CN102442703A - Preparation method of amino functionalized water-soluble manganese ferrate magnetic nanometer particles - Google Patents

Preparation method of amino functionalized water-soluble manganese ferrate magnetic nanometer particles Download PDF

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CN102442703A
CN102442703A CN2011102986223A CN201110298622A CN102442703A CN 102442703 A CN102442703 A CN 102442703A CN 2011102986223 A CN2011102986223 A CN 2011102986223A CN 201110298622 A CN201110298622 A CN 201110298622A CN 102442703 A CN102442703 A CN 102442703A
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dioxoisoindolin
caproic acid
particle
manganese
soluble
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杨仕平
张崇琨
安璐
黄国胜
代安涛
胡鹤
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Shanghai Normal University
University of Shanghai for Science and Technology
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Abstract

The invention discloses a preparation method of amino functionalized water-soluble manganese ferrate magnetic nanometer particles. The method comprises the steps of: firstly, regarding oleylamine and phenylate as solvents; performing high-temperature pyrolysis on 6-(1,3-dioxoisoindoline-2-yl) ferric caproate and 6-(1,3-dioxoisoindoline-2-yl) manganese caproate to obtain oil-soluble magnetic nanometer particles with 6-(1,3-dioxoisoindoline-2-yl) caproic acid as a surface ligand; then eluting phthalic anhydride on the 6-(1,3-dioxoisoindoline-2-yl) caproic acid by using a hydrazine hydrate; and transforming the oil-soluble nanometer particles to amino functionalized water-soluble nanometer particles. As such oil-soluble manganese ferrate nanometer particles can be prepared in a large scale manner through the simple pyrolysis and protection removal of amino is performed easily, large-scale preparation of the amino functionalized water-soluble manganese ferrate can be realized simply. Such preparation method has very low requirements on equipment, needs raw materials at low cost and has pollution-free by-products.

