CN103723773A - Hydrosol of ferroferric oxide nanoparticles and preparation method and application thereof - Google Patents
Hydrosol of ferroferric oxide nanoparticles and preparation method and application thereof Download PDFInfo
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- CN103723773A CN103723773A CN201210392955.7A CN201210392955A CN103723773A CN 103723773 A CN103723773 A CN 103723773A CN 201210392955 A CN201210392955 A CN 201210392955A CN 103723773 A CN103723773 A CN 103723773A
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 title abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000009835 boiling Methods 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
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- 238000000926 separation method Methods 0.000 claims abstract description 7
- 150000007523 nucleic acids Chemical class 0.000 claims abstract description 5
- 102000039446 nucleic acids Human genes 0.000 claims abstract description 5
- 108020004707 nucleic acids Proteins 0.000 claims abstract description 5
- 239000008187 granular material Substances 0.000 claims description 92
- 238000001149 thermolysis Methods 0.000 claims description 22
- 239000001509 sodium citrate Substances 0.000 claims description 17
- -1 carboxylate salt Chemical class 0.000 claims description 16
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 12
- 229940038773 trisodium citrate Drugs 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 7
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 claims description 4
- 238000002595 magnetic resonance imaging Methods 0.000 claims description 4
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 4
- 239000001433 sodium tartrate Substances 0.000 claims description 4
- 229960002167 sodium tartrate Drugs 0.000 claims description 4
- 235000011004 sodium tartrates Nutrition 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004217 benzyl alcohol Drugs 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 14
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 150000007942 carboxylates Chemical class 0.000 abstract 1
- 238000012377 drug delivery Methods 0.000 abstract 1
- 238000013421 nuclear magnetic resonance imaging Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000005415 magnetization Effects 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
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- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 1
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- 238000005537 brownian motion Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 206010063401 primary progressive multiple sclerosis Diseases 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
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- 229940126680 traditional chinese medicines Drugs 0.000 description 1
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- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention discloses a preparation method for hydrosol of ferroferric oxide nanoparticles. The method comprises the following steps: (1) in the presence of high-boiling-point alcohol, performing thermal decomposition on an iron organic precursor, and performing solid-liquid separation to obtain the ferroferric oxide nanoparticles, wherein the boiling point of the high-boiling-point alcohol is from 200 DEG C to 300 DEG C; (2) mixing an aqueous solution of carboxylate containing 2-3 carboxylate radicals with the ferroferric oxide nanoparticles prepared in step (1) to obtain the hydrosol of the ferroferric oxide nanoparticles. The method disclosed by the invention can prepare the hydrosol of the ferroferric oxide nanoparticles with uniform particle size, good stability and good dispersibility, and has relatively wide application prospect in the field of biological medicine and the like, such as nuclear magnetic resonance imaging, targeted drug delivery and nucleic acid adsorption.
Description
Technical field
The present invention relates to water-sol of a kind of ferroferric oxide nano granules and its preparation method and application.
Background technology
The water-sol of ferroferric oxide nano granules is a kind of magnetic Nano material that has major application to be worth in fields such as biological medicines.In prior art, in the Z 250 water-sol prepared by coprecipitation method, the crystal formation of nano particle is poor and easily reunite, dispersed bad; Hydrothermal method is prepared ferroferric oxide nano granules and is needed the harsh reaction conditionss such as High Temperature High Pressure, and energy consumption is higher and react unstable; High temperature thermal decomposition method can be used for preparing the organic liquor colloidal sol of nano particle and can not prepare the good nano particle water-sol, as being applied to biomedicine field, also needs loaded down with trivial details surface ligand displacement link.In prior art, produce technique existence and stability, homogeneity and the dispersed poor defect of the water-sol of Z 250.
Summary of the invention
To the object of the invention is the ferroferric oxide nano granules stability, homogeneity and the dispersed poor defect that in order overcoming, adopt prior art to produce, water-sol of a kind of ferroferric oxide nano granules that can have high stability, high homogeneity and polymolecularity concurrently and its preparation method and application to be provided.
The invention provides a kind of preparation method of the water-sol of ferroferric oxide nano granules, wherein, the method comprises the following steps:
(1) under high-boiling point alcohol exists, the organic precursor of iron is carried out to thermolysis, and carry out solid-liquid separation, obtain ferroferric oxide nano granules, wherein, the boiling point of described high-boiling point alcohol is 200-300 ℃;
(2) aqueous solution of the carboxylate salt that contains 2-3 carboxylate radical is mixed with the ferroferric oxide nano granules that step (1) makes, obtain the water-sol of ferroferric oxide nano granules.
