CN101458985A - Preparation for magnetic fluid and chitosan magnetic micro-sphere - Google Patents
Preparation for magnetic fluid and chitosan magnetic micro-sphere Download PDFInfo
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- CN101458985A CN101458985A CNA2007101957890A CN200710195789A CN101458985A CN 101458985 A CN101458985 A CN 101458985A CN A2007101957890 A CNA2007101957890 A CN A2007101957890A CN 200710195789 A CN200710195789 A CN 200710195789A CN 101458985 A CN101458985 A CN 101458985A
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Abstract
The invention provides a preparation method of magnetic fluid, comprising: adding excessive alkaline aqueous solution into the aqueous solution containing ferrous ions and ferric ions; processing precipitation reaction under protective gas, separating the products of precipitation reaction to obtain Fe3O4; adding the Fe3O4 and surface active agent into carrier liquid to be heated, separating to obtain the product of heating process, and obtaining magnetic fluid, wherein the mol ratio of the ferrous ions and the ferric ions in the aqueous solution containing ferrous ions and ferric ions is 1.4-1.8: 1. The invention further provides a preparation method of magnetic chitosan microsphere, adopting the magnetic fluid prepared by the aforementioned method. The magnetic chitosan microsphere containing the inventive magnetic fluid is more suitable to be the carrier of immobilized enzymes.
Description
Technical field
The invention relates to the preparation method of magnetic fluid and the preparation method of kind chitosan magnetic micro-sphere.
Background technology
Shitosan is a kind of nontoxic and have the alkaline polysaccharide of better bioaffinity, and shitosan has been widely used in the immobilised enzymes field.Immobilised enzymes is meant and utilizes physical absorption or chemical bond method that free enzyme is fixed on the carrier with operational stability that improves enzyme and the technology of recycling enzyme repeatedly.The chitin carrier surface itself has positive electricity, zymoprotein had certain suction-operated, add utilize dialdehyde that chitin carrier is carried out surface treatment after, cause the chitin carrier surface to carry a large amount of aldehyde radical activated groups, these aldehyde radical activated groups combine with the amino covalence on zymoprotein surface, thereby obtain immobilised enzymes.Here, the shitosan of handling with glutaraldehyde is that example is as follows with the procedural representation of chitin immobilized enzyme:
Wherein, Carrier represents the chitosan microball carrier, and E represents protease.
Convenient more for the recovery that makes enzyme, chitin carrier can be made the chitosan magnetic micro-sphere carrier.Can be by making chitosan microball contain magnetic metal or metal oxide (as iron-cobalt-nickel and oxide thereof) has magnetic.Because relatively inexpensive and its preparation of nanoparticles technology comparative maturity of ferromagnet is so use ferromagnet to prepare chitosan magnetic micro-sphere usually.For example, Ren Guangzhi, Li Zhenhua and HeBing Lin disclose a kind of preparation method of chitosan magnetic micro-sphere, this method mainly comprises: (1) is the sodium hydroxide solution rapid mixing of 5mol/L with ferrous chloride (0.123mol/L)-liquor ferri trichloridi (0.103mol/L) of 400ml with 160ml concentration, vigorous stirring 10min, obtain the magnetic fluid suspension of oily, preserve with the suspension state; (2) adding is dissolved with the toluene of a certain amount of Span-80 and the mixed solvent of carbon tetrachloride in the 250ml there-necked flask of electric mixing device is housed, add the shitosan acetic acid solution that is mixed with magnetic fluid then, regulate mixing speed, the glutaraldehyde solution for the treatment of adding a certain amount of 25% after water evenly is as crosslinking agent, at 40 ℃ of reaction 60min; (3) after reaction finishes, with magnet microballoon is separated, used distilled water, acetone cyclic washing successively, 60 ℃ of vacuumizes obtain chitosan magnetic micro-sphere.(Ren Guangzhi, Li Zhenhua, HeBing Lin. chitosan magnetic micro-sphere is used for the preparation and the sign of the kinase whose immobilization research of urea I. chitosan magnetic micro-sphere. ion-exchange and absorption, 2000,16 (4): 304-310).Use the chitosan magnetic micro-sphere of the magnetic fluid that this method obtains to be not easy to reclaim, and use the chitosan magnetic micro-sphere of this magnetic fluid to assemble easily, thereby limited the application of chitosan magnetic micro-sphere as fixed enzyme vector.
