CN109749117A - A kind of preparation method and its usage based on magnetic ferroferric oxide nano-particles-pH response type imprinted material - Google Patents
A kind of preparation method and its usage based on magnetic ferroferric oxide nano-particles-pH response type imprinted material Download PDFInfo
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Abstract
The invention belongs to detect technical field of material, it is related to a kind of preparation method of novel pH response type imprinted material based on magnetic ferroferric oxide nanometer ball；Steps are as follows: preparing ferriferrous oxide nano-particle, synthesizing mesoporous silicon dioxide four ferric oxide nano balls of cladding first, the chemical double bond for then coating four ferric oxide nano balls to mesoporous silicon oxide is modified；Finally obtain the pH response type imprinted material based on magnetic Nano microsphere；PH response type imprinted material prepared by the present invention, can solve substrate material surface, it is difficult to the problem of directly coating upper molecularly imprinted polymer layer；The imprinted material has and the consistent apparent core-shell structure of subject invention；Meanwhile the performance of binding molecule imprinted material of the present invention and pH response intellectual material, it is successfully applied to the efficient detection to sulfamethoxazole.
Description
Technical field
The invention belongs to detect technical field of material, refer specifically to a kind of based on magnetic ferroferric oxide nano-particles-
The preparation method and its usage of pH response type molecular engram material.
Background technique
Sulfonamides compound (SAs) is a kind of for preventing and treating the synthetic antibacterial agents of human body bacterium infection.Relatively
Few sulfa drugs is approved for the mammal of production food.Compared with other kinds of antibacterials, sulfonamides
Object is widely used in veterinary science.Sulfonamides compound is felt commonly used in preventing and treating acute systemic or part
Dye, and the additive as the feed of food production species and drinking water.Sulfamethoxazole (SMX) is a kind of typical sulfamido
Antibiotic is widely used in agricultural production；Inevitably, sulfamethoxazole can remain in milk or meat；Cause
This, Accurate Determining eats such residual in milk and has become a urgent task.Currently, ring can be detected by various methods
Sulfamethoxazole and other sulfa drugs in border, including method of immunity, Electrochemical Detection, Solid Phase Extraction (SPE) and
High performance liquid chromatography (HPLC)；Wherein most widely used is high performance liquid chromatography, its main feature is that may be implemented efficient, quasi-
True detection；However, sulfamethoxazole is existing for trace in agricultural by product, and sample composition is complicated, needs to sample
Carry out series of preprocessing.Therefore, develop that a kind of pair of sulfamethoxazole is sensitive, is quickly enriched with detection technique, to risk assessment
It is protected with public health most important.
Alternatively property adsorbent has been applied to the pretreatment of sulfamido sample to molecularly imprinted polymer.Molecular imprinting technology
It is a kind of with highly selective technology, the memory that it can use template molecule forms the cavity of shape of template, therefore pure
Change and Selective Separation field has received widespread attention.Surface molecule print technology is that imprinted layer is coated in carrier surface, by
It is evenly distributed in its recognition site, fast mass transfer rate and stronger binding ability can be provided.
In addition, stimuli responsive polymers are well known, because under environmental stimuli, such as pH value, temperature, magnetic field and light
Son irradiation, can occur volume phase transition.Currently, this kind of intellectual material has broad application prospects, such as drug delivery, sensor
And isolation technics.According to the type of ionogen, pH sensitivity gel can be divided into cation and anion.Water is responded to pH at present
The research of gel molecular imprinted polymer is less, in existing disclosed Research Literature, the polymerization of pH response water gel molecular engram
Object is applied to sulfonamides compound not yet.
Summary of the invention
In view of the deficienciess of the prior art, present invention seek to address that one of described problem；The present invention provides one kind and is based on
The preparation method of mesoporous silicon oxide coated ferriferrous oxide nano-particle molecular imprinted polymer material solves basis material table
Face, it is difficult to the problem of directly coating upper molecularly imprinted polymer layer, while realizing the Sensitive Detection to sulfamethoxazole in milk.
