CN102320664A - Preparation method for amino-functionalized water-soluble magnetic manganomanganic oxide nanoparticles - Google Patents
Preparation method for amino-functionalized water-soluble magnetic manganomanganic oxide nanoparticles Download PDFInfo
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Abstract
The present invention discloses a method for synthesis of amino-functionalized water-soluble magnetic manganomanganic oxide nanoparticles on a large scale. According to the method, phenyl ether is firstly adopted as a solvent; 6-(1,3-dioxoisoindolin-2-yl)hexanoic acid and a manganese salt are subjected to high temperature pyrolysis to obtain oil-soluble magnetic nanoparticles with a surface ligand of 6-(1,3-dioxoisoindolin-2-yl)hexanoic acid; then phthalic anhydride positioned on the 6-(1,3-dioxoisoindolin-2-yl)hexanoic acid is removed through hydrazine hydrate, such that the oil-soluble nanoparticles are changed into the amino-functionalized water-soluble nanoparticles. According to the present invention, the oil-soluble manganomanganic oxide nanoparticles can be prepared on a large scale through simple pyrolysis, the deprotection of the amino group is easy to perform, such that the large-scale preparation of the amino-functionalized water-soluble manganomanganic oxide can be simply realized; the preparation method has characteristics of low requirements of the equipment, low prices of the raw materials, and pollution-free by-products.
Description
Technical field
The present invention relates to field of nanometer material technology, relate to a kind of preparation method of magnetic nanoparticle, be specifically related to a kind of preparation method of water-soluble manganic manganous oxide nano-material of amino functional.
Background technology
Magnetic Nano material (magnetic nanomaterials) is closely related as a kind of every aspect in informationization, robotization, electromechanical integration, national defence and national economy of nano material.Magnetic Nano material through finishing and functionalization after, in magnetics, biology and medicine and other fields, particularly have tempting application prospect at aspects such as Ultrahigh-Density Data Storage, biomolecules identification, medicine transmission.Cause extensive attention both domestic and external and become the focus of research.
Nmr imaging technique (MRI) is at present rare human body to be had no the methods for clinical diagnosis safely, fast and accurately of injury, because its non-invasive and multifaceted tomography function, but that the main weakness of zeugmatography is sensitivity is low.So in clinical MRI, the diagnosis more than 30% must be used NMR contrast agent, shorten imaging time, improve image contrast and sharpness.All there is strict requirement in field such as biochemistry and medical science to physics, chemistry and pharmacological properties such as chemical constitution, globule size, magnetic function, crystalline structure, adsorptivity, surface topography, solvability and the toxicity of magnetic nano-particle.Therefore to realize the application of magnetic nano-particle, must satisfy several conditions: one, monodispersity, two, have a magnetic performance preferably, three, have water-soluble and active function groups in fields such as these biochemistry and medical science.But mostly present preparation mono-dispersed nano particle is oil-soluble, therefore will realize these requirements, must further carry out surface-treated.The main means of carrying out finishing at present have methods such as coated with silica, organic polymer coating and ligand exchange.Though coated with silica has dispersed preferably, the technology more complicated; Organic polymer coats, and reunites easily, and is not very stable; The method of ligand exchange can well solve the defective of above two kinds of methods, but the efficient of ligand exchange is an insoluble problem always.Therefore above method all not too is fit to enlarge produce.
The magnetic resonance contrast agent kind is a lot, can be divided into paramagnetic contrast medium, manganese magnetic contrast medium and superparamagnetism contrast medium usually.The superparamagnetism contrast medium since its in human body, distribute have specificity, using dosage is few, safety, toxic side effect is little and advantage such as of many uses, has become the focus of present research and development.The key of preparation superparamagnetism contrast medium is how to prepare the magnetic property excellence superparamagnetic material of (high saturation and magnetic intensity and initial susceptibility); And on this basis the magnetic nano particle sub-surface is modified; Obtain hypotoxicity, and have the magnetic Nano material of stable, water-soluble preferably, biocompatibility and active function groups.Bio-compatibility manganate magnetic nano-particle prepares the process more complicated at present, and can not prepare in enormous quantities, has limited the application of this type material in this field greatly.