Summary of the invention
First purpose of the present invention is to exist and be difficult for the shortcoming that reclaims and assemble easily in order to overcome the chitosan magnetic micro-sphere that contains the magnetic fluid that prior art for preparing obtains, and a kind of preparation method of the magnetic fluid that the chitosan magnetic micro-sphere that contains this magnetic fluid is easily reclaimed and be difficult for assembling is provided.
Another object of the present invention provides a kind of preparation method of chitosan magnetic micro-sphere.
The present inventor has carried out careful research to the method for existing preparation chitosan magnetic micro-sphere, and the principal element of finding to influence the chitosan magnetic micro-sphere recyclability is that to contain the magnetic intensity of chitosan magnetic micro-sphere of magnetic fluid relatively poor; The coercive force that influences principal element that chitosan magnetic micro-sphere assembles and be the chitosan magnetic micro-sphere that contains magnetic fluid is too high, thereby causes the gathering of chitosan magnetic micro-sphere.Described coercive force is meant the field strength values when magnet is zero corresponding to magnetic flux density (magnetization), and unit is peace/rice (A/m).
The invention provides a kind of preparation method of magnetic fluid, this method is included in the excessive alkaline aqueous solution of adding in the aqueous solution that contains ferrous ion and ferric ion; Carry out precipitation reaction afterwards under protective gas atmosphere, the precipitation separation product obtains Fe
3O
4With the Fe that obtains
3O
4Join in the carrier fluid with surfactant and to heat, separate the heating product then, obtain magnetic fluid, wherein, in the described aqueous solution that contains ferrous ion and ferric ion, the mol ratio of ferrous ion and ferric ion is 1.4-1.8:1.
The present invention also provides a kind of preparation method of chitosan magnetic micro-sphere, this method comprise with magnetic fluid and shitosan be distributed to water and/or can with the miscible solvent of water in, obtain first suspension; Afterwards first suspension, surfactant and organic solvent are mixed and obtain second suspension; Adding crosslinking agent afterwards in second suspension carries out cross-linking reaction and obtains cross-linking products; Separate cross-linking products then and obtain chitosan magnetic micro-sphere, wherein, described magnetic fluid is the magnetic fluid that obtains by method provided by the invention.
Method provided by the invention is suitably regulated used ferrous ion and ferric ion in the process of preparation magnetic fluid ratio, thereby improved the magnetic intensity of the chitosan magnetic micro-sphere that contains the magnetic fluid for preparing by method provided by the invention, can also reduce the coercive force of this chitosan magnetic micro-sphere, overcome the shortcoming that chitosan magnetic micro-sphere is difficult for recovery and assembles easily, thereby made the chitosan magnetic micro-sphere that obtains be more suitable for being used as the carrier of immobilised enzymes.
Embodiment
The invention provides a kind of preparation method of magnetic fluid, this method is included in the excessive alkaline aqueous solution of adding in the aqueous solution that contains ferrous ion and ferric ion; Carry out precipitation reaction afterwards under protective gas atmosphere, the precipitation separation product obtains Fe
3O
4With the Fe that obtains
3O
4Join in the carrier fluid with surfactant and to heat, separate the heating product then, obtain magnetic fluid, wherein, in the described aqueous solution that contains ferrous ion and ferric ion, the mol ratio of ferrous ion and ferric ion is 1.4-1.8:1.
The present inventor has carried out careful research to existing magnetofluid making method, finds that the mol ratio of ferrous ion and ferric ion directly has influence on the character of the magnetic fluid that obtains when carrying out precipitation reaction; And the inventor finds when the mol ratio of ferrous ion and ferric ion is 1.4-1.8:1 unexpectedly, both can improve the magnetic intensity of the chitosan magnetic micro-sphere that contains the magnetic fluid that this method obtains, can also reduce the coercive force of this chitosan magnetic micro-sphere.