The present invention is achieved through the following technical solutions:
A kind of preparation based on magnetic ferroferric oxide nano-particles-pH response type imprinted material:
Step 1, Fe3O4The preparation of nanoparticle: by ferric chloride hexahydrate (FeCl3·6H2O it) is added into ethylene glycol, into
Row stirs for the first time, until sequentially adding sodium acetate (NaAc), trisodium citrate (Na after solution clarification3Cit) and polyethylene glycol,
It carries out second to stir, mixed liquor is transferred in the stainless steel autoclave of inner liner polytetrafluoroethylene and is reacted, reaction terminates
After naturally cool to room temperature, obtain the sediment of black, then washed respectively with distilled water and ethyl alcohol, after vacuum drying, obtain
Fe3O4Nanoparticle；
Step 2, the Fe for obtaining step 13O4Nanoparticle, which is added, contains cetyl trimethylammonium bromide (CTAB), ammonia
In the mixed solution of water, ethyl alcohol and deionized water, after ultrasonication, tetraethyl orthosilicate (TEOS) is slowly added dropwise to above-mentioned molten
Liquid, then mechanical stirring is reacted, and obtained product is cleaned, through vacuum repeatedly respectively after Magnetic Isolation with water and ethyl alcohol
After drying, obtained nano particle, then the removal CTAB that flowed back at a certain temperature with acetone, the polymer after collecting drying, note
Make Fe3O4@mSiO2；
Step 3, Fe3O4@mSiO2Chemical modification: by Fe obtained in step 23O4@mSiO2Toluene is added in nanoparticle
In, and ultrasonic disperse is uniform；Then, γ-methacryloxypropyl trimethoxy silane (MPS) is slowly added dropwise, in nitrogen
It is stirred under atmosphere, then, nano particle is obtained by Magnetic Isolation, with ethanol washing, remove unreacted components and reaction by-product
Object, the particle after collecting vacuum drying, is denoted as Fe3O4@MPS；
Step 4, by Fe prepared by step 33O4@MPS and ethyl 2-methacrylate (DMA), 4- vinylphenylboronic acid
(VPBA), N, N- methylene-bisacrylamide (MBA) and sulfamethoxazole are added in acetonitrile, ultrasonic dissolution；Then, it is stirred
And it is passed through nitrogen, and it being added ammonium persulfate (APS), is sealed reaction, obtained solid removes sulfamethoxazole with Soxhlet extraction,
It is denoted as Fe3O4@MIPs is as based on magnetic ferroferric oxide nano-particles-pH response type imprinted material.
Preferably, in step 1, the first time mixing time is 20~40min；Second of mixing time be 40~
60min；The condition of the reaction are as follows: 180~220 DEG C of temperature, the time 8~12 hours.
Preferably, in step 1, the use of the ferric chloride hexahydrate, sodium acetate, trisodium citrate, polyethylene glycol, ethylene glycol
Amount is than being 1.2~1.5g:3.2~3.9g:0.50~0.89g:0.7~1.2g:50~80mL.
Preferably, in step 2, the ultrasonic time is 10~30min；The mechanic whirl-nett reaction time is 5~8h；Institute
Stating certain temperature is 85~95 DEG C.
Preferably, in step 2, the Fe3O4, ammonium hydroxide, cetyl trimethylammonium bromide, ethyl alcohol, deionized water, positive silicon
The amount ratio of sour tetra-ethyl ester be 0.25~0.35g:2.5~5mL:0.5~0.7g:60~100mL:15~25mL:2.5~
3.5mL。
Preferably, in step 3, the ultrasonic time is 15~25min；It is described to be vigorously stirred the time as 23~26h.
Preferably, in step 3, the Fe3O4@mSiO2, toluene, γ-methacryloxypropyl trimethoxy silane
Amount ratio be 0.25~0.35g:60~80mL:4~7mL.
Preferably, in step 1~3, the vacuum drying temperature is 60~75 DEG C.
Preferably, in step 4, time of the ultrasonic dissolution is 15~25min, the time of the stirring is 50~
70min；The time of the sealing reaction is 23~26h.
Preferably, in step 4, the Fe3O4@MPS, ethyl 2-methacrylate, 4- vinylphenylboronic acid, N, N- methylene
Base bisacrylamide, sulfamethoxazole, acetonitrile, ammonium persulfate amount ratio be the μ of 0.14~0.16g:320~400 L:0.05~
0.07g:0.08~0.10g:0.05~0.07g:90~120mL:0.05~0.07g.
PH response type molecularly imprinted polymer prepared by the present invention is used to detect the sulfamethoxazole in milk.
In addition, (being denoted as Fe when preparing non-imprinted polymer3O4@NIPs), it is identical as above-mentioned steps, it is unique unlike
Template molecule-sulfamethoxazole is not added.
The utility model has the advantages that
(1) present invention solves the problems, such as that traditional matrix surface difficulty direct polymerization generates imprinted material, passes through utilization
Fe3O4Nanoparticle is matrix, is successfully prepared a kind of pH response type imprinted material, realizes the specificity to sulfamethoxazole
Detection.
(2) the pH response type imprinted material prepared by the present invention has clearly core-shell structure, after tested, has good
PH response performance, can realize extraction to sulfamethoxazole by changing pH.
