CN103550793A - Magnetic nano material, preparation method and application of magnetic nano material in magnetic resonance contrast imaging - Google Patents
Magnetic nano material, preparation method and application of magnetic nano material in magnetic resonance contrast imaging Download PDFInfo
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- CN103550793A CN103550793A CN201310517795.9A CN201310517795A CN103550793A CN 103550793 A CN103550793 A CN 103550793A CN 201310517795 A CN201310517795 A CN 201310517795A CN 103550793 A CN103550793 A CN 103550793A
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Abstract
The invention discloses a magnetic nano material, a preparation method and application of the magnetic nano material in magnetic resonance contrast imaging. The magnetic nano material comprises platinum-cobalt alloy nano-particles, and octadecene polyethylene glycol which is connected to the surfaces of platinum-cobalt alloy nano-particles and used for modifying, wherein the platinum-cobalt alloy nano-particles are shown as molecular formula of Pt3Co; the average particle size of the nano material is 50nm. The magnetic nano material is high in water solubility, relatively high in nuclear magnetic resonance T2 relaxation rate, and applicable to magnetic resonance imaging. The results of short-term and long-term in-vivo and in-vitro toxicity detection of animal show that obvious toxicity does not appear, so that the magnetic nano material can be tried to be used in clinical technology.
Description
Technical field
The present invention relates to a kind of magnetic Nano material, relate to particularly a kind of by the polyethyleneglycol modified platinum cobalt alloy nano material of vaccenic acid, and the preparation method of this nano material and the application in magnetic resonance radiography imaging.
Background technology
Nuclear magnetic resonance (MRI), due to its safety, susceptiveness, has become one of most important image technology in modern medicine clinical diagnosis.In medical MRI scanning, there is the case of 30-40%, need to use all kinds of MRI contrast agent.MRI contrast agent can affect the magnetic property of surrounding tissue, and China's medical circle is generally divided into following 3 classes MRI contrast agent at present: paramagnetism, ferromagnetism, superparamagnetism.
Wherein, the feature of paramagnet is that susceptibility is little, and during without external magnetic field, magnetic can not retain.The existence of paramagnet has aggravated organization internal stray magnetic field, is the key that shortens T1.Paramagnetism MRI contrast agent is transition-metal ion normally, as Fe
3+, Mn
2+, Gd
3+these metal ions have unpaired electron, and the local magnetic field that a plurality of unpaired electron spins produce can shorten the relaxation time of hydrogen proton in contiguous hydrone, and main manifestations is for shortening T1, thereby increased the magnetic resonance signal of contrast agent adjacent domain, improved the contrast of image.Ci Xian Portugal amine (Gd-DTPA) is the contrast agent of wide clinical application, can adopt intravenous injection to be injected into human body, and its toxicity is low, is mainly by changing the relaxation time of hydrogen proton, produces contrast potentiation.As small-molecule substance ，Ci Xian Portugal's amine and derivant thereof, at cell interior or exterior space, easily reach balance, reinforced effects is good.But the shortcoming of this class contrast agent is without specificity, because they are non-selective distribution between each tissue in vivo.And micromolecule metabolism excretion is in vivo very fast, keep enough concentration within the time of imaging, needs the heavy dose of contrast agent of injection.
Ferromagnetic material has higher susceptibility, when without external magnetic field, still can preserve its magnetic, ferromagnetic particle has the magnetic moment higher compared with paramagnet, the relaxation of proton in adjacent tissue is had to obvious acceleration effect, can significantly reduce T2, for the required concentration of imaging far below paramagnet.Another focus of magnetic resonance imaging contrast research is the application of superparamagnetic material.In magnetics, when the volume of ferromagnetic particles reduces to magnetic energy and is less than heat energy, the magnetic domain random fluctuation that warm-up movement causes, make the behavior of magnetic particle the same with paramagnetic particles, now be called superparamagnetism, after externally-applied magnetic field disappears, super paramagnetic material magnetic disappears, this point is similar with paramagnetic material, and difference is that the magnetic moment of superparamagnetic microgranule is much bigger.Superparamagnetic Iron Oxide strengthens the novel type radiographic contrast of reticuloendothelial system video picture as selectivity, recent domestic has more research, but it is in the diagnosis of some disease, and for example the effect of diagnosing cancer of liver aspect and clinical practice are not also very desirable.
