CN102491400B - Amino-functional water-soluble gadolinium oxide nanometer sheet and preparation method and application thereof - Google Patents
Amino-functional water-soluble gadolinium oxide nanometer sheet and preparation method and application thereof Download PDFInfo
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- CN102491400B CN102491400B CN 201110358771 CN201110358771A CN102491400B CN 102491400 B CN102491400 B CN 102491400B CN 201110358771 CN201110358771 CN 201110358771 CN 201110358771 A CN201110358771 A CN 201110358771A CN 102491400 B CN102491400 B CN 102491400B
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Abstract
The invention relates to the material field, specifically a magnetic amino-functional water-soluble gadolinium oxide nanometer sheet with magnetism.The preparation method comprises the following steps of: using oleyl amine and 1,2-hexadecane diol as a novel solvent system, 6-(1,3-dioxo isoindoline-2-group) gadolinium caproate as a precursor, to acquire an oil-soluble Gd3O3 magnetic nanometer sheet by high-temperature pyrolysis; and then, removing phthalic acid on 6-(1,3-dioxo isoindoline-2-group) caproic organic ligand by a de-protection reaction of the amino, so that the oil-soluble nanometer sheet is converted to be a mono-dispersed water-soluble Gd2O3 nanometre sheet with an amino active functional group on the surface, wherein the triangular single crystal structure with a hexagonal system can be well dispersed in water, provided with good biocompatibility, and can be used as nuclear magnetic resonance contrast medium. The preparation method can simply achieve the large-scale preparation of amino-functional water-soluble gadolinium oxide, so that the requirements to the device are low, the needed materials are cheap, and the by-products are harmless.
Description
Technical field
The present invention relates to Material Field, be specially nano material and its large-scale preparation method and application thereof of amino functional water soluble oxidized gadolinium triangular morphology.
Background technology
Nmr imaging technique (MRI) be at present rare to human body the methods for clinical diagnosis safely, fast and accurately without any injury because its non-invasive and multifaceted tomography function, but that the main weakness of Magnetic resonance imaging is sensitivity is low.So in clinical MRI, diagnosis more than 30% must be used NMR contrast agent, shorten imaging time, improve image contrast and sharpness, because magnetic nano-particle has preferably magnetic performance and applies to widely living things system, as be used as contrast medium in magnetic resonance imaging system, bioseparation and magnetic thermotherapy.The field such as biochemistry and medical science has strict requirement to physics, chemistry and the pharmacological properties of magnetic nano-particle as chemical constitution, globule size, magnetic function, crystalline structure, adsorptivity, surface topography, solvability and toxicity.Therefore to realize the application of magnetic nano-particle in fields such as these biochemistry and medical science, must meet several conditions: one but dispersed, two, there is magnetic performance preferably, three, there is water-soluble and active function groups.But mostly the current mono-dispersed nano particle for preparing is oil-soluble, therefore to realize these requirements, must further carry out surface modification.The Main Means that carries out at present finishing has the methods such as coated with silica, organic polymer coating and ligand exchange.Although coated with silica has dispersed preferably, the technique more complicated; Organic polymer coats, and easily reunites, and is not very stable; The method of ligand exchange can well solve the defect of above two kinds of methods, but the efficiency of ligand exchange is an insoluble problem always.Therefore above method all not too is applicable to expanding production.
At present comparatively traditional gadolinium sesquioxide nanoparticle preparation mostly is high-temperature calcination, solvent-thermal method (comprises and take the system that ethylene glycol is solvent, with oleic acid, oleyl amine and high boiling trioctylamine are solvent), the nano material grain that traditional method prepares mostly is oil soluble, need to further pass through ligand exchange, polymer overmold or coated silica, solve functionalization and water-soluble problem, could be used for biological field, be not suitable for large-scale synthesizing, seriously hindered its application aspect biological medicine.
Here we have invented a kind of simple method, not only can realize having the problem of magnetic performance preferably, monodispersity, water-soluble and active function groups, and synthetic method are fairly simple, very easily expanding production.
Summary of the invention
The present invention aims to provide the water-soluble trilateral gadolinium sesquioxide of a kind of amino functional nanometer sheet.
The present invention also provides the preparation method and application of above-mentioned nanometer sheet.
The trilateral gadolinium sesquioxide magnetic Nano sheet of amino functional of the present invention, be to be new solvent system with oleyl amine and 1,2-n-Hexadecane glycol, and it is presoma that 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes gadolinium, the Gd obtained by high temperature pyrolysis
2o
3the magnetic Nano sheet, now caproic acid is not only presoma to 6-(1,3-dioxoisoindolin-2-yl), or Gd
2o
3the part of nanoparticle surface, 6-(1,3-dioxoisoindolin-2-yl) carboxyl and the Gd coordination on caproic acid, this nanoparticle sheet is oil-soluble, surface and 6-(1,3-dioxoisoindolin-2-yl) carboxyl coordination on caproic acid, make 1 of oleophylic, and 3-dioxoisoindolin part outwards; Then for this material is applied in biological field; by amino deprotection reaction; by 6-(1; 3-dioxoisoindolin-2-yl) phthalic acid on the caproic acid organic ligand is sloughed, and oil-soluble nanometer sheet is changed into to the water-soluble Gd that obtains having for monodispersed, surface amino active function groups
2o
3nanometer sheet, be the trilateral single crystal structure nanometer sheet with hexagonal system, can well be scattered in water, and have good biocompatibility.
The preparation method of amino-functional water-soluble gadolinium oxide nanometer sheet comprises the following steps:
(1) by 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes gadolinium in oleyl amine and 1, in the mixed solution of 2-n-Hexadecane glycol, under the condition of anhydrous and oxygen-free, 300～310 ℃ of high temperature pyrolysis, obtaining surface ligand is the oil soluble gadolinium sesquioxide nanometer sheet of 6-(1,3-dioxoisoindolin-2-yl) caproic acid; The mol ratio of gadolinium element and 1,2-n-Hexadecane glycol is 1: 2～1: 3;
(2) by amino deprotection reaction, slough the Tetra hydro Phthalic anhydride on 6-(1,3-dioxoisoindolin-2-yl) caproic acid, obtain amino-functional water-soluble gadolinium oxide nanometer sheet.
Reaction in step (1) is carried out under nitrogen or protection of inert gas, with the speed of 6～12 ℃/min, first is heated to 135～145 ℃, stablizes 30～90min, then with 3～6 ℃/min speed, temperature is elevated to 300～310 ℃ and carries out high temperature pyrolysis.
Described 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes gadolinium and prepares by the following method: 6-(1,3-dioxoisoindolin-2-yl) caproic acid reacts 3～5 hours with gadolinium salt under triethylamine catalysis, washing is dry, obtain 6-(1,3-dioxoisoindolin-2-yl) caproic acid and close gadolinium; The mol ratio of gadolinium element and 6-(1,3-dioxoisoindolin-2-yl) caproic acid is 1: 1.
Prepared by the following method by 6-(1,3-dioxoisoindolin-2-yl) caproic acid: six hexosamines and Tetra hydro Phthalic anhydride were pressed the mol ratio of 1: 1,165～175 ℃ of reactions 3～5 hours.
This nanometer sheet has the trilateral single crystal structure of hexagonal system, take 6-aminocaprolc acid as part, can well be scattered in water, and have good biocompatibility, can be used as the contrast agent material of nucleus magnetic resonance.Because there is larger amino density on the nanometer sheet surface, can utilize amino upper fluorescence molecule (as rhodamine), the tumor targeted molecular (as folic acid) of connecting.Therefore obtained the contrast medium according to the Magnetic resonance imaging of the magneto-optic double-function that photoluminescent property is arranged, made it that potential using value be arranged aspect biological medicine.
At first the present invention adopts the synthetic oil-soluble gadolinium sesquioxide magnetic Nano sheet of the method for high temperature pyrolysis; then the method for protecting with deaminizating; prepare monodispersed, amino functional, water miscible gadolinium sesquioxide nanometer sheet, this is to obtain for the first time the leg-of-mutton gadolinium sesquioxide single crystal structure of hexagonal system nanometer sheet.
By controlling 1,2-n-Hexadecane glycol add-on, can obtain the gadolinium sesquioxide nanoparticle of the overlapped in series of monodispersed gadolinium sesquioxide nanoparticle and self-assembly.Gadolinium and 1, the mol ratio of 2-n-Hexadecane diol solvent is 1: 2 o'clock, can obtain on plane all trilateral gadolinium sesquioxide nanoparticles to disperse, when improving 1,2-n-Hexadecane diol solvent amount, the mol ratio that makes gadolinium and 1,2-n-Hexadecane diol solvent is the gadolinium sesquioxide nanoparticle that can obtain the consecutive stack of self-assembly form at 1: 3 o'clock.
The present invention can simply realize the extensive preparation of the water soluble oxidized gadolinium of amino functional.This preparation method is very low to the requirement of equipment, and desired raw material is cheap, and by product is nuisanceless.
The accompanying drawing explanation
Fig. 1 is the structural representation of organic ligand 6-(1, the 3-dioxoisoindolin-2-yl) caproic acid in the present invention
Fig. 2 is the synthetic route chart of the water soluble oxidized gadolinium nanometer sheet of extensive synthesizing amino functionalization in the present invention
Fig. 3 is that the synthetic surface organic ligands of embodiment 3 is 6-(1,3-dioxoisoindolin-2-yl) caproic acid, gadolinium and 1,2-n-Hexadecane glycol mol ratio=1: 2. descend high temperature pyrolysis, the TEM figure of synthetic gadolinium sesquioxide has monodispersity preferably in chloroform.
Fig. 4 is that the synthetic surface organic ligands of embodiment 6 is 6-aminocaprolc acid, gadolinium and 1,2-n-Hexadecane glycol mol ratio=1: 3. descend the TEM figure of the synthetic gadolinium sesquioxide of high temperature pyrolysis, have monodispersity preferably in the aqueous solution.
Fig. 5 is the XRD figure of gadolinium sesquioxide nanometer sheet before and after amino deprotection synthetic in the present invention, and before and after figure can be clearly seen that deprotection, crystalline form does not occur significantly to change.
Fig. 6 is (a) gray-scale map and the pcolor of amino functional water soluble oxidized gadolinium nanometer sheet Magnetic resonance imaging synthetic in the present invention, (b) r
1, r
2value.
Fig. 7 is the gadolinium sesquioxide deployment conditions in solvent before and after deprotection obtained in the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail and completely:
Embodiment 1
Take the Tetra hydro Phthalic anhydride of six hexosamines of 100mmol (13.1g) and 100mmol (14.8g) in the mono-neck flask of 100ml, add air set pipe 170 ℃ of heating 4 hours, be cooled to room temperature, with the methylene dichloride dilution, with one night of anhydrous magnesium sulfate drying of 20g, suction filtration is removed anhydrous magnesium sulfate, by the clear liquid rotary evaporation obtained, obtain white solid powder 6-(1,3-dioxoisoindolin-2-yl) caproic acid, its structure as shown in Figure 1.
Take Gd (NO
3)
3.6H
2o (1.35g, 2.5mmol) and 6-(1,3-dioxoisoindolin-2-yl) caproic acid (1.95g, 7.5mmol) put into the 100ml round-bottomed flask, then add in the 20ml methylene dichloride, under the condition of room temperature, magnetic agitation, add the 3ml triethylamine under agitation condition, stir 4 hours.Each 10ml water, wash three times, by the filtrate evaporate to dryness, puts into vacuum drying oven dry 12 hours.Obtain white oily matter, be 6-(1,3-dioxoisoindolin-2-yl) caproic acid and close the gadolinium presoma.
The 6-(1 that embodiment 2 is obtained, 3-dioxoisoindolin-2-yl) caproic acid closes gadolinium presoma (2.5mmol) and is dissolved in and contains 1.29g 1,2-n-Hexadecane glycol (5mmol, molecular weight 258.44,1, in 20ml oleyl amine 2-Hexadecanediol), pour in the three-necked flask of 100ml, heating is inserted prolong after dissolving fully, the bottleneck that flask two is surveyed, insert mercurythermometer and measure temperature, another bottleneck connects a nitrogen balloon, in bottle, pours the high pure nitrogen with inertia, flask is vacuumized to the formation return-flow system simultaneously.
After reaction unit completes, under the condition of magnetic agitation, at first the mode with gradient-heated is heated to 140 ℃ by temperature step by step with 10 ℃/min, with the moisture in N2 venting reaction solution, heating 1h, then the speed with 5 ℃/min is warming up to 304 ℃, and reaction 75min makes 6-(1,3-dioxoisoindolin-2-yl) caproic acid close gadolinium and decompose at this temperature; Stopped reaction, be cooled to room temperature, and absolute ethanol washing 5 times are used in centrifugation, obtain white solid, vacuum-drying.This white mass is that surface is the oil-soluble Gd of 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordination
2o
3nanometer sheet has monodispersity preferably in chloroform.TEM figure as shown in Figure 3.
Oil-soluble Gd
2o
3when prepared by nanometer core, because this experiment is to carry out under the condition of anhydrous and oxygen-free, so very important by this step of nitrogen draining under heating condition, temperature is heated to 140 ℃, water better is excluded totally with the state of steam, and precursors can not decompose in this temperature range.Improve temperature to 304 ℃, start to re-assembly, nucleation, crystallization, form oil-soluble trilateral Gd
2o
3the magnetic Nano sheet, the average length of side is in the scope of 50～70nm.
Take the oil-soluble Gd of the prepared 6-of embodiment 3 (1,3-dioxoisoindolin-2-yl) caproic acid coordination
2o
3nanoparticle 0.5g is scattered in 20ml methylene dichloride, 10ml ethanol and 15 ml water, adds the 20ml hydrazine hydrate under agitation condition, stirs 6h, white Gd
2o
3nanoparticle all has the organic phase of lower floor to transfer to upper strata to obtain water.Centrifugation, washing with alcohol several times.Can obtain the water-soluble trilateral Gd of amino functional
2o
3nanometer sheet, its length of side is at 50～70nm.Be scattered in water standby.Embodiment 3 and 4 reaction synthetic route are as shown in Figure 2.
The oil soluble Gd of 6-in embodiment 3 (1,3-dioxoisoindolin-2-yl) caproic acid coordination
2o
3the water-soluble Gd of the 6-aminocaprolc acid coordination in nanometer sheet and embodiment 4 after amino deprotection
2o
3as shown in Figure 5, before and after figure can be clearly seen that deprotection, crystalline form does not occur significantly to change the XRD figure of nanometer sheet.
As shown in Figure 7, left side and right side are respectively as the oil soluble of embodiment 3 and 4 and water-soluble Gd the solvability of embodiment 3 and embodiment 4 nanometer sheet
2o
3nanometer sheet.The oil solubility nanometer sheet of embodiment 3 has good dispersiveness and is water insoluble in methylene dichloride; Water-soluble nano sheet favorable dispersity in water of embodiment 4, and be not dissolved in organic phase.
Under different concns, the gray-scale map of Gd nanometer sheet Magnetic resonance imaging is as Fig. 6 (a), and r1 and r2 are as shown in Fig. 6 (b).
Embodiment 5
The 6-(1 that embodiment 2 is obtained, 3-dioxoisoindolin-2-yl) caproic acid closes the gadolinium presoma, be dissolved in and contain 1,2-n-Hexadecane glycol (1.94g, 0.75mmol) the 20ml oleyl amine in, pour in the three-necked flask of 100ml, under the condition of magnetic agitation, at first be heated to 140 ℃, use N
2moisture in the venting reaction solution, heating 1h, then be warming up to 304 ℃ with 5 ℃/min to speed, reaction 75min, stopped reaction, be cooled to room temperature, and absolute ethanol washing 5 times are used in centrifugation, obtain white solid, vacuum-drying.This white mass is that surface is the oil-soluble Gd of 6-(1,3-dioxoisoindolin-2-yl) caproic acid coordination
2o
3nanometer sheet.
Take the oil-soluble Gd of the prepared 6-of embodiment 5 (1,3-dioxoisoindolin-2-yl) caproic acid coordination
2o
3nanoparticle 0.5g is scattered in 20ml methylene dichloride, 10ml ethanol and 15ml water, adds the 20ml hydrazine hydrate under agitation condition, stirs 6h, white Gd
2o
3nanoparticle all has the organic phase of lower floor to transfer to upper strata to obtain water.Centrifugation, washing with alcohol several times.Can obtain the water-soluble trilateral Gd of amino functional
2o
3the magnetic Nano sheet, be scattered in water, standby.
TEM schemes as shown in Figure 4, the length of side 50～70nm, and having in water of self-assembly overlapped in series is dispersed preferably.
Claims (7)
1. an amino-functional water-soluble gadolinium oxide nanometer sheet, is characterized in that, the average length of side is 50～70nm, and the preparation method comprises the following steps:
(1) by 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes gadolinium in oleyl amine and 1, in the mixed solution of 2-n-Hexadecane glycol, under the condition of anhydrous and oxygen-free, reaction is carried out under nitrogen or protection of inert gas, first be heated to 135～145 ℃ with 6～12 ℃/min, stablize 30～90min, with 3～6 ℃/min speed, temperature is elevated to 300～310 ℃ again and carries out high temperature pyrolysis, obtaining surface ligand is the oil soluble gadolinium sesquioxide nanometer sheet of 6-(1,3-dioxoisoindolin-2-yl) caproic acid; The mol ratio of gadolinium element and 1,2-n-Hexadecane glycol is 1:2～1:3;
(2) by amino deprotection reaction, slough the Tetra hydro Phthalic anhydride on 6-(1,3-dioxoisoindolin-2-yl) caproic acid, obtain amino-functional water-soluble gadolinium oxide nanometer sheet.
2. the described amino-functional water-soluble gadolinium oxide nanometer sheet of claim 1, it is characterized in that, described 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes gadolinium and prepares by the following method: 6-(1,3-dioxoisoindolin-2-yl) caproic acid reacts 3～5 hours with gadolinium salt under triethylamine catalysis, washing is dry, obtains 6-(1,3-dioxoisoindolin-2-yl) caproic acid and closes gadolinium.
3. the water miscible gadolinium sesquioxide trilateral of the described amino functional of claim 2 nanometer sheet, is characterized in that, the mol ratio of gadolinium element and 6-(1,3-dioxoisoindolin-2-yl) caproic acid is 1:1.
4. the described amino-functional water-soluble gadolinium oxide nanometer sheet of claim 2, it is characterized in that, described 6-(1,3-dioxoisoindolin-2-yl) prepared by the following method by caproic acid: six hexosamines and Tetra hydro Phthalic anhydride were pressed the mol ratio of 1:1,165～175 ℃ of reactions 3～5 hours.
5. the described amino-functional water-soluble gadolinium oxide nanometer sheet of claim 1, it is characterized in that, in the deprotection reaction of step (2) amino, by surface ligand, be 6-(1,3-dioxoisoindolin-2-yl) the oil soluble gadolinium sesquioxide nanometer sheet of caproic acid is dispersed in solvent, add deaminizating protection reagent, react 4～10 hours, obtaining surface organic ligands is the water soluble oxidized gadolinium trilateral nanometer sheet of the amino functional of n-aminoalkyl group acid;
Described solvent be one or both in chloroform, ethanol, methylene dichloride by any mixtures than forming the mixed solution with the water composition, wherein the volume ratio of water is 1/4～1/3.
6. the described amino-functional water-soluble gadolinium oxide nanometer sheet of claim 5, is characterized in that, described deaminizating protection reagent is hydrazine hydrate.
7. the described amino-functional water-soluble gadolinium oxide nanometer sheet of claim 1～6 any one is in the application prepared aspect mri contrast agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4647447A (en) * | 1981-07-24 | 1987-03-03 | Schering Aktiengesellschaft | Diagnostic media |
| 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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| US4647447A (en) * | 1981-07-24 | 1987-03-03 | Schering Aktiengesellschaft | Diagnostic media |
| 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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| Title |
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| 张晶晶.部分超顺磁性纳米材料的合成及基于MRI的生物应用.《工程科技Ⅰ辑》.2010,B020-105. |
| 部分超顺磁性纳米材料的合成及基于MRI的生物应用;张晶晶;《工程科技Ⅰ辑》;20100831;B020-105 * |
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