(3) present invention is introduced in material synthesis processes intermediary Porous materials, is greatly increased specific surface area, is increased spy
Anisotropic adsorption site improves imprinted material to the adsorption effect of sulfamethoxazole, and has preferable stability, high selection
Property the features such as, to realize efficient highly selective extraction to sulfamethizole.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph and projection electron microscope of sample prepared by embodiment 2, and wherein a is Fe3O4Nanoparticle
Transmission electron microscope picture, b are the ferriferrous oxide nano-particle of mesoporous silicon oxide cladding, i.e. Fe3O4@mSiO2Transmission electron microscope picture, c
For pH response type imprinted material (Fe3O4@MIPs) transmission electron microscope picture, d be non-imprinted material (Fe3O4@NIPs) transmission electron microscope
Figure.
Fig. 2 is the infrared figure of Fourier of sample prepared by embodiment 2, and wherein a is Fe3O4The infrared figure of nanoparticle, b
For the ferriferrous oxide nano-particle of mesoporous silicon oxide cladding, i.e. Fe3O4@mSiO2Infrared, c Fe3O4@MPS's is infrared
Figure, d are pH response type imprinted material (Fe3O4@MIPs) infrared figure.
Fig. 3 is the nitrogen adsorption isotherm and pore-size distribution of pH response type molecularly imprinted polymer prepared by embodiment 2
Figure.
Fig. 4 is Fe prepared by embodiment 23O4@MIPs and Fe3O4The figure of@NIPs absorption property, wherein (a) is that absorption is dynamic
Force diagram (b) is adsorption isotherm.
Fig. 5 is Fe prepared by embodiment 23O4@MIPs and Fe3O4The figure of the absorption property of@NIPs, wherein a is with bright lattice
Miao Er adsorpting type matched curve figure.
Fig. 6 is Fe prepared by embodiment 23O4@MIPs and Fe3O4The pH response performance figure of@NIPs, wherein (a) is pH pairs
Fe3O4@MIPs and Fe3O4The influence of@NIPs adsorbance is (b) pH to Fe3O4The influence of@MIPs release sulfamethizole behavior.
Fig. 7 is Fe prepared by embodiment 23O4@MIPs and Fe3O4The repetitive research of@NIPs.
Specific embodiment
The invention will be further described in conjunction with specific embodiments for lower surface:
Embodiment 1:
Step 1, Fe3O4The preparation of nanoparticle: by 1.2g FeCl3·6H2O is added into 50mL ethylene glycol, and stirs
20min is clarified to solution, sequentially adds 3.2g sodium acetate (NaAc), 0.5g trisodium citrate (Na3) and the poly- second two of 0.7g Cit
Mixed liquor is transferred in the stainless steel autoclave of inner liner polytetrafluoroethylene by alcohol after magnetic agitation 40min, and 180 DEG C of high temperature are anti-
After answering 8h, room temperature is naturally cooled to；Finally, the sediment of black distilled water and ethyl alcohol wash respectively, it is dried in vacuo, temperature is
60 DEG C, obtain Fe3O4Nanoparticle；
Step 2, the Fe for obtaining step 13O4Nanoparticle takes 0.25g to be added to containing 0.5g cetyl trimethyl bromine
In the mixed solution for changing ammonium (CTAB), 2.5mL ammonium hydroxide, 60mL ethyl alcohol and 15mL deionized water, after ultrasonic 10min, just by 2.5mL
Tetraethyl orthosilicate (TEOS) is slowly added dropwise to above-mentioned solution, and then mechanical stirring 5h, obtained product use water after Magnetic Isolation
It cleans with ethyl alcohol, is then dried in vacuo repeatedly respectively；CTAB is removed in 85 DEG C of reflux of the nano particle acetone finally obtained, is collected
Polymer after drying, is denoted as Fe3O4@mSiO2；
Step 3, Fe3O4@mSiO2Chemical modification: by the Fe in step 23O4@mSiO2Nanoparticle take 0.25g be added to
In 60mL toluene, and ultrasound 15min is uniformly dispersed；Then, by γ-methacryloxypropyl trimethoxy silane of 4mL
(MPS) it is slowly added dropwise into above-mentioned solution, is vigorously stirred 23h in a nitrogen atmosphere；Solution after reaction is obtained by Magnetic Isolation
To nano particle, repeatedly washed with ethyl alcohol, to remove unreacted components and byproduct of reaction, the particle after collecting vacuum drying,
It is denoted as Fe3O4@MPS；
Step 4, by Fe prepared by step 33O4@MPS take 0.14g and 320 μ L ethyl 2-methacrylates (DMA),
0.05g 4- vinylphenylboronic acid (VPBA), 0.08g N,N methylene bis acrylamide (MBA) and 0.05g sulfamethoxazole are molten
Solution is in 90mL acetonitrile, and ultrasound 15min is to being uniformly dispersed；Then, above-mentioned solution is vigorously stirred to and is passed through nitrogen 50min,
It is added 0.05g ammonium persulfate (APS), seals persistently stir 23h later；Obtained solid Soxhlet extraction removes sulfalene and dislikes
Azoles is denoted as Fe3O4@MIPs。
(Fe is denoted as when non-imprinted polymer3O4@NIPs), with Fe3O4The synthetic method of@MIPs is similar, it is unique unlike
Template molecule-sulfamethoxazole is not added.