For the magnetic intensity that further improves the chitosan magnetic micro-sphere that contains the magnetic fluid that this method obtains and the coercive force of the chitosan magnetic micro-sphere that reduction obtains, under the preferable case, in the described aqueous solution that contains ferrous ion and ferric ion, the mol ratio of described ferrous ion and ferric ion is 1.4-1.6:1, and the concentration of ferric ion is the 0.2-0.6 mol.
Among the present invention, in order to make Fe
2++ 2Fe
3++ 8OH
-→ Fe
3O
4+ 4H
2It is more thorough that the O reaction is carried out, and under the preferable case, uses excessive alkaline aqueous solution, and the consumption of described alkaline aqueous solution makes in the reaction system, Fe
3+With OH
-Mol ratio be 1:5-8.Described alkaline aqueous solution has no particular limits, and for example, can be selected from the aqueous solution of ammonia, NaOH and potassium hydroxide one or more.
According to the present invention, in the process of preparation magnetic fluid, the consumption of described surfactant and carrier fluid can in very large range change, under the preferable case, with respect to the Fe of 100 weight portions
3O
4, the consumption of described surfactant is the 500-1000 weight portion, the consumption of described carrier fluid is the 1200-1800 weight portion; More preferably, with respect to the Fe of 100 weight portions
3O
4, the consumption of described surfactant is the 600-900 weight portion, the consumption of described carrier fluid is the 1400-1600 weight portion.
Among the present invention, the condition of described precipitation reaction has no particular limits, and for example, the condition of described precipitation reaction comprises that reaction temperature is 60-80 ℃, and the reaction time is 50-80 minute; Under the preferable case, the condition of described precipitation reaction comprises that reaction temperature is 65-70 ℃, and the reaction time is 55-65 minute.Under the preferable case, described precipitation reaction is carried out under protective gas atmosphere, and it is group 0 element gas and/or nitrogen that described protective gas can be selected from described protective gas.
Among the present invention, the condition of described heating has no particular limits, and for example, the condition of described heating comprises that the temperature of heating is 50-70 ℃, and the time of heating is 50-80 minute; Under the preferable case, the condition of described heating comprises that the temperature of heating is 55-65 ℃, and the time of heating is 55-65 minute.
According to the present invention, described surfactant has no particular limits, and for example, described surfactant can be selected from one or more in polyethylene glycol, sorbitan monooleate, oleic acid and the white oil, is preferably sorbitan monooleate.The surfactant that meets above-mentioned requirements can be commercially available, and for example, the Guangzhou becomes to contain the sorbitan monooleate (Span-80) that chemicals Co., Ltd generates, the white oil that Weifang Zhongye Chemical Co., Ltd. produces.
Among the present invention, described carrier fluid is conventionally known to one of skill in the art, and for example, described carrier fluid can be selected from one or more in water, atoleine, toluene and the carbon tetrachloride.The carrier fluid that meets above-mentioned requirements can be commercially available, for example, and the atoleine that the Bei Canghai of Ningbo City profit Co., Ltd produces.
The preparation method of chitosan magnetic micro-sphere provided by the invention comprise with magnetic fluid and shitosan be distributed to water and/or can with the miscible solvent of water in, obtain first suspension; Afterwards first suspension, surfactant and organic solvent are mixed and obtain second suspension; Adding crosslinking agent afterwards in second suspension carries out cross-linking reaction and obtains cross-linking products; Separate cross-linking products then and obtain chitosan magnetic micro-sphere, wherein, described magnetic fluid is to obtain magnetic fluid by method provided by the invention.
According to the present invention, described can be conventionally known to one of skill in the art with the miscible solvent of water, for example, describedly can be preferably acetate and/or ethanol with the miscible solvent of water.
Described surfactant is conventionally known to one of skill in the art, for example, described surfactant can be selected from one or more in polyethylene glycol, sorbitan monooleate oleic acid and the white oil, be preferably sorbitan monooleate, the surfactant that meets above-mentioned requirements can be commercially available, for example, the Guangzhou becomes to contain the sorbitan monooleate (Span-80) that chemicals Co., Ltd generates.
Described organic solvent is conventionally known to one of skill in the art, and for example, described organic solvent can be selected from one or more in atoleine, toluene and the carbon tetrachloride.
