CN101178961A - water soluble magnetic nanometer crystal with high dissolvability and method of producing the same - Google Patents
water soluble magnetic nanometer crystal with high dissolvability and method of producing the same Download PDFInfo
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Abstract
The invention belongs to the technical fields of material chemistry, nano science and catalytic chemistry as well as medical field and in particular relates to applying a 'one pot' synthesis to prepare magnetic nano crystalline with a high solubility and a high crystallinity in neutral water and a preparation method thereof. The technique of the invention is characterized by applying solvent with a high boiling point, catalytic function, reducing function and polymerization function to carry out thermal decomposition for organometallic precursors or metal inorganic salt compound, so as to form magnetic nano crystalline, realize the modification in situ of water-soluble polymer on the surface of the nano crystalline and obtain water-soluble nano crystalline with a high solubility at the same time. The crystalline is mainly characterized in that: the crystalline can be dissolved in neutral water (PH=6-8); the formed solution keeps stability for a long time; the main inorganic elements include iron, cobalt, nickel, manganeses and oxide thereof; the crystalline is in a ball shape or in a petal shape; the shape and size control is realized by controlling the concentration and heating-up time for the precursors of the magnetic nano crystalline-the organic precursors or the inorganic salt.
Description
Technical field
The technical field of the invention is materials chemistry, nano science, catalytic chemistry and field of medicaments thereof, particularly utilizes " one pot " method to prepare high-crystallinity magnetic nano crystal that has high-dissolvability in neutral water and preparation method thereof.
Background technology
Magnetic nano crystal is widely used in fields such as magnetic fluid, catalyst, biology (medicine) field, data storing.Wherein in the application of biological field, comprising: magnetic resonance imaging reinforcing agent (MRI), cell separation are separated with mark, DNA, the detection of tumour and treatment, target medicine carrier etc. have caused the very big concern of various countries scientist and high-tech enterprise.
At present, the manufacture method of magnetic nanometer particles mainly contains ball-milling method, biological synthesis process, ultrasonic decomposition method, micella (reverse micelle) method, coprecipitation and thermal decomposition method.It is too wide that but the product cut size that ball-milling method makes distributes; Bioanalysis is too loaded down with trivial details; Ultrasonic decomposition method, micella (reverse micelle) method, the pH value that the coprecipitation particle size distribution is wide, degree of crystallinity is low, particulate character too relies on system, and magnetic responsiveness relatively a little less than.Thermolysis process is the fresh approach of the magnetic nano crystal of the synthetic at present narrow distribution of particle diameter, high-crystallinity.The Alisators of the U.S. (J.Am.Chem.Soc., 1999,121,11595～11596), Sun (J.Am.Chem.Soc., 2002,124,8204～8205), Peng (Chem.Mater., 2004,16,3931～3935) and the Hyeon of Korea S (J.Am.Chem.Soc., 2001,123,12798～12801) group utilizes the method for thermal decomposition to prepare high-quality magnetic nano crystal respectively.But they prepare magnetic nano crystal is oil-soluble, can not directly be used to biomedicine field at the yardstick of single particulate.Therefore, complicated water soluble ligand exchange process is that above-mentioned oil-soluble magnetic nano crystal is converted into water-solubility nanometer crystal, and then realizes the only way which must be passed of its biologic applications.This is to practical application, and the cost of the product of Ti Gaoing has not only increased the difficulty of preparation process simultaneously.
Recently, in enclose the brilliant seminar far away of academy of sciences's chemistry institute and developed above-mentioned thermolysis process, by adopting intensive polar solvent as reaction heat transfer medium and ligand solvent, " one pot " method prepared in reaction technology of successfully having set up the water-soluble magnetic nanocrystal (sees Chem.Mater. for details, 2004,16,1391～1393, the patent No. is 03136273.7,03136275.3).Wherein adopt the magnetic nano crystal of 03136275.3 patented method preparation, can only be dissolved in usually in the acidity or alkaline aqueous solution of certain pH value, the solubility in neutral water is very low.Adopt the described method of 03136273.7 patent can obtain in neutral water, having the biological compatibility magnetic nano crystal of high-dissolvability fully, but the polymer that is used for the modified magnetic nanocrystal surface that the is adopted good water-soluble and biocompatibility macromolecule that is prior polymerization.Different with this patented method is, the water-soluble polymer that the present invention adopts is when magnetic nano crystal forms, form in the nanocrystal surface original position, be characterized in and introduce different types of water-soluble free radical monomer simultaneously by the method for copolymerization, realize the diversity of magnetic nano crystal surface water dissolubility modification by the method for copolymerization.
