CN101409125A - Method for preparing specificity function magneto fluid - Google Patents
Method for preparing specificity function magneto fluid Download PDFInfo
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- CN101409125A CN101409125A CNA2008100212353A CN200810021235A CN101409125A CN 101409125 A CN101409125 A CN 101409125A CN A2008100212353 A CNA2008100212353 A CN A2008100212353A CN 200810021235 A CN200810021235 A CN 200810021235A CN 101409125 A CN101409125 A CN 101409125A
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Abstract
The invention relates to a preparation method of a specific functional magnetic fluid; the preparation method is characterized in that water solution containing Fe<+3> and Fe<+2> is taken as raw material, the hydrolysis and the surface modification with NaOH water solution and poly-5-hydroxymethyl-furfural water solution in a supergravity field are carried out to obtain the surface modified magnetic fluid, the surface modified magnetic fluid is further coupled and combined with a synthesis oriented peptide to obtain the specific functional magnetic fluid with biocompatibility, biodegradability, bio-penetrating, magnetic response, nanoparticle property and the like; poly-5-hydroxymethyl-furfural is a soluble polymer organic matter which is obtained by polymerization of a biobased material 5-hydroxymethyl-furfural, the synthesis oriented peptide is generated by peptide formation reaction of various amino acids in an organic solvent under the action of a catalyst and at a certain temperature, and the oriented peptides with the different specific functions and the different uses can be obtained by controlling the types of the amino acids, the mixture ratio, the synthesis process conditions, etc.
Description
Technical field
The present invention relates to a kind of preparation method of specific function magnetic fluid, belong to nanoscale science and technology and biomedicine field.
Background technology
Magnetic fluid claims magnetic liquid again, is one of important applied field of nano material, and it has the magnet of solid and the liquid of fluent material concurrently, is a kind of novel liquid functional material.Early stage magnetic fluid is mainly used in aspects such as sealing, lubricated, separation, printing and dyeing and environmental protection, and has obtained substantial success.In recent years, development and some The application of new technique along with nanoscale science and technology, magnetic nanoparticle finishing and modification have been carried out, make it not only have the common performance of nano particle, and have specificitys such as biocompatibility, biological degradability and magnetic responsiveness, therefore obtained wide application at biomedicine field, as immobilised enzymes, list (two) targeted drug, medicine control release, magnetic resonance imaging imaging, DNA and cell separation technology etc.
The composition of specific function magnetic fluid, can be divided into two parts according to performance: a part is a magnetic core, embodies character, suspension stability, magnetic responsiveness of size, the particle surface of magnetic nanoparticle etc.; Another part is finishing and modification part, performances such as having embodied bio-compatible, degrade and penetrated.These all have remarkable influence to its application at biomedicine field, are the main prerequisites of the preparation and the application of magnetic fluid for biological medicine.Traditional oil base magnet stream is because its non-biocompatible, is restricted in the application of biomedicine field.And surfactants based water-based magnetic fluid is difficult to it is carried out surface-functionalized modification or modification, and its application at biomedicine field also is subjected to restriction to a certain degree.
By natural organic polymer, particularly the synthetic hydrophily organic polymer of specific aim carries out surface coating decoration to the magnet nano particle, improve on the one hand the biocompatibility, suspension stability of magnetic-particle and, prolong its body-internal-circulation time the penetration power of reticuloendothelial system in the organism; On the other hand, the finishing of organic macromolecule active group process is the multiple functional polymer of load (polypeptide, antibody, enzyme, DNA and RNA etc.) simultaneously, thereby can prepare the magnetic nanoparticle material of specific function.Thereby adopt the hydrophily organic polymer to become a kind of biological medicine that has application prospect specific function magnetic fluid as the magnetic fluid of coating material.