Among the present invention, described crosslinking agent has no particular limits, but under the preferable case, described crosslinking agent can be selected from one or more in MDA, butanedial, glutaraldehyde and the hexandial, more preferably glutaraldehyde and/or butanedial.
According to the present invention, described shitosan, water and/or can in very large range change with the consumption of miscible solvent, surfactant and the crosslinking agent of water; Under the preferable case, with respect to the magnetic fluid of 100 weight portions, the consumption of described shitosan is the 2-8 weight portion; Water and/or can be the 50-100 weight portion with the consumption of the miscible solvent of water; The consumption of surfactant is the 50-100 weight portion, and the consumption of crosslinking agent is the 1-2 weight portion; The consumption of organic solvent is the 10-25 weight portion; More preferably, with respect to the magnetic fluid of 100 weight portions, the consumption of described shitosan is the 4-6 weight portion; Water and/or can be the 60-90 weight portion with the consumption of the miscible solvent of water; The consumption of surfactant is the 60-90 weight portion, and the consumption of crosslinking agent is the 1.2-1.6 weight portion; The consumption of organic solvent is the 15-20 weight portion.
Among the present invention, the condition of described cross-linking reaction has no particular limits, and for example, the condition of described cross-linking reaction comprises that crosslinked temperature is 30-70 ℃, and the crosslinked time is 50-80 minute; Under the preferable case, the condition of described cross-linking reaction comprises that crosslinked temperature is 40-50 ℃, and the crosslinked time is 55-65 minute.
Below by embodiment the present invention is described further.
Embodiment 1
Present embodiment is used to illustrate the preparation method of magnetic fluid provided by the invention.
(1) 0.36 mole ferrous chloride and 0.2 mole ferric trichloride are dissolved in 1000 ml waters, obtain the aqueous solution; The concentration that adds 320 milliliters afterwards in this aqueous solution is the sodium hydrate aqueous solution of 3.2 mol, obtains mixed liquor, in this mixed liquor, and Fe
3+With OH
-Mol ratio be 1:5; Afterwards this mixed liquor is moved into blender (Beijing Qi Lidasen instrument Science and Technology Ltd. is housed, RS-4A), warming-in-water and under nitrogen atmosphere, carry out precipitation reaction in 2 of thermometer and condenser pipe liters of four-hole boiling flasks, the temperature of reaction is 60 ℃, the time of reaction is 80 minutes, and mixing speed is 500 rev/mins; Use magnet (magnetic intensity is 100emu/g) to isolate the Fe that obtains afterwards
3O
4, and respectively with 100 ml deionized water washing 3 times, with the Fe that obtains
3O
4Put into drying in the vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616), baking temperature is 60 ℃, and be 120 minutes drying time, obtains 30 gram Fe
3O
4
(2) Fe that 10 gram steps (1) are obtained
3O
4, the carbon tetrachloride of polyethylene glycol, 100 grams of 50 grams and 20 grams distilled water join and carry out the water-bath heating in 500 milliliters the there-necked flask, the temperature of heating is 50 ℃, the time of heating is 80 minutes, use magnet (magnetic intensity is 100emu/g) to isolate bright black pulpous state magnetic fluid particle afterwards, and respectively with 100 ml deionized water washing 3 times, the magnetic fluid particle that obtains is put into vacuum drying chamber (bright forever Medical Instruments factory, 51815235616) dry in, baking temperature is 60 ℃, be 100 minutes drying time, obtains magnetic fluid A1.
Comparative Examples 1
Prepare reference magnetic fluid CA1 according to embodiment 1 described method, the consumption of different is ferrous chloride is 0.24 mole.
Embodiment 2
Present embodiment is used to illustrate the preparation method of magnetic fluid provided by the invention.
