3) unbalanced pulse laser, carries out pulse laser ablation reaction in liquid environment under the effect of laser;
4) react after 30 ~ 60 minutes, close pulse laser, then take out reacted rare-earth ion solution, and drying, separation are carried out to it, finally obtain required nano rare earth doping Gadolinia. bimodal contrast agent; Described rare-earth ion solution is Europium chloride solion.
2. the preparation method of nano rare earth doping Gadolinia. bimodal contrast agent according to claim 1, it is characterized in that: step 4) in adopt the rare-earth ion solution product of deionized water repeatedly after clean dry, to realize being separated, again the product after separation is dried afterwards, just can obtain required nano rare earth doping Gadolinia. bimodal contrast agent.
3. the preparation method of nano rare earth doping Gadolinia. bimodal contrast agent according to claim 1, is characterized in that: described rare-earth ion solution concentration is 1mmol/L-10mmol/L.
4. the preparation method of nano rare earth according to claim 1 doping Gadolinia. bimodal contrast agent, is characterized in that: step 1) described in the upper surface of rare-earth ion solution exceed Gadolinia. target (4) upper surface 5-10mm.
5. the preparation method of nano rare earth doping Gadolinia. bimodal contrast agent according to claim 1, it is characterized in that: step 1) described in the purity of Gadolinia. target (4) be 99%-99.999%, thickness is 3-5mm, and its surface is through polishing process.
6. the preparation method of nano rare earth doping Gadolinia. bimodal contrast agent according to claim 1 or 5, is characterized in that: the shape of described Gadolinia. target (4) is for circular or square.
7. the preparation method of nano rare earth doping Gadolinia. bimodal contrast agent according to claim 1, is characterized in that: the frequency of described pulse laser is 1 ~ 10Hz.
8. the preparation method of nano rare earth doping Gadolinia. bimodal contrast agent according to claim 1, is characterized in that: described reaction vessel (5) is glass container or plastic containers.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262394A (en) * | 1991-12-27 | 1993-11-16 | The United States Of America As Represented By The United States Department Of Energy | Superconductive articles including cerium oxide layer |
| CN102391865A (en) * | 2011-09-21 | 2012-03-28 | 中国科学院福建物质结构研究所 | Preparation method for doping gadolinium oxide nano-powders |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262394A (en) * | 1991-12-27 | 1993-11-16 | The United States Of America As Represented By The United States Department Of Energy | Superconductive articles including cerium oxide layer |
| CN102391865A (en) * | 2011-09-21 | 2012-03-28 | 中国科学院福建物质结构研究所 | Preparation method for doping gadolinium oxide nano-powders |
Non-Patent Citations (1)
| Title |
|---|
| Ligand-free gadolinium oxide for in vivo T1-weighted magnetic resonance imaging;Ningqi Luo 等;《Phys. Chem. Chem. Phys》;20130517;第15卷;第12235-12240页 * |
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