CN1312046C - Super paramagnetic ferric oxide composite nanometre particle preparation method - Google Patents
Super paramagnetic ferric oxide composite nanometre particle preparation method Download PDFInfo
- Publication number
- CN1312046C CN1312046C CNB2005100190609A CN200510019060A CN1312046C CN 1312046 C CN1312046 C CN 1312046C CN B2005100190609 A CNB2005100190609 A CN B2005100190609A CN 200510019060 A CN200510019060 A CN 200510019060A CN 1312046 C CN1312046 C CN 1312046C
- Authority
- CN
- China
- Prior art keywords
- solution
- trisodium citrate
- concentration
- spion
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention discloses a preparation method for the compound nanometer particles of super-paramagnetic iron oxide, which comprises the following steps: firstly, by simultaneously adding ammonia water and trisodium citrate in a controllable speed rate, Fe3 ions and Fe2 ions are coprecipitated to generate the nanometer particles of Fe3O4 under an alkaline condition, and citric acid radicals are absorbed on the surfaces of the nanometer particles dispersed in a water phase; next, the nanometer particles of Fe3O4 are used as the crystal seeds of the reduction reaction of the trisodium citrate and hydrogen tetrachloroaurate, and gold-coated SPION nanometer particles are formed. The nanometer particles with the nucleus-shell structure of Fe3O4-Au have both magnetism and the gold coating layers, and citric acid radicals absorbed on the surfaces of the particles can be replaced by radicals with various chemical functions by coordination exchange reactions. In the method, the nucleation speed and the growth speed of the nanometer particles of ferroferric oxide can be delayed, the prepared nanometer particles of the ferroferric oxide have good dispersion in the water phase, and the condition of caking by aggregation is minimized. After the gold coating layers are coated, the highly dispersed SPION is no longer sensitive to oxidation, and the magnetism of SPION can be kept stable. In addition, the stability of SPION with multiple applications is enhanced.
Description
Technical field
The invention belongs to the nano magnetic material technical field, relate to a kind of preparation method of water dispersive magnetic composite nano particle.
Background technology
The material of nanoscale becomes the hot research field of Materials science because of being different from the unique physical chemical property of its bulk.Study peculiar rerum natura of nano material and mechanism, and its characteristic is used, constituted the core content of nanometer science and technology.In recent years, nano material, especially nano particle are applied to the progress of biomedical sector, make nanometer biotechnology separate at the magnetic of protein and cell, quantum dot substitutes fluorescein, and aspects such as nucleus magnetic resonance contrast medium and DNA medical diagnosis have all obtained stem-winding achievement.
(superparamagnetic iron oxide nanoparticles SPION) and disperse the magnetic fluid that constituted in suitable carrier, since its nineteen sixty occurs, has obtained extensively reaching deep research to super paramagnetic iron oxide nano particle.The magnetic property of ferric oxide reduces with volume and changes, and when the particle diameter of magnetic iron oxide particle during less than 20nm, has superparamagnetism.Promptly at ambient temperature, after externally-applied magnetic field was cancelled, the magnetic moment of magnetic ferric oxide nano particle ordered arrangement can return in stochastic distribution again because of thermal motion, no longer show special magnetic biasing to, thereby on macroscopic view, show as nonmagnetic.This physical size by material determines that the phenomenon of material character is exactly present known quantum size effect.Magnetic fluid has been widely used in many technical fields, as the loud speaker of sealing, bearing, damper and the dynamo-electric aspect of mechanical aspects, stepper-motor, transmitter etc.Because hypotoxicity and biocompatibility that water dispersive SPION is had, people concentrate on application biological and medical field more to its interest at present, as the High-gradient Magnetic isolation technique, and magnetic and medicated target technology, magnetic is crossed heat cure, magnetic resonance imaging contrast etc.