(1) 0.32 mole ferrous chloride and 0.2 mole ferric trichloride are dissolved in 800 ml waters, obtain the aqueous solution; The concentration that adds 500 milliliters afterwards in this aqueous solution is the potassium hydroxide aqueous solution of 3.2 mol, obtains mixed liquor, in this mixed liquor, and Fe
3+With OH
-Mol ratio be 1:8; Afterwards this mixed liquor is moved into blender (Beijing Qi Lidasen instrument Science and Technology Ltd. is housed, RS-4A), warming-in-water and under nitrogen atmosphere, carry out precipitation reaction in 2 of thermometer and condenser pipe liters of four-hole boiling flasks, the temperature of reaction is 80 ℃, the time of reaction is 50 minutes, and mixing speed is 500 rev/mins; Use magnet (magnetic intensity is 100emu/g) to isolate the Fe that obtains afterwards
3O
4, and respectively with 100 ml deionized water washing 3 times, with the Fe that obtains
3O
4Put into drying in the vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616), baking temperature is 60 ℃, and be 60 minutes drying time, obtains 28 gram Fe
3O
4
(2) Fe that 10 grams are obtained
3O
4, the toluene of oleic acid, 160 grams of 100 grams and 20 gram water join and carry out the water-bath heating in 500 milliliters the there-necked flask, the temperature of heating is 70 ℃, the time of heating is 50 minutes, use magnet (magnetic intensity is 100emu/g) to isolate bright black pulpous state magnetic fluid particle afterwards, and respectively with 100 ml deionized water washing 3 times, the magnetic fluid particle that obtains is put into vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616) dry in, baking temperature is 60 ℃, be 70 minutes drying time, obtains magnetic fluid A2.
Embodiment 3
Present embodiment is used to illustrate the preparation method of magnetic fluid provided by the invention.
(1) 0.28 mole ferrous chloride and 0.2 mole ferric trichloride are dissolved in 900 ml waters, obtain the aqueous solution; The concentration that adds 374 milliliters afterwards in this aqueous solution is the potassium hydroxide aqueous solution of 3.2 mol, obtains mixed liquor, in this mixed liquor, and Fe
3+With OH
-Mol ratio be 1:6; Afterwards this mixed liquor is moved into blender (Beijing Qi Lidasen instrument Science and Technology Ltd. is housed, RS-4A), warming-in-water and under helium atmosphere, carry out precipitation reaction in 2 of thermometer and condenser pipe liters of four-hole boiling flasks, the temperature of reaction is 65 ℃, the time of reaction is 70 minutes, and mixing speed is 500 rev/mins; Use magnet (magnetic intensity is 100emu/g) to isolate the Fe that obtains afterwards
3O
4, and respectively with 100 ml deionized water washing 3 times, with the Fe that obtains
3O
4Put into drying in the vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616), baking temperature is 65 ℃, and be 70 minutes drying time, obtains 25 gram Fe
3O
4
(2) Fe that 10 gram steps (1) are obtained
3O
4Sorbitan monooleate (Gutian, Nanjing chemical industry Co., Ltd of 90 grams, Span-80), the distilled water that the atoleines (Bei Canghai of Ningbo City moisten Co., Ltd) of 140 grams and 20 restrain join and carry out water-bath in 500 milliliters the there-necked flask and heat, the temperature of heating is 55 ℃, the time of heating is 70 minutes, use magnet (magnetic intensity is 100emu/g) to isolate bright black pulpous state magnetic fluid particle afterwards, and respectively with 100 ml deionized water washing 3 times, the magnetic fluid particle that obtains is put into vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616) dry in, baking temperature is 60 ℃, be 70 minutes drying time, obtains magnetic fluid A3.
Embodiment 4
Present embodiment is used to illustrate the preparation method of magnetic fluid provided by the invention.