Embodiment 2:
Step 1, Fe3O4The preparation of nanoparticle: by 1.35g FeCl3·6H2O is added into 60mL ethylene glycol, and stirs
30min is clarified to solution, sequentially adds 3.6g sodium acetate (NaAc), 0.72g trisodium citrate (Na3) and 1g polyethylene glycol Cit；
After magnetic agitation 50min, mixed liquor is transferred in the stainless steel autoclave of inner liner polytetrafluoroethylene, 200 DEG C of pyroreactions
After 10h, room temperature is naturally cooled to；Finally, the sediment of black distilled water and ethyl alcohol wash respectively, it is dried in vacuo, temperature is
65 DEG C, obtain Fe3O4Nanoparticle；
Step 2, the Fe for obtaining step 13O4Nanoparticle takes 0.3g to be added to containing 0.6g cetyl trimethyl bromination
Ammonium (CTAB), 3mL ammonium hydroxide, 80mL ethyl alcohol and 20mL deionized water mixed solution in, after ultrasonic 15min, by the positive silicic acid four of 3mL
Ethyl ester (TEOS) is slowly added dropwise to above-mentioned solution, then mechanical stirring 6h, and obtained product is after Magnetic Isolation, with water and ethyl alcohol
It cleans, is then dried in vacuo repeatedly respectively.CTAB is removed in 90 DEG C of the nano particle acetone finally obtained reflux, after collecting drying
Polymer, be denoted as Fe3O4@mSiO2；
Step 3, Fe3O4@mSiO2Chemical modification: by the Fe in step 23O4@mSiO2Nanoparticle take 0.3g be added to
In 70mL toluene, and ultrasound 20min is uniformly dispersed.Then, by 5mL γ-methacryloxypropyl trimethoxy silane
(MPS) it is slowly added dropwise into above-mentioned solution, is vigorously stirred in a nitrogen atmosphere for 24 hours.Solution after reaction is obtained by Magnetic Isolation
To nano particle, repeatedly washed with ethyl alcohol, to remove unreacted components and byproduct of reaction, the particle after collecting vacuum drying,
It is denoted as Fe3O4@MPS；
Step 4, by Fe prepared by step 33O4@MPS take 0.15g and 360 μ L ethyl 2-methacrylates (DMA),
0.06g 4- vinylphenylboronic acid (VPBA), 0.09g N,N methylene bis acrylamide (MBA) and 0.06g sulfamethoxazole are molten
Solution is in 100mL acetonitrile, and ultrasound 20min is to being uniformly dispersed.Then, above-mentioned solution is vigorously stirred to and is passed through nitrogen 60min,
It is added 0.06g ammonium persulfate (APS), the lasting stirring of sealing later is for 24 hours；Obtained solid Soxhlet extraction removes sulfalene and dislikes
Azoles is denoted as Fe3O4@MIPs。
(Fe is denoted as when non-imprinted polymer3O4@NIPs), with Fe3O4The synthetic method of@MIPs is similar, it is unique unlike
Template molecule-sulfamethoxazole is not added.