Poly N-vinyl pyrrolidone (PVP) and monomer N-vinyl pyrrolidones (NVP) thereof not only have excellent solubility property, chemical stability, film forming, hypotoxicity, physiology inertia, cohere ability and the effect of protection glue, and can and many inorganic compounds and organic chemistry material carry out combination.The application of PVP in biomedicine field is the important embodiment of its vitality, and PVP has good physiology intermiscibility, do not participate in human body metabolism, organ is not formed tangible stimulation.The magnetic nano crystal that obtains by the present invention, its finishing has the poly N-vinyl pyrrolidone of original position formation or the copolymer of N-vinyl pyrrolidone and the formation of other free radical monomer, this modification provides extraordinary water-soluble for magnetic nano crystal on the one hand, also provides excellent biological compatibility for above-mentioned magnetic nano crystal simultaneously.
N-vinyl pyrrolidone (NVP) is high polarity and higher boiling point (214～215 ℃ of boiling points) free radical monomer, and this monomer as easy as rolling off a log generation heat polymerization under heated condition generates polyvinylpyrrolidone (PVP).Therefore thermal polymerization is regarded as a kind of polymerization methods of passiveness usually by everybody, in the preservation of monomer, radical polymerization, everybody often will be by the thermal polymerization of various means prevention monomers.And we exactly utilize this special polymerization methods, utilize the thermal polymerization of high boiling point monomers, when magnetic nano crystal forms, realize that water-soluble polymer is at its surperficial in-situ modification, thereby prepare the magnetic nano crystal that is dissolved in neutral water by single step reaction, this technology of preparing is not appeared in the newspapers in document and domestic and international patent.
Summary of the invention
One of purpose of the present invention mainly provides and can be dissolved in neutral water, superparamagnetism high-dissolvability, high-crystallinity, paramagnetism or ferromagnetic magnetic nano crystal, this magnetic nano crystal can have higher solubility in neutral water, and magnetic nano crystal has good biocompatibility.
It is extraordinary water-soluble that two of purpose of the present invention is to provide magnetic nano crystal to show in the neutral water of pH=6～8, and its solubility can be up to 50g/L.
Three of purpose of the present invention is to provide the shape of product of magnetic nano crystal to be mainly spherical or petal.
Four of purpose of the present invention mainly provides the preparation method of superparamagnetism, paramagnetism or the ferromagnetism magnetic nano crystal that can have high-dissolvability, high-crystallinity in neutral water, this preparation method is the extension of the existing patented technology of the applicant, is characterized in that course of reaction is a single step reaction.Reaction dissolvent N-vinyl pyrrolidone promptly serves as reaction medium, serves as the surface coordination solvent again, also can form polymer-modified layer at magnetic nano crystal surface in situ polymerization reaction take place simultaneously.
Five of purpose of the present invention is to provide the shape of magnetic nano crystal to regulate and control by reaction condition.
Six of purpose of the present invention is that it is in the magnetic nano crystal forming process that the water-soluble and biocompatibility macromolecule of magnetic nano crystal finishing is provided, and forms in the nanocrystal surface original position by thermal polymerization.
Seven of purpose of the present invention is to provide the water-soluble and biocompatibility macromolecule of magnetic nano crystal finishing, and it is formed with structure can realize regulation and control by the ratio that adds water-soluble free radical monomer and N-vinyl pyrrolidone.
Eight of purpose of the present invention is to provide the water-soluble and biocompatibility macromolecule of magnetic nano crystal finishing, and its content can be regulated and control by reaction condition.
Nine of purpose of the present invention is the size of magnetic nano crystal to be provided and to distribute to regulate and control by reaction condition.
The present invention reacts by " one pot " method, with the N-vinyl pyrrolidone as high bp polar solvent and polymerization single polymerization monomer, by pyrolysis organometallic precursor or metal inorganic salt compound, when magnetic nano crystal forms, realize the water-soluble and biocompatibility macromolecule of its finishing, obtain having the water-soluble magnetic nanocrystal of high-dissolvability.Magnetic nano crystal mainly comprises iron, cobalt, nickel, manganese and oxide crystal thereof, and its size and pattern can obtain regulation and control by concentration, heating time, the temperature programming process of organic precursor or inorganic salts.
