CN102641702A

CN102641702A - Ionic liquid functionalized magnetic nanoparticle and preparation method and application thereof

Info

Publication number: CN102641702A
Application number: CN2012101482854A
Authority: CN
Inventors: 魏芸; 李言
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2012-05-14
Filing date: 2012-05-14
Publication date: 2012-08-22
Anticipated expiration: 2032-05-14
Also published as: CN102641702B

Abstract

The invention relates to an ionic liquid functionalized magnetic nanoparticle and a preparation method and application thereof. FeCl3.6H2O and anhydrous sodium acetate are dissolved in glycol, and react under 200 DEG C, so that Fe3O4 magnetic nanoparticles are obtained; the Fe3O4 magnetic nanoparticles are weighed and mixed with H2O and ethanol, pH is regulated to 9 to 10, tetraethoxysilane is added for reaction, and after vacuum drying, Fe3O4/SiO2 is obtained; the Fe3O4/SiO2 is dispersed and suspended in toluene, and after 3-chloropropyltrimethylsilane and triethylamine are added for reaction, chloropropyl magnetic nanoparticles are obtained by way of vacuum drying; the chloropropyl magnetic nanoparticles are added into toluene, N-alkylimidazole derivative is added for reaction, and after vacuum drying, the ionic liquid functionalized magnetic nanoparticles are obtained. When being used for separating target standard protein, the ionic liquid functionalized magnetic nanoparticle has the characteristics of good selectivity and high adsorbing capacity, and cannot contaminate target separated product.

Description

The ion liquid functionalization magnetic nano-particle

Technical field

The present invention relates to a kind of ion liquid functionalization magnetic nano-particle.

Background technology

Along with the completion of the Human Genome Project, life science welcomes the genome times afterwards comprehensively, and the proteomics gate is opened thereupon.Because the characteristics of protein physicochemical property cause not only not being applicable to the Study on general technology of most of albumen, also not as the amplification technique of DNA, thereby obtain q.s, the unusual difficulty of highly purified protein.In order to increase protein articles purity or specific activity; Improve efficient, speed, yield and the purity of Separation of Proteins; Need particularly separate target protein the foreign protein from whole other compositions of cell, still remain with the BA and the chemical integrity of polypeptide simultaneously.The isolation technics of protein mainly concentrates on electrophoretic separation and chromatography aspect at present, needs perfect place badly but all have.In recent years, the separating and purifying technology that develops rapidly target product of biotechnology has proposed to upgrade and higher requirement.The magnetic inorganic nano particle is meant that mainly the nano particle that has a superparamagnetism by inorganic matter matrixes such as metal and silica and some forms; In recent years; Earth silicon material is because of its stable physicochemical characteristics; Excellent biological compatibility demonstrates good prospects for application as the protectiveness shell of various inner nuclear materials.The silicon shell magnetic nanoparticles is except the superparamagnetism that possesses inner nuclear material, and – NH is also introduced on its silicon shell surface ₂Multiple functional groups such as 、 – COOH 、 – OH with biochemical activity.Utilize its surperficial functional group, the silicon shell magnetic nanoparticles can combine various functional moleculars, and like antibody, DNA, protein etc., thereby the silicon shell magnetic nanoparticles has broad application prospects in the bio-separation field as the novel protein separating medium.In recent years, ionic liquid has caused widely to be paid close attention to, in catalysis, and electrochemical analysis, all there is the very application of innovation the isolation technics aspect.Selecting the N-methylimidazole is raw material, carries out reacting forming ion liquid functional magnetic nano-particle with the shell nuclear magnetism nanoparticle surface that is modified with chloropropyl, thereby obtains with the magnetic Nano parting material of methylimidazole ionic liquid as the functionalization group.The research that present ion liquid functionalization magnetic particle is applied to Separation of Proteins does not also appear in the newspapers; Through selectivity electrical function and the complexing of this functional particles to protein; Can and whether have blood red group according to the Acidity of Aikalinity of protein, realize the high selectivity of hemoglobin and other protein and separating and purification of high adsorption capacity.Can under externally-applied magnetic field, carry out the magnetic ball through particle magnetic and separate, realize reclaiming fully and reusing with the quick of end liquid, environmental protection and economy, practical value is high.

Summary of the invention

The purpose of this invention is to provide a kind of ion liquid functionalization magnetic nano-particle; It is bonding imidazole ion liquid on magnetic nano-particle; Obtain ion liquid functionalization magnetic nano-particle product, and be implemented in the application of Separation of Proteins aspect.

Ion liquid functionalization magnetic nano-particle of the present invention, its structural formula is:

Wherein,

Represent Fe ₃O ₄Magnetic nano-particle; Represent SiO ₂The silicon shell; Represent coated Si O ₂The Fe of silicon fiml ₃O ₄Magnetic nano-particle;

R ₁Be selected from C ₁-C ₁₆Alkyl, Cl or Br, R ₂Be selected from H or CH ₄

Or R ₁Be selected from C ₁-C ₆Alkyl, R ₂Be selected from C ₂-C ₅Alkyl;

Or R ₁=NH ₂, R ₂Be selected from H, C ₁-C ₃Alkyl or NH ₂

Or R ₁=OH, R ₂Be selected from H or C ₁-C ₂Alkyl;

Or R ₁=Ph, R ₂Be selected from H or C ₁-C ₄Alkyl;

Or R ₁=COOH, R ₂Be selected from H or CH ₄

Or R ₁Be selected from C ₁-C ₁₂Alkyl, R ₂=Ph;

Or R ₁Be selected from C ₁-C ₄Alkyl, R ₂=COOH;

Or R ₁Be selected from C ₁-C ₄Alkyl, R ₂Be selected from Cl, Br or I;

Or

Wherein,

Represent Fe ₃O ₄Magnetic nano-particle;

Represent SiO ₂The silicon shell;

Represent coated Si O ₂The Fe of silicon fiml ₃O ₄Magnetic nano-particle;

R ₃Be selected from H, NH ₂, CF ₃, OH, CH ₂Cl, OEt, COOH, Cl, Br or I;

The preparation method of ion liquid functionalization magnetic nano-particle of the present invention:

⑴ Fe ₃O ₄The preparation of magnetic nano-particle: with FeCl ₃.6H ₂O1-2g; Anhydrous sodium acetate 2-4g is dissolved in the 40mL ethylene glycol, puts into the 50mL agitated reactor in 200 ℃ of reaction 6-10h, after the cooling respectively with ethanol and deionized water ultrasonic give a baby a bath on the third day after its birth inferior; Use externally-applied magnetic field to separate, preserve with the ultrasonic dispersion of ethanol back at last and promptly obtain Fe ₃O ₄Magnetic nano-particle;

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄Magnetic nano-particle 0.1-1g adds H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 10-30min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=9-10; Heat up back adding 0.1-4ml ethyl orthosilicate (TEOS) in solution, and isothermal reaction 1-12h is transferred to the centrifuge tube centrifugation with reactant mixture; With deionized water and ethanol (EtOH) washing, get product F e behind the 60-120 ℃ of vacuum drying ₃O ₄/ SiO ₂Shell nuclear magnetism nano particle;

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.1-0.8g dispersion suspension that makes in the 70-150mL dry toluene, add 3-chloropropyl trimethyl silane 0.1-5mL and triethylamine 0.5-2mL (catalyst), under the nitrogen protection; System agitating heating backflow 24-48 hour; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle;

2. the chloropropyl magnetic nano-particle 0.1-0.5g that obtains is joined in the 70-150mL dry toluene, the back adds 0.1-5mLN-alkyl imidazole derivative, back flow reaction 24-48 hour; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of glyoxaline ion liquid functionalization.

Reaction equation (is example with bonding N-methylimidazole ionic liquid):

The evaluation of ion liquid functionalization magnetic nano-particle Separation of Proteins performance:

Use above-mentioned ion liquid functionalization magnetic nano-particle; Target criteria protein is carried out discrete testing; Change through detect the absorbance that separates the front and back protein solution with ultraviolet-uisible spectrophotometer, disclose the selective adsorption capacity of magnetic particle protein.Use the phosphate buffer solution of pH value 2-11 to come the various standard protein solution 1-5mLs of compound concentration as 0.05mg/mL; The magnetic nano-particle that adds 1-10mg, mechanical agitation 1-30 minute, the static absorption in back 5-10 minute; With magnet with mother liquor and separate particles; Take out supernatant, measure the solution absorbency of off-line lock out operation front and back, thereby obtain the ion liquid functionalization magnetic nano-particle for the absorption of proteins effect.Can find out from the result; Because protein is different with the surface charging amount of magnetic particle under the different pH values; So effect (adsorption rate) difference of absorption; And because the complexing of Fe in glyoxaline cation and the blood red group make particle for the protein with blood red group higher adsorbance arranged, thereby realization is to the selective absorption and the desorption of protein such as hemoglobin.

Ion liquid functionalization magnetic nano-particle of the present invention is used for protein and separates, have disengaging time short, simple to operation, to advantage such as Separation of Proteins is effective.And this magnetic particle can thoroughly separate with end liquid under externally-applied magnetic field, neither can pollute and can reclaim fully the target separator, thereby reach the economy purpose of environmental protection again.

The specific embodiment

Embodiment 1

⑴ Fe ₃O ₄The preparation of magnetic nano-particle

With FeCl ₃.6H ₂O1g, anhydrous sodium acetate 2g is dissolved in the 40mL ethylene glycol, puts into the 50mL agitated reactor in 200 ℃ of reaction 6h, gives a baby a bath on the third day after its birth time with ethanol and deionized water are ultrasonic respectively after the cooling, uses externally-applied magnetic field to separate, and promptly obtains Fe with preservation after the ultrasonic dispersion of ethanol at last ₃O ₄Magnetic nano-particle.

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄0.1g, add H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 10min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=9, and the intensification back adds 0.1mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 1h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 60 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.1g dispersion suspension that makes in the 70mL dry toluene, add 3-chloropropyl trimethyl silane 0.1mL and triethylamine 0.5mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 24 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.1g that obtains is joined in the 70mL dry toluene, the back adds 0.1mL1-chloro-glyoxal ethyline, back flow reaction 24 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-chloro-glyoxal ethyline ion liquid functionalization.

Separation of Proteins performance evaluation:

Use the phosphate buffer solution of pH value 6.8 to come the hemoglobin solutions 2mL of compound concentration, add the magnetic nano-particle of 3mg, mechanical agitation 10 minutes as 0.1mg/mL; The static absorption in back 5 minutes; With mother liquor and separate particles, take out supernatant with magnet, measure the solution absorbency of off-line lock out operation front and back; Calculating adsorption rate is 100%, obtains the ion liquid functionalization magnetic nano-particle for the absorption of proteins effect with the method.

Embodiment 2:

⑴ Fe ₃O ₄The preparation of magnetic nano-particle: with FeCl ₃.6H ₂O1g, anhydrous sodium acetate 2g is dissolved in the 40mL ethylene glycol, puts into the 50mL agitated reactor in 200 ℃ of reaction 6h, gives a baby a bath on the third day after its birth time with ethanol and deionized water are ultrasonic respectively after the cooling, uses externally-applied magnetic field to separate, and promptly obtains Fe with preservation after the ultrasonic dispersion of ethanol at last ₃O ₄Magnetic nano-particle.

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

2. the chloropropyl magnetic nano-particle 0.1g that obtains is joined in the 70mL dry toluene, the back adds 0.1mL1-chlorine imidazoles, back flow reaction 24 hours; Drop to room temperature, use methyl alcohol, water successively; Methanol wash, final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-chlorine imidazole ion liquid functionalization.

Embodiment 3:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

2. the chloropropyl magnetic nano-particle 0.1g that obtains is joined in the 70mL dry toluene, the back adds 0.1mL1-chloro-glyoxal ethyline, back flow reaction 24 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-bromo-glyoxal ethyline ion liquid functionalization.

Embodiment 4:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

2. the chloropropyl magnetic nano-particle 0.1g that obtains is joined in the 70mL dry toluene, the back adds 0.1mL1-chlorine imidazoles, back flow reaction 24 hours; Drop to room temperature, use methyl alcohol, water successively; Methanol wash, final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-bromine imidazole ion liquid functionalization.

Embodiment 5:

⑴ Fe ₃O ₄The preparation of magnetic nano-particle: with FeCl ₃.6H ₂O1.1g, anhydrous sodium acetate 2.2g is dissolved in the 40mL ethylene glycol, puts into the 50mL agitated reactor in 200 ℃ of reaction 6h, gives a baby a bath on the third day after its birth time with ethanol and deionized water are ultrasonic respectively after the cooling, uses externally-applied magnetic field to separate, and promptly obtains Fe with preservation after the ultrasonic dispersion of ethanol at last ₃O ₄Magnetic nano-particle.

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄0.2g, add H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 20min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=9, and the intensification back adds 0.2mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 2h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 60 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.2g dispersion suspension that makes in the 70mL dry toluene, add 3-chloropropyl trimethyl silane 0.2mL and triethylamine 0.6mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 30 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.1g that obtains is joined in the 70mL dry toluene, after add 0.2mL1, the 2-methylimidazole; Back flow reaction 30 hours drops to room temperature, uses methyl alcohol successively; Water, methanol wash, final vacuum is dry; Promptly obtained 1, the magnetic nano-particle of 2-methylimidazole ion liquid functionalization.

Embodiment 6:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 70mL dry toluene, add 3-chloropropyl trimethyl silane 0.2mL and triethylamine 0.6mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 30 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 70mL dry toluene, after add 0.2mL1-amyl group imidazoles, back flow reaction 30 hours; Drop to room temperature, use methyl alcohol, water successively; Methanol wash, final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-amyl group imidazole ion liquid functionalization.

Embodiment 7:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 100mL dry toluene, add 3-chloropropyl trimethyl silane 0.2mL and triethylamine 0.6mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 30 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 100mL dry toluene, after add 0.2mL1-cetyl imidazoles, back flow reaction 30 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-cetyl imidazole ion liquid functionalization.

Embodiment 8:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 100mL dry toluene, after add 0.2mL1-heptyl-glyoxal ethyline, back flow reaction 30 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, promptly obtained the magnetic nano-particle of 1-heptan-glyoxal ethyline ion liquid functionalization.

Embodiment 9:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 100mL dry toluene, after add 0.2mL1-hexadecane-glyoxal ethyline, back flow reaction 30 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-hexadecane-glyoxal ethyline ion liquid functionalization.

Embodiment 10:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

2. the chloropropyl magnetic nano-particle 0.3g that obtains is joined in the 100mL dry toluene, after add 0.2mL1-cetyl imidazoles, back flow reaction 30 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-cetyl imidazole ion liquid functionalization.

Embodiment 11:

⑴ Fe ₃O ₄The preparation of magnetic nano-particle: with FeCl ₃.6H ₂O1.3g, anhydrous sodium acetate 3g is dissolved in the 40mL ethylene glycol, puts into the 50mL agitated reactor in 200 ℃ of reaction 7h, gives a baby a bath on the third day after its birth time with ethanol and deionized water are ultrasonic respectively after the cooling, uses externally-applied magnetic field to separate, and promptly obtains Fe with preservation after the ultrasonic dispersion of ethanol at last ₃O ₄Magnetic nano-particle.

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄0.3g, add H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 15min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=9, and the intensification back adds 0.5mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 3h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 60 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 100mL dry toluene, add 3-chloropropyl trimethyl silane 0.3mL and triethylamine 0.7mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 32 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.3g that obtains is joined in the 100mL dry toluene, the back adds 0.5mL1-amino-2-methyl imidazoles, back flow reaction 32 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-amino-2-methyl imidazole ion liquid functionalization.

Embodiment 12:

⑴ Fe ₃O ₄The preparation of magnetic nano-particle: with FeCl ₃.6H ₂O1.35g, anhydrous sodium acetate 3.6g is dissolved in the 40mL ethylene glycol, puts into the 50mL agitated reactor in 200 ℃ of reaction 8h, gives a baby a bath on the third day after its birth time with ethanol and deionized water are ultrasonic respectively after the cooling, uses externally-applied magnetic field to separate, and promptly obtains Fe with preservation after the ultrasonic dispersion of ethanol at last ₃O ₄Magnetic nano-particle.

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O40.1g adds H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 20min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=10, and the intensification back adds 0.8mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 5h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 60 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 100mL dry toluene, add 3-chloropropyl trimethyl silane 0.4mL and triethylamine 0.8mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 36 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.3g that obtains is joined in the 100mL dry toluene, the back adds 0.8mL1-hydroxy-2-methyl imidazoles, back flow reaction 36 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-hydroxy-2-methyl imidazole ion liquid functionalization.

Embodiment 13:

⑴ Fe ₃O ₄The preparation of magnetic nano-particle: with FeCl ₃.6H ₂O1.5g, anhydrous sodium acetate 2.5g is dissolved in the 40mL ethylene glycol, puts into the 50mL agitated reactor in 200 ℃ of reaction 10h, gives a baby a bath on the third day after its birth time with ethanol and deionized water are ultrasonic respectively after the cooling, uses externally-applied magnetic field to separate, and promptly obtains Fe with preservation after the ultrasonic dispersion of ethanol at last ₃O ₄Magnetic nano-particle.

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄0.6g, add H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 25min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=10, and the intensification back adds 1mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 5h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 60 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 100mL dry toluene, add 3-chloropropyl trimethyl silane 1mL and triethylamine 1.2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 36 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.3g that obtains is joined in the 100mL dry toluene, the back adds 1.5mL1-phenyl-glyoxal ethyline, back flow reaction 36 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-phenyl-glyoxal ethyline ion liquid functionalization.

Embodiment 14:

⑴ Fe ₃O ₄The preparation of magnetic nano-particle: with FeCl ₃.6H ₂O1.6g, anhydrous sodium acetate 3.2g is dissolved in the 40mL ethylene glycol, puts into the 50mL agitated reactor in 200 ℃ of reaction 8h, gives a baby a bath on the third day after its birth time with ethanol and deionized water are ultrasonic respectively after the cooling, uses externally-applied magnetic field to separate, and promptly obtains Fe with preservation after the ultrasonic dispersion of ethanol at last ₃O ₄Magnetic nano-particle.

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄0.7g, add H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 30min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=10, and the intensification back adds 1.8mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 8h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 100 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 120mL dry toluene, add 3-chloropropyl trimethyl silane 2mL and triethylamine 1.8mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 100mL dry toluene, the back adds 3mL1-carboxyl-glyoxal ethyline, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-carboxyl-glyoxal ethyline ion liquid functionalization.

Embodiment 15:

⑴ Fe ₃O ₄The preparation of magnetic nano-particle: with FeCl ₃.6H ₂O1.8g, anhydrous sodium acetate 3.8g is dissolved in the 40mL ethylene glycol, puts into the 50mL agitated reactor in 200 ℃ of reaction 10h, gives a baby a bath on the third day after its birth time with ethanol and deionized water are ultrasonic respectively after the cooling, uses externally-applied magnetic field to separate, and promptly obtains Fe with preservation after the ultrasonic dispersion of ethanol at last ₃O ₄Magnetic nano-particle.

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄0.8g, add H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 30min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=9, and the intensification back adds 2mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 10h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 110 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 120mL dry toluene, add 3-chloropropyl trimethyl silane 2.5mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 100mL dry toluene, the back adds 4mL1-methyl-2-aminooimidazole, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-aminooimidazole ion liquid functionalization.

Embodiment 16:

⑴ Fe ₃O ₄The preparation of magnetic nano-particle: with FeCl ₃.6H ₂O2g, anhydrous sodium acetate 4g is dissolved in the 40mL ethylene glycol, puts into the 50mL agitated reactor in 200 ℃ of reaction 10h, gives a baby a bath on the third day after its birth time with ethanol and deionized water are ultrasonic respectively after the cooling, uses externally-applied magnetic field to separate, and promptly obtains Fe with preservation after the ultrasonic dispersion of ethanol at last ₃O ₄Magnetic nano-particle.

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄1g adds H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 30min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=10, and the intensification back adds 5mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 10h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 120 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 120mL dry toluene, add 3-chloropropyl trimethyl silane 4mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 100mL dry toluene, the back adds 4.5mL1-methyl-2-phenylimidazole, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-phenylimidazole ion liquid functionalization.

Embodiment 17:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 120mL dry toluene, add 3-chloropropyl trimethyl silane 4.5mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 120mL dry toluene, the back adds 4.5mL1-methyl-2-carboxyl imidazoles, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-carboxyl imidazole ion liquid functionalization.

Embodiment 18:

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄1g adds H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 30min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=9, and the intensification back adds 5mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 10h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 120 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 120mL dry toluene, add 3-chloropropyl trimethyl silane 5mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 120mL dry toluene, the back adds 5mL1-methyl-2-chlorine imidazoles, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-chlorine imidazole ion liquid functionalization.

Embodiment 19:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.2g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 0.1mL and triethylamine 0.5mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 24 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 150mL dry toluene, the back adds 0.1mLN-methylimidazole, back flow reaction 24 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of N-methylimidazole ion liquid functionalization.

Embodiment 20:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 0.2mL and triethylamine 0.6mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 30 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 150mL dry toluene, after add the 0.2mLN-methylimidazole, back flow reaction 30 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of N-methylimidazole ion liquid functionalization.

Embodiment 21:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.4g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 0.3mL and triethylamine 0.7mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 32 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.3g that obtains is joined in the 150mL dry toluene, the back adds 0.5mLN-methylimidazole, back flow reaction 32 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of N-methylimidazole ion liquid functionalization.

Embodiment 22:

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄0.1g, add H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 20min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=10, and the intensification back adds 0.8mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 5h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 60 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.4g dispersion suspension that makes in the 120mL dry toluene, add 3-chloropropyl trimethyl silane 0.4mL and triethylamine 0.8mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 36 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.3g that obtains is joined in the 120mL dry toluene, the back adds 0.8mLN-methylimidazole, back flow reaction 36 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of N-methylimidazole ion liquid functionalization.

Embodiment 23:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.5g dispersion suspension that makes in the 100mL dry toluene, add 3-chloropropyl trimethyl silane 1mL and triethylamine 1.2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 36 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.4g that obtains is joined in the 100mL dry toluene, the back adds 1.5mLN-methylimidazole, back flow reaction 36 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of N-methylimidazole ion liquid functionalization.

Embodiment 24:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.5g dispersion suspension that makes in the 120mL dry toluene, add 3-chloropropyl trimethyl silane 2mL and triethylamine 1.8mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 120mL dry toluene, the back adds 3mLN-methylimidazole, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of N-methylimidazole ion liquid functionalization.

Embodiment 25:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.6g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 2.5mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.3g that obtains is joined in the 150mL dry toluene, the back adds 4mLN-methylimidazole, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of N-methylimidazole ion liquid functionalization.

Embodiment 26:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.6g dispersion suspension that makes in the 120mL dry toluene, add 3-chloropropyl trimethyl silane 4mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 120mL dry toluene, the back adds 4.5mLN-methylimidazole, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of N-methylimidazole ion liquid functionalization.

Embodiment 27:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.7g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 4.5mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.5g that obtains is joined in the 150mL dry toluene, the back adds 4.5mLN-methylimidazole, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of N-methylimidazole ion liquid functionalization.

Embodiment 28:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.4g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 5mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 150mL dry toluene, the back adds 5mLN-methylimidazole, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of N-methylimidazole ion liquid functionalization.

Embodiment 29:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.4g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 0.1mL and triethylamine 0.5mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 24 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 150mL dry toluene, the back adds 0.1mL1-tolimidazole, back flow reaction 24 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-tolimidazole ion liquid functionalization.

Embodiment 30:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.7g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 0.2mL and triethylamine 0.6mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 30 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 150mL dry toluene, after add the amino benzimidazole of 0.2mL1-methyl-2-, back flow reaction 30 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of the amino benzo imidazole ion liquid of 1-methyl-2-functionalization.

Embodiment 31:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.8g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 0.3mL and triethylamine 0.7mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 32 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.5g that obtains is joined in the 150mL dry toluene, the back adds 0.5mL1-Methyl-2-trifluoromethyl benzimidazole, back flow reaction 32 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-Methyl-2-trifluoromethyl benzimidazole ion liquid functionalization.

Embodiment 32:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.8g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 0.4mL and triethylamine 0.8mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 36 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.5g that obtains is joined in the 150mL dry toluene, the back adds 0.8mL1-methyl-2-hydroxy benzo imidazoles, back flow reaction 36 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-hydroxy benzo imidazole ion liquid functionalization.

Embodiment 33:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.4g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 2mL and triethylamine 1.8mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 150mL dry toluene, the back adds 3mL1-methyl-2-chloromethyl benzimidazole, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-chloromethyl benzimidazole ion liquid functionalization.

Embodiment 34:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.3g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 2.5mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 150mL dry toluene, the back adds 4mL1-methyl-2-ethyoxyl benzo imidazoles, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-ethyoxyl benzo imidazole ion liquid functionalization.

Embodiment 35:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.4g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 4mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.2g that obtains is joined in the 150mL dry toluene, the back adds 4.5mL1-methyl-2-carboxy benzimidazole, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-carboxy benzimidazole ion liquid functionalization.

Embodiment 36:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.5g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 4.5mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.3g that obtains is joined in the 150mL dry toluene, the back adds 4.5mL1-methyl-2-chloro benzimidazole, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-chloro benzimidazole ion liquid functionalization.

Embodiment 37:

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.8g dispersion suspension that makes in the 150mL dry toluene, add 3-chloropropyl trimethyl silane 5mL and triethylamine 2mL (catalyst), under the nitrogen protection; The system agitating heating refluxed 48 hours; Use toluene successively after reducing to room temperature, ethanol/water (it is complete that remaining methoxyl group continues hydrolysis in the water-washing process), deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle.

2. the chloropropyl magnetic nano-particle 0.4g that obtains is joined in the 70-150mL dry toluene, the back adds 5mL1-methyl-2-bromobenzene and imidazoles, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-bromobenzene and imidazole ion liquid functionalization.

Embodiment 38:

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄1g adds H ₂O and ethanol (EtOH), 1/4 mixes by volume, ultrasonic dispersion 30min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=10, and the intensification back adds 4mL ethyl orthosilicate (TEOS) in solution, and isothermal reaction 12h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind 120 ℃ of vacuum dryings ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

2. the chloropropyl magnetic nano-particle 0.3g that obtains is joined in the 150mL dry toluene, the back adds 5mL1-methyl-2-iodobenzene and imidazoles, back flow reaction 48 hours; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, has promptly obtained the magnetic nano-particle of 1-methyl-2-iodobenzene and imidazole ion liquid functionalization.

