CN102491400A - 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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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 field of materials, be specially nano material and its large-scale preparation method and the application of amino functional water soluble oxidized gadolinium triangular morphology.
Background technology
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; 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 living things system widely, as being used as contrast medium in the magnetic resonance imaging system, bioseparation and magnetic thermotherapy.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.
Mostly at present comparatively traditional gadolinium sesquioxide nanoparticle preparation is high-temperature calcination; Solvent-thermal method (comprise with terepthaloyl moietie being the system of solvent, with oleic acid, oleyl amine and high boiling trioctylamine are solvent); Mostly the nano material grain that traditional method prepares is oil soluble; Need further to pass through ligand exchange, polymer overmold or coated silica, solve functionalization and water-soluble problem, just can 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 compound method are fairly simple, can enlarge production very easily.
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 the application of above-mentioned nanometer sheet.
The trilateral gadolinium sesquioxide magnetic Nano sheet of amino functional of the present invention is with oleyl amine and 1, and 2-n-Hexadecane glycol is new solvent system, and it is presoma that 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes gadolinium, the Gd that obtains through high temperature pyrolysis
2O
3The magnetic Nano sheet, caproic acid is not only presoma to 6-this moment (1,3-dioxoisoindolin-2-yl), or Gd
2O
3The part of nanoparticle surface, carboxyl and Gd coordination on 6-(1, the 3-dioxoisoindolin-2-yl) caproic acid; This nanoparticle sheet is oil-soluble, the carboxyl coordination on surface and 6-(1, the 3-dioxoisoindolin-2-yl) caproic acid; Make lipophilicly 1,3-dioxoisoindolin part outwards; Then for this material is used in biological field; Deprotection reaction through amino; With 6-(1; 3-dioxoisoindolin-2-yl) phthalic acid on the caproic acid organic ligand is sloughed, and oil-soluble nanometer sheet is changed into the water-soluble Gd that obtains having for monodispersed, surface amino active function groups
2O
3Nanometer sheet is the trilateral single crystal structure nanometer sheet with hexagonal system, can well be scattered in the water, and have good biocompatibility.
The preparation method of amino functional water soluble oxidized gadolinium trilateral nanometer sheet may further comprise the steps:
(1) 6-(1,3-dioxoisoindolin-2-yl) caproic acid is closed 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; Gadolinium element and 1, the mol ratio of 2-n-Hexadecane glycol is 1: 2～1: 3;
(2) through amino deprotection reaction, slough the Tetra hydro Phthalic anhydride on 6-(1, the 3-dioxoisoindolin-2-yl) caproic acid, obtain amino functional water soluble oxidized gadolinium trilateral nanometer sheet.
Being reflected under nitrogen or the protection of inert gas in the step (1) carried out, and is heated to 135～145 ℃ earlier with the speed of 6～12 ℃/min, stablizes 30～90min, with 3～6 ℃/min speed temperature is elevated to 300～310 ℃ again and carries out high temperature pyrolysis.
Described 6-(1; 3-dioxoisoindolin-2-yl) caproic acid closes gadolinium and prepares through following method: 6-(1,3-dioxoisoindolin-2-yl) caproic acid and gadolinium salt reacted 3～5 hours under triethylamine catalysis, and 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.
6-(1,3-dioxoisoindolin-2-yl) caproic acid prepares through following method: six hexosamines and Tetra hydro Phthalic anhydride were pressed 1: 1 mol ratio, 165～175 ℃ of reactions 3～5 hours.
This nanometer sheet has the trilateral single crystal structure of hexagonal system, is part with the 6-aminocaprolc acid, can well be scattered in the water, and have good biocompatibility, can be used as the contrast agent material of nucleus magnetic resonance.Because there is bigger amino density on the nanometer sheet surface, can utilize amino the connection to go up fluorescence molecule (like rhodamine), tumor targeted molecular (like folic acid).Therefore obtained contrast medium, made it that potential using value arranged aspect biological medicine according to the zeugmatography of the magneto-optic double-function that photoluminescent property is arranged.
The present invention at first adopts the synthetic oil-soluble gadolinium sesquioxide magnetic Nano sheet of the method for high temperature pyrolysis; The method of protecting with deaminizating then; Prepare monodispersed, amino functional, water miscible gadolinium sesquioxide nanometer sheet, this is to obtain the leg-of-mutton gadolinium sesquioxide single crystal structure of hexagonal system nanometer sheet for the first time.
Through 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 the plane all with dispersive trilateral gadolinium sesquioxide nanoparticle, when improving 1,2-n-Hexadecane diol solvent amount; Make gadolinium and 1, the mol ratio of 2-n-Hexadecane diol solvent is the synergetic gadolinium sesquioxide nanoparticle of consecutive that can obtain the self-assembly form at 1: 3 o'clock.
The present invention can simply realize the mass 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.
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 oxidized gadolinium nanometer sheet of extensive synthesizing amino functionalization among the present invention
Fig. 3 is that embodiment 3 synthetic surface organic ligands are 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 embodiment 6 synthetic surface organic ligands are 6-aminocaprolc acids, gadolinium and 1,2-n-Hexadecane glycol mol ratio=1: 3. descend the TEM figure of high temperature pyrolysis synthetic gadolinium sesquioxide, in the aqueous solution, have monodispersity preferably.
Fig. 5 is the XRD figure of synthetic gadolinium sesquioxide nanometer sheet before and after amino deprotection among the present invention, can be clearly seen that from figure obvious variation does not take place deprotection front and back crystalline form.
Fig. 6 is synthetic amino functional water soluble oxidized gadolinium nanometer sheet zeugmatography (a) gray-scale map and pcolor, (b) r among the present invention
1, r
2Value.
Fig. 7 is the gadolinium sesquioxide deployment conditions in solvent before and after deprotection that obtains among the present invention.
Embodiment
Below in conjunction with embodiment the present invention is done further in detail, intactly explains:
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; With the methylene dichloride dilution, 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, its structure is as shown in Figure 1.
Take by weighing 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, add then in the 20ml methylene dichloride, under the condition of room temperature; Magnetic agitation adds the 3ml triethylamine under agitation condition, stirred 4 hours.Each 10ml water washs three times, and the evaporate to dryness of will filtrating was put 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.
6-(1, the 3-dioxoisoindolin-2-yl) caproic acid that embodiment 2 is obtained closes gadolinium presoma (2.5mmol) and is dissolved in and contains 1.29g 1,2-n-Hexadecane glycol (5mmol; Molecular weight 258.44,1 is 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 inserts mercurythermometer and measures temperature, and another bottleneck connects a nitrogen balloon; In bottle, pour and have the inert high pure nitrogen, simultaneously flask is vacuumized the formation return-flow system.
After reaction unit is accomplished; Under the condition of magnetic agitation, at first the mode with gradient-heated is heated to 140 ℃ with temperature with 10 ℃/min step by step, with the moisture in the N2 venting reaction solution; Heating 1h; Speed with 5 ℃/min is warming up to 304 ℃ then, and reaction 75min makes 6-(1,3-dioxoisoindolin-2-yl) caproic acid close gadolinium and under this temperature, decompose; Stopped reaction is cooled to room temperature, and spinning with absolute ethanol washing 5 times, obtains white solid, vacuum-drying.This white mass promptly is that the surface is 6-(1,3-dioxoisoindolin-2-yl) the oil-soluble Gd of caproic acid coordinate
2O
3Nanometer sheet has monodispersity preferably in chloroform.TEM figure is as shown in Figure 3.
Oil-soluble Gd
2O
3During the preparation of nanometer nuclear; Because this experiment is 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 is heated to 140 ℃; Water better is excluded totally with the state of steam, and can decompose at this TR internal reaction presoma.Improve temperature to 304 ℃, begin 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 by weighing embodiment 3 prepared 6-(1,3-dioxoisoindolin-2-yl) the oil-soluble Gd of caproic acid coordinate
2O
3Nanoparticle 0.5g is scattered in 20ml methylene dichloride, 10ml ethanol and the 15 ml water, and agitation condition adds the 20ml Hydrazine Hydrate 80 down, stirs 6h, white Gd
2O
3Nanoparticle 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 trilateral Gd of amino functional
2O
3Nanometer sheet, its length of side is at 50～70nm.Be scattered in the water subsequent use.Embodiment 3 and 4 reaction synthetic route are as shown in Figure 2.
6-among the embodiment 3 (1,3-dioxoisoindolin-2-yl) caproic acid coordinate oil soluble Gd
2O
3The water-soluble Gd of 6-aminocaprolc acid coordinate among nanometer sheet and the embodiment 4 behind the amino deprotection
2O
3The XRD figure of nanometer sheet is as shown in Figure 5, can be clearly seen that from figure obvious variation does not take place deprotection front and back crystalline form.
The solvability of embodiment 3 and embodiment 4 nanometer sheet is as shown in Figure 7, and left side and right side are respectively and are the oil soluble of embodiment 3 and 4 and water-soluble Gd
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 good dispersibility in water of embodiment 4, and be not dissolved in organic phase.
The gray-scale map of Gd nanometer sheet zeugmatography such as Fig. 6 (a) under the different concns, r1 and r2 are shown in Fig. 6 (b).
Embodiment 5
6-(1, the 3-dioxoisoindolin-2-yl) caproic acid that embodiment 2 is obtained closes the gadolinium presoma, is dissolved in and contains 1; (1.94g in 20ml oleyl amine 0.75mmol), pours in the three-necked flask of 100ml 2-n-Hexadecane glycol; Under the condition of magnetic agitation, at first be heated to 140 ℃, use N
2Moisture in the venting reaction solution, heating 1h is warming up to 304 ℃ with 5 ℃/min to speed then, reaction 75min, stopped reaction is cooled to room temperature, and spinning with absolute ethanol washing 5 times, obtains white solid, vacuum-drying.This white mass promptly is that the surface is 6-(1,3-dioxoisoindolin-2-yl) the oil-soluble Gd of caproic acid coordinate
2O
3Nanometer sheet.
Embodiment 6
Take by weighing embodiment 5 prepared 6-(1,3-dioxoisoindolin-2-yl) the oil-soluble Gd of caproic acid coordinate
2O
3Nanoparticle 0.5g is scattered in 20ml methylene dichloride, 10ml ethanol and the 15ml water, and agitation condition adds the 20ml Hydrazine Hydrate 80 down, stirs 6h, white Gd
2O
3Nanoparticle 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 trilateral Gd of amino functional
2O
3The magnetic Nano sheet is scattered in the water, and is subsequent use.
TEM figure is as shown in Figure 4, the length of side 50～70nm, and in water, having of self-assembly overlapped in series is dispersed preferably.
Embodiment 5 and 6 oil soluble and the dispersiveness of water-soluble nano sheet in water and organic phase are with embodiment 3 and 4.Crystalline form behind the deprotection is compared with embodiment 5 obvious variation is not taken place.
Claims (9)
1. the preparation method of an amino functional water soluble oxidized gadolinium trilateral nanometer sheet is characterized in that, may further comprise the steps:
(1) 6-(1,3-dioxoisoindolin-2-yl) caproic acid is closed 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; Gadolinium element and 1, the mol ratio of 2-n-Hexadecane glycol is 1: 2～1: 3;
(2) through amino deprotection reaction, slough the Tetra hydro Phthalic anhydride on 6-(1, the 3-dioxoisoindolin-2-yl) caproic acid, obtain amino functional water soluble oxidized gadolinium trilateral nanometer sheet.
2. the preparation method of the said amino functional water soluble oxidized of claim 1 gadolinium trilateral nanometer sheet; It is characterized in that described 6-(1,3-dioxoisoindolin-2-yl) caproic acid closes gadolinium and prepares through following method: 6-(1; 3-dioxoisoindolin-2-yl) caproic acid and gadolinium salt reacted 3～5 hours under triethylamine catalysis; Washing is dry, obtains 6-(1,3-dioxoisoindolin-2-yl) caproic acid and closes gadolinium.
3. the preparation method of the water miscible gadolinium sesquioxide trilateral of the said 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 preparation method of the said amino functional water soluble oxidized of claim 2 gadolinium trilateral nanometer sheet; It is characterized in that; Said 6-(1; 3-dioxoisoindolin-2-yl) caproic acid prepares through following method: six hexosamines and Tetra hydro Phthalic anhydride were pressed 1: 1 mol ratio, 165～175 ℃ of reactions 3～5 hours.
5. the preparation method of the said amino functional water soluble oxidized of claim 1 gadolinium trilateral nanometer sheet; It is characterized in that; Being reflected under nitrogen or the protection of inert gas in the step (1) carried out; Be heated to 135～145 ℃ earlier 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.
6. the preparation method of the said amino functional water soluble oxidized of claim 1 gadolinium trilateral nanometer sheet; It is characterized in that, in the deprotection reaction of step (2) amino, be 6-(1 with surface ligand; 3-dioxoisoindolin-2-yl) the oil soluble gadolinium sesquioxide nanometer sheet of caproic acid is dispersed in the solvent; Add deaminizating protection reagent, reacted 4～10 hours, obtaining surface organic ligands is the water-soluble ferroferric oxide nanoparticle of the amino functional of n-aminoalkyl group acid;
Described 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, wherein the volume ratio of water is 1/4～1/3.
7. the preparation method of the said amino functional water soluble oxidized of claim 6 gadolinium trilateral nanometer sheet is characterized in that, said deaminizating protection reagent is Hydrazine Hydrate 80.
8. an amino functional water soluble oxidized gadolinium trilateral nanometer sheet is characterized in that, through each described method preparation of claim 1～5, the average length of side is 50～70nm.
9. the application of the said amino functional water soluble oxidized of claim 8 gadolinium trilateral nanometer sheet aspect the preparation mri contrast agent.
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| CN106421820A (en) * | 2016-10-31 | 2017-02-22 | 华东师范大学 | Gadolinium-containing MRI contrast agents and preparation method of gadolinium-containing MRI contrast agents |
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| US4647447A (en) * | 1981-07-24 | 1987-03-03 | Schering Aktiengesellschaft | Diagnostic media |
| US7754173B2 (en) * | 2004-03-30 | 2010-07-13 | University Of Florida Research Foundation, Inc. | Rare earth oxide nanocrystals and methods of forming |
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