At present, the coating material of existing magnetic fluid for biological medicine mainly contains: polyethylene glycol, glucan, shitosan etc.Wherein, polyethylene glycol is not ideal enough as the effect of coating material; And hydrophily organic polymers such as glucan and shitosan on the one hand cost is very high, the magnetic fluid magnetic responsiveness of existing on the other hand synthetic method preparation a little less than.Employing emulsification complex techniques such as domestic Qiu Guang is bright are prepared the magnetic spherex that particle diameter is 50 ~ 375nm, have dispersion stabilization (Qiu Guangliang, Li Yonglan etc., chemistry science and technology, 2001,9 (4): 15 ~ 18) preferably at aqueous phase.But because magnetic starch composite particles particle diameter is bigger, particle size distribution is wide, has limited its application in biomedicine field, especially the application in the magnetic target medicine technology.Thereby, develop new cheaply, particle diameter less than 50nm and monodispersity good, strong magnetic rings and the biological medicine of high stability still has great practical significance with the specific function magnetic fluid.
Summary of the invention
First purpose of the present invention is to propose a kind of specific function magnetic fluid, and it not only has the nanometer sign property and the magnetic responsiveness of magnetic nanoparticle, and has specificitys such as bio-compatible, biodegradation and biology penetrate.Its composition can be divided into two parts according to performance: a part is a magnetic Nano nuclear, embodies the character, suspension stability, magnetic responsiveness of size, the particle surface of magnetic nanoparticle etc.; Another part is finishing and modification part, performances such as having embodied bio-compatible, degrade and penetrated.Described biological medicine is further characterized in that with the specific function magnetic fluid, the magnet inorganic nano particle is that a footpath is the Fe3O4 particle of 10 ~ 25nm, and the particle diameter of the magnetic nanoparticle of the synthetic polypeptide of surface organic synthesising biological sill of coating and coupling combination is less than 45nm.
Second purpose of the present invention provides a kind of preparation method of described specific function magnetic fluid.
A kind of preparation method of specific function magnetic fluid, the concrete operations step is as follows:
First step raw material is prepared
Raw material is FeCl3.6H2O, FeSO4.7H2O, NaOH or NH3.H2O, soluble poly hydroxymethylfurfural, its molecular weight are 15000 ~ 23000, synthetic polypeptide, its peptide chain numerical control is built in 15～20, raw materials used be analyze pure.
The preparation of the second step reactant liquor
Prepare molysite mixed aqueous solution and NaOH or the ammonia spirit of Fe3+ and Fe2+ respectively, the concentration of Fe3+ ion is 0.2 ~ 0.5mol/L in the molysite mixed aqueous solution, and the concentration of Fe2+ is 0.1 ~ 0.3mol/L, and the concentration of NaOH or ammonia spirit is 0.1 ~ 0.5mol/L; The concentration of targeted peptide is 0.2～2.5mg/ml.
The magnetic fluid preparation of the 3rd step magnetic core and finishing
With the iron salt solutions that contains Fe3+, Fe2+ ion of metering with by the soluble poly 5 hydroxymethyl furfural of 3 ~ 5 parts of weight and the aqueous solution that redistilled water was mixed with of 40 parts of weight, join in the supergravity reactor (RPB), 70 ~ 80 ℃ of control temperature and adjustment rotating speed reach the hypergravity that can produce centrifugal acceleration 300～900g.In 1.5～2.5 hours, drip the NaOH or the ammonia spirit of metering, and continue to keep super gravity field 1 hour.Stop the rotation, in resulting black magnetic suspension, regulate the pH value to 7 of this suspension with watery hydrochloric acid, sediment in the centrifugal removal solution, then, sample is removed free poly-5 hydroxymethyl furfural and other non magnetic compositions of not effect through redistilled water dialysis 2 ~ 3 days, the solution of gained uses redistilled water and phosphate buffer solution PBS (pH=7.40) to clean respectively, gets product (through the magnetic fluid of organic polymer finishing) after concentrating.