The SPION of preparation water stable dispersion has certain degree of difficulty technically.The same with other nano particle, difficulty at first comes from its great surface volume ratio.As everyone knows, nano particle diameter is minimum, and specific surface area is big.Therefore, surface atom is compared inner atom, and is bigger to the influence of character such as particulate physical chemistry.Because the hovering chemical bond of surperficial mismatch is many, active big, cause greatly (＞100dyn/cm of particulate surface energy
2), make its tend to assemble agglomerating, to reduce surface energy.In addition, intergranular magnetic dipole adelphotaxy also makes SPION tend to assemble agglomerating.For solving the difficulty of this two aspect, an inevitable way is exactly in preparation, or thereafter, introduces ionic or steric hindrance type surface stabilizer.Interact by the interionic Coulomb repulsion that is adsorbed in nano grain surface, or the shock absorption between chain molecule, modulate or offset the gathering tendency of SPION, help its stable dispersion.Generally speaking, the introducing of surface stabilizer divides in-situ treatment and two kinds of situations of aftertreatment.The former introduces in chemosynthesis SPION, and the latter closes introducing synthetic the finishing of SPION.In organic phase,, obtain all even finely disseminated SPION of particle diameter easily with the SPION of thermal degradation method preparation.But the trouble of bringing for the denaturing treatment of avoiding organic phase SPION (the water-soluble SPION of being is applied to the common requirement of biomedical sector), directly preparation can be in the aqueous phase stable dispersion, and the SPION of being convenient to carry out subsequently surface chemical modification is the easiest way.Chemical coprecipitation is the common method of preparation water SPION.Although after the synthetic SPION of chemical coprecipitation, introduce chain molecules such as oleic acid, also can obtain oil phase dispersive SPION; But if what introduce is the ionic surface stabilizer, obtain that aqueous phase disperses fully and stable SPION but and be not easy.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of super paramagnetic ferric oxide composite nanometre particle, this method can obtain the super paramagnetic ferric oxide composite nanometre particle that aqueous phase has good dispersion and stability.
The preparation method of a kind of super paramagnetic ferric oxide composite nanometre particle provided by the invention, its step comprises:
(1), synthetic water dispersive super-paramagnetic ferriferrous oxide nano particle:
(1.1) preparation FeCl
3And FeCl
2Mixing solutions, require Fe
3+: Fe
2+Molar concentration rate be 2: 1, Fe
3+And Fe
2+Concentration be 0.05-0.3mol/L;
(1.2) compound concentration is the sodium citrate solution of 0.5-3.0mol/L;
(1.3) be that the ammoniacal liquor of 0.5-3mol/L drops in the sodium citrate solution with concentration, make reaction soln finally can reach the pH value of 9-13, and mix;
(1.4) under the nitrogen atmosphere protection, to FeCl
3And FeCl
2Mixing solutions slowly add the ammoniacal liquor and the Trisodium Citrate mixed solution of above-mentioned preparation, Fe
3++ Fe
2+With the mol ratio of Trisodium Citrate be 1: 0.2-1: 1, temperature of reaction is 40 ℃-80 ℃;
(1.5) treat that ammoniacal liquor and Trisodium Citrate mixed solution dropwise after, continue to stir, promptly obtain super paramagnetic iron oxide nano particle stoste;
(2), with the ferric oxide nanometer particle of step (1) preparation as crystal seed, carry out Trisodium Citrate-Jin chloric acid reduction reaction, prepare the super paramagnetic ferric oxide composite nanometre particle of golden clad surface:
(2.1) stirring and heat concentration is the sodium citrate solution of 0.75-35mmol/L;
(2.2) temperature reaches when boiling, adds the some milliliters of super paramagnetic iron oxide nano particle stoste of aforementioned preparation, makes that iron oxide concentration is 0.002-0.1mmol/L in the solution;
(2.3) after a while, add HAuCl again
4The some milliliters of solution, making the GOLD FROM PLATING SOLUTION ionic concn is 0.12-3.0mmol/L;
(2.4) cooling, stirring, afterwards, the dark red solution that will naturally cool to room temperature takes out and preserves.
As a further improvement on the present invention, in the step (1.1), Fe
3++ Fe
2+Total mol concentration be 0.08-0.15mol/L; In the step (1.4), the rate of addition of ammoniacal liquor and Trisodium Citrate mixed solution is 1-8ml/min, Fe
3++ Fe
2+With the mol ratio of Trisodium Citrate be 1: 0.5-1: 0.8, the rate of addition of ammoniacal liquor and Trisodium Citrate mixed solution is 4-6ml/min.
