CN103065754B - Magnetic material of finishing benzene sulfonic acid and its preparation method and application - Google Patents
Magnetic material of finishing benzene sulfonic acid and its preparation method and application Download PDFInfo
- Publication number
- CN103065754B CN103065754B CN201210514809.7A CN201210514809A CN103065754B CN 103065754 B CN103065754 B CN 103065754B CN 201210514809 A CN201210514809 A CN 201210514809A CN 103065754 B CN103065754 B CN 103065754B
- Authority
- CN
- China
- Prior art keywords
- magnetic
- magnetic material
- sulfonic acid
- benzene sulfonic
- particle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses preparation and the application thereof of the magnetic material of finishing benzene sulfonic acid, adopt FeCl
3for raw material, ethylene glycol is dispersion, and anhydrous sodium acetate is reducing agent, prepares Fe 3 O 4 magnetic microballoon by hydro thermal method; Then be distributed in the mixed solution of ethanol/water, add ammoniacal liquor and tetraethoxy-silicane, make tetraethoxy-silicane in the polymerization of magnetic microsphere surface hydrolysis, obtain core-shell type magnetic material; Be distributed to after drying in the mixed solution of toluene and DMF, add 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane, obtained the magnetic material of finishing benzene sulfonic acid by Silanization reaction.Magnetic material of the present invention has abundant active group, can stable dispersion in the solution, renewable and recycling; As adsorbent, surface area is large, and selectivity is strong, can adsorb alkaline compound by the hydrophobic effect of sulfonic strong electrostatic interaction and phenyl ring from matrix, adopts simple magnetic field action to realize fast separating concentration.
Description
Technical field
The invention belongs to functional material and analysis technical field, more particularly, be specifically related to a kind of Fe of finishing benzene sulfonic acid
3o
4the preparation method and application of magnetic material.
Background technology
Vancomycin and Norvancomycin are two kinds of conventional glycopeptide antibiotics, clinically for the infection caused by prevention and therapy gram-positive bacteria.At present, glycopeptide antibiotics is also widely used in feed addictive and the veterinary drug of poultry, ox, pig etc., for promoting growth of animal and treatment livestock and poultry.But such antibiotic also has certain kidney poison, ototoxicity.Along with widely using of glycopeptide antibiotics, these antibiotic residues are in water quality or food and can enter human body by the transmission of food chain, are detrimental to health.Therefore be necessary to carry out limit examine to glycopeptide antibiotic.But environmental sample matrix is complicated, and target compound content is lower, therefore effective sample pre-treatments comprises separations, purification and enrichment is the prerequisite and the guarantee that realize accurate, efficient analysis.At present conventional Sample Pretreatment Technique comprises liquid-liquid extraction, SPE etc., but said method ubiquity complex operation, the deficiency such as waste time and energy.Compared with traditional abstraction technique, magnetic nano-particle has the advantages such as simple, quick, efficient as the Magnetic solid phases abstraction technique of adsorbent.Magnetic nano-particle has the advantages such as superparamagnetic characteristic, size is little, surface area is large, and it fully can contact to ensure efficient adsorption in the solution with analyte; Under additional magnetic fields, magnetic nano-particle can be separated magnetic material with mother liquor fast, and after removing externally-applied magnetic field, it can disperse in the solution again, and centre does not need to filter and the step such as centrifugal.Therefore simple, quick, efficient separation and the enrichment of determinand in complex system is applicable to.But its limited sorption capacity of simple magnetic material, therefore needs to carry out suitable modification on its surface to improve selectivity and absorption property.Conventional modification group comprises C18, phenyl, amino, polymer etc., and wherein the magnetic material of hydrophobic group modification is most widely used general, and the magnetic material report that ionic groups is modified is less.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method preparing the magnetic material of finishing benzene sulfonic acid is in a mild condition provided, this material has superparamagnetism and has good dispersiveness in the solution, can carry out fast, is efficiently separated and enrichment alkaline compound in complex matrices.
Object of the present invention is achieved by following technical proposals:
The preparation method of the magnetic material of finishing benzene sulfonic acid, carries out according to following step:
(1) synthesizing magnetic Fe
3o
4nano particle, with FeCl
36H
2o and FeSO
46H
2o be raw material with both (1 ~ 2): the mol ratio of 1 is dissolved in deionized water, and then add alkali lye under fast stirring and be greater than 11 to make system pH, under Keep agitation, anti-life can generate magnetic Fe
3o
4nano particle, specifically, with FeCl
36H
2o and FeSO
46H
2o be raw material with both (1 ~ 2): the mol ratio of 1 is dissolved in 50mL deionized water, 400-800 turns/min rapid stirring under add the sodium hydrate aqueous solution solution (1.5mol/L) of 10-40mL, at 25 ~ 80 DEG C, then stir 1 ~ 24h can generate magnetic Fe
3o
4nano particle; Externally-applied magnetic field auxiliary under collect magnetic nano-particle, with deionized water and ethanol purge 3 ~ 6 times, vacuumize 6 ~ 24h at 25 ~ 80 DEG C, obtains dry magnetic Fe
3o
4nano particle, specifically can list of references Y.P.He, S.Q.Wang, C.R.Li, Y.M.Miao, Z.Y.Wu, andB.S.Zou, J.Phy.D:Appl.Phys.2005,38,1342-1350.