The water soluble magnetic nanometer crystal of high-dissolvability of the present invention is sphere or petal shape, have superparamagnetism, paramagnetism or ferromagnetism, and the polymer that the surface of magnetic nano crystal is modified is the controlled water-soluble and biocompatibility macromolecule of molecular weight, and described weight percentage water-soluble and biocompatibility macromolecule is 3%～45%.
Described magnetic nano crystal is almost monocrystalline.
A kind of in described magnetic nano crystal chosen from Fe, cobalt, nickel, manganese or their oxide crystal.
The particle diameter of described magnetic nano crystal is 3～100 nanometers.
The finishing coat of described magnetic nano crystal is in the presence of N-vinyl pyrrolidone, forms by the original position Raolical polymerizable.It is formed except poly N-vinyl pyrrolidone, also comprises the N-vinyl pyrrolidone and contains the copolymer of carboxyl or carboxylic monomer or the copolymer of N-vinyl pyrrolidone and N-isopropyl third rare acid amides.Above-mentioned copolymer decorative layer contains carboxyl, hydroxyl radical free radical monomer or N-isopropyl third rare acid amides and realizes by introducing before reaction, and wherein containing the molar content that carboxyl, hydroxyl radical free radical monomer or N-isopropyl third rare acid amides account for whole polymerisable monomer is 0%～50%.
Described water-soluble and biocompatibility macromolecule is poly N-vinyl pyrrolidone, N-vinyl pyrrolidone and contains carboxyl or the copolymer of the copolymer of carboxylic monomer or N-vinyl pyrrolidone and N-isopropyl third rare acid amides, wherein, above-mentioned copolymer when copolymerization the N-vinyl pyrrolidone with contain carboxyl or carboxylic monomer, or the molar ratio of N-vinyl pyrrolidone and N-isopropyl third rare acid amides is 50%～100%.
Describedly contain carboxyl or carboxylic monomer is acrylic acid, methacrylic acid, methacrylic acid-beta-hydroxy ethyl ester or acrylic acid-B-hydroxyl ethyl ester.
The preparation method of the water soluble magnetic nanometer crystal of high-dissolvability involved in the present invention, its course of reaction are single step reaction, and this method may further comprise the steps:
(1) organo-metallic compound presoma or inorganic metal salt compound are dissolved in form solution in the intensive polar solvent, wherein intensive polar solvent is made up of polymerisable free radical monomer, comprising: N-vinyl pyrrolidone, N-vinyl pyrrolidone and contain carboxyl or mixed solvent that carboxylic monomer forms or be dissolved with the N-vinyl pyrrolidone of N-isopropyl third rare acid amides; Wherein, containing carboxyl or the carboxylic monomer molar content in mixed solvent is 0%～50%, preferred 5%～20%, and the molar content of N-isopropyl third rare acid amides in the N-vinyl pyrrolidone is 0%～50%, preferred 5%～30%; Organo-metallic compound presoma in the solution or inorganic metal salt compound concentration are 0.001mol/L～2mol/L, and preferred concentration is 0.01～0.5mol/L;
(2) solution of step (1) is put into reaction vessel, feed the oxygen in the inert gas eliminating reaction system, the heating reaction system, reaction temperature is controlled between 140～300 ℃, preferred 160～250 ℃; Reaction time is 0.1～20 hour, preferred 0.5～10 hour; When magnetic nano crystal forms, form water-soluble and biocompatibility macromolecule in the nanocrystal surface original position;
(3) reaction solution with step (2) is cooled to room temperature, the adding volume can be organic solvent (methyl alcohol, ethanol, acetone, ether etc. or their any mixture) precipitation of 1～100 times of reaction system, obtain magnetic nanometer particles by magnetic separation or centrifugation again, pass through repeatedly washing precipitate of organic solvent (methyl alcohol, ethanol, acetone, ether etc. or their any mixture) then, magnetic separation and centrifugation just obtain the water soluble magnetic nanometer crystal of high-crystallinity, narrow dispersion, strong magnetic response.
Described organo-metallic compound presoma is praseodynium iron, diacetyl acetone iron, iron pentacarbonyl, praseodynium nickel, diacetyl acetone nickel, four carbon back nickel, praseodynium cobalt, diacetyl acetone cobalt, eight carbon backs, two cobalts, praseodynium manganese, diacetyl acetone manganese or cyclopentadiene tricarbonyl manganese etc.