Summary of the invention
The objective of the invention is to above-mentioned deficiency of the prior art; Propose a kind of preparation method of water-soluble trimanganese tetroxide nano magnetic particle of amino functional, solve the problem that existing magnetic nano-particle can not have magnetic performance preferably, monodispersity, water-soluble and active function groups simultaneously.
The present invention realizes through following technical scheme:
A kind of preparation method of water-soluble trimanganese tetroxide magnetic nano-particle of amino functional may further comprise the steps:
(1) takes by weighing manganous salt and 6-(1,3-dioxoisoindolin-2-yl) caproic acid and triethylamine and at room temperature be dispersed in the solvent, stirred 20～30 hours, obtain chocolate oily 6-(1,3-dioxoisoindolin-2-yl) caproic acid and close the manganese presoma;
Said solvent is for pressing 1: (0.5～2) volume ratio blended methylene dichloride and absolute ethyl alcohol;
Said manganous salt is selected from Manganous chloride tetrahydrate, manganese acetate or manganous nitrate; The mol ratio of divalent manganesetion, 6-(1,3-dioxoisoindolin-2-yl) caproic acid and triethylamine is 1: (1～5): (1～10);
(2) with the resulting 6-(1 of step (1); 3-dioxoisoindolin-2-yl) caproic acid closes the manganese presoma and is dissolved in the phenylate, and the mode with gradient-heated under nitrogen atmosphere or protection of rare gas element atmosphere and the whipped state is promoted to 120～140 ℃ with temperature with 5 ℃/min step by step, stablizes 1～1.5h; Again temperature is promoted to 158～173 ℃ with 5 ℃/min; Stablize 4～5h, obtain 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate oil soluble trimanganese tetroxide nano particle;
Said rare gas element atmosphere is helium-atmosphere, neon atmosphere and argon atmospher;
(3) the oil soluble trimanganese tetroxide nano particle that obtains is scattered in the solvent, adds deaminizating protection reagent, refluxed 4～5 hours, what obtain surface organic ligands and be 6-aminocaprolc acid is the trimanganese tetroxide magnetic nano-particle of amino functional;
Said solvent be in chloroform, ethanol, the methylene dichloride one or both by any than the mixed solution of the mixture of forming with the water composition, the volume ratio of water is 1/5～1/4 in the mixed solution;
The preferred Hydrazine Hydrate 80 of said deaminizating protective material, with the mass ratio that obtains 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate oil soluble trimanganese tetroxide nano particle be 5: 1～1: 5, preferred 1: 1～1: 5.
It is presoma that the present invention closes manganese with 6-(1,3-dioxoisoindolin-2-yl) caproic acid, is that to close manganese with 6-(1,3-dioxoisoindolin-2-yl) caproic acid be presoma, the Mn that obtains through high temperature pyrolysis
3O
4Magnetic nano-particle, the carboxyl coordination on this nanoparticle surface and 6-(1, the 3-dioxoisoindolin-2-yl) caproic acid makes 1, and 3-dioxoisoindolin part outwards has oleophilicity; For this material is used in biological field, through the method for deaminizating protection, the phthalic acid on 6-(1,3-dioxoisoindolin-2-yl) the caproic acid organic ligand is sloughed, obtain the Mn that the surface has amino active function groups
3O
4Magnetic nano-particle, this nanoparticle can well be scattered in the water, and has good biocompatibility.
In this method, oil-soluble Mn
3O
4During the preparation of nanometer nuclear, owing to be under the condition of anhydrous and oxygen-free, to carry out, heating condition is very important with this step of nitrogen draining down; Temperature should be heated to 120～140 ℃; In this TR, water better is excluded totally with the state of steam and again temperature is promoted to 158～173 ℃ with 5 ℃/min, and afterreaction finished in 4～5 hours; Atom re-assemblies nucleation, crystallization, forms Mn
3O
4Nanoparticle.