Embodiment 3:
Step 1, Fe3O4The preparation of nanoparticle: by 1.5g FeCl3·6H2O is added into 80mL ethylene glycol, and stirs
40min is clarified to solution, sequentially adds 3.9g sodium acetate (NaAc), 0.89g trisodium citrate (Na3) and the poly- second two of 1.2g Cit
Alcohol；After magnetic agitation 60min, mixed liquor is transferred in the stainless steel autoclave of inner liner polytetrafluoroethylene.220 DEG C of high temperature are anti-
After answering 12h, room temperature is naturally cooled to.Finally, the sediment of black distilled water and ethyl alcohol wash respectively, and vacuum drying, temperature
It is 75 DEG C, obtains Fe3O4Nanoparticle；
Step 2, the Fe for obtaining step 13O4Nanoparticle takes 0.35g to be added to containing 0.7g cetyl trimethyl bromine
In the mixed solution for changing ammonium (CTAB), 5mL ammonium hydroxide, 100mL ethyl alcohol and 25mL deionized water, after ultrasonic 30min, just by 3.5mL
Tetraethyl orthosilicate (TEOS) is slowly added dropwise to above-mentioned solution, and then mechanical stirring 8h, obtained product use water after Magnetic Isolation
It cleans with ethyl alcohol, is then dried in vacuo repeatedly respectively, CTAB is removed in 95 DEG C of reflux of the nano particle acetone finally obtained, is collected
Polymer after drying, is denoted as Fe3O4@mSiO2；
Step 3, Fe3O4@mSiO2Chemical modification: by the Fe in step 23O4@mSiO2Nanoparticle take 0.35g be added to
In 80mL toluene, and ultrasound 25min is uniformly dispersed；Then, by γ-methacryloxypropyl trimethoxy silane of 7mL
(MPS) it is slowly added dropwise into above-mentioned solution, is vigorously stirred 26h in a nitrogen atmosphere, the solution after reaction is obtained by Magnetic Isolation
To nano particle, repeatedly washed with ethyl alcohol, to remove unreacted components and byproduct of reaction, the particle after collecting vacuum drying,
It is denoted as Fe3O4@MPS；
Step 4, by Fe prepared by step 33O4@MPS take 0.16g and 400 μ L ethyl 2-methacrylates (DMA),
0.07g 4- vinylphenylboronic acid (VPBA), 0.10g N,N methylene bis acrylamide (MBA) and 0.07g sulfamethoxazole are molten
Solution is in 120mL acetonitrile, and ultrasound 25min is to being uniformly dispersed.Then, above-mentioned solution is vigorously stirred to and is passed through nitrogen 70min,
It is added 0.07g ammonium persulfate (APS), seals persistently stir 26h later, obtained solid Soxhlet extraction removes sulfalene and dislikes
Azoles is denoted as Fe3O4@MIPs。
(Fe is denoted as when non-imprinted polymer3O4@NIPs), with Fe3O4The synthetic method of@MIPs is similar, it is unique unlike
Template molecule-sulfamethoxazole is not added.
Fig. 1 is the scanning electron microscope (SEM) photograph and projection electron microscope of sample prepared by embodiment 2, and wherein a is Fe3O4Nanoparticle
Transmission electron microscope picture, it can be seen that the Fe of preparation3O4For size 300nm or so spheric granules；B is mesoporous silicon oxide cladding
Ferriferrous oxide nano-particle, i.e. Fe3O4@mSiO2Transmission electron microscope picture, two for showing apparent core-shell structure, and coating
Silicon oxide thickness is about 70nm；C and d is respectively pH response type imprinted material (Fe3O4@MIPs) and non-imprinted material (Fe3O4@
NIPs the transmission electron microscope picture of transmission electron microscope picture), the two has no significant difference, is three-decker.
Fig. 2 is the infrared figure of Fourier of sample prepared by embodiment 2, and wherein a is Fe3O4The infrared figure of nanoparticle, b
For the ferriferrous oxide nano-particle of mesoporous silicon oxide cladding, i.e. Fe3O4@mSiO2Infrared, c Fe3O4@MPS's is infrared
Figure, d are pH response type imprinted material (Fe3O4@MIPs) infrared figure.Wherein 592.85cm-1The peak value at place is due to Fe3O4Magnetic
Property nano particle Fe-O stretch caused by.For Fe3O4@mSiO2,1088.59cm-1And 801.31cm-1The different peak values at place point
Do not meet the vibration of Si-O-Si asymmetrical stretch and midplane extrusion vibration, 950.58cm-1The peak value at place has Si-O-H bending vibration
Feature.Fe3O4About 1635.7cm in@MPS-1Peak value be C-C double bond.In Fe3O4In the spectrum of@MIP, 3430.79cm-1Place
Peak value it is consistent with DMA.
Fig. 3 is the nitrogen adsorption isotherm and pore-size distribution of pH response type molecularly imprinted polymer prepared by embodiment 2
Figure；Wherein, illustration is graph of pore diameter distribution.It can be seen from the figure that Fe3O4The adsorption/desorption process of@MIP meets typical IV type
Thermoisopleth shows that porous structure is clear.In addition, the specific surface area of imprinted material is measured as 651.7080m2g-1, desorption branch
The average pore diameter of material is 2.2312nm.