(2) by magnetic Fe prepared by step (1)
3o
4nano particle is re-dispersed in the mixed solution of second alcohol and water, and the volume ratio of second alcohol and water is (1 ~ 10): 1, adds excessive concentrated ammonia liquor and tetraethoxy-silicane, magnetic Fe prepared by described step (1)
3o
4nano particle, mass fraction are the concentrated ammonia liquor of 25 ~ 28% and the mass ratio of tetraethoxy-silicane is 1: (1-10): (0.2-10), and room temperature with constant stirs, and to make tetraethoxy-silicane in the polymerization of magnetic particle surface hydrolysis, obtains Fe
3o
4/ SiO
2magnetic material, wherein concentrated ammonia liquor is base catalyst, and for reaction system provides alkaline environment, tetraethoxy-silicane obtains the shell mechanism of tetraethoxy-silicane in the polymerization of magnetic particle surface hydrolysis, specifically:
By magnetic Fe prepared by step (1)
3o
4nano particle is re-dispersed in the mixed solution of second alcohol and water, the volume ratio of second alcohol and water is (1 ~ 10): 1, then concentrated ammonia liquor 1 ~ 10g that mass fraction is 25 ~ 28% is added, tetraethoxy-silicane 0.2 ~ 10g, room temperature 20-25 DEG C of mechanical agitation 3 ~ 24h, make tetraethoxy-silicane in the polymerization of magnetic particle surface hydrolysis, obtain Fe
3o
4/ SiO
2magnetic material.Externally-applied magnetic field auxiliary under collect magnetic particle, with deionized water and ethanol purge 3 ~ 6 times, vacuumize 6 ~ 24h at 40 ~ 80 DEG C, obtains dry Fe
3o
4/ SiO
2magnetic particle.
(3) magnetic material prepared by step (2) is distributed to toluene and N, in the mixed solution of dinethylformamide, ultrasonic disperse is even, then the dichloromethane solution of excessive 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is added, fully react to make it, the mass ratio of the dichloromethane solution of magnetic material prepared by described step (2) and 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is 1: 1 ~ 20, at 25 ~ 60 DEG C, Keep agitation obtains the magnetic material of finishing benzene sulfonic acid by Silanization reaction, specifically:
Get the magnetic material 1.0g that (2) are obtained, be distributed to toluene and N, in the mixed solution of dinethylformamide, toluene and N, the volume ratio of dinethylformamide is 1: (1 ~ 10), ultrasonic disperse is even, then dichloromethane solution (the 50wt% of 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is added, Acros company of Belgium produces) 1 ~ 20g, mechanical agitation 2 ~ 24h at 25 ~ 60 DEG C, obtains the magnetic material of finishing benzene sulfonic acid by Silanization reaction.Externally-applied magnetic field auxiliary under collect magnetic particle, with deionized water and ethanol purge 3 ~ 6 times, vacuumize 6 ~ 24h at 40 ~ 80 DEG C, obtains the Fe of dry finishing benzene sulfonic acid
3o
4/ SiO
2magnetic particle.
Technical scheme of the present invention is utilized to obtain the Fe of finishing benzene sulfonic acid
3o
4/ SiO
2magnetic particle, and then adopt transmission electron microscope (TEM), PPMS (PPMS), zeta potential instrument, Fourier infrared spectrograph (IR), cation exchange capacity to measure to carry out sign to magnetic material as follows:
(1) particle diameter and morphology characterization
TecnaiG2F20 type transmission electron microscope (FEI Co. of the U.S.) is adopted to observe particle diameter and the pattern of the magnetic particle of preparation.Fe as can be seen from Figure 2
3o
4nano particle is that class is spherical, and particle diameter is about 10nm, the Fe of finishing benzene sulfonic acid
3o
4/ SiO
2magnetic particle outer layer covers layer of silicon dioxide, whole particle presents nucleocapsid structure.
(2) magnetic characterization
Adopt PPMS-9 type PPMS (QuantumDesign company of the U.S.) to characterize the magnetic property of magnetic material, its magnetic hysteresis loop is shown in Fig. 3, Fe
3o
4with the Fe of finishing benzene sulfonic acid
3o
4/ SiO
2the remanent magnetism of nano particle and coercive force all go to zero, show as typical paramagnetism, its saturation magnetization is respectively 66 and 51emu/g.Due to SiO
2magnetic response performance is not had, Fe with silane reagent
3o
4parcel SiO
2obviously decline with saturation magnetization after silane reagent.High saturation and magnetic intensity and superparamagnetism make magnetic material can be separated faster with solution under additional magnetic fields, can be distributed in solution easily again after removing magnetic field.