Described inorganic metal salt compound is anhydrous ferric trichloride, anhydrous ferrous chloride, four iron chloride hexahydrate, Iron(III) chloride hexahydrate, ferric oxalate, ferrous sulfate, anhydrous chlorides of rase nickel, Nickel dichloride hexahydrate, nickel oxalate, citric acid nickel, nickel acetate, cobalt chloride, cobalt acetate, cobalt chloride hexahydrate, cobalt oxalate, citric acid cobalt, capric acid cobalt, manganese chloride, manganese acetate, manganese oxalate, manganese citrate or manganese gluconate etc.
By controlling the different heating reaction time, obtain spherical magnetic nano crystal in initial reaction stage, just obtain the petal-shaped magnetic nano crystal in the reaction later stage.The solubility of this magnetic nano crystal in water can reach 10～50g/L, and pH value of aqueous solution is between 6～8; Weight percentage water-soluble and biocompatibility macromolecule can reach 3%～45%; The saturation magnetization of magnetic nano crystal can reach 10～70emu/g.
By the hot copolymerization of N-vinyl pyrrolidone and N-isopropyl third rare acid amides, obtain the magnetic nano crystal of the water-soluble and biocompatibility macromolecule of finishing, the neutral aqueous solution of magnetic nano crystal has temperature sensitivity.
Can the catalysis relevant organic reaction of nickel in the water soluble magnetic nanometer crystal of high-dissolvability of the present invention, cobalt and oxide magnetic nanocrystal thereof, and can reuse, to reuse number of times and be no less than 6 times, catalytic efficiency is not less than 95%.
The water soluble magnetic nanometer crystal of high-dissolvability of the present invention obtains the magnetic PVP-I with Iod R in ethanol, have directed sterilizing function, is expected to be used for the interior sterilization of animal body.
The water soluble magnetic nanometer crystal of high-dissolvability of the present invention can be dissolved in pH=6～8 neutral waters.
The initiation material of the preparation magnetic nano crystal that the present invention adopts is cheap and easy to get, and technology path is easy, promptly can realize the preparation of above-mentioned nanocrystal a step by " one pot " reaction, resultant nanocrystal narrow particle size distribution and size adjustable.
Description of drawings
Fig. 1. the transmission electron microscope photo of the embodiment of the invention 1 gained sample.
Fig. 2. the electronic diffraction photo of the embodiment of the invention 1 gained sample.
Fig. 3. the magnetic hysteresis loop of the embodiment of the invention 1 gained sample.
Fig. 4. the transmission electron microscope photo of the embodiment of the invention 3 gained samples.
Fig. 5. the high-resolution-ration transmission electric-lens photo of the embodiment of the invention 3 gained samples.
Fig. 6. the electronic diffraction photo of the embodiment of the invention 3 gained samples.
Fig. 7. the transmission electron microscope photo of the embodiment of the invention 6 gained samples.
Fig. 8. the electronic diffraction photo of the embodiment of the invention 6 gained samples.
Fig. 9. the transmission electron microscope photo of 2 hours gained samples of the embodiment of the invention 7 reactions.
Figure 10. the transmission electron microscope photo of 4 hours gained samples of the embodiment of the invention 7 reactions.
Figure 11. the embodiment of the invention 7 gained sample transmission electron microscope photos.
Figure 12. the electronic diffraction photo of the embodiment of the invention 7 gained samples.
Figure 13. the embodiment of the invention 14 products obtained therefroms are in the photo in the certain magnetic field at normal temperatures.
Figure 14. the embodiment of the invention 14 gained samples are in the photo in the certain magnetic field under being higher than 32 ℃ of temperature.
Reference numeral
1. magnet
Embodiment
The 7.2345g ferric acetyl acetonade is dissolved in the 500mL N-vinyl pyrrolidone forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, fed the nitrogen deoxygenation then 30～90 minutes, heating was reacted in 0.5～3 hour under 190～210 ℃, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Then reactant liquor is cooled to room temperature,, obtains having the magnetic-particle of strong magnetic response by magnetic separation or centrifugation the mixed solvent precipitation of reactant liquor with ethanol and ether.Repeatedly wash by ethanol and ether mixed solvent, magnetic separation and centrifugation obtain the ferroferric oxide magnetic nano crystal of high-crystallinity, narrow dispersion, strong magnetic response again.To obtain product and be dissolved in the ultra-pure water, and utilize transmission electron microscope (TEM) to characterize, accompanying drawing 1 is the transmission electron microscope photo of this magnetic nano crystal, magnetic nano crystal is shaped as sphere, add up as can be known that particle diameter is 5.5 nanometers, particle diameter relative standard deviation (Cv) is 15%, shows monodispersity preferably.Utilize shown in the electronic diffraction accompanying drawing 2, show that this magnetic nano crystal has higher degree of crystallinity.Accompanying drawing 3 is the magnetic hysteresis loop of this magnetic nano crystal, and the saturation magnetization of crystal is 64.2emu/g, has superparamagnetism.Measuring the saturation solubility of magnetic nano crystal in ultra-pure water by weight method is 28g/L.