The preparation of the 5th step specific function magnetic fluid
In PBS, compound concentration is targeted peptide 0.5～2.0ml of 0.5～2.0mg/ml, adding concentration is carbodiimide solution 0.5～2.0ml of 0.5～2.0mg/ml, add magnetic fluid 100～200ml that the 4th step made again, lucifuge is with frequency oscillation 20～26h of 200～400r/min under 15～25 ℃ the temperature, PBS cleans, and obtains having the specific function magnetic fluid.
The present invention has following characteristics and effect:
1, the magnetic fluid of being invented is a kind of biological medicine water-based magnetic fluid, has excellent biological compatibility, biological degradability, biological penetrability, suspension stability and magnetic responsiveness.
2, two kinds of reactive functional groups (furans and ether-O-), but the multiple functional polymer of load (polypeptide, antibody, enzyme dna and RNA etc.) are contained in the poly-5 hydroxymethyl furfural composite nanometer particle surface of magnetic in the magnetic fluid.
3, the magnetic of institute's invention magnetic fluid nuclear, adopt hydro-thermal hypergravity reaction method synthetic, by optimizing synthesis technique (reactant concentration, alkali lye rate of addition, reaction temperature, time and hypergravity acceleration), nucleation rate, nucleus growth speed and the nanometer particle size of having controlled nano particle effectively distribute.The average grain diameter of the poly-5 hydroxymethyl furfural composite nanometer particle of magnetic is less than 45nm in the magnetic fluid of preparation, and monodispersity is good, can be used for numerous areas such as target administration, cell separation, tumor thermotherapy and magnetic resonance imaging imaging.
4, the targeted peptide of magnetic nanoparticle surface institute coupling combination is the peptide of synthetic 12～15 links, its synthetic method is: in THF or DMF, add a spot of concentrated sulfuric acid, control 20 ℃～65 ℃, substep and component add glycine, arginine, glutamic acid, lysine and L-leucine or L-citrulling etc., control amino acid whose kind, proportioning and synthetic technological condition, control peptide chain footing is a 12-15 amino acid, can obtain the targeted peptide of different specific performances and different purposes.
5, preparation method of the present invention is simple, adopts synthetic organic polymer as stabilizer, can reduce production costs and improve the performance of product significantly.
Below in conjunction with specific embodiment, the invention will be further elaborated.The invention is not restricted to these specific embodiments.
Embodiment
All embodiment all operate by above-mentioned preparation method's operating procedure.
Embodiment 1
Prepare mixed solution and the 0.2mol/L NaOH solution of 0.6mol/L Fe2+ and 0.3mol/L Fe3+ respectively with redistilled water.The poly-5 hydroxymethyl furfural of 3 parts of weight added in 40 parts the redistilled water, be heated to 60 ℃ and make its dissolving.
The mixed solution 50ml that gets molysite adds in the poly-5 hydroxymethyl furfural solution, joins rotating packed-bed reactor simultaneously, regulates rotary speed, and control produces the hypergravity of centrifugal acceleration 300～900g.70 ~ 80 ℃ of control temperature in 1.5～2.5 hours, drip the NaOH aqueous solution of metering, and continue to keep super gravity field 1 hour.Stop the rotation, in resulting black magnetic suspension, regulate the pH value to 7 of this suspension with watery hydrochloric acid, sediment in the centrifugal removal solution, then, sample is removed free poly-5 hydroxymethyl furfural and other non magnetic compositions of not effect through redistilled water dialysis 2 ~ 3 days, the solution of gained uses redistilled water and phosphate buffer solution PBS (pH=7.40) to clean respectively, gets product (through the magnetic fluid of organic polymer finishing) after concentrating.
In 200mlTHF, add the 0.5ml concentrated sulfuric acid, control 20 ℃～65 ℃, divide three times and add glycine, arginine, glutamic acid, lysine and each 5g such as L-leucine or L-citrulling, insulation reaction 15～20 hours.Condensing crystallizing and isolate product is used the alcohol recrystallization again, targeted peptide.By controlling amino acid whose kind, proportioning and synthetic technological condition, control peptide associated number is a 12-15 amino acid, can obtain the targeted peptide of different specific performances and different purposes.