(3) Zeta potential characterizes
NanoZS type zeta potential instrument (Malvern company of Britain) is adopted to characterize the charged situation on magnetic material surface, the Fe of finishing benzene sulfonic acid as can be seen from Figure 4
3o
4/ SiO
2nano particle in the scope that pH value is 1 ~ 10, be negative value.Because sulfonic group is strong acid group, it within the scope of the pH of 1 ~ 10 all ionization and electronegative, result shows that benzene sulfonic acid is successfully modified at Fe
3o
4/ SiO
2nanoparticle surface.
(4) functional group characterizes
Nicolet6700 type Fourier infrared spectrograph (ThermoFisher company of the U.S.) is adopted to characterize functional group's change of magnetic material, the Fe of finishing benzene sulfonic acid as can be seen from Figure 5
3o
4/ SiO
2nano particle 2855 and 2922cm
-1occurred the absworption peak of C-H, this absworption peak is by the CH on silane reagent
2group produces, and shows the success that surface silanization reacts.
(5) cation exchange capacity measures
Adopt the method for National Standard of the People's Republic of China GB/T8144-2008 to measure the cation exchange capacity of magnetic material, its cation exchange capacity is 0.61mmol/g (mean value).
The magnetic material of the finishing benzene sulfonic acid prepared utilizing technical solution of the present invention is used for extracting vancomycin and Norvancomycin in environmental water sample, within the scope of 10 ~ 300 μ g/L, the mass concentration of vancomycin and Norvancomycin and peak area have good linear relationship.Equal 3 and 10 with signal to noise ratio (S/N) and calculate the lowest detection line of this analytical method and minimum quantitative limit respectively, result shows that the lowest detectable limit of vancomycin and Norvancomycin is respectively 3.0 and 2.0 μ g/L, and minimum quantitative limit is respectively 10.0 and 6.7 μ g/L.
Compared with prior art, the invention has the advantages that:
(1) preparation method of the magnetic material of finishing benzene sulfonic acid is simply effective, and obtained magnetic material has superparamagnetism, not oxidizable;
(2) magnetic material of finishing benzene sulfonic acid that the present invention obtains has abundant active group, and dispersion that can be stable in the solution, can regenerate and reuse;
(3) magnetic material of finishing benzene sulfonic acid that obtains of the present invention is as adsorbent, surface area is large, selectivity is strong, alkaline compound can be adsorbed from complex matrices by the hydrophobic effect of sulfonic strong electrostatic interaction and phenyl ring, adopt simple magnetic field action to realize fast separating concentration.
Accompanying drawing explanation
Fig. 1 is the synthetic method schematic diagram of the magnetic material of finishing benzene sulfonic acid
Fig. 2 is the transmission electron microscope picture of magnetic material, (a) Fe
3o
4, the Fe of (b) finishing benzene sulfonic acid
3o
4/ SiO
2magnetic particle (transmission electron microscope is TecnaiG2F20)
Fig. 3 is magnetic hysteresis loop (a) Fe of magnetic material
3o
4, (b) Fe
3o
4/ SiO
2, the Fe of (c) finishing benzene sulfonic acid
3o
4/ SiO
2magnetic particle (abscissa is magnetic field intensity (Oe), and ordinate is saturation magnetization (emu/g))
Fig. 4 is the zeta potential diagram of magnetic material, (a) Fe
3o
4, (b) Fe
3o
4/ SiO
2, the Fe of (c) finishing benzene sulfonic acid
3o
4/ SiO
2magnetic particle (abscissa is pH value, and ordinate is Zeta potential (mV))
Fig. 5 is the infrared spectrogram of magnetic material, (a) Fe
3o
4, (b) Fe
3o
4/ SiO
2, the Fe of (c) finishing benzene sulfonic acid
3o
4/ SiO
2(abscissa is wave number (cm to magnetic particle
-1), ordinate is transmitance (%))
Fig. 6 is the magnetic material SPE flow chart of finishing benzene sulfonic acid.
Fig. 7 is calibration curve and equation of linear regression, wherein (a) vancomycin, (b) Norvancomycin.
Embodiment
Technical scheme of the present invention is set forth further below in conjunction with embodiment.Wherein said room temperature is 20-25 degree Celsius, described concentrated ammonia liquor to be mass concentration be 25 ~ 28% concentrated ammonia liquor, 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane (50wt% dichloromethane solution, Belgian Acros company produces).