Fig. 4 is Fe prepared by embodiment 23O4@MIPs and Fe3O4The figure of@NIPs absorption property, wherein (a) is that absorption is dynamic
Force diagram, it can be seen that Fe3O4@MIP and Fe3O4The Q value of@NIP increases sharply in preceding 40min, starts only 80min and just reaches
Adsorption equilibrium.The result shows that the Fe of preparation3O4The@MIP nano particle rate of adsorption is fast because magnetic nano-particle surface have it is abundant
Imprinted sites；It (b) is adsorption isotherm, discovery is as SMX concentration is from 0.1mmolL-1Increase to 0.5mmolL-1Mistake
Cheng Zhong, Fe3O4@MIP/Fe3O4The Q value of@NIP significantly increases.Further, since trace effect, Fe3O4The Q value of@MIP is obvious high
In Fe3O4The Q value of@NIP.
Fig. 5 is Fe prepared by embodiment 23O4@MIPs and Fe3O4Research of the@NIPs to sulfamethizole specific adsorption
Figure.By from sulfamethoxazole (SMX) and its analogue sulphadiazine (SDZ), sulfamethazine (SMZ) and different
The binding ability of structural compounds tetrabromobisphenol A (TBBPA) compares, and has rated the specificity of trace nano particle.Fe3O4@MIP
Nanoparticle is shown to the higher binding ability of sulfamethoxazole, imprinting factor (IF) also higher (IF=2.14 of SMX, SDZ
IF=1.33, the IF=1.09 of the IF=1.28 and TBBPA of SMZ), disclose, propose Fe3O4The selective absorption of@MIP SMX,
This process formed dependent on conformation memory marking print decayed tooth.In addition, analogue and template SMX-S having the same (=
O)2-Group, this causes the combination of they and trace nanoparticle to be significantly higher than TBBPA.Obviously, Fe3O4@MIP is to these chemical combination
The adsorption capacity of object is apparently higher than Fe3O4@NIP。
Fig. 6 is the pH response performance figure of Fe3O4@MIPs and Fe3O4@NIPs prepared by embodiment 2, wherein (a) is pH
Influence to Fe3O4@MIPs and Fe3O4@NIPs adsorbance, with the increase of pH value, the adsorption capacity of SMX increases, in pH=7
When reach balance.This is mainly due to the hydrogen bonds between target molecule and function monomer to dissociate when pH is less than 4, when pH is greater than 6
It is formed.Compared with Fe3O4@NIP, the adsorption capacity of Fe3O4@MIP is higher, this is because imprinted polymer surface form with
The matched specific recognition cavity of SMX.(b) influence for discharging sulfamethizole behavior to Fe3O4@MIPs for pH, can observe
Burst size to SMX is reduced as environmental pH is increased to 8 from 2.In addition, washing 3 times with PB buffer solution (pH=2), often
Secondary 1h can almost discharge all templates.This pH response release of SMX is close with the dilation behavior of trace nano particle
It is related.
Fig. 7 is Fe prepared by embodiment 23O4@MIPs and Fe3O4The repetitive research of@NIPs.After circulation 8 times,
Fe3O4@MIP/Fe3O4@NIP is still renewable, and adsorption capacity is without being substantially reduced.This is because the release of SMX is by changing ring
Border pH value realizes, rather than realized by harsh organic solvent, because organic solvent would generally block trace chamber,
Cause poor reusability.
Illustrate: above embodiments are only to illustrate the present invention and not limit the technical scheme described by the invention；Therefore,
Although this specification is referring to above-mentioned each embodiment, the present invention has been described in detail, the common skill of this field
Art personnel should be appreciated that and still can modify to the present invention or equivalent replacement；And all do not depart from spirit of the invention and
The technical solution and its improvement of range, should all cover in scope of the presently claimed invention.
Claims (10)
1. a kind of preparation method based on magnetic ferroferric oxide nano-particles-pH response type imprinted material, which is characterized in that step
It is rapid as follows:
Step 1, Fe3O4The preparation of nanoparticle: ferric chloride hexahydrate is added into ethylene glycol, first time stirring is carried out, until molten
After liquid clarification, sodium acetate, trisodium citrate and polyethylene glycol are sequentially added, second is carried out and stirs, mixed liquor is transferred to interior
It is reacted in the stainless steel autoclave of lining teflon, naturally cools to room temperature after reaction, obtain the precipitating of black
Object, then washed respectively with distilled water and ethyl alcohol, after vacuum drying, obtain Fe3O4Nanoparticle；
Step 2, the Fe for obtaining step 13O4Nanoparticle is added containing cetyl trimethylammonium bromide, ammonium hydroxide, ethyl alcohol and goes
In the mixed solution of ionized water, after ultrasound, tetraethyl orthosilicate is added, then mechanical stirring is reacted, obtained product warp
After Magnetic Isolation, it is respectively washed with water and ethyl alcohol, after vacuum dried, obtained nano particle；Again with acetone in certain temperature
It flows away next time and removes cetyl trimethylammonium bromide, the polymer after collecting drying is denoted as Fe3O4@mSiO2；
Step 3, Fe3O4@mSiO2Chemical modification: by Fe obtained in step 23O4@mSiO2Nanoparticle is added in toluene, surpasses
Sound dispersion；Then, γ-methacryloxypropyl trimethoxy silane is added dropwise, is stirred in a nitrogen atmosphere, then,
Nano particle is obtained by Magnetic Isolation, with ethanol washing, the particle after being dried in vacuo is collected, is denoted as Fe3O4@MPS；
Step 4, by Fe prepared by step 33O4@MPS and ethyl 2-methacrylate, 4- vinylphenylboronic acid, N, N- methylene
Bisacrylamide and sulfamethoxazole are added in acetonitrile, ultrasonic dissolution；Then, it is stirred and is passed through nitrogen, adds over cure
Sour ammonium is sealed reaction, and obtained solid removes sulfamethoxazole with Soxhlet extraction, is denoted as Fe3O4@MIPs is as based on magnetic
Property ferriferrous oxide nano-particle-pH response type imprinted material.