In PBS, compound concentration is the targeted peptide 5.5ml of 1.3mg/ml, adding concentration is the carbodiimide solution 4.0ml of 0.9mg/ml, add the magnetic fluid 200ml that the 4th step made again, lucifuge is with frequency oscillation 20～22h of 200～400r/min under 22～30 ℃ the temperature, PBS cleans, and obtains having the specific function magnetic fluid.
The magnetic nanoparticle that poly-5 hydroxymethyl furfural coats in the magnetic fluid is shaped as flexible subsphaeroidal, and monodispersity is good, and particle diameter is between 30 ~ 45nm, and specific saturation magnetization is 46emu/g.Contain Fe3O4～12mg/ml in the magnetic fluid, the poly-about 2.0mg/ml of 5 hydroxymethyl furfural, the about 1.0mg/ml of targeted peptide.The magnetic fluid sample has good suspension stability, and the sedimentation phenomenon that produced owing to action of gravity in 3 ~ 5 months is not obvious.
Embodiment 2
Prepare mixed solution and the 0.4mol/L NaOH solution of 0.8mol/L Fe2+ and 0.3mol/L Fe3+ respectively with redistilled water.The poly-5 hydroxymethyl furfural of 5 parts of weight added in 50 parts the redistilled water, be heated to 60 ℃ and make its dissolving.
The mixed solution 80ml that gets molysite adds in the poly-5 hydroxymethyl furfural solution, joins rotating packed-bed reactor simultaneously, regulates rotary speed, and control produces the hypergravity of centrifugal acceleration 500～800g.80 ~ 90 ℃ of control temperature in 1.5～2.0 hours, drip the NaOH aqueous solution of metering, and continue to keep super gravity field 1.5 hours.Stop the rotation, in resulting black magnetic suspension, regulate the pH value to 7 of this suspension with watery hydrochloric acid, sediment in the centrifugal removal solution, then, sample is removed free poly-5 hydroxymethyl furfural and other non magnetic compositions of not effect through redistilled water dialysis 2 ~ 3 days, the solution of gained uses redistilled water and phosphate buffer solution PBS (pH=7.40) to clean respectively, gets product (through the magnetic fluid of organic polymer finishing) after concentrating.
The preparation method of targeted peptide is with example 1.
In PBS, compound concentration is the targeted peptide 6.5ml of 1.5mg/ml, adding concentration is the carbodiimide solution 4.2ml of 1.2mg/ml, add the magnetic fluid 160ml that the 4th step made again, lucifuge is with frequency oscillation 20～22h of 300～350r/min under 25～30 ℃ the temperature, PBS cleans, and obtains having the specific function magnetic fluid.
The magnetic nanoparticle that poly-5 hydroxymethyl furfural coats in the magnetic fluid is shaped as flexible subsphaeroidal, and monodispersity is good, and particle diameter is between 38 ~ 45nm, and specific saturation magnetization is～48emu/g.Contain Fe3O4～15mg/ml in the magnetic fluid, the poly-about 1.8mg/ml of 5 hydroxymethyl furfural, the about 1.1mg/ml of targeted peptide.The magnetic fluid sample has good suspension stability, and the sedimentation phenomenon that produced owing to action of gravity in 4 ~ 5 months is not obvious.
Embodiment 3
Prepare mixed solution and the 0.5mol/L NaOH solution of 0.6mol/L Fe2+ and 0.3mol/L Fe3+ respectively with redistilled water.The poly-5 hydroxymethyl furfural of 8 parts of weight added in 60 parts the redistilled water, be heated to 60 ℃ and make its dissolving.