Embodiment 1: the preparation of the magnetic material of finishing benzene sulfonic acid
The preparation of magnetic microsphere
Take the FeCl of 1.3g
36H
2the FeSO of O and 0.7g
46H
2o is dissolved in 50mL deionized water, adds the sodium hydrate aqueous solution (1.5mol/L) (namely take 1.2g NaOH and be dissolved in 20mL deionized water) of 20mL under rapid stirring, then at room temperature stirs 3h and can generate magnetic Fe
3o
4nano particle; Externally-applied magnetic field auxiliary under collect magnetic nano-particle, with deionized water and ethanol purge 6 times, vacuumize 24h at 6O DEG C, obtains dry magnetic Fe
3o
4nano particle, can specifically with reference to Y.P.He, S.Q.Wang, C.R.Li, Y.M.Miao, Z.Y.Wu, andB.S.Zou, J.Phy.D:Appl.Phys.2005,38,1342-1350.
Fe
3o
4/ SiO
2the preparation of microballoon
Get magnetic Fe
3o
4nano particle 1.0g, is re-dispersed in the deionized water mixed solution of 120mL ethanol and 40mL, adds the concentrated ammonia liquor 3g that mass concentration is 25 ~ 28%, tetraethoxy-silicane 1g, room temperature mechanical stirs 24h, makes tetraethoxy-silicane in the polymerization of magnetic microsphere surface hydrolysis, obtains hud typed Fe
3o
4/ SiO
2magnetic material.Externally-applied magnetic field auxiliary under collect magnetic particle, with deionized water and ethanol purge 6 times, vacuumize 24h at 80 DEG C, obtains dry Fe
3o
4/ SiO
2magnetic particle.
The volume ratio of wherein said second alcohol and water is (1 ~ 10): 1; Magnetic Fe prepared by described step (1)
3o
4nano particle, mass fraction are the concentrated ammonia liquor of 25 ~ 28% and the mass ratio of tetraethoxy-silicane is 1: (1-10): (0.2-10), when getting magnetic Fe
3o
4during nano particle 1.0g, mass fraction is the concentrated ammonia liquor 1 ~ 10g of 25 ~ 28%, tetraethoxy-silicane 0.2 ~ 10g; All Fe can be prepared
3o
4/ SiO
2magnetic particle.
The preparation of the magnetic material of finishing benzene sulfonic acid
By 1gFe
3o
4/ SiO
2magnetic particle is distributed to the N of 120mL, in the toluene mixed solution of dinethylformamide and 40mL, ultrasonic disperse is even, then the dichloromethane solution 5g of 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is added, at room temperature mechanical agitation 24h, obtains the magnetic material of finishing benzene sulfonic acid by Silanization reaction.Externally-applied magnetic field auxiliary under collect magnetic particle, with deionized water and ethanol purge 6 times, vacuumize 24h at 80 DEG C, obtains the Fe of dry finishing benzene sulfonic acid
3o
4/ SiO
2magnetic particle
The mass ratio of the dichloromethane solution of magnetic material prepared by wherein said step (2) and 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is 1: 1 ~ 20, as toluene solution 1 ~ 20g that the magnetic material that step (2) is obtained is 1.0g, 2-(4-chlorosulfonyl)-ethyl trichlorosilane; In the mixed solution of toluene and DMF, the volume ratio of toluene and DMF is 1: (1 ~ 10); Described reaction is mechanical agitation 2 ~ 24h at 25 ~ 60 DEG C, all obtains the magnetic material of finishing benzene sulfonic acid by Silanization reaction.
Embodiment 2: the magnetic material of finishing benzene sulfonic acid is for extracting vancomycin and Norvancomycin in environmental water sample
The serial mixed standard solution being 10,20,50,100,150,200,300 μ g/L with deionized water preparation vancomycin and Norvancomycin mass concentration carries out liquid chromatogram measuring, INSTRUMENT MODEL is ShimazuHPLC-20A, business men is Japanese Shimadzu Corporation, instrument configuration SPD-M20A type diode array (DAD) detector, CTO-20AC column oven, SIL-20AC automatic sampler; Chromatographic column is SpursilC18 post, and business men is Beijing Di Kema Science and Technology Ltd.; Mobile phase is acetonitrile: 5mmol potassium phosphate buffer (by phosphoric acid adjust ph to 3.2) (volume ratio is 90: 10), flow velocity is 1ml/min, sample size is 20 μ L, determined wavelength is 230nm, with the mass concentration x of standard liquid for abscissa, peak area y is ordinate mapping, and carry out linear regression by least square method, the calibration curve regression equation obtaining vancomycin and Norvancomycin is respectively y=857.09x+219.4868 (coefficient R simultaneously
2=0.99931), y=965.06x+674.44 (coefficient R
2=0.99947), result shows that the mass concentration of vancomycin and Norvancomycin and peak area have good linear relationship within the scope of 10 ~ 300 μ g/L.Equal 3 and 10 with signal to noise ratio (S/N) and calculate the lowest detection line of this analytical method and minimum quantitative limit respectively, result shows that the lowest detectable limit of vancomycin and Norvancomycin is respectively 3.0 and 2.0 μ g/L, and minimum quantitative limit is respectively 10.0 and 6.7 μ g/L.