The present invention's while, speed controllably add ammoniacal liquor and Trisodium Citrate, make Fe under the alkaline condition
3+With Fe
2+The ion co-precipitation generates water dispersive Fe
3O
4Nano particle.The Fe that generates with traditional coprecipitation method
3O
4Nano particle relies in magnetic cleaning, processing such as centrifugal back and adds the Fe that ionic or steric hindrance type surface stabilizer guarantee to form stable dispersion
3O
4The method of magnetic fluid is compared, the Fe of the present invention's preparation
3O
4Nano particle does not need aftertreatment just can directly disperse at water, has greatly simplified processing step.Among the present invention, SPION is at Trisodium Citrate-Jin chloric acid (HAuCl
4) in the reduction reaction as crystal seed, help forming golden shell on its surface.Because citrate is Au
3+Reductive agent, also be surface stabilizer.Therefore it is adsorbed in the SPION surface, can promote Au
3+Nucleation and growth on the surface have greatly reduced the productive rate of pure gold particles.The Fe that the present invention obtained
3O
4/ Au nuclear shell structured nano-particle has the golden coating layer of magnetic and kinds of surface chemically modified concurrently.Because the citrate of gold surface absorption belongs to weak chemical bond, can easily be replaced by multiple strong chemical bond through the coordination permutoid reaction.Under the situation of strong chemical bond the other end linkage function group, can form functional magnetic nano particle stable, that have specific affine and identity.According to the size of magnetic kernel, such magnetic nanoparticle can carry out screening and separating with the high-gradient magnetic field separator, obtains uniform functional magnetic particle.Particularly, the present invention has following technique effect:
(1) the adding speed of control ammoniacal liquor and Trisodium Citrate mixed solution, can delay the nucleation and growth speed of ferroferric oxide nano granules, make citrate have enough time to be adsorbed in particle surface, and when playing the stable particle effect, unlikely again inhibition particle is grown up, or changes the chemical ingredients of final product.
(2) ferroferric oxide nano granules made of this method disperses fabulously at aqueous phase, and the situation of assembling caking minimizes.Under 4 ℃ of conditions, can preserve for a long time and unlikely appearance precipitation.
(3) behind the golden shell of coating, the SPION of these high dispersing is no longer to oxidation-sensitive, and it is stable that magnetic can keep.
(4) owing to the citrate that is adsorbed in golden coating layer is a kind of weak chemical bond,, substituted by many stronger chemical bonds easily by the coordination permutoid reaction.Therefore, if be strong chemical bond and the other end contains the chemical molecular of certain specific function group carries out permutoid reaction with an end, these composite magnetic nano particles just can connect needed chemical group, thereby have specific function of surface.At present, the finishing chemistry that customs gold unit arranged is very ripe, can be on gold surface connects many kinds of functional groups, SPION that these gold are coated have many purposes, its water stability also may therefore and further improve.
Description of drawings
Fig. 1 observes figure for the phenomenon of SPION magnetic fluid on the magnetic spacer plate of the present invention's preparation;
Fig. 2 is for coating the electromicroscopic photograph of golden shell front and back nano particle;
Fig. 3 is that the phenomenon on the magnetic spacer plate is observed figure behind the gold coating SPION.
Embodiment
The present invention is further detailed explanation below in conjunction with example.
1. directly use improved chemical coprecipitation one-step synthesis water dispersive super-paramagnetic ferriferrous oxide nano particle, concrete steps comprise:
(1) deionized water (the 18.2M Ω cm of usefulness deoxidation
-1) preparation FeCl
3And FeCl
2Mixing solutions 50-300ml, require Fe
3+: Fe
2+Molar concentration rate be 2: 1, (Fe
3++ Fe
2+) concentration range is at 0.05-0.3mol/L;
(2) with the deionized water preparation sodium citrate solution of deoxidation, concentration range is at 0.5-3.0mol/L;
(3) be that the ammoniacal liquor of 0.5-3mol/L shakes up with the sodium citrate solution of having prepared and mixes with concentration, the add-on of ammoniacal liquor is in the 0.01-0.3 molar range, and purpose is to make the final pH value of reaction soln can reach 9-13, Fe
3++ Fe
2+With the mol ratio of Trisodium Citrate be 1: 0.2-1: 1;
(4) iron of to vigorous stirring under nitrogen atmosphere protection and the ferrous salt mixed solution ammoniacal liquor and the Trisodium Citrate mixed solution that drip above-mentioned preparation, drop rate is controlled at 1-8ml/min, and temperature of reaction is controlled at 40 ℃-80 ℃ of constant temperature;
(5) treat ammoniacal liquor and Trisodium Citrate mixed solution splash into finish after, reaction and stir continuing 30-100 minute promptly obtains the super paramagnetic iron oxide nano particle of aqueous phase good distribution; To surpass paramagnetic iron oxide nano particle magnetic fluid and move into the container sealing preservation rapidly.