In sum, for above-mentioned deficiency, be necessary to propose a kind of novel type radiographic contrast being applied in magnetic resonance radiography imaging.
Summary of the invention
In view of this, the invention provides the polyethyleneglycol modified magnetic Nano material of a kind of vaccenic acid, to overcome the unburned refractory material of existing part before coming into operation, it is subject to the poor problem of impact property of physics and chemistry.
One of to achieve these goals, the invention provides a kind of magnetic Nano material, it comprises:
Platinum cobalt alloy nano-particle and the vaccenic acid Polyethylene Glycol that plays modification that is connected in platinum cobalt alloy nano grain surface, the molecular formula of described platinum cobalt alloy nano-particle is Pt
3co.
As a further improvement on the present invention, described platinum cobalt alloy nano-particle is cube structure, and the distance between two apparent surfaces of described cube structure is 6nm.
For realizing above-mentioned another goal of the invention, the invention provides a kind of method of preparing magnetic Nano material as above, its lower step:
The acetylacetone,2,4-pentanedione platinum that is 2:1 by mol ratio and cobalt octacarbonyl join in 1,2-dodecanediol, then the mixture of formation is dissolved in the first solvent, heating is reacted, and then slowly heats up and continues reaction, and reaction finishes rear cooling, product is cleaned, obtain platinum cobalt alloy nano-particle;
By platinum cobalt alloy nanoparticulate dispersed in the second solvent, after mix homogeneously, the solution that adds vaccenic acid Polyethylene Glycol and the second solvent to form, under normal temperature condition, stir and react, reaction finishes after-blow dry doubling and is dissolved in water, and obtaining surface has the polyethyleneglycol modified platinum cobalt alloy nano material of vaccenic acid.
As a further improvement on the present invention, described the first solvent is that volume ratio is the mixture of benzylic ether, oleyl amine and the oleic acid formation of 8:8:1.
As a further improvement on the present invention, the course of reaction of preparing platinum cobalt alloy nano-particle is carried out under nitrogen atmosphere.
As a further improvement on the present invention, while preparing platinum cobalt alloy nano-particle, be heated to 100 ℃ of reaction 2h, be then slowly warmed up to 200 ℃ of reaction 2h.
As a further improvement on the present invention, while preparing platinum cobalt alloy nano-particle, after reaction finishes, be cooled to 80 ℃, and add 50ml ethanol, utilize twice of ethanol centrifuge washing.
As a further improvement on the present invention, described the second solvent is chloroform.
As a further improvement on the present invention,, when platinum cobalt alloy nano-particle is modified, after finishing, reaction utilize nitrogen to dry up.
For realizing an above-mentioned goal of the invention again, the invention provides the application of a kind of magnetic Nano material as above in magnetic resonance radiography imaging.
Compared with prior art, the invention has the beneficial effects as follows:
(1) magnetic Nano material preparation method of the present invention is simple, and magnetic Nano material water solublity is good, and has high nuclear magnetic resonance, NMR T2 relaxation rate, is applicable to nuclear magnetic resonance;
(2) apply magnetic Nano material of the present invention, when low concentration, at tumor by local, show good nuclear magnetic resonance, NMR T2 radiography effect, compare with the T2 contrast agent Tie Suo Portugal amine of same concentrations, there is obvious advantage;
(3) apply magnetic Nano material of the present invention, by the toxicity inside and outside short-term and long-term animal body, detect, do not find overt toxicity, can try out in clinical technology.