2. the system according to claim 1 based on magnetic ferroferric oxide nano-particles-pH response type molecular engram material
Preparation Method, which is characterized in that in step 1, the first time mixing time is 20~40min；Second of mixing time be
40~60min；The condition of the reaction are as follows: 180~220 DEG C of temperature, the time 8~12 hours.
3. the system according to claim 1 based on magnetic ferroferric oxide nano-particles-pH response type molecular engram material
Preparation Method, which is characterized in that the ferric chloride hexahydrate, sodium acetate, trisodium citrate, polyethylene glycol, ethylene glycol amount ratio
For 1.2~1.5g:3.2~3.9g:0.50~0.89g:0.7~1.2g:50~80mL.
4. the system according to claim 1 based on magnetic ferroferric oxide nano-particles-pH response type molecular engram material
Preparation Method, which is characterized in that in step 2, the ultrasonic time is 10~30min；The mechanic whirl-nett reaction time be 5~
8h；The certain temperature is 85~95 DEG C.
5. the system according to claim 1 based on magnetic ferroferric oxide nano-particles-pH response type molecular engram material
Preparation Method, which is characterized in that in step 2, the Fe3O4, ammonium hydroxide, cetyl trimethylammonium bromide, ethyl alcohol, deionized water, just
The amount ratio of tetraethyl orthosilicate be 0.25~0.35g:2.5~5mL:0.5~0.7g:60~100mL:15~25mL:2.5~
3.5mL。
6. the system according to claim 1 based on magnetic ferroferric oxide nano-particles-pH response type molecular engram material
Preparation Method, which is characterized in that in step 3, the time of the ultrasonic disperse is 15~25min；The time of the stirring be 23~
26h。
7. the system according to claim 1 based on magnetic ferroferric oxide nano-particles-pH response type molecular engram material
Preparation Method, which is characterized in that in step 3, the Fe3O4@mSiO2, toluene, γ-methacryloxypropyl trimethoxy
The amount ratio of silane is 0.25~0.35g:60~80mL:4~7mL.
8. the system according to claim 1 based on magnetic ferroferric oxide nano-particles-pH response type molecular engram material
Preparation Method, which is characterized in that in step 4, time of the ultrasonic dissolution is 15~25min, the time of the stirring is 50~
70min；The time of the sealing reaction is 23~26h.
9. the system according to claim 1 based on magnetic ferroferric oxide nano-particles-pH response type molecular engram material
Preparation Method, which is characterized in that in step 4, the Fe3O4@MPS, ethyl 2-methacrylate, 4- vinylphenylboronic acid, N, N- are sub-
Bisacrylamide, sulfamethoxazole, acetonitrile, ammonium persulfate amount ratio be the μ of 0.14~0.16g:320~400 L:0.05
~0.07g:0.08~0.10g:0.05~0.07g:90~120mL:0.05~0.07g.