With the ferric oxide nanometer particle of method for preparing as crystal seed, carry out Trisodium Citrate-Jin chloric acid reduction reaction, prepare the super paramagnetic ferric oxide composite nanometre particle of golden clad surface:
(1) stirring and heat concentration is the sodium citrate solution (100-250ml) of 0.75-35mmol/L;
When (2) temperature reaches boiling, add the super paramagnetic iron oxide nano particle stoste 0.05-2.0ml of aforementioned preparation, the add-on of super paramagnetic iron oxide nano particle is 0.5-10*10
-3Mmole;
(3) after a while, add golden chloric acid HAuCl fast
4Solution, its add-on are golden chloric acid 0.3-3.0*10
-4Mole;
(4) golden chloric acid adds the back that finishes and just removed thermal source in 5-15 minute; And continue to stir 15-30 minute;
(5) dark red solution that will naturally cool to room temperature takes out, and preserves under 4 ℃ of conditions.
Preferable range: Fe
3++ Fe
2+Total mol concentration be 0.08-0.15mol/L, with the mol ratio of Trisodium Citrate be 1: 0.5-1: 0.8; To FeCl
3And FeCl
2The speed of mixed solution dropping ammonia and Trisodium Citrate mixed solution is 4-6ml/min; When preparing the reaction of golden clad surface, the add-on of Trisodium Citrate is 0.05-1.50*10
-4Mole; The add-on of super paramagnetic iron oxide nano particle stoste is 0.8-1.2ml; Gold chloric acid add-on is 1.25-2.5*10
-4Mole.
Embodiment 1
1.1. with 4.64 gram FeCl
36H
2O (17mmol) and 1.70 gram FeCl
24H
2O (8.5mmol) is dissolved in deionized water (the 18.2M Ω cm of 250ml deoxidation
-1) after, put into the three mouthfuls of round bottom reaction flasks of 500ml that are equipped with the mechanical stirring rod, and be subjected to nitrogen atmosphere protection; With concentration be the concentration of the deionized water preparation of the ammoniacal liquor 100ml of 1mol/L and deoxidation be the sodium citrate solution 19ml of 1mol/L mixed after, splash in the iron and ferrous salt solution of rapid stirring by the speed of 4ml/min; It is brown that solution colour turns gradually, is aterrimus at last; After mixed solution dropwised, stirring reaction was proceeded more than 30 minutes; In entire reaction course, temperature is controlled at about 50 ℃ all the time; The super paramagnetic iron oxide nano particle magnetic fluid that obtains is moved into container sealing rapidly to be preserved;
1.2. adding 200ml concentration in three mouthfuls of round bottom reaction flasks (joining the condensing reflux pipe) of a 250ml is the 7.76mmol/L sodium citrate solution, beginning is sharply stirred, and be heated to boil after, add the super paramagnetic iron oxide nano particle stoste of the aforementioned acquisition of 1.2ml; Add the HAuCl that 10ml concentration is 10mmol/L after a while fast
4Solution can be found flaxen at the beginning solution becomes dark-brown, and purpling redness again presents the feature scarlet of gold colloid at last; Add behind the golden solution chlorate after 15 minutes, remove thermal source, and continue to stir 15 minutes; The dark red solution that naturally cools to room temperature is taken out, and under 4 ℃ of conditions, preserve.
Embodiment 2
2.1. with 3.712 gram FeCl
36H
2O (13.6mmol) and 1.368 gram FeCl
24H
2After O (6.8mmol) is dissolved in 50ml deoxidation deionized water, puts into the three mouthfuls of round bottom reaction flasks of 100ml that are equipped with the mechanical stirring rod, and be subjected to nitrogen atmosphere protection; With concentration be the concentration of the ammoniacal liquor 67ml of 3mol/L and the preparation of deoxidation deionized water be the sodium citrate solution 5.1ml of 3mol/L mixed after, splash in the iron and ferrous salt solution of rapid stirring by the speed of 2ml/min; It is brown that solution colour turns gradually, is aterrimus at last; After mixed solution dropwised, stirring reaction was proceeded more than 30 minutes; In entire reaction course, temperature is controlled at about 80 ℃ all the time; The super paramagnetic iron oxide nano particle magnetic fluid that obtains is moved into container sealing rapidly to be preserved;
2.2. adding 100ml concentration in three mouthfuls of round bottom reaction flasks (joining the condensing reflux pipe) of a 250ml is the sodium citrate solution of 31.04mmol/L, beginning is sharply stirred, and be heated to boil after, add the super paramagnetic iron oxide nano particle stoste of the aforementioned acquisition of 0.2ml; Add the HAuCl that 25ml concentration is 10mmol/L after a while fast
4Solution can be found flaxen at the beginning solution becomes dark-brown, becomes the feature redness of gold colloid more gradually; Add behind the golden solution chlorate after 5 minutes, remove thermal source, and continue to stir 15 minutes; The dark red solution that naturally cools to room temperature is taken out, and under 4 ℃ of conditions, preserve.