(1) 0.3 mole ferrous chloride and 0.2 mole ferric trichloride are dissolved in 1000 ml waters, obtain the aqueous solution; The concentration that adds 440 milliliters afterwards in this aqueous solution is the sodium hydrate aqueous solution of 3.2 mol, obtains mixed liquor, in this mixed liquor, and Fe
3+With OH
-Mol ratio be 1:7; Afterwards this mixed liquor is moved into blender (Beijing Qi Lidasen instrument Science and Technology Ltd. is housed, RS-4A), thermometer and condenser pipe rises in the four-hole boiling flask warming-in-water and carry out precipitation reaction under nitrogen atmosphere, the temperature of reaction is 65 ℃, the time of reaction is 60 minutes, and mixing speed is 500 rev/mins; Use magnet (magnetic intensity is 100emu/g) to isolate the Fe that obtains afterwards
3O
4, and respectively with 100 ml deionized water washing 3 times, with the Fe that obtains
3O
4Put into drying in the vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616), baking temperature is 70 ℃, and be 60 minutes drying time, obtains 26 gram Fe
3O
4
(2) Fe that 10 gram steps (1) are obtained
3O
4The white oil (Weifang Zhongye Chemical Co., Ltd.) of 60 grams, the distilled water of the carbon tetrachloride of 120 grams and 20 grams join and carry out the water-bath heating in 500 milliliters the there-necked flask, the temperature of heating is 65 ℃, the time of heating is 60 minutes, use magnet (magnetic intensity is 100emu/g) to isolate bright black pulpous state magnetic fluid particle afterwards, and respectively with 100 ml deionized water washing 3 times, the magnetic fluid particle that obtains is put into vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616) dry in, baking temperature is 60 ℃, be 60 minutes drying time, obtains magnetic fluid A4.
Embodiment 5
Present embodiment is used to illustrate the preparation method of chitosan magnetic micro-sphere provided by the invention.
Magnetic fluid A1 and 0.2 gram shitosan that 10 gram embodiment 1 are obtained are distributed in the distilled water of 10 grams, obtain first suspension; (Gutian, Nanjing chemical industry Co., Ltd Span-80) mixes with 1.2 gram carbon tetrachloride with first suspension, 10 sorbitan monooleates that restrain afterwards; Add the MDA of 0.1 gram then and under 60 ℃, react and obtained chitosan magnetic micro-sphere suspension in 70 minutes; Use magnet (magnetic intensity is 100emu/g) from described suspension, to separate chitosan magnetic micro-sphere afterwards, and respectively with 100 ml deionized water washing 3 times, the magnetic fluid particle that obtains is put into vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616) dry in, baking temperature is 60 ℃, be 70 minutes drying time, obtains chitosan magnetic micro-sphere B1.
Comparative Examples 2
Prepare reference chitosan magnetic micro-sphere CB1 according to the method identical, the magnetic fluid A1 that the reference magnetic fluid CA1 alternate embodiment 1 that difference is to use Comparative Examples 1 to obtain obtains with embodiment 5.
Embodiment 6
Present embodiment is used to illustrate the preparation method of chitosan magnetic micro-sphere provided by the invention.
Magnetic fluid A2 and 0.8 gram shitosan that 10 gram embodiment 2 are obtained are distributed in the distilled water of 5 grams, obtain first suspension; (Gutian, Nanjing chemical industry Co., Ltd Span-80) mixes with 2.5 gram toluene with first suspension, 5 sorbitan monooleates that restrain afterwards; Add the butanedial of 0.2 gram then and under 55 ℃, react and obtained chitosan magnetic micro-sphere suspension in 80 minutes; Use magnet (magnetic intensity is 100emu/g) from described suspension, to isolate chitosan magnetic micro-sphere afterwards, and respectively with 100 ml deionized water washing 3 times, the magnetic fluid particle that obtains is put into vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616) dry in, baking temperature is 60 ℃, be 60 minutes drying time, obtains chitosan magnetic micro-sphere B2.
Embodiment 7
Present embodiment is used to illustrate the preparation method of chitosan magnetic micro-sphere provided by the invention.
It is in the acetate of 80 weight % that the 10 gram magnetic fluid A3 that obtain of embodiment 3 and 0.6 gram shitosan are distributed to 9 gram concentration, obtains first suspension; (Gutian, Nanjing chemical industry Co., Ltd Span-80) mixes with 2 gram carbon tetrachloride with first suspension, 9 sorbitan monooleates that restrain afterwards; Add the MDA of 0.16 gram then and under 65 ℃, react and obtained chitosan magnetic micro-sphere suspension in 60 minutes; Use magnet (magnetic intensity is 100emu/g) from described suspension, to separate chitosan magnetic micro-sphere afterwards, and respectively with 100 ml deionized water washing 3 times, the magnetic fluid particle that obtains is put into vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616) dry in, baking temperature is 65 ℃, be 65 minutes drying time, obtains chitosan magnetic micro-sphere B3.