Claims

1. ion liquid functionalization magnetic nano-particle is characterized in that:

Its structural formula is:

Wherein,

Represent Fe ₃O ₄Magnetic nano-particle;

Represent SiO ₂The silicon shell;

Represent coated Si O ₂The Fe of silicon fiml ₃O ₄Magnetic nano-particle;

R ₁Be selected from C ₁-C ₁₆Alkyl, Cl, Br; R ₂Be selected from H or CH ₄

Or R ₁=NH ₂, R ₂Be selected from H, C ₁-C ₃Alkyl or NH ₂

Or R ₁=OH, R ₂Be selected from H or C ₁-C ₂Alkyl;

Or R ₁=Ph, R ₂Be selected from H or C ₁-C ₄Alkyl;

Or R ₁=COOH, R ₂Be selected from H or CH ₄

Or R ₁Be selected from C ₁-C ₈Alkyl, R ₂=NH ₂

Or R ₁Be selected from C ₁-C ₁₂Alkyl, R ₂=Ph;

Or R ₁Be selected from C ₁-C ₄Alkyl, R ₂=COOH;

R ₁Be selected from C ₁-C ₄Alkyl, R ₂Be selected from Cl, Br or I;

Or

Wherein,

Represent Fe ₃O ₄Magnetic nano-particle;

Represent SiO ₂The silicon shell; Represent coated Si O ₂The Fe of silicon fiml ₃O ₄Magnetic nano-particle;

R ₃Be selected from H, NH ₂, CF ₃, OH, CH ₂Cl, OEt, COOH, Cl, Br or I.

2. the preparation method of the described ion liquid functionalization magnetic nano-particle of claim 1 is characterized in that:

(2) Fe ₃O ₄/ SiO ₂The preparation of shell nuclear magnetism nano particle: weighing (1) product F e ₃O ₄Magnetic nano-particle 0.1-1g adds H ₂O and ethanol, 1/4 mixes by volume, ultrasonic dispersion 10-30min, logical N ₂, stir adding NH down ₃.H ₂O is adjusted to pH=9-10, and the intensification back adds the 0.1-4mL ethyl orthosilicate in solution, and isothermal reaction 1-12h is transferred to the centrifuge tube centrifugation with reactant mixture, with deionized water and EtOH washing, gets product F e behind the 60-120 ℃ of vacuum drying ₃O ₄/ SiO ₂

(3) the ion liquid functionalization magnetic nano-particle is synthetic:

1. with the shell nuclear magnetism nano particle 0.1-0.8g dispersion suspension that makes in the 70-150mL dry toluene, add 3-chloropropyl trimethyl silane 0.1-5mL and triethylamine 0.5-2mL, under the nitrogen protection; System agitating heating backflow 24-48 hour; Use toluene successively after reducing to room temperature, ethanol/water, deionized water; After the methanol wash, vacuum drying obtains the chloropropyl magnetic nano-particle;

2. the chloropropyl magnetic nano-particle 0.1-0.5g that obtains is joined in the 70-150mL dry toluene, the back adds 0.1-5mLN-alkyl imidazole derivative, back flow reaction 24-48 hour; Drop to room temperature; Use methyl alcohol successively, water, methanol wash; Final vacuum is dry, promptly obtains the magnetic nano-particle of glyoxaline ion liquid functionalization.

3. the application of the described ion liquid functionalization magnetic nano-particle of claim 1; It is characterized in that: with ion liquid functionalization magnetic nano-particle and protein solution mix contact adsorb after; Outside magnetic field helps down; Supernatant and magnetic particle are separated taking-up, realize the separation of target protein.