Embodiment 3
3.1. with 2.784 gram FeCl
36H
2O (10.2mmol) and 1.02 gram FeCl
24H
2After O (5.1mmol) is dissolved in 200ml deoxidation deionized water, puts into the three mouthfuls of round bottom reaction flasks of 500ml that are equipped with the mechanical stirring rod, and be subjected to nitrogen atmosphere protection; With concentration be behind the ammoniacal liquor 36ml of 0.5mol/L and the deoxidation receive the concentration of pure water preparation be the sodium citrate solution 20ml of 0.5mol/L mixed after, splash in the iron and ferrous salt solution of rapid stirring by the speed of 5ml/min; Solution colour becomes aterrimus gradually; After mixed solution dropwised, stirring reaction was proceeded more than 30 minutes; In entire reaction course, temperature is controlled at about 40 ℃ all the time; The super paramagnetic iron oxide nano particle magnetic fluid that obtains is moved into container sealing rapidly to be preserved;
3.2. adding 250ml concentration in three mouthfuls of round bottom reaction flasks (joining the condensing reflux pipe) of a 500ml is the 4.85mmol/L sodium citrate solution, beginning is sharply stirred, and be heated to boil after, add the super paramagnetic iron oxide nano particle stoste of the aforementioned acquisition of 0.1ml; Add the HAuCl that 5ml concentration is 10mmol/L after a while fast
4Solution can be found the dark purple black of flaxen at the beginning solution becomes, becomes purplish color in the last redness more gradually; Add behind the golden solution chlorate after 10 minutes, remove thermal source, and continue to stir 15 minutes; The dark red solution that naturally cools to room temperature is taken out, and under 4 ℃ of conditions, preserve.
Embodiment 4-13: its composition and proportioning see the following form, and its preparation process is with example 1-3:
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Fe 3++Fe 2+(mmole)/mole * liter -1/ milliliter | 25.5 | 25.5 | 25.5 | 25.5 | 20.4 |
| 0.101 | 0.101 | 0.101 | 0.101 | 0.204 | |
| 250 | 250 | 250 | 250 | 100 | |
| Trisodium Citrate (mole * liter -1)/milliliter | 1 | 1 | 1 | 1 | 3 |
| 19 | 25 | 12 | 6 | 5.1 | |
| Ammoniacal liquor (mole * liter -1)/milliliter | 1 | 1 | 1 | 1 | 3 |
| 100 | 100 | 100 | 100 | 67 | |
| Fe 3++Fe 2+With the Trisodium Citrate mol ratio | 1∶0.75 | 1∶0.98 | 1∶0.47 | 1∶0.24 | 1∶0.75 |
| Speed (ml/min) | 4 | 2 | 6 | 8 | 2 |
| Sodium citrate solution (mmole * liter -1)/milliliter | 7.76 | 7.76 | 7.76 | 7.76 | 31 |
| 200 | 200 | 200 | 200 | 100 | |
| Ferric oxide (mmole) | 3.24*10 -3 (1.2ml) | 4.05*10 -3 (1.5ml) | 62*10 -3 (0.6ml) | 0.54*10 -3 (0.2ml) | 7.9*10 -3 |
| Gold chloric acid (mmole * liter -1)/milliliter | 10 | 10 | 10 | 10 | 10 |
| 10 | 10 | 10 | 10 | 25 |
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | |
| Fe 3++Fe 2+(mmole)/mole * liter -1/ milliliter | 20.4 | 20.4 | 15.3 | 15.3 | 15.3 |
| 0.204 | 0.204 | 0.0765 | 0.0765 | 0.0765 | |
| 100 | 100 | 200 | 200 | 200 | |
| Trisodium Citrate (mole * liter -1)/milliliter | 3 | 3 | 0.5 | 0.5 | 0.5 |
| 5.1 | 5.1 | 20 | 15 | 25 | |
| Ammoniacal liquor (mole * liter -1)/milliliter | 3 | 3 | 0.5 | 0.5 | 0.5 |
| 45 | 90 | 36 | 28 | 44 | |
| Fe 3++Fe 2+With the Trisodium Citrate mol ratio | 1∶0.75 | 1∶0.75 | 1∶0.65 | 1∶0.49 | 1∶0.82 |
| Speed (ml/min) | 1 | 3 | 5 | 3 | 7 |
| Sodium citrate solution (mmole * liter -1)/milliliter | 31 | 31 | 4.85 | 0.97 | 1.95 |
| 100 | 100 | 250 | 250 | 250 | |
| Ferric oxide (mmole) | 4.5*10-3 | 7.0*10 -3 | 2.00*10 -3 | 2.00*10 -3 | 2.00*10 -3 |
| Gold chloric acid (mmole * liter -1)/milliliter | 10 | 10 | 10 | 10 | 10 |
| 25 | 25 | 5 | 5 | 5 |
Fig. 1 illustrates the high dispersing of SPION at aqueous phase, is followed successively by a, b, c, d by the time.Wherein, the magnetic spacer plate is the flat board that magneticstrength is 2000 Gausses' a cylindrical magnet that is built-in with of magnetic cell separator.The synthetic product is Fe
3O
4Nano particle has magnetic, as shown in Figure 1a.Be oxidized to magnetic γ-Fe under the room temperature gradually
2O
3After, magnetic weakens, and suffered magnetic force no longer is enough to fetter it in original position, and thermal motion causes it to external diffusion, as Fig. 1 b, 1c.Blackspot dissipates fully at last and illustrates that SPION is the extreme dispersed particles, as Fig. 1 d.