Description

The preparation method of the water-soluble manganous ferrite magnetic nano-particle of amino functional
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 manganous ferrite magnetic nano-particle 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 but dispersed, two, have 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.Present bio-compatibility manganate magnetic nano-particle preparation process more complicated, and can not prepare in enormous quantities, limited of the application of this type material greatly in this field.
Summary of the invention
The method that the purpose of this invention is to provide a kind of water-soluble manganous ferrite magnetic nano-particle of mass preparation amino functional; The nanoparticle of this method preparation not only has magnetic performance, monodispersity, water-soluble and active function groups preferably; And compound method is fairly simple, can enlarge production very easily.
The present invention realizes through following technical scheme:
The preparation method of the water-soluble manganous ferrite magnetic nano-particle of amino functional may further comprise the steps:
(1) with manganous salt and 6-(1; 3-dioxoisoindolin-2-yl) caproic acid, trivalent iron salt and 6-(1,3-dioxoisoindolin-2-yl) caproic acid is dissolved in respectively in methylene dichloride or the chloroform; Under the condition that triethylamine exists, stir 20~30h; Obtain that chocolate oily 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes the manganese presoma and blood red oily 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes the iron presoma;
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);
Said trivalent iron salt is selected from iron(ic)chloride, iron acetate, iron nitrate or ferric sulfate); The mol ratio of ferric ion, 6-(1,3-dioxoisoindolin-2-yl) caproic acid and triethylamine is 1: (1~5): (1~10);
(2) with the prepared 6-(1 of step (1); 3-dioxoisoindolin-2-yl) caproic acid closes the manganese presoma and 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes the iron presoma and is dissolved in respectively in the solvent, and the mode with gradient-heated under nitrogen atmosphere or the rare gas element atmosphere is promoted to 120 ℃~140 ℃ step by step with temperature; Stablized 1~2 hour; Steam in the solution is evaporated fully, again with 5 ℃/min with temperature increase to 210 ℃~220 ℃, stablized 2~3 hours; Make two kinds of precursor mixtures under this temperature, form stable MOX separately; With 10 ℃/min temperature increase to 250 ℃~260 ℃ was stablized 1~2 hour then, obtained 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate oil soluble manganous ferrite nano-particle;
It is 1: 2 that said 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes the mol ratio that manganese presoma and 6-(1,3-dioxoisoindolin-2-yl) caproic acid close the iron presoma;
Said rare gas element atmosphere is helium-atmosphere, neon atmosphere and argon atmospher;
Said solvent is oleyl amine or phenylate, or both are by any mixture than composition;
(3) the oil soluble manganous ferrite nano-particle that step (1) is obtained is scattered in the solvent, adds deaminizating protection reagent, refluxes 4~5 hours, sloughs Tetra hydro Phthalic anhydride, and obtaining the surface is amino ferrous acid manganese magnetic nano-particle;
Said deaminizating protective material is a Hydrazine Hydrate 80, with the ratio that obtains 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate oil soluble ferrous acid manganese magnetic nano-particle be 5: 1~1: 5, preferred 1: 1~1: 5;
Said solvent be in 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 1/20~1/5 in the mixed solution.
The water-soluble manganous ferrite magnetic Nano material of amino functional of the present invention is to close iron with 6-(1,3-dioxoisoindolin-2-yl) caproic acid, and it is presoma that 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes manganese, the MnFe that obtains through high temperature pyrolysis 2O 4Magnetic nano-particle, the carboxyl coordination on this nanoparticle surface and 6-(1, the 3-dioxoisoindolin-2-yl) caproic acid; Make 1; 3-dioxoisoindolin part is outwards passed through amino deprotection reaction, with 6-(1 then; 3-dioxoisoindolin-2-yl) phthalic acid on the caproic acid organic ligand is sloughed, and obtains having for the surface MnFe of amino active function groups 2O 4Nanoparticle, this nanoparticle can well be scattered in the water, and has good biocompatibility.
In this method, oil-soluble MnFe 2O 4During the preparation of nanometer nuclear, owing to be under the condition of anhydrous and oxygen-free, to carry out, so heating condition is very important with this step of nitrogen draining down, temperature should be heated to 120 ℃~140 ℃, and in this TR, water better is excluded totally with the state of steam; 210 ℃~220 ℃ of heating pyrolytic the first step TRs, in this TR, presoma begins to form stable oxidation state; Be heated to 250 ℃~260 ℃, atom begins to re-assembly, nucleation, crystallization, forms MnFe 2O 4Nanoparticle.In this method, oil-soluble MnFe 2O 4Nanoparticle is sloughed through Hydrazine Hydrate 80 and is used for protecting amino Tetra hydro Phthalic anhydride, can obtain the water miscible MnFe of amino functional 2O 4Nanoparticle.
The MnFe that the present invention makes 2O 4The magnetic nanoparticle pattern is main with sphere mainly, and mean sizes shows as paramagnetism in the scope of 10nm.The present invention changes oil-soluble nanoparticle into the water miscible manganous ferrite nano-particle of amino functional dexterously, and this water soluble nanometer particles has also shown the better action effect aspect zeugmatography.
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 manganous ferrite magnetic nano-particle of amino functional among the present invention.
Fig. 3 is that the embodiment of the invention 1 synthetic surface organic ligands is the TEM figure of the ferrous acid manganese 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 ferrous acid manganese of 6-aminocaprolc acid.
Fig. 5 is the XRD figure of synthetic ferrous acid manganese before and after amino deprotection in the embodiment of the invention 1.
Fig. 6 is the IR figure of synthetic ferrous acid manganese before and after amino deprotection in the embodiment of the invention 1.
Fig. 7 be in the embodiment of the invention 1 synthetic ferrous acid manganese before and after amino deprotection the deployment conditions in solvent and in the aqueous solution magnetic effect.
Fig. 8 is that the embodiment of the invention 1 synthetic deprotection front surface organic ligand is that the ferrous acid manganese of 6-(1,3-dioxoisoindolin-2-yl) caproic acid is at 25 ℃ magnetic hysteresis loop figure.