The Mn that the present invention makes
3O
4The magnetic nanoparticle pattern is main with sphere mainly, the paramagnetism that mean sizes shows as in the scope of 8-10nm; Prepared magnetic nano-particle has magnetic performance, monodispersity, water-soluble and active function groups preferably simultaneously, and compound method is simple, convenient extensive synthetic production.
Description of drawings
Fig. 1 is the structural representation of organic ligand 6-(1, the 3-dioxoisoindolin-2-yl) caproic acid among the present invention.
Fig. 2 is the synthetic route chart of the water-soluble trimanganese tetroxide of synthesizing amino functionalization among the present invention.
Fig. 3 is that the embodiment of the invention 1 synthetic surface organic ligands is the TEM figure of the trimanganese tetroxide of 6-(1,3-dioxoisoindolin-2-yl) caproic acid.
Fig. 4 is that the embodiment of the invention 1 synthetic surface organic ligands is the TEM figure of the trimanganese tetroxide of 6-aminocaprolc acid.
Fig. 5 is the XRD figure of the embodiment of the invention 1 synthetic trimanganese tetroxide before and after amino deprotection.
Fig. 6 is the IR figure of the embodiment of the invention 1 synthetic trimanganese tetroxide before and after amino deprotection.
Fig. 7 is the embodiment of the invention 1 synthetic trimanganese tetroxide deployment conditions in solvent before and after amino deprotection.
Fig. 8 is that the embodiment of the invention 1 synthetic surface organic ligands is that the trimanganese tetroxide of 6-(1,3-dioxoisoindolin-2-yl) caproic acid is at 25 ℃ magnetic hysteresis loop figure.
Fig. 9 is that the embodiment of the invention 1 synthetic surface organic ligands is that the trimanganese tetroxide of 6-aminocaprolc acid is at 25 ℃ magnetic hysteresis loop figure.
Figure 10 is that the embodiment of the invention 1 synthetic surface organic ligands is that 6-(1,3-dioxoisoindolin-2-yl) trimanganese tetroxide of caproic acid and the trimanganese tetroxide that surface organic ligands is 6-aminocaprolc acid are the T of measured nucleus magnetic resonance under 0.57mM, 1.15mM, 2.31mM, 4.63mM, the 9.26mM in concentration
1, T
2Value and the NMR relaxation rate value that simulates thus are respectively r
1=1.23s
-1And r
2=2.93s
-1
Figure 11 is that the embodiment of the invention 1 synthetic surface organic ligands is that 6-(1,3-dioxoisoindolin-2-yl) trimanganese tetroxide of caproic acid and the trimanganese tetroxide that surface organic ligands is 6-aminocaprolc acid are the T under 0.57mM, 1.15mM, 2.31mM, 4.63mM, the 9.26mM in concentration
1, T
2The zeugmatography gray-scale map.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment are interpreted as only being used to the present invention is described and are not used in restriction protection scope of the present invention.After the content of having read the present invention's record, those skilled in the art can do various changes or modification to the present invention, and these equivalences change and modify and fall into claim of the present invention institute restricted portion equally.
Embodiment 1:
The Tetra hydro Phthalic anhydride of six hexosamines and 100mmol (14.8g) that takes by weighing 100mmol (13.1g) adds air set pipe 170 ℃ of heating 4 hours in the single neck flask of 100ml, be cooled to room temperature; Dilute with methylene dichloride; With one night of anhydrous magnesium sulfate drying of 20g, suction filtration is removed anhydrous magnesium sulfate, with the clear liquid rotary evaporation that obtains; Get white solid powder 6-(1,3-dioxoisoindolin-2-yl) caproic acid.