Embodiment 8
Present embodiment is used to illustrate the preparation method of chitosan magnetic micro-sphere provided by the invention.
Magnetic fluid A4 and 0.4 gram shitosan that 10 gram embodiment 4 are obtained are distributed in the distilled water of 6 grams, obtain first suspension; (Gutian, Nanjing chemical industry Co., Ltd Span-80) mixes with 2 gram carbon tetrachloride with first suspension, 6 sorbitan monooleates that restrain afterwards; Add the glutaraldehyde of 0.12 gram then and under 60 ℃, react and obtained chitosan magnetic micro-sphere suspension in 70 minutes; Use magnet (magnetic intensity is 100emu/g) from described suspension, to separate chitosan magnetic micro-sphere afterwards, and respectively with 100 ml deionized water washing 3 times, the magnetic fluid particle that obtains is put into vacuum drying chamber (the bright forever Medical Instruments in Beijing factory, 51815235616) dry in, baking temperature is 65 ℃, be 70 minutes drying time, obtains chitosan magnetic micro-sphere B4.
Embodiment 9-12
According to ZB N24002-88 standard, (U.S. Quantum Design company detects magnetic intensity and the coercive force of the chitosan magnetic micro-sphere B1-B4 that embodiment 5-8 obtains on NbTi) respectively, and the result is as shown in table 1 at vibration magnetic strength instrument.
Comparative Examples 3
According to the described method of embodiment 9-12, magnetic intensity and the coercive force of the reference chitosan magnetic micro-sphere CB1 that detection Comparative Examples 2 obtains, the result is as shown in table 1.
Table 1
| The embodiment numbering | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Comparative Examples 3 |
| The microballoon numbering | B1 | B2 | B3 | B4 | CB1 |
| Magnetic intensity (emu/g) | 26.73 | 28.91 | 30.23 | 29.14 | 20.26 |
| Coercive force (A/m) | 0.043 | 0.042 | 0.036 | 0.035 | 0.064 |
As can be seen from Table 1, the reference chitosan magnetic micro-sphere CB1 that obtains with respect to Comparative Examples 2, embodiment of the invention 4-8 to the magnetic intensity of chitosan magnetic micro-sphere B1-B4 improve significantly, and coercive force significantly descends, illustrate that magnetic fluid that method provided by the invention obtains both can improve the magnetic intensity of the chitosan magnetic micro-sphere that contains this magnetic fluid that obtains, can also reduce the coercive force of the chitosan magnetic micro-sphere that contains this magnetic fluid, overcome the shortcoming that existing chitosan magnetic micro-sphere is difficult for recovery and assembles easily, thereby made the chitosan magnetic micro-sphere that obtains be more suitable for being used as the carrier of immobilised enzymes.
Claims (12)
1, a kind of preparation method of magnetic fluid, this method are included in the excessive alkaline aqueous solution of adding in the aqueous solution that contains ferrous ion and ferric ion; Carry out precipitation reaction afterwards under protective gas atmosphere, the precipitation separation product obtains Fe
3O
4With the Fe that obtains
3O
4Join in the carrier fluid with surfactant and to heat, separate the heating product then, obtain magnetic fluid, it is characterized in that, in the described aqueous solution that contains ferrous ion and ferric ion, the mol ratio of ferrous ion and ferric ion is 1.4-1.8:1.
2, method according to claim 1, wherein, in the described aqueous solution that contains ferrous ion and ferric ion, the mol ratio of ferrous ion and ferric ion is 1.4-1.6:1, the concentration of ferric ion is the 0.2-0.6 mol.
3, method according to claim 1, wherein, with respect to the Fe of 100 weight portions
3O
4, the consumption of described surfactant is the 500-1000 weight portion, the consumption of described carrier fluid is the 1200-1800 weight portion.
4, method according to claim 3, wherein, with respect to the Fe of 100 weight portions
3O
4, the consumption of described surfactant is the 600-900 weight portion, the consumption of described carrier fluid is the 1400-1600 weight portion.
5, method according to claim 1, wherein, the condition of described precipitation reaction comprises that reaction temperature is 60-80 ℃, and the reaction time is 50-80 minute, and described protective gas is group 0 element gas and/or nitrogen.