Fig. 9 is that the ferrous acid manganese of surface organic ligands 6-aminocaprolc acid behind the embodiment of the invention 1 synthetic deprotection is at 25 ℃ magnetic hysteresis loop figure.
Figure 10 is that the embodiment of the invention 1 synthetic surface organic ligands is the ferrous acid manganese of 6-(1,3-dioxoisoindolin-2-yl) caproic acid and ferrous acid manganese measured T when concentration is 0.59mM, 1.19mM, 2.39mM, 4.79mM, 9.58mM that organic ligand is 6-aminocaprolc acid 2Nuclear magnetic resonance value and the NMR relaxation rate value that simulates thus are respectively R 2=34.78s -1
Figure 11 is that the embodiment of the invention 1 synthetic surface organic ligands is that 6-(1,3-dioxoisoindolin-2-yl) ferrous acid manganese of caproic acid and the ferrous acid manganese that organic ligand is 6-aminocaprolc acid are T under 0.59mM, 1.19mM, 2.39mM, 4.79mM, the 9.58mM in concentration 2The zeugmatography gray-scale map.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1:
The first step, preparation 6-(1,3-dioxoisoindolin-2-yl) caproic acid:
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.
In second step, preparation 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes manganese and 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes iron:
The MnCI of difference weighing 6mmol (0.6g) 24H 2O and 12mmol (1.6g) 6-(1,3-dioxoisoindolin-2-yl) caproic acid, the FeCl of 12mmol (1.6g) 3In 18mmol (4.7g) 6-(1,3-dioxoisoindolin-2-yl) caproic acid to single neck flask; The methylene dichloride that adds 20ml more respectively drips the triethylamine of 3ml again, is stirred to solid and dissolves fully; Wash 3 times, add an amount of anhydrous MgSO 4, sealed dry 12 hours.
The 3rd step, preparation 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate MnFe 2O 4Nanoparticle: the 6-(1 that drying is good; 3-dioxoisoindolin-2-yl) caproic acid closes manganese (6mmol) and closes iron (12mmol) respectively with the dissolving of 10mL phenylate with 6-(1,3-dioxoisoindolin-2-yl) caproic acid, mixes after the dissolving; At 120 ℃ of excluding airs; Nitrogen protection is rapidly heated to 210 ℃ of heating 2 hours, is warming up to 260 ℃ of heating 1.5 hours once more.Reaction finishes to naturally cool to room temperature, centrifugal oil-soluble 6-(1,3-dioxoisoindolin-2-yl) the caproic acid coordinate MnFe that obtains 2O 4Nanoparticle.Its TEM figure is as shown in Figure 3.
The 4th step is with resulting 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate MnFe 2O 4(6mmol 1.5g) is dissolved in the 10mL methylene dichloride, adds the 10mL85% Hydrazine Hydrate 80, and 10mL ethanol stirred 4 hours, and obtaining surface organic ligands is the water-soluble MnFe of the amino functional of 6-aminocaprolc acid 2O 4Nanoparticle.Its TEM figure is as shown in Figure 4.
The XRD figure of synthetic ferrous acid manganese 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 ferrous acid manganese surface that obtains and the thinking of design are consistent.
In the present embodiment synthetic ferrous acid manganese before and after amino deprotection the deployment conditions in solvent and in the aqueous solution magnetic effect as shown in Figure 7; A can find out from figure; It has monodispersity preferably in methylene dichloride, B can find out that it has monodispersity preferably in the aqueous solution from figure; C can find out that gained ferrous acid manganese particle has magnetic, assembles to magnetic field under the situation of externally-applied magnetic field from figure.
Present embodiment synthetic surface organic ligands is 6-(1; 3-dioxoisoindolin-2-yl) the ferrous acid manganese of the caproic acid ferrous acid manganese that is 6-aminocaprolc acid in 25 ℃ magnetic hysteresis loop figure and surface organic ligands at 25 ℃ magnetic hysteresis loop figure respectively like Fig. 8 and shown in Figure 9; Show superparamagnetism preferably by the visible resulting nanoparticle of figure; The saturation magnetization rate reaches 28.4emu/g and 28.6emu/g respectively, and the saturation magnetization rate before and after the deaminizating protection changes little.
Present embodiment synthetic surface organic ligands is the ferrous acid manganese r of 6-aminocaprolc acid behind the ferrous acid manganese deprotection of 6-(1,3-dioxoisoindolin-2-yl) caproic acid 2Relaxation rate is shown in figure 10, by the visible resulting nanoparticle of figure very high relaxation rate is arranged, and its value reaches r 2=34.78s -1MM -1
Present embodiment synthetic surface organic ligands is 6-(1; 3-dioxoisoindolin-2-yl) the ferrous acid manganese zeugmatography effect of 6-aminocaprolc acid is shown in figure 11 behind the ferrous acid manganese deprotection of caproic acid; Even can find out obviously that by diagram its imaging effect is still fine under the very low concentration of nanoparticle.
Embodiment 2:
Weigh 10mmol 6-(1, the 3-dioxoisoindolin-2-yl) caproic acid that embodiment 1 second step makes and close the manganese presoma, 20mmol 6-(1; 3-dioxoisoindolin-2-yl) caproic acid closes the iron presoma; Be dissolved in respectively in the mixed solution of 40ml phenylate and 2ml oleyl amine composition, after treating to dissolve fully, place on the magnetic agitation well heater; Under nitrogen protection atmosphere, temperature is promoted to 140 step by step with the mode of gradient-heated ℃,Stablized 1 hour, the steam in the solution is evaporated fully; Again with temperature increase to 220 , stablized 2 hours, make two kinds of precursor mixtures under this temperature, form stable MOX separately; Then with temperature increase to 260 , stablized 1.5 hours, obtain 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate oil soluble manganous ferrite nano-particle.
With the 6-that obtains (1,3-dioxoisoindolin-2-yl) the oil-soluble MnFe of caproic acid coordinate 2O 4Nanoparticle 0.6g is scattered in the mixed solution of 35ml methylene dichloride, 20ml ethanol and 15ml water composition, and agitation condition adds the 20ml Hydrazine Hydrate 80 down, reacts black MnFe 4 hours 2O 4Nanoparticle has all been transferred to the water on upper strata by the organic phase of lower floor; Spinning, washing with alcohol, obtaining surface organic ligands is the water-soluble MnFe of the amino functional of 6-aminocaprolc acid 2O 4Nanoparticle.
The prepared MnFe of present embodiment 2O 4Nanoparticle shows and embodiment 1 prepared MnFe 2O 4The proterties that nanoparticle is identical.
The foregoing description is interpreted as only being used to the present invention is described and is 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.