Fig. 2 further specify the good distribution of SPION and coat after the change that brings.Because SPION causes particle aggregation can not observe the dispersive pattern because of water evaporates at the copper mesh sample of preparation Electronic Speculum at ordinary times, as Fig. 2 a.Small-particle electromicroscopic photograph after the present invention coats with gold confirms the deployment conditions of SPION, as Fig. 2 b.Small-particle after these gold coat is taken from certain part of low magnification electromicroscopic photograph Fig. 2 c.Can see except that the good small-particle of a large amount of dispersions, also having the above macrobead of some particle diameter 15nm from Fig. 2 c.
Fig. 3 illustrates that gold grain has magnetic response.Original equally distributed red solution under the effect of underlying cylindrical magnet, gradually becomes red distribution of circle spot shape; After 72 hours, red accumulating in substantially in the erythema corresponding with cylindrical magnet.
Claims (5)
1, a kind of preparation method of super paramagnetic ferric oxide composite nanometre particle, its step comprises:
(1), synthetic water dispersive super-paramagnetic ferriferrous oxide nano particle:
(1.1) preparation FeCl
3And FeCl
2Mixing solutions, require Fe
3+: Fe
2+Molar concentration rate be 2: 1, Fe
3+And Fe
2+Concentration be 0.05-0.3mol/L;
(1.2) compound concentration is the sodium citrate solution of 0.5-3.0mol/L;
(1.3) be that the ammoniacal liquor of 0.5-3mol/L drops in the sodium citrate solution with concentration, make reaction soln finally can reach the pH value of 9-13, and mix;
(1.4) under the nitrogen atmosphere protection, to FeCl
3And FeCl
2Mixing solutions slowly add the ammoniacal liquor and the Trisodium Citrate mixed solution of above-mentioned preparation, Fe
3++ Fe
2+With the mol ratio of Trisodium Citrate be 1: 0.2-1: 1, temperature of reaction is 40 ℃-80 ℃;
(1.5) treat that ammoniacal liquor and Trisodium Citrate mixed solution dropwise after, continue to stir, promptly obtain super paramagnetic iron oxide nano particle stoste;
(2), with the ferric oxide nanometer particle of step (1) preparation as crystal seed, carry out Trisodium Citrate-Jin chloric acid reduction reaction, prepare the super paramagnetic ferric oxide composite nanometre particle of golden clad surface:
(2.1) stirring and heat concentration is the sodium citrate solution of 0.75-35mmol/L;
(2.2) temperature reaches when boiling, adds the some milliliters of super paramagnetic iron oxide nano particle stoste of aforementioned preparation, makes that iron oxide concentration is 0.002-0.1mmol/L in the solution;
(2.3) after a while, add HAuCl again
4The some milliliters of solution, making the GOLD FROM PLATING SOLUTION ionic concn is 0.12-3.0mmol/L;
(2.4) cooling, stirring, afterwards, the dark red solution that will naturally cool to room temperature takes out and preserves.
2, method according to claim 1 is characterized in that: in the step (1.1), and Fe
3++ Fe
2+Total mol concentration be 0.08-0.15mol/L.
3, method according to claim 1 and 2 is characterized in that: in the step (1.4), the rate of addition of ammoniacal liquor and Trisodium Citrate mixed solution is 1-8ml/min.
4, method according to claim 3 is characterized in that: in the step (1.4), and Fe
3++ Fe
2+With the mol ratio of Trisodium Citrate be 1: 0.5-1: 0.8.