The absorption property selecting vancomycin and Norvancomycin effects on surface to modify the magnetic material of benzene sulfonic acid is tested, also the magnetic material utilizing technical solution of the present invention to prepare is used for extracting vancomycin and Norvancomycin in environmental water sample, concrete Optimization Technology is as follows:
(1) the magnetic material 50mg getting finishing benzene sulfonic acid is placed in 50mL centrifuge tube, and add 5mL methyl alcohol and 5mL deionized water washing activation successively, then under externally-applied magnetic field (selecting magnet) is auxiliary, collect magnetic material, solution discards;
(2) get 40mL and contain vancomycin and Norvancomycin water sample, described water sample pH value formic acid is adjusted to 2, join in centrifuge tube, mix and the 6min that vibrates with the magnetic material after activation, at the externally-applied magnetic field magnetic material of target compound of having assisted lower collection to adsorb, solution discards;
(3) magnetic material adsorbing target compound is added respectively 1mL deionized water and the drip washing of 1mL methyl alcohol; Then divide and add methyl alcohol-ammoniacal liquor eluant, eluent for 3 times (volume ratio is 95: 5, the mass percent of described ammoniacal liquor is 25-28%), each 1mL, the target compound of room temperature 20 DEG C vibration 1min wash-out absorption, under externally-applied magnetic field is auxiliary, is separated magnetic material, collects and merge elute soln, drying up with nitrogen at 40 DEG C, residue deionized water again dissolves and is settled to 1mL, gets 20 these solution of μ L at every turn and carries out liquid-phase chromatographic analysis to measure the concentration of each target compound in concentrate.
According to vancomycin in three various water samples of Analysis result calculation and average recovery rate, the relative standard deviation of going first mould through the ages, result shows, the analytical method that application the present invention sets up extracts and measures vancomycin and the Norvancomycin of environmental water sample, its recovery of standard addition is respectively between 86.7 ~ 93.4% and 79.5 ~ 90.6%, relative standard deviation is all less than 9.7%, the rate of recovery of visible the method is higher, and the reappearance of analysis result is better.
Table 1 vancomycin and the Norvancomycin rate of recovery in water sample
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.
Claims (10)
1. the magnetic material of finishing benzene sulfonic acid, is characterized in that, is prepared according to following step:
(1) synthesizing magnetic Fe
3o
4nano particle, with FeCl
36H
2o and FeSO
46H
2o be raw material with both (1 ~ 2): the mol ratio of 1 is dissolved in deionized water, and then add alkali lye under fast stirring and be greater than 11 to make system pH, under Keep agitation, anti-life can generate magnetic Fe
3o
4nano particle;
(2) by magnetic Fe prepared by step (1)
3o
4nano particle is re-dispersed in the mixed solution of second alcohol and water, and the volume ratio of second alcohol and water is (1 ~ 10): 1, adds excessive concentrated ammonia liquor and tetraethoxy-silicane, magnetic Fe prepared by described step (1)
3o
4nano particle, mass fraction are the concentrated ammonia liquor of 25 ~ 28% and the mass ratio of tetraethoxy-silicane is 1:(1-10): (0.2-10), room temperature with constant stirs, and to make tetraethoxy-silicane in the polymerization of magnetic particle surface hydrolysis, obtains Fe
3o
4/ SiO
2magnetic material, wherein concentrated ammonia liquor provides alkaline environment for reaction system, and tetraethoxy-silicane obtains the shell mechanism of tetraethoxy-silicane in the polymerization of magnetic particle surface hydrolysis;
(3) magnetic material prepared by step (2) is distributed to toluene and N; in the mixed solution of dinethylformamide; ultrasonic disperse is even; then the dichloromethane solution of excessive 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is added; fully react to make it; the mass ratio of the toluene solution of magnetic material prepared by described step (2) and 2-(4-chlorosulfonyl)-ethyl trichlorosilane is 1:1 ~ 20, and at 25 ~ 60 DEG C, Keep agitation obtains the magnetic material of finishing benzene sulfonic acid by Silanization reaction.
2. the magnetic material of finishing benzene sulfonic acid according to claim 1, is characterized in that, in described step (1) specifically, with FeCl
36H
2o and FeSO
46H
2o be raw material with both (1 ~ 2): the mol ratio of 1 is dissolved in 50mL deionized water, 10-40mL is added under 400-800 turns/min rapid stirring, the sodium hydrate aqueous solution solution of 1.5mol/L, then stirs 1 ~ 24h and can generate magnetic Fe at 25 ~ 80 DEG C
3o
4nano particle; Externally-applied magnetic field auxiliary under collect magnetic nano-particle, with deionized water and ethanol purge 3 ~ 6 times, vacuumize 6 ~ 24h at 25 ~ 80 DEG C, obtains dry magnetic Fe
3o
4nano particle.
3. the magnetic material of finishing benzene sulfonic acid according to claim 1, is characterized in that, in described step (2) specifically, by magnetic Fe prepared by step (1)
3o
4nano particle is re-dispersed in the mixed solution of second alcohol and water, the volume ratio of second alcohol and water is (1 ~ 10): 1, then concentrated ammonia liquor 1 ~ 10g that mass fraction is 25 ~ 28% is added, tetraethoxy-silicane 0.2 ~ 10g, room temperature 20-25 DEG C of mechanical agitation 3 ~ 24h, make tetraethoxy-silicane in the polymerization of magnetic particle surface hydrolysis, obtain Fe
3o
4/ SiO
2magnetic material; Externally-applied magnetic field auxiliary under collect magnetic particle, with deionized water and ethanol purge 3 ~ 6 times, vacuumize 6 ~ 24h at 40 ~ 80 DEG C, obtains dry Fe
3o
4/ SiO
2magnetic particle.
4. the magnetic material of finishing benzene sulfonic acid according to claim 1, it is characterized in that, in described step (3) specifically, get the magnetic material 1.0g that (2) are obtained, be distributed to toluene and N, in the mixed solution of dinethylformamide, toluene and N, the volume ratio of dinethylformamide is 1:(1 ~ 10), ultrasonic disperse is even, then the dichloromethane solution 1 ~ 20g of 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is added, the mass percentage of described 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is 50wt%, mechanical agitation 2 ~ 24h at 25 ~ 60 DEG C, the magnetic material of finishing benzene sulfonic acid is obtained by Silanization reaction, externally-applied magnetic field auxiliary under collect magnetic particle, with deionized water and ethanol purge 3 ~ 6 times, vacuumize 6 ~ 24h at 40 ~ 80 DEG C, obtains the Fe of dry finishing benzene sulfonic acid
3o
4/ SiO
2magnetic particle.
5. a preparation method for the magnetic material of finishing benzene sulfonic acid, is characterized in that, is prepared according to following step:
(1) synthesizing magnetic Fe
3o
4nano particle, with FeCl
36H
2o and FeSO
46H
2o be raw material with both (1 ~ 2): the mol ratio of 1 is dissolved in deionized water, and then add alkali lye under fast stirring and be greater than 11 to make system pH, under Keep agitation, anti-life can generate magnetic Fe
3o
4nano particle;
(2) by magnetic Fe prepared by step (1)
3o
4nano particle is re-dispersed in the mixed solution of second alcohol and water, and the volume ratio of second alcohol and water is (1 ~ 10): 1, adds excessive concentrated ammonia liquor and tetraethoxy-silicane, magnetic Fe prepared by described step (1)
3o
4nano particle, mass fraction are the concentrated ammonia liquor of 25 ~ 28% and the mass ratio of tetraethoxy-silicane is 1:(1-10): (0.2-10), room temperature with constant stirs, and to make tetraethoxy-silicane in the polymerization of magnetic particle surface hydrolysis, obtains Fe
3o
4/ SiO
2magnetic material, wherein concentrated ammonia liquor provides alkaline environment for reaction system, and tetraethoxy-silicane obtains the shell mechanism of tetraethoxy-silicane in the polymerization of magnetic particle surface hydrolysis;
(3) magnetic material prepared by step (2) is distributed to toluene and N; in the mixed solution of dinethylformamide; ultrasonic disperse is even; then the dichloromethane solution of excessive 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is added; fully react to make it; the mass ratio of the toluene solution of magnetic material prepared by described step (2) and 2-(4-chlorosulfonyl)-ethyl trichlorosilane is 1:1 ~ 20, and at 25 ~ 60 DEG C, Keep agitation obtains the magnetic material of finishing benzene sulfonic acid by Silanization reaction.
6. the preparation method of the magnetic material of a kind of finishing benzene sulfonic acid according to claim 5, is characterized in that, in described step (1) specifically, with FeCl
36H
2o and FeSO
46H
2o be raw material with both (1 ~ 2): the mol ratio of 1 is dissolved in 50mL deionized water, add the sodium hydrate aqueous solution solution of 10-40mL1.5mol/L under 400-800 turns/min rapid stirring, at 25 ~ 80 DEG C, then stir 1 ~ 24h can generate magnetic Fe
3o
4nano particle; Externally-applied magnetic field auxiliary under collect magnetic nano-particle, with deionized water and ethanol purge 3 ~ 6 times, vacuumize 6 ~ 24h at 25 ~ 80 DEG C, obtains dry magnetic Fe
3o
4nano particle.