Embodiment 2
Take by weighing 4.9258g iron pentacarbonyl (Fe (CO)
5) be dissolved in the 500mL N-vinyl pyrrolidone and form solution, above-mentioned solution is put into the there-necked flask of 1000mL, fed the nitrogen deoxygenation then 30～90 minutes, heated 0.5～2 hour down at 190～210 ℃, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Then reactant liquor is cooled to room temperature, reactant liquor is precipitated with methanol solvate, separate, obtain black precipitate through centrifugal or magnetic.To precipitate again with methanol solvate dissolving, precipitation centrifugally, oven dry obtains the ferroferric oxide magnetic nano crystal of high-crystallinity, narrow dispersion, strong magnetic response.This magnetic nano crystal can be fine be dissolved in (pH=6～8) in the neutral water, thereby obtain neutral magnetic fluid, have superparamagnetism.Shape of particle is spherical, and its particle diameter is between 5～8 nanometers.
Embodiment 3
Taking by weighing the 4.8862g anhydrous ferric chloride is dissolved in the 500mL N-vinyl pyrrolidone and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, fed the nitrogen deoxygenation then 30～90 minutes, heated 1～4 hour down at 190～210 ℃, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Then reactant liquor is cooled off room temperature, processing method such as embodiment 1.Be dissolved in (pH=6～8) in the neutral water with getting black precipitate after the drying, obtain the neutral magnetic fluid of strong magnetic response, have superparamagnetism.Shape of particle is spherical magnetic nano crystal, and its particle diameter is between 10～14 nanometers.
Embodiment 4
Taking by weighing the 7.3256g ferric acetyl acetonade is dissolved in the 500mL N-vinyl pyrrolidone and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, fed the nitrogen deoxygenation then 30～90 minutes, heated 3～7 hours down at 190～210 ℃, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Then reactant liquor is cooled to room temperature, processing method such as embodiment 1.Precipitation is dissolved in (pH=6～8) in the neutral water, obtains the neutral magnetic fluid of strong magnetic response, have superparamagnetism.Utilizing transmission electron microscope (TEM) to characterize, is 22.7 nanometers as the average diameter of accompanying drawing 4 nanocrystals, and nanocrystal shape is a petal-shaped; The high resolution electron microscopy photo as shown in Figure 5, whole nanometer petal is a monocrystalline.Electronic diffraction shows that the nanometer petal of gained has very high-crystallinity as shown in Figure 6.The saturation solubility that utilizes weight method to measure magnetic nano crystal is 32g/L.
Embodiment 5
Taking by weighing 9.5133g six Ferric Chloride Hydrateds is dissolved in the 500mL N-vinyl pyrrolidone and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, logical then nitrogen deoxygenation 30～90 minutes, heated 1～4 hour down at 190～215 ℃, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Then reactant liquor is cooled to room temperature, processing method such as embodiment 1.The particle of the black powder shape that obtains after the processing can well dissolve (pH=6～8) in the neutral water, makes to have the neutral magnetic fluid of higher magnetic response, has superparamagnetism.Shape of particle is spherical magnetic nano crystal, and its particle diameter is between 9～13 nanometers.Utilize weight method to measure the saturation solubility of this magnetic nano crystal in ultra-pure water and be 30g/L.
Embodiment 6
Taking by weighing nickel acetylacetonate 5.2598g is dissolved in the 500mL N-vinyl pyrrolidone and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, logical then nitrogen deoxygenation 30～90 minutes, heated 1～3 hour down at 190～210 ℃, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Then reactant liquor is cooled to room temperature, processing method such as embodiment 1.The pulverous particle that obtains after the processing can well dissolve (pH=6～8) in the neutral water, makes to have the neutral magnetic fluid of certain magnetic response, has ferromagnetism.Utilize transmission electron microscope that the particle that obtains is characterized, as shown in Figure 7, the particle size distribution of nanocrystal is narrower as can be seen, is 55 nanometers through the statistics particle diameter.This crystal is carried out electronic diffraction characterize as shown in Figure 8, the electronic diffraction picture shows that the diffraction pattern of crystal is made up of the point of many symmetries, shows that crystal has higher degree of crystallinity.