Take by weighing MnCl
24H
2O (0.6g, 3mmol) and 6-(1,3-dioxoisoindolin-2-yl) caproic acid (1.6g; 6mmol) put into the 100ml round-bottomed flask, add then in 20ml methylene dichloride and the 20ml absolute ethyl alcohol, in room temperature; Add the 3ml triethylamine under the magnetic agitation condition, stirred 24 hours.Each 10ml water washs three times, and through Rotary Evaporators, the evaporate to dryness of will filtrating obtains chocolate oily matter, is 6-(1,3-dioxoisoindolin-2-yl) caproic acid and closes the manganese presoma.Put into the dry 12h of vacuum drying oven.
Resulting 6-(1,3-dioxoisoindolin-2-yl) caproic acid is closed the manganese presoma, be dissolved in the 20ml phenylate, pour in the three-necked flask of 100ml, under the condition of magnetic agitation, at first be heated to 140 ℃ and use N
2Moisture in the venting reaction solution, heating 1h is warming up to 160 ℃, N then
2Protection, reaction 4.5h.Be cooled to room temperature, spinning is washed several times with absolute ethyl alcohol more, obtains atrament, vacuum-drying.This atrament promptly is that the surface is 6-(1,3-dioxoisoindolin-2-yl) the oil-soluble Mn of caproic acid coordinate
3O
4Nanoparticle.Its TEM figure is as shown in Figure 3.
Take by weighing 6-(1,3-dioxoisoindolin-2-yl) the oil-soluble Mn of caproic acid coordinate
3O
4Nanoparticle 0.6g is scattered in 35ml methylene dichloride, 20ml ethanol and the 15ml water, and agitation condition adds the 20ml Hydrazine Hydrate 80 down, and afterreaction stopped in 4 hours.Tawny Mn
3O
4Nanoparticle all has the organic phase of lower floor to transfer to the upper strata to get water.Spinning, washing with alcohol are several times.Can obtain the water-soluble Mn of amino functional
3O
4Nanoparticle.Its TEM figure is as shown in Figure 4, and the mean diameter of gained trimanganese tetroxide particle is 8～10nm.
The XRD figure of synthetic trimanganese tetroxide before and after amino deprotection is as shown in Figure 5 in the present embodiment, can be clearly seen that from figure obvious variation does not take place deprotection front and back crystalline form; Both IR figure are as shown in Figure 6, can see from the contrast of scheming to go up with pure organic ligand, and the organic ligand on the trimanganese tetroxide surface that obtains and the thinking of design are consistent.
The deployment conditions of synthetic trimanganese tetroxide before and after amino deprotection is as shown in Figure 7 in the present embodiment; As can be seen from the figure, before deprotection, shown in A among the figure; It has monodispersity preferably in methylene dichloride; Behind deprotection, shown in B among the figure, it has monodispersity preferably in the aqueous solution.
Present embodiment synthetic surface organic ligands is 6-(1; 3-dioxoisoindolin-2-yl) trimanganese tetroxide of caproic acid and the surface organic ligands trimanganese tetroxide that is 6-aminocaprolc acid at magnetic hysteresis loop figure such as Fig. 8 and shown in Figure 9 of 25 ℃; Show paramagnetism preferably by the visible resulting nanoparticle of figure; Susceptibility reaches 0.366emu/g and 0.367emu/g respectively, and the saturation magnetization rate before and after the deaminizating protection changes little.
Present embodiment synthetic surface organic ligands is the r of 6-aminocaprolc acid manganese oxide behind the manganese oxide deprotection of 6-(1,3-dioxoisoindolin-2-yl) caproic acid
1, r
2Relaxation rate is shown in figure 10, has its value of very high relaxation rate to reach r by the visible resulting nanoparticle of figure
1=1.23s
-1MM
-1, r
2=2.93s
-1MM
-1
Present embodiment synthetic surface organic ligands is 6-(1; 3-dioxoisoindolin-2-yl) the manganese oxide zeugmatography effect of 6-aminocaprolc acid is shown in figure 11 behind the manganese oxide deprotection of caproic acid; Even can obviously find out under the very low concentration of nanoparticle its T by diagram
1, T
2The zeugmatography effect is all very good.