10. pH response molecular engram material prepared by preparation method described in any one of claim 1 to 9 is applied to detection
Sulfamethoxazole in milk.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111346675A (en) * | 2020-02-15 | 2020-06-30 | 江苏大学 | Preparation method and application of acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst |
| CN111495344A (en) * | 2020-03-23 | 2020-08-07 | 江苏大学 | Photoresponse type molecularly imprinted polymer based on magnetic mesoporous silicon nanoparticles, preparation method and application |
| CN111499886A (en) * | 2020-04-29 | 2020-08-07 | 南京工业大学 | Structural color granular gel and preparation method thereof |
| CN112300347A (en) * | 2020-10-19 | 2021-02-02 | 江苏大学 | Preparation method and application of magnetic ferroferric oxide nanoparticle-based photoresponse imprinted material |
| CN113058576A (en) * | 2021-03-08 | 2021-07-02 | 中国农业科学院北京畜牧兽医研究所 | Hollow core-shell structure nano magnetic microsphere, preparation method and application thereof |
| CN114192123A (en) * | 2021-11-18 | 2022-03-18 | 江苏大学 | Photoresponse molecular imprinting material, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784626A (en) * | 2012-08-08 | 2012-11-21 | 江苏大学 | Temperature-sensitive magnetic sulfadimidine molecular imprinted adsorbent as well as preparation method and application thereof |
| CN103100377A (en) * | 2013-02-27 | 2013-05-15 | 江苏大学 | Green preparation method of magnetic molecular imprinting sorbent |
| US20150079270A1 (en) * | 2013-09-18 | 2015-03-19 | Lei Wang | Fabrication of Magnetic Nanoparticles |
| CN105107482A (en) * | 2015-09-11 | 2015-12-02 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method |
| CN105254785A (en) * | 2015-11-20 | 2016-01-20 | 哈尔滨工业大学 | Method for preparing glucose difunctional monomer magnetic molecularly imprinted polymer |
| CN107096514A (en) * | 2017-06-16 | 2017-08-29 | 江苏科技大学 | Boronate tin oxide trace composite nano-microsphere, its preparation method and its application of a kind of hollow structure |
-
2019
- 2019-02-16 CN CN201910118473.4A patent/CN109749117B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784626A (en) * | 2012-08-08 | 2012-11-21 | 江苏大学 | Temperature-sensitive magnetic sulfadimidine molecular imprinted adsorbent as well as preparation method and application thereof |
| CN103100377A (en) * | 2013-02-27 | 2013-05-15 | 江苏大学 | Green preparation method of magnetic molecular imprinting sorbent |
| US20150079270A1 (en) * | 2013-09-18 | 2015-03-19 | Lei Wang | Fabrication of Magnetic Nanoparticles |
| CN105107482A (en) * | 2015-09-11 | 2015-12-02 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method |
| CN105254785A (en) * | 2015-11-20 | 2016-01-20 | 哈尔滨工业大学 | Method for preparing glucose difunctional monomer magnetic molecularly imprinted polymer |
| CN107096514A (en) * | 2017-06-16 | 2017-08-29 | 江苏科技大学 | Boronate tin oxide trace composite nano-microsphere, its preparation method and its application of a kind of hollow structure |
Non-Patent Citations (1)
| Title |
|---|
| WEIWEI ZHAO ET AL.: "Novel Method To Investigate the Interaction Force between Etoposide and APTES-Functionalized Fe3O4@nSiO2@mSiO2 Nanocarrier for Drug Loading and Release Processes", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111346675A (en) * | 2020-02-15 | 2020-06-30 | 江苏大学 | Preparation method and application of acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst |
| CN111346675B (en) * | 2020-02-15 | 2022-09-16 | 江苏大学 | Preparation method and application of acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst |
| CN111495344A (en) * | 2020-03-23 | 2020-08-07 | 江苏大学 | Photoresponse type molecularly imprinted polymer based on magnetic mesoporous silicon nanoparticles, preparation method and application |
| CN111495344B (en) * | 2020-03-23 | 2023-02-17 | 江苏大学 | Photoresponse type molecularly imprinted polymer based on magnetic mesoporous silicon nanoparticles, preparation method and application |
| CN111499886A (en) * | 2020-04-29 | 2020-08-07 | 南京工业大学 | Structural color granular gel and preparation method thereof |
| CN111499886B (en) * | 2020-04-29 | 2022-12-09 | 南京工业大学 | Structural color granular gel and preparation method thereof |
| CN112300347A (en) * | 2020-10-19 | 2021-02-02 | 江苏大学 | Preparation method and application of magnetic ferroferric oxide nanoparticle-based photoresponse imprinted material |
| CN112300347B (en) * | 2020-10-19 | 2022-05-20 | 江苏大学 | Preparation method and application of magnetic ferroferric oxide nanoparticle-based photoresponse imprinted material |
| CN113058576A (en) * | 2021-03-08 | 2021-07-02 | 中国农业科学院北京畜牧兽医研究所 | Hollow core-shell structure nano magnetic microsphere, preparation method and application thereof |
| CN113058576B (en) * | 2021-03-08 | 2024-01-26 | 中国农业科学院北京畜牧兽医研究所 | Hollow core-shell structure nano magnetic microsphere, preparation method and application thereof |
| CN114192123A (en) * | 2021-11-18 | 2022-03-18 | 江苏大学 | Photoresponse molecular imprinting material, preparation method and application |
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