6, method according to claim 1, wherein, the condition of described heating comprises that the temperature of heating is 50-70 ℃, the time of heating is 50-80 minute.
7, method according to claim 1, wherein, described surfactant is selected from one or more in polyethylene glycol, sorbitan monooleate, oleic acid and the white oil; Described carrier fluid is selected from one or more in water, atoleine, toluene and the carbon tetrachloride; Described alkaline aqueous solution is selected from one or more in the aqueous solution of ammonia, NaOH and potassium hydroxide.
8, a kind of preparation method of chitosan magnetic micro-sphere, this method comprise with magnetic fluid and shitosan be distributed to water and/or can with the miscible solvent of water in, obtain first suspension; Afterwards first suspension, surfactant and organic solvent are mixed and obtain second suspension; Adding crosslinking agent afterwards in second suspension carries out cross-linking reaction and obtains cross-linking products; Separate cross-linking products then and obtain chitosan magnetic micro-sphere, it is characterized in that, described magnetic fluid is by any magnetic fluid that described method prepares among the claim 1-7.
9, method according to claim 8, wherein, magnetic fluid with respect to 100 weight portions, the consumption of described shitosan is the 2-8 weight portion, water and/or can be the 50-100 weight portion with the consumption of the miscible solvent of water, the consumption of surfactant is the 50-100 weight portion, and the consumption of crosslinking agent is the 1-2 weight portion, and the consumption of organic solvent is the 10-25 weight portion.
10, method according to claim 9, wherein, with respect to the magnetic fluid of 100 weight portions, the consumption of described shitosan is the 4-6 weight portion; Water and/or can be the 60-90 weight portion with the consumption of the miscible solvent of water, the consumption of surfactant is the 60-90 weight portion, and the consumption of crosslinking agent is the 1.2-1.6 weight portion, and the consumption of organic solvent is the 15-20 weight portion.
11, method according to claim 8, wherein, described can be acetate and/or ethanol with the miscible solvent of water, described surfactant is selected from one or more in polyethylene glycol, sorbitan monooleate, oleic acid and the white oil, described organic solvent is selected from one or more in atoleine, toluene and the carbon tetrachloride, and described crosslinking agent is selected from one or more in MDA, butanedial, glutaraldehyde and the hexandial.
12, method according to claim 8, wherein, the condition of described cross-linking reaction comprises that the temperature of cross-linking reaction is 30-70 ℃, the time of cross-linking reaction is 50-80 minute.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892217A (en) * | 2010-06-02 | 2010-11-24 | 中国水产科学研究院黄海水产研究所 | Preparation method of magnetic chitosan compound microsphere immobilized marine alkaline proteinase |
| CN103804699A (en) * | 2014-02-10 | 2014-05-21 | 广西民族大学 | Cassava starch magnetic microsphere and preparation method thereof |
| CN108640262A (en) * | 2018-07-06 | 2018-10-12 | 福建师范大学福清分校 | Magnetic Nano chitosan microball and preparation method thereof |
| CN108893460A (en) * | 2018-06-29 | 2018-11-27 | 华侨大学 | A kind of method of the quick immobilized cell of magnetically fixed bed |
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2007
- 2007-12-13 CN CN2007101957890A patent/CN101458985B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892217A (en) * | 2010-06-02 | 2010-11-24 | 中国水产科学研究院黄海水产研究所 | Preparation method of magnetic chitosan compound microsphere immobilized marine alkaline proteinase |
| CN103804699A (en) * | 2014-02-10 | 2014-05-21 | 广西民族大学 | Cassava starch magnetic microsphere and preparation method thereof |
| CN103804699B (en) * | 2014-02-10 | 2016-03-30 | 广西民族大学 | A kind of tapioca (flour) magnetic microsphere and preparation method thereof |
| CN108893460A (en) * | 2018-06-29 | 2018-11-27 | 华侨大学 | A kind of method of the quick immobilized cell of magnetically fixed bed |
| CN108640262A (en) * | 2018-07-06 | 2018-10-12 | 福建师范大学福清分校 | Magnetic Nano chitosan microball and preparation method thereof |
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| CN101458985B (en) | 2012-08-22 |
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