The present invention also provides the water-sol of the ferroferric oxide nano granules being prepared by aforesaid method, and wherein, the hydraulic radius of the ferroferric oxide nano granules in the described water-sol can regulate and control in 8-16nm.
In addition the application of the water-sol that, the present invention also provides above-mentioned ferroferric oxide nano granules in Magnetic resonance imaging, target administration and nucleic acid absorption.
Adopt method provided by the invention to prepare ferroferric oxide nano granules, by the organic precursor of iron is carried out to thermolysis, and with the carboxylate salt that contains 2-3 carboxylate radical, the ferroferric oxide nano granules of gained is modified, can obtain the water-sol of the ferroferric oxide nano granules of homogeneous grain diameter, good stability, good dispersity.The water-sol of the ferroferric oxide nano granules of being prepared by the inventive method is at biomedicine field, as Magnetic resonance imaging, target administration and nucleic acid absorption etc. have more wide application prospect.In addition, method of the present invention is easy, easy handling, mild condition, and can realize batch production.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the ferroferric oxide nano granules that makes in the step (1) of embodiment 1;
Fig. 2 A and 2B are respectively transmission electron microscope photo and the particle size distribution figure of the ferroferric oxide nano granules making in the step (1) of embodiment 1;
Fig. 3 is the magnetzation curve figure of the ferroferric oxide nano granules modified through Trisodium Citrate in the water-sol prepared of the ferroferric oxide nano granules before modifying with Trisodium Citrate of making in the step (1) of embodiment 1 and the method that adopts embodiment 1;
Fig. 4 is the hydraulic radius figure of ferroferric oxide nano granules in the water-sol of embodiment 1 preparation.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
According to the preparation method of the water-sol of ferroferric oxide nano granules provided by the invention, wherein, the method comprises the following steps:
(1) under high-boiling point alcohol exists, the organic precursor of iron is carried out to thermolysis, and carry out solid-liquid separation, obtain ferroferric oxide nano granules, wherein, the boiling point of described high-boiling point alcohol is 200-300 ℃;
(2) aqueous solution of the carboxylate salt that contains 2-3 carboxylate radical is mixed with the ferroferric oxide nano granules that step (1) makes, obtain the water-sol of ferroferric oxide nano granules.
According to the present invention, in step (1), the effect of described high-boiling point alcohol is as stablizer and reductive agent.Range of choice for described high-boiling point alcohol is wider, only need its boiling point higher than the temperature of reaction of described thermolysis, the boiling point of described high-boiling point alcohol is 200-300 ℃, under preferable case, described high-boiling point alcohol is selected from one or more in phenylcarbinol, polyoxyethylene glycol (number-average molecular weight is 200-1000, preferably 400-600), glycol ether and triglycol.
According to the present invention, in step (1), organic precursor of described iron can be existing various organic precursors that can decompose the iron that generates ferroferric oxide nano granules, for example, can be selected from one or more in ferric acetyl acetonade, pentacarbonyl-iron and iron oleate.
The present invention is not particularly limited the quality of the organic precursor of described iron and the ratio of the volume of described high-boiling point alcohol, under preferable case, in the quality of the organic precursor of 0.5g iron, the consumption of described high-boiling point alcohol is 10-30mL, more preferably 15-25mL.
According to the present invention, in step (1), the condition of described thermolysis is not particularly limited, as long as can make organic precursor of iron decompose, generate ferroferric oxide nano granules, for example, the condition of described thermolysis generally includes heat decomposition temperature and thermal decomposition time, preferably, described heat decomposition temperature is 150-200 ℃, and thermal decomposition time is 1-4 hour.
According to the present invention; in step (1); in order to make the better effects if of described pyrolysis; preferably; described pyrolysis carries out under inert atmosphere protection and/or under anhydrous condition; described inert atmosphere refers to not any one gas or the gaseous mixture with reactant and product generation chemical reaction, as one or more in nitrogen and periodic table of elements zero group gas.Keep inert atmosphere method can in reaction system, pass into above-mentioned not with any one gas or the gaseous mixture of reactant and product generation chemical reaction.Described anhydrous condition refers to and is not containing H
2in the situation of O, described high-boiling point alcohol mixed with organic precursor of described iron and carry out pyrolysis.