7. the preparation method of the magnetic material of a kind of finishing benzene sulfonic acid according to claim 5, is characterized in that, in described step (2) specifically, by magnetic Fe prepared by step (1)
3o
4nano particle is re-dispersed in the mixed solution of second alcohol and water, the volume ratio of second alcohol and water is (1 ~ 10): 1, then concentrated ammonia liquor 1 ~ 10g that mass fraction is 25 ~ 28% is added, tetraethoxy-silicane 0.2 ~ 10g, room temperature 20-25 DEG C of mechanical agitation 3 ~ 24h, make tetraethoxy-silicane in the polymerization of magnetic particle surface hydrolysis, obtain Fe
3o
4/ SiO
2magnetic material; Externally-applied magnetic field auxiliary under collect magnetic particle, with deionized water and ethanol purge 3 ~ 6 times, vacuumize 6 ~ 24h at 40 ~ 80 DEG C, obtains dry Fe
3o
4/ SiO
2magnetic particle.
8. the preparation method of the magnetic material of a kind of finishing benzene sulfonic acid according to claim 5, it is characterized in that, in described step (3) specifically, get the magnetic material 1.0g that (2) are obtained, be distributed to toluene and N, in the mixed solution of dinethylformamide, toluene and N, the volume ratio of dinethylformamide is 1:(1 ~ 10), ultrasonic disperse is even, then the dichloromethane solution 1 ~ 20g of 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is added, the mass percentage of described 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane is 50wt%, mechanical agitation 2 ~ 24h at 25 ~ 60 DEG C, the magnetic material of finishing benzene sulfonic acid is obtained by Silanization reaction, externally-applied magnetic field auxiliary under collect magnetic particle, with deionized water and ethanol purge 3 ~ 6 times, vacuumize 6 ~ 24h at 40 ~ 80 DEG C, obtains the Fe of dry finishing benzene sulfonic acid
3o
4/ SiO
2magnetic particle.
9. the application of the magnetic material of finishing benzene sulfonic acid as claimed in claim 1 in extraction environmental water sample in vancomycin and Norvancomycin, is characterized in that, carry out activating and extracting according to following step:
(1) the magnetic material 50mg getting finishing benzene sulfonic acid is placed in 50mL centrifuge tube, and add 5mL methyl alcohol and 5mL deionized water washing activation successively, then under externally-applied magnetic field is auxiliary, collect magnetic material, solution discards;
(2) get 40mL and contain vancomycin and Norvancomycin water sample, described water sample pH value formic acid is adjusted to 2, join in centrifuge tube, mix and the 6min that vibrates with the magnetic material after activation, at the externally-applied magnetic field magnetic material of target compound of having assisted lower collection to adsorb, solution discards;
(3) magnetic material adsorbing target compound is added respectively 1mL deionized water and the drip washing of 1mL methyl alcohol; Then divide and add methyl alcohol-ammoniacal liquor for 3 times as eluant, eluent, the volume ratio of described methyl alcohol and ammoniacal liquor is 95:5, the mass percent of described ammoniacal liquor is 25-28%, each 1mL, the target compound of room temperature 20 DEG C vibration 1min wash-out absorption, magnetic material is separated under externally-applied magnetic field is auxiliary, collect and merge elute soln, dry up with nitrogen at 40 DEG C, residue deionized water again dissolves and is settled to 1mL, gets 20 these solution of μ L at every turn and carries out liquid-phase chromatographic analysis to measure the concentration of each target compound in concentrate.
10. the application of magnetic material in extraction environmental water sample in vancomycin and Norvancomycin of finishing benzene sulfonic acid according to claim 9, it is characterized in that, within the scope of 10 ~ 300 μ g/L, the mass concentration of vancomycin and Norvancomycin and peak area have good linear relationship, equal 3 and 10 with signal to noise ratio (S/N) and calculate the lowest detection line of this analytical method and minimum quantitative limit respectively, result shows that the lowest detectable limit of vancomycin and Norvancomycin is respectively 3.0 and 2.0 μ g/L, minimum quantitative limit is respectively 10.0 and 6.7 μ g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210514809.7A CN103065754B (en) | 2012-12-04 | 2012-12-04 | Magnetic material of finishing benzene sulfonic acid and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210514809.7A CN103065754B (en) | 2012-12-04 | 2012-12-04 | Magnetic material of finishing benzene sulfonic acid and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103065754A CN103065754A (en) | 2013-04-24 |
| CN103065754B true CN103065754B (en) | 2016-01-06 |
Family
ID=48108338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210514809.7A Expired - Fee Related CN103065754B (en) | 2012-12-04 | 2012-12-04 | Magnetic material of finishing benzene sulfonic acid and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103065754B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104209106B (en) * | 2014-08-29 | 2016-04-20 | 广西师范大学 | The Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle and synthetic method thereof and application |