Embodiment 2:
The Tetra hydro Phthalic anhydride of six hexosamines and 100mmol (148g) that takes by weighing 1000mmol (131g) adds air set pipe 170 ℃ of heating 4 hours in the single neck flask of 1000ml, be cooled to room temperature; Dilute with methylene dichloride; With one night of anhydrous magnesium sulfate drying of 100g, suction filtration is removed anhydrous magnesium sulfate, with the clear liquid rotary evaporation that obtains; Get white solid powder 6-(1,3-dioxoisoindolin-2-yl) caproic acid.
Take by weighing MnCl
24H
2O (6g, 30mmol) and 6-(1,3-dioxoisoindolin-2-yl) caproic acid (16g; 60mmol) put into the 100ml round-bottomed flask, add then in 100ml methylene dichloride and the 200ml absolute ethyl alcohol, in room temperature; Add the 30ml triethylamine under the magnetic agitation condition, stirred 24 hours.Each 100ml water washs three times, and through Rotary Evaporators, the evaporate to dryness of will filtrating obtains chocolate oily matter, is 6-(1,3-dioxoisoindolin-2-yl) caproic acid and closes the manganese presoma.Put into the dry 12h of vacuum drying oven.
Resulting 6-(1,3-dioxoisoindolin-2-yl) caproic acid is closed the manganese presoma, be dissolved in the 200ml phenylate, pour in the three-necked flask of 1000ml, under the condition of magnetic agitation, at first be heated to 140 ℃ and use N
2Moisture in the venting reaction solution, heating 1h is warming up to 160 ℃, N then
2Protection, reaction 4.5h.Be cooled to room temperature, spinning is washed several times with absolute ethyl alcohol more, obtains atrament, vacuum-drying.This atrament promptly is that the surface is 6-(1,3-dioxoisoindolin-2-yl) the oil-soluble Mn of caproic acid coordinate
3O
4Nanoparticle.
Take by weighing 6-(1,3-dioxoisoindolin-2-yl) the oil-soluble Mn of caproic acid coordinate
3O
4Nanoparticle 6g is scattered in the mixed solution of 100ml methylene dichloride, 200ml ethanol and 150ml water composition, and agitation condition adds the 200ml Hydrazine Hydrate 80 down, and afterreaction stopped in 4 hours.Tawny Mn
3O
4Nanoparticle all has the organic phase of lower floor to transfer to the upper strata to get water.Spinning, washing with alcohol are several times.Can obtain the water-soluble Mn of amino functional
3O
4Nanoparticle has monodispersity preferably in the aqueous solution.
Claims (6)
1. the preparation method of the water-soluble trimanganese tetroxide magnetic nano-particle of amino functional is characterized in that, may further comprise the steps:
(1) manganous salt and 6-(1,3-dioxoisoindolin-2-yl) caproic acid and triethylamine at room temperature are dispersed in the solvent, stirred 20～30 hours, obtain 6-(1,3-dioxoisoindolin-2-yl) caproic acid and close the manganese presoma;
Said solvent is for pressing 1: (0.5～2) volume ratio blended chloroform and absolute ethyl alcohol;
Said manganous salt is selected from Manganous chloride tetrahydrate, manganese acetate or manganous nitrate); The mol ratio of divalent manganesetion, 6-(1,3-dioxoisoindolin-2-yl) caproic acid and triethylamine is 1: (1～5): (1～10);
(2) with the resulting 6-(1 of step (1); 3-dioxoisoindolin-2-yl) caproic acid closes the manganese presoma and is dissolved in the phenylate, and the mode with gradient-heated under nitrogen atmosphere or protection of rare gas element atmosphere and the whipped state is promoted to 120～140 ℃ with temperature with 5 ℃/min step by step, stablizes 1～1.5h; Again temperature is promoted to 158～173 ℃ with 5 ℃/min; Stablize 4～5h, obtain 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate oil soluble trimanganese tetroxide nano particle;
(3) the oil soluble trimanganese tetroxide nano particle that obtains is scattered in the solvent, adds deaminizating protection reagent, refluxed 4～5 hours, what obtain surface organic ligands and be 6-aminocaprolc acid is the trimanganese tetroxide magnetic nano-particle of amino functional;
Said solvent be in chloroform, ethanol, the methylene dichloride one or both by any than the mixed solution of the mixture of forming with the water composition, the volume ratio of water is 1/5～1/4 in the mixed solution.
2. the preparation method of the water-soluble trimanganese tetroxide magnetic nano-particle of the described amino functional of claim 1; It is characterized in that; The mol ratio of described divalent manganesetion, 6-(1,3-dioxoisoindolin-2-yl) caproic acid and triethylamine is 1: (2～4): (5～10).
3. the preparation method of the water-soluble trimanganese tetroxide magnetic nano-particle of the described amino functional of claim 1 is characterized in that, said rare gas element atmosphere is helium-atmosphere, neon atmosphere or argon atmospher.
4. the preparation method of the water-soluble trimanganese tetroxide magnetic nano-particle of the described amino functional of claim 1 is characterized in that, said deaminizating protective material is a Hydrazine Hydrate 80.
5. the preparation method of the water-soluble trimanganese tetroxide magnetic nano-particle of the described amino functional of claim 4; It is characterized in that; The mass ratio of Hydrazine Hydrate 80 and 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate oil soluble trimanganese tetroxide nano particle is 5: 1～1: 5.
6. the preparation method of the water-soluble trimanganese tetroxide magnetic nano-particle of the described amino functional of claim 5; It is characterized in that; The mass ratio of Hydrazine Hydrate 80 and 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate oil soluble trimanganese tetroxide nano particle is 1: 1～1: 5.
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Cited By (4)
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| CN102923782A (en) * | 2012-11-12 | 2013-02-13 | 上海师范大学 | Preparation method and biological application of T1-T1 synergistic effect gadolinium chelate manganous-manganic oxide nano particle |
| CN103007304A (en) * | 2013-01-15 | 2013-04-03 | 上海师范大学 | CT/MRI (computerized tomography/magnatic resonance imaging) double-function Mn3O4 nanoparticles and preparation method thereof |
| CN103656690A (en) * | 2012-09-11 | 2014-03-26 | 南京逐陆医药科技有限公司 | Method for preparing manganese chloride oral solution |
| CN106848295A (en) * | 2017-02-20 | 2017-06-13 | 北京理工大学 | Mn oxide and preparation method thereof and aluminium ion battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103656690A (en) * | 2012-09-11 | 2014-03-26 | 南京逐陆医药科技有限公司 | Method for preparing manganese chloride oral solution |
| CN103656690B (en) * | 2012-09-11 | 2016-04-27 | 南京逐陆医药科技有限公司 | A kind of preparation method of manganese chloride oral solution |
| CN102923782A (en) * | 2012-11-12 | 2013-02-13 | 上海师范大学 | Preparation method and biological application of T1-T1 synergistic effect gadolinium chelate manganous-manganic oxide nano particle |
| CN102923782B (en) * | 2012-11-12 | 2014-10-29 | 上海师范大学 | Preparation method and biological application of T1-T1 synergistic effect gadolinium chelate manganous-manganic oxide nano particle |
| CN103007304A (en) * | 2013-01-15 | 2013-04-03 | 上海师范大学 | CT/MRI (computerized tomography/magnatic resonance imaging) double-function Mn3O4 nanoparticles and preparation method thereof |
| CN103007304B (en) * | 2013-01-15 | 2014-12-10 | 上海师范大学 | CT/MRI (computerized tomography/magnatic resonance imaging) double-function Mn3O4 nanoparticles and preparation method thereof |
| CN106848295A (en) * | 2017-02-20 | 2017-06-13 | 北京理工大学 | Mn oxide and preparation method thereof and aluminium ion battery |
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Application publication date: 20120118 |