According to the present invention, in step (1), the organic precursor of iron is carried out after thermolysis, the thermal decomposition product obtaining is carried out to the method that solid-liquid separation obtains ferroferric oxide nano granules and can be the conventional various solid-liquid separating methods in this area, as long as can separation obtain ferroferric oxide nano granules, for example, the method such as gravity settling, centrifugation, filtration.Because ferroferric oxide nano granules has magnetic, therefore, can preferably adopt the method for magnetic separation to carry out solid-liquid separation and obtain ferroferric oxide nano granules, for example, magnet is being attached on container outer wall, to attract ferroferric oxide nano granules, and solvent is being discharged from container.
According to the present invention, in step (2), in order to make the over-all properties of the water-sol of ferroferric oxide nano granules of preparation better, preferably, described in contain 2-3 carboxylate radical carboxylate salt be Trisodium Citrate and/or sodium tartrate, more preferably Trisodium Citrate.The concentration of the aqueous solution of the carboxylate salt of the described 2-3 of a containing carboxylate radical is not particularly limited, under preferable case, when the concentration of the aqueous solution of the carboxylate salt of the described 2-3 of a containing carboxylate radical is more than or equal to 0.01mol/L, more preferably during 0.01-0.05mol/L, the performance of the water-sol of the ferroferric oxide nano granules of gained is better.
According to the present invention; for the carboxylate salt that contains 2-3 carboxylate radical described in making mixes more even with ferroferric oxide nano granules; thereby obtain the water-sol of the ferroferric oxide nano granules of homogeneous grain diameter; under preferable case, described in contain 2-3 carboxylate radical the aqueous solution of carboxylate salt and being blended under vibration or ultrasonic effect of ferroferric oxide nano granules carry out.
According to the present invention, described preparation method can also comprise: the ferroferric oxide nano granules obtaining with the alcohol washing step (1) of low carbon chain, and to remove high-boiling point alcohol wherein.The object of described washing is in order to remove the high-boiling point alcohol on the ferroferric oxide nano granules surface that thermolysis obtains in step (1), thereby makes the over-all properties of ferroferric oxide nano granules of preparation more excellent.The alcohol of described low carbon chain can be selected from the alcohol of the various low carbon chain of this area routine, as, the alcohol that carbonatoms is C1-C4, specifically can be selected from one or more in methyl alcohol, ethanol, propyl alcohol and butanols, but from composite factors such as price and environmental protection, consider, the alcohol of described low carbon chain is preferably ethanol.
The present invention also provides the water-sol of the ferroferric oxide nano granules obtaining by aforesaid method, wherein, can be by make the hydraulic radius of the ferroferric oxide nano granules in the described water-sol be distributed in the scope of 8-16nm to regulate and control to the regulation and control of ferroferric oxide nano granules mean particle size.
Method provided by the invention can regulate and control the hydraulic radius of the ferroferric oxide nano granules of preparation.Specifically, in the step (1) of the method for the invention, by controlling the feed way of organic precursor and the condition of thermolysis of high-boiling point alcohol and iron, can control the mean particle size of the ferroferric oxide nano granules obtaining, then the hydraulic radius of the ferroferric oxide nano granules water-sol can corresponding control obtaining by step (2).
For durther example details:
The organic precursor of example 1 iron and the ratio of high-boiling point alcohol are 0.5g:20mL, after mixed once is even, carry out thermolysis, described heat decomposition temperature is 190-200 ℃, thermal decomposition time is 2-3 hour, pass through thus step (1) and can obtain the ferroferric oxide nano granules that mean particle size is 7nm, then pass through step (2) and can obtain the Z 250 water-sol that hydraulic radius is 8-9 nanometer;
Reinforced and the thermolysis of example 2 is divided into two sections and carries out, first paragraph, the organic precursor of iron and the ratio of high-boiling point alcohol are 0.5g:20mL, after mixing, carry out first paragraph thermolysis, described heat decomposition temperature is 160-170 ℃, thermal decomposition time is 0.5-1 hour, second segment, organic precursor and the each additional amount of high-boiling point alcohol (ratio is 0.5g:20mL) of adding twice iron are the 20-30% of each raw material in first paragraph, the timed interval of adding material for twice is 25-35min, add after having expected and carry out second segment thermolysis, heat decomposition temperature is 190-200 ℃, thermal decomposition time is 1-2 hour, pass through thus step (1) and can obtain the ferroferric oxide nano granules that mean particle size is 8nm, pass through again step (2) and can obtain the Z 250 water-sol that hydraulic radius is 9-10 nanometer,
Reinforced and the thermolysis of example 3 is divided into two sections and carries out, first paragraph, the organic precursor of iron and the ratio of high-boiling point alcohol are 0.5g:20mL, after mixing, carry out first paragraph thermolysis, described heat decomposition temperature is 160-170 ℃, thermal decomposition time is 0.5-1 hour, second segment, organic precursor and the each additional amount of high-boiling point alcohol (ratio is 0.5g:20mL) of adding three iron are the 20-30% of each raw material in first paragraph, the timed interval of adding material for twice is 25-35min, add after having expected and carry out second segment thermolysis, temperature is 190-200 ℃, thermal decomposition time is 1-2 hour, pass through thus step (1) and can obtain the ferroferric oxide nano granules that mean particle size is 9nm, pass through again step (2) and can obtain the Z 250 water-sol that hydraulic radius is 10-11 nanometer.