Embodiment 7
Taking by weighing the 14.7598g ferric acetyl acetonade is dissolved in the 500mL N-vinyl pyrrolidone and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, fed the nitrogen deoxygenation then 30～90 minutes, reaction system is 190～210 ℃ of heating down, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Respectively in reaction 2 hours and sampling in 4 hours, through processing method as example 1.Two kinds of precipitations are dissolved in (pH=6～8) in the neutral water respectively, all can obtain the neutral magnetic fluid of strong magnetic response, all have superparamagnetism.The sample of handling well is characterized by transmission electron microscope, and the gained sample that accompanying drawing 9 and accompanying drawing 10 are respectively reaction 2 hours and 4 hours gets transmission electron microscope photo, and adding up as can be known to particle diameter, the particle diameter of two samples is respectively 12.2 nanometers and 14 nanometers.Simultaneously also two kinds of products that obtain are carried out thermogravimetic analysis (TGA) (TGA) respectively, the surperficial macromolecule weight content of two products is respectively 6.8% and 10%, and this shows that the technology of the present invention can control the size and the surperficial high molecular content of magnetic nano crystal by controlling reaction time.
Embodiment 8
Taking by weighing acetylacetone cobalt 5.7815g is dissolved in the 500mL N-vinyl pyrrolidone and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, fed the nitrogen deoxygenation then 30～90 minutes, heated 2～6 hours down at 190～220 ℃, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Then reactant liquor is cooled to room temperature, processing method such as embodiment 1.The product that obtains is dissolved into (pH=6～8) in the neutral water, obtains having the neutral magnetic fluid of certain magnetic response, have ferromagnetism.Utilize transmission electron microscope that the crystal that obtains is characterized, as shown in figure 11, the particle size distribution of nanocrystal is narrower as can be seen, is 46 nanometers through the statistics particle diameter.Crystal is carried out electronic diffraction characterize as shown in figure 12, the electronic diffraction picture shows that the diffraction pattern of crystal is made up of the point of many symmetries, shows that crystal has higher degree of crystallinity.
Embodiment 9
Taking by weighing eight carbon backs, two cobalt 8.5667g is dissolved in the 500mL N-vinyl pyrrolidone and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, fed the nitrogen deoxygenation then 30～90 minutes, heated 1～5 hour down at 190～220 ℃, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Then reactant liquor is cooled to room temperature, processing method such as embodiment 1.Obtain the magnetic nano crystal of celadon after the processing, this magnetic nano crystal can be good at being dissolved in (pH=6～8) in the neutral water, thereby obtains neutral magnetic fluid, has paramagnetism.Its grain size is between 25～35 nanometers.
Embodiment 10
Taking by weighing cobalt chloride 3.3258g is dissolved in the 500mL N-vinyl pyrrolidone and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, logical then nitrogen deoxygenation 30～90 minutes, heated 1～5 hour down at 210 ℃, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Then reactant liquor is cooled to room temperature, processing method such as embodiment 1.Obtain the magnetic nano crystal of celadon after the processing, this nanocrystal can be good at being dissolved in (pH=6～8) in the neutral water, obtains having the neutral magnetic fluid of certain magnetic response, has paramagnetism.Grain size is between 10～45 nanometers.The saturation solubility that utilizes weight method to measure magnetic nano crystal is 25g/L.
Embodiment 11
Taking by weighing the 7.5124g ferric acetyl acetonade is dissolved in 500mL N-vinyl pyrrolidone and the acrylic acid mixed solvent and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, wherein N-vinyl pyrrolidone and acrylic acid volume ratio are 9: 1, fed nitrogen then 30～90 minutes, reaction system was 180～210 ℃ of reactions 1～6 hour, when magnetic nano crystal forms, form water-soluble and biocompatibility N-vinyl pyrrolidone and acrylic acid copolymer macromolecule in the nanocrystal surface original position.Then the reaction system cool to room temperature, processing method such as example 1.The passable nanocrystal that obtains black after the processing.This nanocrystal can be good at being dissolved in (pH=6～8) in the neutral water, obtains the neutral magnetic fluid of the higher magnetic response of tool, has superparamagnetism.Particle diameter is between 8～18 nanometers, and titration is measured carboxyl-content at 1～3mmol/g.