The mixed solution 120ml that gets molysite adds in the poly-5 hydroxymethyl furfural solution, joins rotating packed-bed reactor simultaneously, regulates rotary speed, and control produces the hypergravity of centrifugal acceleration 800～900g.80 ~ 95 ℃ of control temperature in 1.5～2.0 hours, drip the NaOH aqueous solution of metering, and continue to keep super gravity field 2.0 hours.Stop the rotation, in resulting black magnetic suspension, regulate the pH value to 7 of this suspension with watery hydrochloric acid, sediment in the centrifugal removal solution, then, sample is removed free poly-5 hydroxymethyl furfural and other non magnetic compositions of not effect through redistilled water dialysis 2 ~ 3 days, the solution of gained uses redistilled water and phosphate buffer solution PBS (pH=7.40) to clean respectively, gets product (through the magnetic fluid of organic polymer finishing) after concentrating.
The preparation method of targeted peptide is with example 1.
In PBS, compound concentration is the targeted peptide 3.0ml of 2.0mg/ml, adding concentration is the carbodiimide solution 3.5ml of 1.5mg/ml, add the magnetic fluid 120ml that the 4th step made again, lucifuge is with frequency oscillation 18～20h of 350～450r/min under 25～33 ℃ the temperature, PBS cleans, and obtains having the specific function magnetic fluid.
Water-based magnetic fluid of the present invention has excellent biological compatibility, biodegradability, biological penetrability, suspension stability and magnetic responsiveness, can be used for biomedicine fields such as cell separation, tumor thermotherapy, the imaging of nulcear magnetic resonance (NMR) shadow and target administration.
Claims (5)
1, the present invention relates to a kind of preparation method of specific function magnetic fluid, it is characterized in that to contain Fe
+ 3, Fe
+ 2The aqueous solution be raw material, with the NaOH aqueous solution or the ammoniacal liquor and the poly-5 hydroxymethyl furfural aqueous solution, through reaction of hydro-thermal hypergravity and finishing, and obtain the magnetic fluid of finishing, combine with synthetic targeted peptide coupling again, obtain having biocompatibility, specific function magnetic fluid such as biological degradability, biological penetrability, magnetic responsiveness and characteristics of nanoparticles.
2, described according to claim 1, it is characterized in that magnetic core and finishing, be in super gravity field, Fe
3+, Fe
2+Ion generation hydro-thermal hypergravity reacts and generation Fe
3O
4Nanometer magnetic nuclear, and with poly-5 hydroxymethyl furfural generation finishing effect, the magnetic nanoparticle particle diameter after the finishing is less than 45nm.
3, described according to claim 1, it is characterized in that the magnetic nanoparticle behind the surface modification combines with the coupling of synthetic targeted peptide, be in PBS, targeted peptide and carbodiimide, carry out surperficial coupling with magnetic nanoparticle behind the surface modification and combine, obtain having the specific function magnetic fluid.
4, described according to claim 1, it is characterized in that the synthetic of targeted peptide, is in organic solvent, under catalyst and control uniform temperature, generated through peptide formation by several amino acids, the amino acid kind has glycine, arginine, glutamic acid, lysine and L-leucine or L-citrulling; Organic solvent is oxolane or N, and dinethylformamide, catalyst are the concentrated sulfuric acid, and control peptide chain footing is a 12-15 amino acid, controls amino acid whose kind, proportioning and synthetic technological condition, can obtain the targeted peptide of different specific function and different purposes.
5, the preparation method of claim 1 or 2～4 described a kind of specific function magnetic fluids is characterized in that, the concrete operations step:
First step raw material is prepared
Raw material is FeCl3.6H2O, FeSO4.7H2O, NaOH or NH3.H2O, soluble poly hydroxymethylfurfural, its molecular weight are 15000～23000, synthetic polypeptide, its peptide chain numerical control is built in 15～20, raw materials used be analyze pure.
The preparation of the second step reactant liquor
Prepare molysite mixed aqueous solution and NaOH or the ammonia spirit of Fe3+ and Fe2+ respectively, the concentration of Fe3+ ion is 0.2～0.5mol/L in the molysite mixed aqueous solution, the concentration of Fe2+ is 0.1～0.3mol/L, and the concentration of NaOH or ammonia spirit is 0.1～0.5mol/L; The concentration of targeted peptide is 0.2～2.5mg/ml.