Claims (5)

1. the preparation method of the water-soluble manganous ferrite magnetic nano-particle of amino functional may further comprise the steps:
(1) with manganous salt and 6-(1; 3-dioxoisoindolin-2-yl) caproic acid, trivalent iron salt and 6-(1,3-dioxoisoindolin-2-yl) caproic acid is dissolved in respectively in methylene dichloride or the chloroform; Under the condition that triethylamine exists, stir 20~30h; Obtain that 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes the manganese presoma and 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes the iron presoma;
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);
Said trivalent iron salt is selected from iron(ic)chloride, iron acetate, iron nitrate or ferric sulfate); The mol ratio of ferric ion, 6-(1,3-dioxoisoindolin-2-yl) caproic acid and triethylamine is 1: (1~5): (1~10);
(2) the prepared 6-of step (1) (1,3-dioxoisoindolin-2-yl) caproic acid is closed the manganese presoma and 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes the iron presoma and is dissolved in the solvent respectively; Mode with gradient-heated under nitrogen atmosphere or the rare gas element atmosphere is promoted to 120 ℃~140 ℃ step by step with temperature, stablizes 1~2 hour, and the steam in the solution is evaporated fully; Again temperature is promoted to 210 ℃~220 ℃ with 5 ℃/min; Stablized 2~3 hours, then with 10 ℃/min with temperature increase to 250 ℃~260 ℃, stablized 1~2 hour; Obtain 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordinate oil soluble manganous ferrite nano-particle;
It is 1: 2 that said 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes the mol ratio that manganese presoma and 6-(1,3-dioxoisoindolin-2-yl) caproic acid close the iron presoma;
Said solvent is oleyl amine or phenylate, or both are by any mixture than composition;
(3) the oil soluble manganous ferrite nano-particle that step (1) is obtained is scattered in the solvent; Add deaminizating protection reagent; Refluxed 4~5 hours, and sloughed Tetra hydro Phthalic anhydride, obtaining surface ligand is the ferrous acid manganese magnetic nano-particle of the amino functional of 6-aminocaprolc acid;
Said solvent be in methylene dichloride, the ethanol one or both by any than the mixed solution of the mixture of forming with the water composition, the volume ratio of water is 1/20~1/5 in the mixed solution.
2. the preparation method of the water-soluble manganous ferrite 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 and argon atmospher.
3. the preparation method of the water-soluble manganous ferrite magnetic nano-particle of the described amino functional of claim 1 is characterized in that, said deaminizating protective material is a Hydrazine Hydrate 80.
4. the preparation method of the water-soluble manganous ferrite magnetic nano-particle of the described amino functional of claim 3 is characterized in that, the mass ratio of the ferrous acid manganese magnetic nano-particle of said Hydrazine Hydrate 80 and amino functional is 5: 1~1: 5.
5. the preparation method of the water-soluble manganous ferrite magnetic nano-particle of the described amino functional of claim 4 is characterized in that, the mass ratio of the ferrous acid manganese magnetic nano-particle of said Hydrazine Hydrate 80 and amino functional is 1: 1~1: 5.
CN2011102986223A 2011-09-30 2011-09-30 Preparation method of amino functionalized water-soluble manganese ferrate magnetic nanometer particles Pending CN102442703A (en)

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Publication number Priority date Publication date Assignee Title
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CN101525157A (en) * 2009-04-14 2009-09-09 上海师范大学 Method for preparing water-soluble ferrite nano-particle
CN101697303A (en) * 2009-10-16 2010-04-21 上海师范大学 Preparation method of water-soluble ferroferric oxide magnetic nanoparticle with functional amidogen
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Application publication date: 20120509