Embodiment 12
Taking by weighing the 7.5124g ferric acetyl acetonade is dissolved in 500mL N-vinyl pyrrolidone and the methacrylic acid-beta-hydroxy ethyl ester mixed solvent and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, wherein the volume ratio of N-vinyl pyrrolidone and methacrylic acid-beta-hydroxy ethyl ester is 8: 2, fed the nitrogen deoxygenation then 30～90 minutes, reaction system was 180～210 ℃ of reactions 1～6 hour, when magnetic nano crystal forms, form water-soluble and biocompatibility N-vinyl pyrrolidone and methacrylic acid-beta-hydroxy ethyl ester copolymerized macromolecule in the nanocrystal surface original position.Then the reaction system cool to room temperature, processing method such as example 1.The passable magnetic nano crystal that obtains black after the processing.This nanocrystal can be good at being dissolved in (pH=6～8) in the neutral water, obtains the neutral magnetic fluid of the higher magnetic response of tool, has superparamagnetism.Particle diameter is between 7～20 nanometers, and hydroxy radical content is at 0.5～5mmol/g.
Embodiment 13
Take by weighing the product 0.0725g of embodiment 8 preparations, add in the static oxygen uptake reaction unit of a band 10mL round-bottomed flask and reflux condensation mode, add a certain amount of paraxylene then.Electromagnetic agitation, oil bath is heated to reaction temperature, and the time recording oxygen absorbed is to follow the tracks of the roughly degree of reaction.Product is carried out efficient liquid phase chromatographic analysis, thus the conversion ratio of assaying reaction.The result shows: the product of embodiment 8 preparations has showed good activity and selectivity.Utilize magnetic to separate more than 6 times, catalytic activity is constant substantially, reacts 5～6 hours, and the yield of p-methylbenzoic acid reaches more than 45%.
Embodiment 14
Taking by weighing the 7.8546g ferric acetyl acetonade is dissolved in 500mL and is dissolved in the N-vinyl pyrrolidone solution of N-isopropyl third rare acid amides (NIPAM) and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, wherein NIPAM and N-vinyl pyrrolidone mol ratio are 0.02～0.5, logical then nitrogen deoxygenation 30～90 minutes, reaction system was 170～210 ℃ of reactions 1～6 hour, when magnetic nano crystal forms, form water-soluble and biocompatibility N-vinyl pyrrolidone and N-isopropyl third rare acid amides copolymerized macromolecule in the nanocrystal surface original position.Then the reaction system cool to room temperature, processing method such as example 1.The passable precipitation that obtains black after the processing.The product of handling well is dissolved into (pH=6～8) in the neutral water, and magnetic fluid is solution state at normal temperatures, and after being elevated to more than 32 ℃, fluid becomes suspension, and black product is separated out from solution under the effect in magnetic field, thereby shows stronger temperature sensitive property.The particle diameter of particle is between 5～25 nanometers.Accompanying drawing 13 is a product fluid photo at normal temperatures, and accompanying drawing 14 is that fluid is at the photo that is in certain magnetic field more than 32 ℃.Product has superparamagnetism.
Embodiment 15
The product powder 0.089g that gets among the embodiment 1 is dissolved in the 100mL ethanol, add a certain amount of elemental iodine, above-mentioned solution is put in the 250mL flask, normal-temperature reaction is 10～20 hours under electromagnetic agitation, after adding ether, acetone and other organic solvent centrifugation then, after the vacuumize, be dissolved into again (pH=6～8) in the neutral water, be prepared into the magnetic Betagen Solution.This solution has stronger magnetic responsiveness, is expected to use target sterilization in animal body.
Embodiment 16
Taking by weighing manganese acetylacetonate 8.5874g is dissolved in the 500mL N-vinyl pyrrolidone and forms solution, above-mentioned solution is put into the there-necked flask of 1000mL, logical then nitrogen deoxygenation 30～90 minutes, heated 1～5 hour down at 190～220 ℃, when magnetic nano crystal forms, form water-soluble and biocompatibility poly N-vinyl pyrrolidone macromolecule in the nanocrystal surface original position.Be cooled to room temperature then, processing method such as embodiment 1.Obtain magnetic oxygenated manganese nanocrystal after the processing, this nanocrystal can be good at being dissolved in (pH=6～8) in the neutral water, obtains having the neutral magnetic fluid of certain magnetic response, has superparamagnetism.Grain size is between 25～35 nanometers.
Claims (11)
1. the water soluble magnetic nanometer crystal of a high-dissolvability, it is characterized in that: described magnetic nano crystal is sphere or petal shape, have superparamagnetism, paramagnetism or ferromagnetism, and the polymer that the surface of magnetic nano crystal is modified is the controlled water-soluble and biocompatibility macromolecule of molecular weight.
2. magnetic nano crystal according to claim 1 is characterized in that: described weight percentage water-soluble and biocompatibility macromolecule is 3%～45%.
3. magnetic nano crystal according to claim 1, it is characterized in that: the solubility of described magnetic nano crystal in water is 10～50g/L, pH value of aqueous solution is between 6～8, and the saturation magnetization of resulting magnetic nano crystal is 10～70emu/g.
4. according to claim 1 or 3 described magnetic nano crystals, it is characterized in that: the particle diameter of described magnetic nano crystal is 3～100 nanometers, a kind of in chosen from Fe, cobalt, nickel, manganese or their oxide crystal.
5. magnetic nano crystal according to claim 1 and 2, it is characterized in that: described water-soluble and biocompatibility macromolecule is poly N-vinyl pyrrolidone, N-vinyl pyrrolidone and contains carboxyl or the copolymer of the copolymer of carboxylic monomer or N-vinyl pyrrolidone and N-isopropyl third rare acid amides, wherein, above-mentioned copolymer when copolymerization the N-vinyl pyrrolidone with contain carboxyl or carboxylic monomer, or the molar ratio of N-vinyl pyrrolidone and N-isopropyl third rare acid amides is 50%～100%.
6. magnetic nano crystal according to claim 5 is characterized in that: describedly contain carboxyl or carboxylic monomer is acrylic acid, methacrylic acid, methacrylic acid-beta-hydroxy ethyl ester or senecioate-hydroxyl ethyl ester.
7. the preparation method according to each described magnetic nano crystal of claim 1～6 is characterized in that, course of reaction is that the method for single step reaction may further comprise the steps:
(1) organo-metallic compound presoma or inorganic metal salt compound are dissolved in form solution in the intensive polar solvent, wherein, organo-metallic compound presoma in the solution or inorganic metal salt compound concentration are 0.001mol/L～2mol/L;
(2) solution of step (1) is put into reaction vessel, feed the oxygen in the inert gas eliminating reaction system, the heating reaction system, reaction temperature is controlled between 140～300 ℃, and the reaction time is 0.1～20 hour; When magnetic nano crystal forms, form water-soluble and biocompatibility macromolecule in the nanocrystal surface original position;
(3) reaction solution with step (2) is cooled to room temperature, add the organic solvent deposit magnetic nano crystal, obtain magnetic nanometer particles by magnetic separation or centrifugation again, using the organic solvent washing sediment then, is sphere or petal shape through the water soluble magnetic nanometer crystal that magnetic separates and centrifugation obtains high-dissolvability;
Described intensive polar solvent is made up of polymerisable free radical monomer.
8. method according to claim 7 is characterized in that: described organo-metallic compound presoma is praseodynium iron, diacetyl acetone iron, iron pentacarbonyl, praseodynium nickel, diacetyl acetone nickel, four carbon back nickel, praseodynium cobalt, diacetyl acetone cobalt, eight carbon backs, two cobalts, praseodynium manganese, diacetyl acetone manganese or cyclopentadiene tricarbonyl manganese.
9. method according to claim 7 is characterized in that: described inorganic metal salt compound is anhydrous ferric trichloride, anhydrous ferrous chloride, four iron chloride hexahydrate, Iron(III) chloride hexahydrate, ferric oxalate, ferrous sulfate, anhydrous chlorides of rase nickel, Nickel dichloride hexahydrate, nickel oxalate, citric acid nickel, nickel acetate, cobalt chloride, cobalt acetate, cobalt chloride hexahydrate, cobalt oxalate, citric acid cobalt, capric acid cobalt, manganese chloride, manganese acetate, manganese oxalate, manganese citrate or manganese gluconate.
10. method according to claim 7 is characterized in that: the described intensive polar solvent of being made up of polymerisable free radical monomer is selected from N-vinyl pyrrolidone, N-vinyl pyrrolidone and contains carboxyl or mixed solvent that carboxylic monomer forms or be dissolved with the N-vinyl pyrrolidone of N-isopropyl third rare acid amides; Wherein, containing carboxyl or the carboxylic monomer molar content in mixed solvent is 0%～50%, and the molar content of N-isopropyl third rare acid amides in the N-vinyl pyrrolidone is 0%～50%.
11. method according to claim 10 is characterized in that: described carboxylic monomer is acrylic or methacrylic acid; The monomer of hydroxyl is methacrylic acid-beta-hydroxy ethyl ester or senecioate-hydroxyl ethyl ester.
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