5, method according to claim 4 is characterized in that: in the step (1.4), the rate of addition of ammoniacal liquor and Trisodium Citrate mixed solution is 4-6ml/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100190609A CN1312046C (en) | 2005-07-07 | 2005-07-07 | Super paramagnetic ferric oxide composite nanometre particle preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100190609A CN1312046C (en) | 2005-07-07 | 2005-07-07 | Super paramagnetic ferric oxide composite nanometre particle preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1736881A CN1736881A (en) | 2006-02-22 |
| CN1312046C true CN1312046C (en) | 2007-04-25 |
Family
ID=36079871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100190609A Expired - Fee Related CN1312046C (en) | 2005-07-07 | 2005-07-07 | Super paramagnetic ferric oxide composite nanometre particle preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1312046C (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101707134B (en) * | 2009-11-02 | 2011-08-31 | 浙江大学 | Preparation method of high-temperature resistant superparamagnetic tin dioxide coated iron oxide nano materials |
| CN101728040B (en) * | 2010-01-20 | 2012-03-14 | 江南大学 | Preparing method of pomegranate-shaped magnetic nanometer particle congery and applications thereof in DNA separation and purification |
| CN101774649B (en) * | 2010-01-28 | 2011-08-31 | 东北电力大学 | Method and device for continuously preparing nano ferroferric oxide through hollow fiber ultrafiltration dual-membrane |
| WO2012000529A1 (en) * | 2010-07-01 | 2012-01-05 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e. V. | Process for preparing magnetite or maghemite nanoparticles with controlled size using mild conditions |
| CN103084147B (en) | 2011-11-08 | 2015-02-25 | 纳科石油化工有限公司 | Iron oxide magnetic nano particle, preparation method and application method thereof in desulfurization |
| CN102528027B (en) * | 2012-02-24 | 2013-06-26 | 哈尔滨工业大学 | Preparation method for gold-shell magnetic ellipsoid |
| CN102850209B (en) * | 2012-09-21 | 2015-03-25 | 中粮生物化学（安徽）股份有限公司 | Production method of calcium citrate and application of calcium citrate |
| CN103286311A (en) * | 2012-12-13 | 2013-09-11 | 华东理工大学 | Multifunctional composite nanoparticle and preparation method and application thereof |
| CN103128307B (en) * | 2013-02-05 | 2015-12-02 | 西安金磁纳米生物技术有限公司 | A kind of preparation method of gold-magnetic particles |
| WO2015044444A1 (en) | 2013-09-30 | 2015-04-02 | Mærsk Olie Og Gas A/S | Water treatment suited for oil production wells |
| NO346984B1 (en) | 2013-09-30 | 2023-03-27 | Maersk Olie & Gas | Method and System for Recovering of Crude Oil |
| DK179840B1 (en) | 2013-09-30 | 2019-07-30 | Total E&P Danmark A/S | Method and system for the enhanced recovery of oil, using water that has been depleted in ions using magnetic particles |
| CN105992808B (en) * | 2013-09-30 | 2018-10-19 | 综合E&P丹麦股份有限公司 | Magnetic nano-particle is used to exhaust the purposes of the aromatic compounds in oil |
| CN103641072B (en) * | 2013-12-06 | 2015-06-03 | 北京科技大学 | Method for preparing transition nanometer oxide with uniform grain size by coprecipitation method |
| CN104098156B (en) * | 2014-07-30 | 2016-05-11 | 中国科学院新疆理化技术研究所 | The purposes of poly-dopamine composite magnetic micro-nano granules in oily waste water treatment |
| CN104528636B (en) * | 2014-12-18 | 2016-04-27 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of functional method of magnetic-particle finishing gold nano grain |
| CA2984506A1 (en) * | 2015-05-01 | 2016-11-10 | BioLegend, Inc. | Stable nanomagnetic particle dispersions |
| CN105967241B (en) * | 2016-05-06 | 2018-01-16 | 华侨大学 | One kind prepares Fe3O4The method of nanoscale magnetic bead |
| CN106315687B (en) * | 2016-08-03 | 2018-10-09 | 安徽八一化工股份有限公司 | A kind of waste water with chlorobenzene production prepares Fe3O4Method |
| CN106348416B (en) * | 2016-08-30 | 2019-03-26 | 马鞍山金泉工业介质科技有限公司 | It is a kind of that super-paramagnetism nano Fe is prepared by acid, the hot galvanizing industrial wastewater containing iron ion3O4Method |
| CN106511299B (en) * | 2016-10-19 | 2019-10-11 | 常州大学 | Ferroso-ferric oxide/gold/Nano particles of silicon dioxide preparation of a kind of core-shell structure and near infrared light Drug controlled release |