Accompanying drawing explanation
The structural representation of the specific embodiment that Fig. 1 (a) is magnetic Nano material of the present invention;
The transmission electron microscope picture of the specific embodiment that Fig. 1 (b) is magnetic Nano material of the present invention;
The angle of elevation annular details in a play not acted out on stage, but told through dialogues scanning transmission electron microscope figure of the specific embodiment that Fig. 2 (a) is magnetic Nano material of the present invention;
The energy dispersion X ray spectrogram under STEM pattern of the specific embodiment that Fig. 2 (b) is magnetic Nano material of the present invention;
The X-ray diffractogram of the specific embodiment that Fig. 3 (a) is magnetic Nano material of the present invention;
The grain size scattergram of the specific embodiment that Fig. 3 (b) is magnetic Nano material of the present invention, grain size utilizes dynamic optical to shine and measures;
Fig. 4 (a) is magnetic Nano material of the present invention, comparison Fe
3o
4-DA and comparison Tie Suo Portugal amine (Resovist) the nuclear magnetic resonance, NMR T2 weighting striograph when variable concentrations, due to aberration, wherein dotted line is in order better to use the position of image, it is in practice and is non-existent;
Fig. 4 (b) is magnetic Nano material of the present invention, comparison Fe
3o
4the rectilinear of-DA and comparison Tie Suo Portugal amine (Resovist) corresponding relaxation rate when variable concentrations;
The B-H loop that Fig. 4 (c) is magnetic Nano material of the present invention;
Fig. 5 (a) for the magnetic Nano material of variable concentrations of the present invention respectively the cell line different from three kinds cultivate the contrast block diagram of cell line relative activity after a day;
Fig. 5 (b) for the magnetic Nano material of variable concentrations of the present invention respectively the cell line different from three kinds cultivate the contrast block diagram of cell line relative activity two days later;
Fig. 5 (c) is for utilizing the contrast block diagram of the cell membrane integrity degree of magnetic Nano material cultured cells of the present invention;
Fig. 5 (d) is for utilizing the contrast block diagram of the intracellular reactive oxygen content of magnetic Nano material cultured cells of the present invention;
Fig. 6 (a) is for after utilizing magnetic Nano material of the present invention to inject tumor-bearing mice, the nuclear magnetic resonance, NMR T2 image of tumor by local when different time points;
Fig. 6 (b) is for after utilizing magnetic Nano material of the present invention to inject tumor-bearing mice, the T2 signal value-time diagram of tumor by local when different time points;
Fig. 6 (c) is for after utilizing magnetic Nano material of the present invention to inject tumor-bearing mice, the nuclear magnetic resonance, NMR T2 image at liver position when different time points;
Fig. 6 (d) is for after utilizing magnetic Nano material of the present invention to inject tumor-bearing mice, the T2 signal value-time diagram at liver position when different time points;
Fig. 7 (a) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the bio distribution figure of Pt in liver,spleen,kidney, the heart, lung, stomach, small intestinal, skin, muscle and bone when different time points;
Fig. 7 (b) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the hematoxylin of mice critical organ and eosin colored graph when different time points;
Fig. 8 (a) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the content block diagram of the glutamate pyruvate transaminase when different time points in Mice Body, alkali phosphatase and glutamic oxaloacetic transaminase, GOT;
Fig. 8 (b) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the albumin when different time points in Mice Body and globulin ratio block diagram;
Fig. 8 (c) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the horizontal block diagram of blood urea nitrogen when different time points in Mice Body;
Fig. 8 (d) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the leucocyte content block diagram when different time points in Mice Body;
Fig. 8 (e) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the erythrocyte content block diagram when different time points in Mice Body;
Fig. 8 (f) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the content of hemoglobin block diagram when different time points in Mice Body;
Fig. 8 (g) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the mean corpuscular volume (MCV) block diagram when different time points in Mice Body;
Fig. 8 (h) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the mean corpusular hemoglobin block diagram when different time points in Mice Body;
Fig. 8 is (i) for after utilizing magnetic Nano material of the present invention to inject healthy mice, the platelet content block diagram when different time points in Mice Body;
Fig. 8 (j) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the mean corpuscular hemoglobin concentration (MCHC) block diagram when different time points in Mice Body;
Fig. 8 (k) is for after utilizing magnetic Nano material of the present invention to inject healthy mice, the hematocrit block diagram when different time points in Mice Body.
The specific embodiment
Below the technical scheme in the embodiment of the present invention is described in detail, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, the every other embodiment that those of ordinary skills obtain under the prerequisite of not making creative work, belongs to the scope of protection of the invention.
The invention provides a kind of magnetic Nano material, it comprises: platinum cobalt alloy nano-particle and the vaccenic acid Polyethylene Glycol that plays modification that is connected in platinum cobalt alloy nano grain surface, the molecular formula of described platinum cobalt alloy nano-particle is Pt
3co, the mean diameter of described nano material is 50nm.Above-mentioned platinum cobalt alloy nano-particle is cube structure, and the distance between two apparent surfaces of this cube structure is 6nm, thereby the particle diameter of platinum cobalt alloy nano-particle is about 6nm.Magnetic Nano material water solublity of the present invention is good, has high nuclear magnetic resonance, NMR T2 relaxation rate, is applicable to nuclear magnetic resonance; And it detects by the toxicity inside and outside short-term and long-term animal body, does not find overt toxicity, can try out in clinical technology.
Based on above-mentioned magnetic Nano material, the present invention also provides a kind of application in magnetic resonance radiography imaging by above-mentioned magnetic Nano material magnetic Nano material.
Embodiment mono-
The present invention also provides a kind of method of the above-mentioned magnetic Nano material of preparation, and as a specific embodiment, said method comprises:
In the three-neck flask that the acetylacetone,2,4-pentanedione platinum that is 2:1 by mol ratio and cobalt octacarbonyl join 50ml, add 1 of 0.15mmol, 2-dodecanediol, then add 1ml oleic acid, 8ml oleyl amine and 8ml benzyl ether in three-neck flask.Under the protection group of nitrogen is used, be first heated to 100 ℃ and maintain 0.5h, be then slowly warmed up to 200 ℃ of reaction 2h.Whole course of reaction remains under the protection of nitrogen carries out.Reaction finishes to be cooledly to add 50ml ethanol to 80 ℃ afterwards, with ethanol centrifuge washing twice, obtains platinum cobalt alloy nano-particle.
The platinum cobalt alloy nanoparticulate dispersed obtaining, in 5ml chloroform, is obtained to the chloroform soln of platinum cobalt alloy nano-particle.Wherein, platinum cobalt alloy nano grain surface contains a large amount of hydrophobic macromolecule oleic acid.In another three-neck flask, by 100mg molecular weight, be
5000 vaccenic acid Polyethylene Glycol is dissolved in the chloroform of 3ml, and it is slowly joined in the chloroform soln of platinum cobalt alloy nano-particle, under normal temperature condition, stir 2h, reaction finishes with nitrogen, to dry up afterwards, and add water ultrasonic dissolution, obtaining surface has the polyethyleneglycol modified platinum cobalt alloy nano material of vaccenic acid.
As shown in Fig. 1 (a), Fig. 1 (b), the structural representation that wherein Fig. 1 (a) is magnetic Nano material, platinum cobalt alloy nano-particle, i.e. Pt in figure in figure
3co and vaccenic acid Polyethylene Glycol link together by hydrophobic interaction; The transmission electron microscope picture that Fig. 1 (b) is magnetic Nano material can observe directly the cube structure of platinum cobalt alloy nano-particle from figure.
As shown in Fig. 2 (a), Fig. 2 (b), the angle of elevation annular details in a play not acted out on stage, but told through dialogues scanning transmission electron microscope figure that wherein Fig. 2 (a) is magnetic Nano material; Fig. 2 (b) is the energy dispersion X ray spectrogram of magnetic Nano material under STEM pattern.As seen from the figure, Pt, the Co that magnetic Nano material of the present invention contains and Cu element are mainly from platinum cobalt alloy nano-particle.
As shown in Fig. 3 (a), Fig. 3 (b), the X-ray diffractogram that wherein Fig. 3 (a) is magnetic Nano material, this figure has illustrated that magnetic Nano material of the present invention has the crystal structure of cube crystalline phase; Fig. 3 (b) measures the grain size scattergram of magnetic Nano material of the present invention for utilizing dynamic optical to shine, and the particle diameter of magnetic Nano material is about 50nm as seen from the figure.
Embodiment bis-
Below the radiography ability of magnetic Nano material of the present invention is described by a comparative example.