The magnetic fluid preparation of the 3rd step magnetic core and finishing
With the iron salt solutions that contains Fe3+, Fe2+ ion of metering with by the soluble poly 5 hydroxymethyl furfural of 3～5 parts of weight and the aqueous solution that redistilled water was mixed with of 40 parts of weight, join in the supergravity reactor (RPB), 70～80 ℃ of control temperature and adjustment rotating speed reach the hypergravity that can produce centrifugal acceleration 300～900g.In 1.5～2.5 hours, drip the NaOH or the ammonia spirit of metering, and continue to keep super gravity field 1 hour.Stop the rotation, in resulting black magnetic suspension, regulate the pH value to 7 of this suspension with watery hydrochloric acid, sediment in the centrifugal removal solution, then, sample is removed free poly-5 hydroxymethyl furfural and other non magnetic compositions of not effect through redistilled water dialysis 2～3 days, the solution of gained uses redistilled water and phosphate buffer solution PBS (pH=7.40) to clean respectively, gets product (through the magnetic fluid of organic polymer finishing) after concentrating.
The preparation of the 5th step specific function magnetic fluid
In PBS, compound concentration is targeted peptide 0.5～2.0ml of 0.5～2.0mg/ml, adding concentration is carbodiimide solution 0.5～2.0ml of 0.5～2.0mg/ml, add magnetic fluid 100～200ml that the 4th step made again, lucifuge is with frequency oscillation 20～26h of 200～400r/min under 15～25 ℃ the temperature, PBS cleans, and obtains having the specific function magnetic fluid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559984B (en) * | 2009-05-27 | 2010-09-01 | 山东大学 | Preparation method of superparamagnetic Fe3O4 nano-particles |
| CN102344170A (en) * | 2011-08-28 | 2012-02-08 | 山东理工大学 | Method for preparing water-based Fe3O4 magnetic fluid by using polyamide-amine dendrimer as template |
| CN105469920A (en) * | 2015-11-27 | 2016-04-06 | 中北大学 | Supergravity preparation method of cysteine modified magnetic nano-material |
| CN105489330A (en) * | 2015-11-27 | 2016-04-13 | 中北大学 | Supergravity preparation method for chitosan-based magnetic nanomaterial |
| CN111303872A (en) * | 2018-12-12 | 2020-06-19 | 北京化工大学 | Hypergravity preparation method of lead sulfide quantum dots |
-
2008
- 2008-08-06 CN CNA2008100212353A patent/CN101409125A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559984B (en) * | 2009-05-27 | 2010-09-01 | 山东大学 | Preparation method of superparamagnetic Fe3O4 nano-particles |
| CN102344170A (en) * | 2011-08-28 | 2012-02-08 | 山东理工大学 | Method for preparing water-based Fe3O4 magnetic fluid by using polyamide-amine dendrimer as template |
| CN105469920A (en) * | 2015-11-27 | 2016-04-06 | 中北大学 | Supergravity preparation method of cysteine modified magnetic nano-material |
| CN105489330A (en) * | 2015-11-27 | 2016-04-13 | 中北大学 | Supergravity preparation method for chitosan-based magnetic nanomaterial |
| CN105489330B (en) * | 2015-11-27 | 2017-10-31 | 中北大学 | A kind of hypergravity preparation method of chitosan-based magnetic Nano material |
| CN105469920B (en) * | 2015-11-27 | 2017-12-19 | 中北大学 | A kind of hypergravity preparation method of the magnetic Nano material of cysteine modified |
| CN111303872A (en) * | 2018-12-12 | 2020-06-19 | 北京化工大学 | Hypergravity preparation method of lead sulfide quantum dots |
| CN111303872B (en) * | 2018-12-12 | 2021-06-01 | 北京化工大学 | Hypergravity preparation method of lead sulfide quantum dots |
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Open date: 20090415 |