Above three examples are just controlled the granularity of ferroferric oxide nano granules and the several concrete mode of water-sol hydraulic radius thereof according to the inventive method; the present invention is not limited to this, prepares the mode that is different from the ferroferric oxide nano granules of the disclosed granularity of above-mentioned example or the Z 250 water-sol of different hydraulic radiuses be still included in protection scope of the present invention according to same thinking.
The water-sol of the ferroferric oxide nano granules that the method according to this invention obtains can be widely used at biomedicine field, for example, and Magnetic resonance imaging, target administration and nucleic acid absorption.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below with reference to embodiment, the present invention is further illustrated, but therefore do not limit the present invention.
In following embodiment, ferric acetyl acetonade (III), pentacarbonyl-iron and iron oleate are purchased from Sigma-Aldrich company, and phenylcarbinol, Trisodium Citrate, polyoxyethylene glycol, triglycol are purchased from chemical reagents corporation of traditional Chinese medicines group;
In the water-sol, the saturation magnetization of ferroferric oxide nano granules is measured by Analysis of Physical instrument (PPMS);
In the water-sol, the hydraulic radius of ferroferric oxide nano granules is measured by nano particle size and Zeta potential analyser (DLS); Wherein, described hydraulic radius refers to the hydraulic radius of nano particle, refers to that one and true particle have the radius of the imaginary spheroid of identical rate of diffusion, is based on pedesis, by Stokes-Einstein Equation for Calculating, is obtained.
Embodiment 1
The present embodiment is for illustrating the preparation of the water-sol of ferroferric oxide nano granules provided by the invention.
(1) in the there-necked flask of 100 milliliters, add 0.5 gram of ferric acetyl acetonade (III) and 20 milliliters of phenylcarbinols.Under agitation, logical argon gas deoxygenation 30 minutes, and under argon atmosphere, is warming up to 190 ℃ with the speed of 6 ℃/min, and at 190 ℃, reacts 2 hours, after magnetic resolution, obtains black ferroferric oxide nano particle, and quality is about 0.11 gram.
(2) get 1 milliliter of ferroferric oxide nano granules being made by step (1) (being about 5 milligrams), by twice of washing with alcohol, the sodium citrate aqueous solution that is 0.01mol/L by nano particle with 10 ml concns again mixes, at lower ultrasonic (the frequency 40KHz of room temperature (25 ℃), power 100% rated output 250W, lower with) 5 minutes, obtain the water-sol of homogeneous, transparent ferroferric oxide nano granules.
As shown in Figure 1, X-ray diffractogram is known, and the product that the present embodiment step (1) makes is ferroferric oxide nano granules.
As shown in Figure 2 A and 2B, the size-grade distribution of being added up from transmission electron microscope picture, the size-grade distribution of the nano particle making in step (1) is compared with homogeneous, and mean particle size is 7nm.
As shown in Figure 3, the nano particle of the unmodified making with step (1) is compared, and the magnetic of the ferroferric oxide nano granules of modifying through Trisodium Citrate prepared by the present embodiment is still very strong, and its saturation magnetization is 51.5emu/g.
As shown in Figure 4, the hydraulic radius of the ferroferric oxide nano granules after Trisodium Citrate is modified is less, and narrow distribution, concentrates and is distributed in 8-9nm, has shown good dispersiveness and stability.
Embodiment 2
The present embodiment is for illustrating the preparation of the water-sol of ferroferric oxide nano granules provided by the invention.
(1) in 100 milliliters of there-necked flasks, add 0.5 gram of ferric acetyl acetonade (III) and 20 milliliters of phenylcarbinols.Under agitation, logical argon gas deoxygenation 30 minutes, and under argon atmosphere, is warming up to 190 ℃ with the speed of 6 ℃/min, and at 190 ℃, reacts 2 hours, after magnetic resolution, obtains black ferroferric oxide nano particle, and quality is about 0.11 gram.Prepared nano particle mean particle size is 7nm.
(2) get 1 milliliter of ferroferric oxide nano granules being made by step (1) (being about 5 milligrams), by twice of methanol wash, the sodium citrate aqueous solution that is 0.02mol/L by nano particle with 10 ml concns again mixes, in room temperature (25 ℃), descend ultrasonic 5 minutes, obtain the water-sol of homogeneous, transparent ferroferric oxide nano granules, wherein the saturation magnetization of the ferroferric oxide nano granules after Trisodium Citrate is modified is 52emu/g, hydraulic radius is less, and narrow distribution, concentrates and is distributed in 8-9nm.
Embodiment 3
The present embodiment is for illustrating the preparation of the water-sol of ferroferric oxide nano granules provided by the invention.
(1) in the there-necked flask of 100 milliliters, add 0.5 gram of ferric acetyl acetonade (III) and 20 milliliters of phenylcarbinols.Under agitation, logical argon gas deoxygenation 30 minutes, and under argon atmosphere, rises to 190 ℃ with the speed of 6 ℃/min, and at 190 ℃, reacts 2 hours, after magnetic resolution, obtains black ferroferric oxide nano particle, and quality is about 0.11 gram.Prepared nano particle mean particle size is 7nm.
(2) get 1 milliliter of ferroferric oxide nano granules being made by step (1) (being about 5 milligrams), by twice of washing with alcohol, the sodium citrate aqueous solution that is 0.05mol/L by nano particle with 10 ml concns again mixes, in room temperature (25 ℃), descend ultrasonic 5 minutes, obtain homogeneous, the transparent ferroferric oxide nano granules water-sol, wherein the saturation magnetization of the ferroferric oxide nano granules after Trisodium Citrate is modified is 51.7emu/g, hydraulic radius is less, and narrow distribution, concentrates and is distributed in 8-9nm.
Embodiment 4
The present embodiment is for illustrating the preparation of the water-sol of ferroferric oxide nano granules provided by the invention.
(1) in the there-necked flask of 100 milliliters, add 0.5 gram of ferric acetyl acetonade (III) and 20 milliliters of phenylcarbinols.Under agitation, logical argon gas deoxygenation 30 minutes, and under argon atmosphere, is warming up to 190 ℃ with the speed of 6 ℃/min, and at 190 ℃, reacts 2 hours, after magnetic resolution, makes black ferroferric oxide nano particle, and quality is about 0.11 gram.Prepared nano particle mean particle size is 7nm.
(2) get 1 milliliter of ferroferric oxide nano granules being made by step (1) (being about 5 milligrams), by twice of washing with alcohol, the sodium citrate aqueous solution that is 0.05mol/L by nano particle with 10 ml concns again mixes, in room temperature (25 ℃), descend ultrasonic 5 minutes, obtain the water-sol of homogeneous, transparent ferroferric oxide nano granules, wherein the saturation magnetization of the ferroferric oxide nano granules after Trisodium Citrate is modified is 51.2emu/g, hydraulic radius is less, and narrow distribution, concentrates and is distributed in 8-9nm.
Embodiment 5
The present embodiment is for illustrating the preparation of the water-sol of ferroferric oxide nano granules provided by the invention.
(1) in the there-necked flask of 100 milliliters, add 0.5 gram of pentacarbonyl-iron and 15 milliliters of polyoxyethylene glycol (number-average molecular weight is 600), under agitation, logical argon gas deoxygenation 30 minutes, and under argon atmosphere, speed with 6 ℃/min is warming up to 180 ℃, and at 180 ℃, reacts 4 hours, after magnetic resolution, make black ferroferric oxide nano particle, quality is about 0.11 gram.Prepared nano particle mean particle size is 8nm.
(2) get 1 milliliter of ferroferric oxide nano granules being made by step (1) (being about 5 milligrams), use propyl alcohol washed twice, the sodium citrate aqueous solution that is 0.03mol/L by nano particle with 10 ml concns again mixes, in room temperature (25 ℃), descend ultrasonic 5 minutes, obtain the water-sol of homogeneous, transparent ferroferric oxide nano granules, wherein the saturation magnetization of the ferroferric oxide nano granules after Trisodium Citrate is modified is 50.5emu/g, hydraulic radius is less, and narrow distribution, concentrates and is distributed in 9-10nm.