Particularly, by magnetic Nano material, Fe
3o
4-DAHe Tie carboxylic Portugal amine (Resovist) is diluted to respectively identical Concentraton gradient, i.e. 0.0117mM, 0.0235mM, 0.0469mM, 0.0938mM, 0.1876mM, and on magnetic resonance imaging system, implement magnetic resonance radiography imaging.
Result is as Fig. 4 (a)-4(c) as shown in, by the known increase along with the polyethyleneglycol modified platinum cobalt alloy concentrations of nanoparticles of vaccenic acid of Fig. 4 (a), the image of T2 contrast imaging becomes, and darkness deepens.Magnetic Nano material is when concentration reaches 0.0938mM, and magnetic resonance image (MRI) shows blackening completely.And for Fe
3o
4-DAHe Tie carboxylic Portugal amine (Resovist) needs higher concentration, just can reach identical effect.
Fig. 4 (b) represents the relaxation rate of each sample correspondence under variable concentrations.By measuring the T2 signal intensity of each sample, get its inverse and obtain relaxation rate R2 corresponding under each concentration.Known in figure, relaxation rate R2 and concentration have good linear relationship, by digital simulation slope of a curve, can obtain each material relaxation coefficient r2.Relaxation coefficient r2 is larger, shows that the radiography ability of material is stronger.Wherein, the relaxation coefficient of magnetic Nano material is 451.2mM
-1s
-1, compare Fe
3o
4the 83.9mM of-DA
-1s
-1the 193.4mM of He Tie carboxylic Portugal amine (Resovist)
-1s
-1all much bigger.Hence one can see that, and magnetic Nano material of the present invention has stronger radiography ability, and it can heighten the sensitivity of nuclear magnetic resonance, and more early, more accurate diagnostic result are provided.
The B-H loop that Fig. 4 (c) is magnetic Nano material, this curve shows that above-mentioned magnetic Nano material has superparamagnetism.
Embodiment tri-
Now the toxicity of magnetic Nano material of the present invention is studied, particularly, choose three kinds of different cell line (4T1, HL7702, Sk-br-3cells), utilize 3-(4,5-dimethylthiazole-2)-2, the cytoactive after 5-diphenyl tetrazole bromine salt (MTT) detection magnetic Nano material and cell are hatched.The magnetic Nano material of variable concentrations is joined respectively in 96 orifice plates of having cultivated in advance cell, cultivate respectively 1 day and 2 days, then by the method for MTT, detect the activity of cell.Utilize the seepage of lactic acid dehydrogenase to measure the integrity degree of cell membrane.The magnetic Nano material of variable concentrations and cell culture, after a period of time, utilize microplate reader to detect the seepage of lactic acid dehydrogenase.Take that to add the cell that cell pyrolysis liquid was processed be positive control, simple Cell sap takes the integrity of qualitative characterize cells film for negative contrast.After magnetic Nano material and cell culture, the generation of reactive oxygen species (reactive oxygen species) can detect with dihydro second pyridine (DHE) probe.Magnetic Nano material and cell are cultivated after one day in 96 orifice plates, and cell collects after washing away magnetic Nano material, and then are distributed in the cell culture fluid that contains 1 μ M dihydro second pyridine (DHE) probe, finally use flow cytometry analysis.
Experimental result is as Fig. 5 (a)-Fig. 5 (d), and wherein by shown in Fig. 5 (a) and Fig. 5 (b), the relative activity of three kinds of different cell lines is being cultivated one day with magnetic Nano material and two days later, significantly do not reduced.Thereby illustrate, magnetic Nano material of the present invention can not affect the normal growth of cell.
Fig. 5 (c) has showed the integrity degree of cell membrane, Fig. 5 (d) has showed the situation of reactive oxygen species, as seen from the figure, when magnetic Nano material of the present invention and cell are hatched, can not destroy the integrity of cell membrane, also no longer cause the generation of reactive oxygen species.Thereby state, magnetic Nano material of the present invention has good biocompatibility, thereby can be further used for the magnetic resonance radiography research of live body level.
Embodiment tetra-
Below by another group contrast test, the actual contrast imaging level to magnetic Nano material of the present invention in live body describes.
By 200 μ l, the magnetic Nano material He Tie carboxylic Portugal amine (Resovist) of 4.5mM arrives in Balb/c Mice Body by tail vein injection.Every mice inoculates respectively tumor (4T1, a 60-70mm
3).At different time points, utilize toy coil the tumor of every mice and liver to be carried out to the T2 signal value intensity of T2 nuclear magnetic resonance measurement target region.
To the imaging at mouse tumor position and measurement result, as shown in Fig. 6 (a), Fig. 6 (b), from Fig. 6 (a), the tumor locus of the mice of injection magnetic Nano material is dark than injection Tie Suo Portugal amine (Resovist) obviously; From figure (b), magnetic Nano material Yu Tie carboxylic Portugal amine (Resovist) is compared, after injection, the T2 signal value of same time point is also much smaller, particularly, in administration after 24 hours, the T2 signal value of the tumor region of the mice of injection magnetic Nano material declines in 84.8% ，Er Tie carboxylic Portugal amine (Resovist) injection group, only has 29.6% T2 signal value reduction.Thereby illustrate, magnetic Nano material Bi Tie carboxylic Portugal amine (Resovist) has better radiography effect at tumor locus.
To the imaging of mouse liver and measurement result, as shown in Fig. 6 (c), Fig. 6 (d), in figure, information is known, and magnetic Nano material Yu Tie carboxylic of the present invention Portugal's amine (Resovist) is compared, and also has good radiography effect at liver position.
Embodiment five
The mode that is 40mg/kg magnetic Nano material by tail vein by dosage is expelled in healthy Balb/c Mice Body.Then, respectively in different time points: after 1 day, 7 days, 30 days and 60 days, mouse is put to death, take out major organs, major organs is liver,spleen,kidney, the heart, lung, stomach, small intestinal, skin, muscle and bone, transfers in 10mL chloroazotic acid (volume ratio of HCl, HNO3, HClO4 is 3:1:1) after weighing, and is heated to 200 ℃, finally be settled to 10mL, by the concentration of Pt ion in inductively coupled plasma emission spectrometry solution.Select critical organ, critical organ is liver, spleen, and kidney, the heart, lung and small intestinal, fix with 4% formaldehyde, section, and dye by hematoxylin and eosin.At come card optical microphotograph Microscopic observation magnetic Nano material, main internal organs are had to not damaged.
Result, as shown in Fig. 7 (a), Fig. 7 (b), as seen from the figure, is expelled to the mainly enrichment in liver, spleen organ of magnetic Nano material in Balb/c Mice Body.As time goes on, at these intraorganic enriching quantities, reduce gradually.And, by relatively injecting magnetic Nano material, find with hematoxylin and the eosin stained of the major organs of the mice that is left intact, although magnetic Nano material can enrichment in some organs, do not affect the normal function of organ, do not find the variation of cellular morphology yet.
Embodiment six
In 20 Balb/c Mice Bodies, inject magnetic Nano material, at different time points: within 1 day, 7 days, 30 days and 60 days, put to death afterwards, every mouse is taken out about 0.8mL blood and does blood biochemistry and routine analysis of blood.The mice that separately get five health, is left intact as a control group.In conjunction with each reference index, observe, above-mentioned reference index comprises: liver function index, albumin and globulin ratio, blood urea nitrogen level, leucocyte content, erythrocyte content, hemoglobin, mean corpuscular volume (MCV), mean corpusular hemoglobin, platelet content, mean corpuscular hemoglobin concentration (MCHC) and hematocrit.Wherein, liver function index is mainly measured glutamate pyruvate transaminase, alkali phosphatase and the content of three kinds of materials of glutamic oxaloacetic transaminase, GOT in Mice Body.
Result is as shown in Fig. 8 (a)-Fig. 8 (k), and as seen from the figure, the blood of the mice of administration biochemistry and routine blood test indices do not have notable difference with the indices of the healthy mouse being left intact, and within being all distributed in normal range.Thereby show, magnetic Nano material of the present invention has good biocompatibility.
The present invention also provides a kind of unburned refractory material being obtained by above-mentioned processing method, and this unburned refractory material comprises the unburned flame retardant coating of aluminium oxide-magnesium oxide and is covered at least in part the aluminum-spinel layer on the unburned flame retardant coating of described aluminium oxide-magnesium oxide.This aluminum-spinel layer, before the unburned flame retardant coating of aluminium oxide-magnesium oxide comes into operation, is well protected it, has improved the decay resistance at material initial stage, has reached the object increasing the service life.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and in the situation that not deviating from spirit of the present invention or basic feature, can realize the present invention with other concrete form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, is therefore intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in scope.
In addition, be to be understood that, although this description is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of description is only for clarity sake, those skilled in the art should make description as a whole, and the technical scheme in each embodiment also can, through appropriately combined, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (10)
1. a magnetic Nano material, is characterized in that, described nano material comprises:
Platinum cobalt alloy nano-particle and the vaccenic acid Polyethylene Glycol that plays modification that is connected in platinum cobalt alloy nano grain surface, the molecular formula of described platinum cobalt alloy nano-particle is Pt
3co.
2. magnetic Nano material according to claim 1, is characterized in that, described platinum cobalt alloy nano-particle is cube structure, and the distance between two apparent surfaces of described cube structure is 6nm.
3. a method of preparing magnetic Nano material as claimed in claim 1, is characterized in that, described method comprises the steps:
The acetylacetone,2,4-pentanedione platinum that is 2:1 by mol ratio and cobalt octacarbonyl join in 1,2-dodecanediol, then the mixture of formation is dissolved in the first solvent, heating is reacted, and then slowly heats up and continues reaction, and reaction finishes rear cooling, product is cleaned, obtain platinum cobalt alloy nano-particle;
By platinum cobalt alloy nanoparticulate dispersed in the second solvent, after mix homogeneously, the solution that adds vaccenic acid Polyethylene Glycol and the second solvent to form, under normal temperature condition, stir and react, reaction finishes after-blow dry doubling and is dissolved in water, and obtaining surface has the polyethyleneglycol modified platinum cobalt alloy nano material of vaccenic acid.
4. the method for preparing magnetic Nano material according to claim 3, is characterized in that, described the first solvent is that volume ratio is the mixture of benzylic ether, oleyl amine and the oleic acid formation of 8:8:1.
5. the method for preparing magnetic Nano material according to claim 3, is characterized in that, prepares the course of reaction of platinum cobalt alloy nano-particle and carries out under nitrogen atmosphere.
6. the method for preparing magnetic Nano material according to claim 3, is characterized in that, while preparing platinum cobalt alloy nano-particle, is heated to 100 ℃ of reaction 2h, is then slowly warmed up to 200 ℃ of reaction 2h.
7. the method for preparing magnetic Nano material according to claim 3, is characterized in that, while preparing platinum cobalt alloy nano-particle, is cooled to 80 ℃, and adds 50ml ethanol after reaction finishes, and utilizes twice of ethanol centrifuge washing.
8. the method for preparing magnetic Nano material according to claim 3, is characterized in that, described the second solvent is chloroform.
9. the method for preparing magnetic Nano material according to claim 3, is characterized in that, when platinum cobalt alloy nano-particle is modified, after reaction finishes, utilizes nitrogen to dry up.
10. a magnetic Nano material as claimed in claim 1 application in magnetic resonance radiography imaging.
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| CN108042509A (en) * | 2018-02-09 | 2018-05-18 | 四川大学 | Nucleocapsid mesoporous silica nano-particle of controllable temperature-sensitive peptide nanometer valve modification and preparation method and application |
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| SHENGNAN YIN 等: "Magnetic PEGylated Pt3Co nanoparticles as a novel MR contrast agent: in vivo MR imaging and long-term toxicity study", 《NANOSCALE》 * |
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| CN108042509A (en) * | 2018-02-09 | 2018-05-18 | 四川大学 | Nucleocapsid mesoporous silica nano-particle of controllable temperature-sensitive peptide nanometer valve modification and preparation method and application |
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