| CN105504023A (en) * | 2016-02-23 | 2016-04-20 | 华北制药集团新药研究开发有限责任公司 | Capreomycin preparation method |
| CN105506042A (en) * | 2016-02-23 | 2016-04-20 | 华北制药集团新药研究开发有限责任公司 | Method for producing capreomycin by fermentation |
| CN111229188B (en) * | 2018-11-28 | 2022-03-29 | 天津大学 | Glycopeptide antibiotic functionalized magnetic composite material and preparation method and application thereof |
| CN111349270B (en) * | 2020-04-03 | 2022-02-08 | 广东彤泰新材料科技有限公司 | Filler composition modified by solvents with different polarities, preparation method and application |
| CN112034164B (en) * | 2020-08-28 | 2022-05-27 | 武汉生之源生物科技股份有限公司 | Chemiluminescence immune magnetic ball and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102091605A (en) * | 2010-12-01 | 2011-06-15 | 中国科学院生态环境研究中心 | Preparation and application of high-capacity magnetic mesoporous silica gel solid phase extracting agent |
| US20110237862A1 (en) * | 2010-03-26 | 2011-09-29 | Board Of Trustees Of The University Of Arkansas | MULTIFUNCTIONAL Fe3O4 CORED MAGNETIC-QUANTUM DOT FLUORESCENT NANOCOMPOSITES FOR RF NANO-HYPERTHERMIA OF CANCER CELLS |
| CN102357363A (en) * | 2011-07-23 | 2012-02-22 | 上海海事大学 | Nano-Fe3O4/SiO2/TiO2-loaded magnetical visible-light catalyst and preparation method thereof |
-
2012
- 2012-12-04 CN CN201210514809.7A patent/CN103065754B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110237862A1 (en) * | 2010-03-26 | 2011-09-29 | Board Of Trustees Of The University Of Arkansas | MULTIFUNCTIONAL Fe3O4 CORED MAGNETIC-QUANTUM DOT FLUORESCENT NANOCOMPOSITES FOR RF NANO-HYPERTHERMIA OF CANCER CELLS |
| CN102091605A (en) * | 2010-12-01 | 2011-06-15 | 中国科学院生态环境研究中心 | Preparation and application of high-capacity magnetic mesoporous silica gel solid phase extracting agent |
| CN102357363A (en) * | 2011-07-23 | 2012-02-22 | 上海海事大学 | Nano-Fe3O4/SiO2/TiO2-loaded magnetical visible-light catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103065754A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103065754B (en) | Magnetic material of finishing benzene sulfonic acid and its preparation method and application | |
| CN108620048B (en) | Preparation method and application of polyethyleneimine modified magnetic microspheres | |
| CN102974314B (en) | Magnetic gold nanoparticle composite material, and preparation method and application thereof | |
| CN103041773B (en) | Magnetic carbon nanotube composite material and preparation method and application thereof | |
| CN104258807B (en) | Magnetic nano material solid phase extracting agent as well as preparation method and application thereof | |
| CN101574645B (en) | Magnetic nano-material extractant and preparation method thereof | |
| CN108262019A (en) | A kind of magnetism sulfonic functional COFs materials and its preparation method and application | |
| CN102091605A (en) | Preparation and application of high-capacity magnetic mesoporous silica gel solid phase extracting agent | |
| CN104722274A (en) | Preparation and application of magnetic MOF-5 nano compound adsorbing agent | |
| CN102895938A (en) | Preparation method of graphene covered silica gel | |
| CN103028351B (en) | Benzene sulfonic acid modified magnetic microsphere and preparation method and application thereof | |
| CN110841612A (en) | Magnetic NH2Preparation and application of-MOFs nano material | |
| CN101664669A (en) | Preparation method and application of carboxylated single-walled carbon nanotube-alginic acid solid phase extracting disk | |
| CN103524742A (en) | Preparation method for magnetic multiple-template steroid estrogen molecular imprinting nanospheres | |
| CN105597713B (en) | Magnetic solid-phase extraction material and preparation method and application thereof | |
| Li et al. | Macro-microporous zeolitic imidazole framework-8/cellulose aerogel for semi-automated pipette tip solid phase extraction of fluoroquinolones in water | |
| CN110180516A (en) | Hydroxyethyl cellulose/polyethyleneimine composite magnetic adsorption material preparation method | |
| CN114471476B (en) | Magnetic porous organic framework material and preparation method and application thereof | |
| Fan et al. | Application of core–satellite polydopamine-coated Fe 3 O 4 nanoparticles–hollow porous molecularly imprinted polymer combined with HPLC-MS/MS for the quantification of macrolide antibiotics | |
| CN105413642A (en) | Preparation and application method of nickel ion imprinted magnetic chitosan nanometer material | |
| CN108079978B (en) | Fe3O4-NH2Preparation method and application of-PEI magnetic nano material | |
| CN111229169A (en) | Protein functionalized magnetic composite material and preparation method and application thereof | |
| CN111715198B (en) | Magnetic fullerene nano material and application thereof in magnetic dispersion solid-phase extraction of methyl methoxyacrylate pesticides | |
| CN111229188B (en) | Glycopeptide antibiotic functionalized magnetic composite material and preparation method and application thereof | |
| CN108339540B (en) | Preparation method and application of functional core-shell type magnetic solid-phase extractant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160106 Termination date: 20201204 |