Embodiment 6
The present embodiment is for illustrating the preparation of the water-sol of ferroferric oxide nano granules provided by the invention.
(1) in the there-necked flask of 100 milliliters, add 0.5 gram of iron oleate and 25 milliliters of triglycols, under agitation, logical argon gas deoxygenation 30 minutes, and under argon atmosphere, speed with 6 ℃/min is warming up to 190 ℃, and at 190 ℃, reacts 3 hours, after magnetic resolution, make black ferroferric oxide nano particle, quality is about 0.11 gram.Prepared nano particle mean particle size is 6nm.
(2) get 1 milliliter of ferroferric oxide nano granules being made by step (1) (being about 5 milligrams), use butanols washed twice, the sodium tartrate aqueous solution that is 0.04mol/L by nano particle and 10 ml concns again, in room temperature (25 ℃), descend ultrasonic 5 minutes, obtain the water-sol of homogeneous, transparent ferroferric oxide nano granules, wherein the saturation magnetization of the ferroferric oxide nano granules after sodium tartrate is modified is 50.6emu/g, hydraulic radius is less, and narrow distribution, concentrates and is distributed in 7-9nm.
Result from embodiment 1-6, adopt method provided by the invention to prepare ferroferric oxide nano granules, by the organic precursor of iron is carried out to thermolysis, and the modification of the ferroferric oxide nano granules of gained being carried out with the carboxylate salt that contains 2-3 carboxylate radical, can obtain the water-sol of the ferroferric oxide nano granules of homogeneous grain diameter, good stability, good dispersity.Method of the present invention is easy, easy handling, mild condition, and can realize batch production.
Claims (10)
1. a preparation method for the water-sol of ferroferric oxide nano granules, is characterized in that, the method comprises the following steps:
(1) under high-boiling point alcohol exists, the organic precursor of iron is carried out to thermolysis, and carry out solid-liquid separation, obtain ferroferric oxide nano granules, wherein, the boiling point of described high-boiling point alcohol is 200-300 ℃;
(2) aqueous solution of the carboxylate salt that contains 2-3 carboxylate radical is mixed with the ferroferric oxide nano granules that step (1) makes, obtain the water-sol of ferroferric oxide nano granules.
2. preparation method according to claim 1, wherein, in step (1), described high-boiling point alcohol is selected from one or more in phenylcarbinol, polyoxyethylene glycol, glycol ether and triglycol; Organic precursor of described iron is selected from one or more in ferric acetyl acetonade, pentacarbonyl-iron and iron oleate.
3. preparation method according to claim 1 and 2, wherein, in step (1), in the quality of the organic precursor of 0.5g iron, the consumption of described high-boiling point alcohol is 10-30mL, is preferably 15-25mL.
4. preparation method according to claim 1, wherein, in step (1), the condition of described thermolysis comprises: the temperature of thermolysis is 150-200 ℃, the time of thermolysis is 1-4 hour.
5. according to the preparation method described in claim 1 or 4, wherein, described thermolysis is carried out under inert atmosphere protection and/or under anhydrous condition.
6. preparation method according to claim 1, wherein, in step (2), described carboxylate salt is Trisodium Citrate and/or sodium tartrate.
7. according to the preparation method described in claim 1 or 6, wherein, in step (2), the concentration of the aqueous solution of described carboxylate salt, for being more than or equal to 0.01mol/L, is preferably 0.01-0.05mol/L.
8. preparation method according to claim 1, wherein, this preparation method also comprises: the ferroferric oxide nano granules obtaining with the alcohol washing step (1) of low carbon chain, to remove high-boiling point alcohol wherein, wherein, the alcohol of described low carbon chain is the alcohol of C1-C4, and the alcohol of preferred described low carbon chain is selected from one or more in methyl alcohol, ethanol, propyl alcohol and butanols.
9. the water-sol of the ferroferric oxide nano granules that in claim 1-8 prepared by the preparation method described in any one, wherein, the hydraulic radius of the ferroferric oxide nano granules in the described water-sol can regulate and control in 8-16nm.
10. the application of the water-sol of ferroferric oxide nano granules claimed in claim 9 in Magnetic resonance imaging, target administration and nucleic acid absorption.
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