| CN106824093A (en) * | 2017-02-23 | 2017-06-13 | 中国石油大学(北京) | A kind of magnetic adsorbent for desulfurizing oil and its preparation method and application |
| CN108403716B (en) * | 2018-06-25 | 2021-11-05 | 博瑞生物医药（苏州）股份有限公司 | Preparation method of superparamagnetic iron oxide |
| CN109085150A (en) * | 2018-08-14 | 2018-12-25 | 苏州工业职业技术学院 | The preparation method of gold-coated ferroferric oxide nanometer star as circulation SERS substrate |
| CN110240733B (en) * | 2019-06-17 | 2021-11-12 | 湖北工业大学 | Ferroferric oxide copper-loaded nano particle, preparation method thereof and application thereof in preparing root-resisting material |
| CN110255627A (en) * | 2019-07-12 | 2019-09-20 | 中国恩菲工程技术有限公司 | Nano ferriferrous oxide and preparation method thereof and system |
| CN116259459A (en) * | 2023-02-22 | 2023-06-13 | 上海蓝载信息科技有限公司 | Super-magnetic citric acid coated iron oxide nanoparticle, and synthesis method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1421392A (en) * | 2002-12-24 | 2003-06-04 | 华中科技大学 | Prepn process of nanometer granular Fe3O4 |
-
2005
- 2005-07-07 CN CNB2005100190609A patent/CN1312046C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1421392A (en) * | 2002-12-24 | 2003-06-04 | 华中科技大学 | Prepn process of nanometer granular Fe3O4 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1736881A (en) | 2006-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1312046C (en) | Super paramagnetic ferric oxide composite nanometre particle preparation method | |
| Liu et al. | Preparation, surface functionalization and application of Fe3O4 magnetic nanoparticles | |
| Ali et al. | Synthesis, characterization, applications, and challenges of iron oxide nanoparticles | |
| Wang et al. | A molecularly imprinted polymer-coated nanocomposite of magnetic nanoparticles for estrone recognition | |
| Cui et al. | Synthesis of orientedly bioconjugated core/shell Fe3O4@ Au magnetic nanoparticles for cell separation | |
| Ansari et al. | Green synthesis of magnetic chitosan nanocomposites by a new sol–gel auto-combustion method | |
| KR101043251B1 (en) | Magnetic Resonance Imaging Contrast Agents Comprising Zinc Containing Magnetic Metal Oxide Nanoparticles | |
| Tai et al. | Recent research progress on the preparation and application of magnetic nanospheres | |
| Ma et al. | Synthesis and surface modification of magnetic particles for application in biotechnology and biomedicine | |
| US7547473B2 (en) | Magnetic nanoparticles and method for producing the same | |
| Nadar et al. | Recent progress in nanostructured magnetic framework composites (MFCs): synthesis and applications | |
| JPWO2004083124A1 (en) | Noble metal / magnetic metal oxide composite fine particles and production method thereof | |
| CN100362605C (en) | Water-based magnetic liquid and method for making same | |
| CN110665465B (en) | Magnetic covalent organic framework material for glycopeptide enrichment and preparation method and application thereof | |
| CN111423878B (en) | Fluorescent magnetic composite nano-particles, preparation method thereof and biological probe prepared from fluorescent magnetic composite nano-particles | |
| Srivastava et al. | Magnetic nanoparticles: a review on stratagems of fabrication an d its biomedical applications | |
| Khan et al. | Magnetic nanoparticles: properties, synthesis and biomedical applications | |
| Reddy et al. | A simple approach to the design and functionalization of Fe3O4–Au nanoparticles for biomedical applications | |
| JP4979492B2 (en) | Noble metal / magnetic metal oxide composite fine particles and production method thereof | |
| CN100573751C (en) | The preparation method of gelatine cladding water-based magnetofluid | |
| Somaskandan et al. | Surface protected and modified iron based core-shell nanoparticles for biological applications | |
| CN100573750C (en) | Double cladding water-based magnetofluid and preparation method thereof | |
| Park et al. | Mannose-functionalized core@ shell nanoparticles and their interactions with bacteria | |
| CN100461310C (en) | Double function magnetic fluid and its preparing method | |
| Wang et al. | Preparation of Fe 3 O 4@ Au nano-composites by self-assembly technique for immobilization of glucose oxidase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |