CN108404891A - Magnetic molecularly imprinted adsorbent of a kind of hollow single hole of Ianus type and preparation method thereof - Google Patents
Magnetic molecularly imprinted adsorbent of a kind of hollow single hole of Ianus type and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to magnetic molecularly imprinted adsorbents of a kind of hollow single hole of Ianus type and preparation method thereof, belong to specific isolation functional material preparing technical field；The invention firstly uses anisotropic emulsion template methods to prepare the hollow silicon ball of Ianus type single hole, carboxyl is introduced after the amido functional group and anhydride reaction of hollow single hole nano silicon spheres inner surface, the magnetic ferric oxide nano particles of preparation are chemically bound on the carboxyl of hollow single hole nano silicon spheres inner surface by the pyrolytic through ferric acetyl acetonade, obtain magnetic hollow single hole nano silicon spheres；It is function monomer using the vinylphenylboronic acid with boron affinity interaction, using cyanidenon as template molecule, the imprinted polymer of cyanidenon molecule is modified in the outer surface of single hole hollow magnetic silicon ball through atom transfer radical polymerization again, obtains Ianus type single hole hollow magnetic trace adsorbent；Last Binding experiment verification, material of the invention have specific isolation performance to cyanidenon, have excellent magnetism.
Description
Technical field
The present invention relates to magnetic molecularly imprinted adsorbents of a kind of hollow single hole of Ianus type and preparation method thereof, more particularly to
It is a kind of to prepare refined exert through anisotropy emulsion template, the high temperature pyrolysis of ferric acetyl acetonade and atom transferred free radical trace polymerization
The method of this magnetic molecularly imprinted adsorbent of hollow single hole of (Janus) type belongs to specific isolation functional material preparing technical field.
Background technology
Molecular imprinting technology is to prepare the method for having specific recognition effect polymer to a certain molecule, the polymerization of preparation
Object is molecularly imprinted polymer（MIPs）.Because of its specific recognition, extensive practicability and chemical stability, molecularly imprinted polymer
It has been widely used in isolating and purifying field.However traditional MIPs is generally highly cross-linked converging network, template molecule
Elution and the dynamic performance identified again are poor.Hollow imprinted polymer（H-MIPs）It is smaller with unique hollow structure
Density and higher specific surface area can significantly increase binding kinetics and saturated adsorption capacity.The MIPs of hollow single hole arrangements makees
For the H-MIPs of special shape, gather around that there are one single hole, external sample solution or elutions in original hollow skeleton structure
Liquid energy enters by single hole duct inside MIPs, therefore can further improve the binding kinetics performance of trace binding site.
Magnetic molecularly imprinted polymer（MMIPs）It is coated on superparamagnetic nano-particle (such as using imprinting material
Fe3O4With γ-Fe2O3Deng) surface obtain magnetic composite.MMIPs utilizes the affine specificity of imprinting, by
The lock out operation such as target molecule can be identified, loads, delivers and unload in magnetic separation device, to simplify target point
The separation and concentration process of son.Because prepared by MMIPs different technology paths, existing side are adhered to separately from the design of hollow single hole arrangements
Superparamagnetic nano-particle is often introduced the surfaces hollow single hole arrangements MIPs by method by the means of physical dispersion, chemical graft.This
Way will seriously occupy effective trace binding site, cause the reduction of adsorption capacity.Therefore, be badly in need of find guarantee do not embed with
Under the premise of preventing take up binding site while introducing the effective ways in trace polymerization site and superparamagnetic nano-particle.
Ianus（Janus）Nano material can assign same nano-particle multi-functional due to its two-sided structure.If adopting
The hollow single hole magnetism MIPs of Ianus type is prepared with suitable method, will effectively solve above-mentioned problem.Emulsion template method is to prepare
One of the important method of hollow structure microsphere nano material.However the work that Ianus type MIPs is prepared using the strategy is not appeared in the newspapers
Road.Cyanidenon (LTL) has antimicrobial antiphlogistic, antiviral and antitumor, anti-oxidant as one of natural organic flavonoids drug
The medical values such as property.Mainly there are the heavy method of acid, thin layer chromatography, gradient extraction for the isolation and purification method of cyanidenon at present
Column, chromatography and macroporous resin adsorption partition method etc..These traditional methods are often associated with the difficult separation of difficult elution, poor selectivity etc.
Problem.Therefore, the hollow single hole magnetism MIPs of Ianus type is prepared, and for specific recognition and isolates and purifies cyanidenon by pole
Tool economy, society and learning value.
Invention content
The present invention is prepared for the hollow silicon ball of Ianus type single hole using anisotropic emulsion template method（SHH-Si）, SHH-
The outer surface of Si and inner surface contain chlorine atom and amido functional group respectively；Draw after the amido functional group and anhydride reaction of inner surface
Enter carboxyl（SHH-Si-COOH）, the magnetic ferric oxide nano particles of preparation are chemically bonded by the pyrolytic through ferric acetyl acetonade
On the carboxyl of SHH-Si-COOH inner surfaces, single hole hollow magnetic silicon ball is obtained（MSHH-Si）；Cause in silicon ball outer surface and prints
Mark polymerize, and is function monomer using the vinylphenylboronic acid with boron affinity interaction, using cyanidenon as template molecule, then through original
Sub- transferring free-radical polymerization has modified the imprinted polymer of cyanidenon molecule in the outer surface of single hole hollow magnetic silicon ball, obtains
Ianus type single hole hollow magnetic trace adsorbent（SHH-MMIPs）.Staticadsorption experiment is finally combined, wood is applied to
Being selectively adsorbing and separating for rhinoceros grass element, demonstrates specific isolation performances of the SHH-MMIPs to cyanidenon.
Present invention firstly provides a kind of magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type, the adsorbent combines
The advantage of hollow single hole arrangements, Magnetic Isolation and molecular engram is source of iron using pyrolytic ferric acetyl acetonade, passes through atom
Transferring free-radical polymerization method realizes boric acid base group trace polymerization, and while not influencing mutual advantage, for cyanidenon
Absorption, adsorption/desorption process simultaneously, protect ferroso-ferric oxide not by acid etching.
The technical solution adopted by the present invention is：
（1）Hollow single hole nano silicon spheres（SHH-Si）Preparation：
Polyvinylpyrrolidone is dissolved in n-amyl alcohol, the ammonia spirit of ethyl alcohol and sodium citrate is added；By above-mentioned solution
Mixing is placed in mechanical agitation in three-necked flask, while sequentially adding tetraethyl orthosilicate, gamma-aminopropyl-triethoxy-silane and chlorine
Propyl trimethoxy silicane；Stop after stirring a period of time, after being washed several times successively with second alcohol and water, vacuum is dry at 40 DEG C
It is dry, hollow single hole nano silicon spheres are made（SHH-Si）.
Wherein, the dosage of the polyvinylpyrrolidone and n-amyl alcohol is 2.0-4.0g：20-30mL；The ethyl alcohol, lemon
The dosage of lemon acid sodium and ammonium hydroxide is 2-5 mL：0.1-0.5 g：5-10 mL.
The tetraethyl orthosilicate of the addition, the amount of gamma-aminopropyl-triethoxy-silane and r-chloropropyl trimethoxyl silane
Volume ratio is 0.10-0.35：0.02-0.06：0.01-0.05.
The churned mechanically time is 2-2.5h.
（2）Magnetic hollow single hole nano silicon spheres（MSHH-Si）Preparation：
First succinic anhydride is dissolved in dimethylformamide, hollow single hole nano silicon spheres stirring is added for 24 hours, through dimethyl formyl
Amine washs, 40 DEG C of vacuum drying, then its ultrasonic disperse is warming up to 150- under nitrogen protection in N-Methyl pyrrolidone
200 DEG C, ferric acetyl acetonade is added and is washed with ethyl alcohol after being cooled to room temperature after magneton stirring, magnet is collected, in 40 DEG C of baking ovens
It is dry, magnetic hollow single hole nano silicon spheres are made（MSHH-Si）.
Wherein, hollow single hole nano silicon spheres 50-100mg is added in every 0.1 gram of succinic anhydride.
The 0.1-1g succinic anhydrides are dissolved in the dimethylformamide of 10-100mL；The succinic anhydride, N- methyl
Pyrrolidones, ferric acetyl acetonade dosage be 0.1-1g：20-50mL：0.1-0.5g.
The magneton mixing time is 1-3h.
（3）Ianus type single hole hollow magnetic trace adsorbent（SHH-MMIPs）Preparation：
It weighs cyanidenon and 4- vinylphenylboronic acids is dissolved in the mixed solution of first alcohol and water, after being protected from light standing；It is separately added into
Step（2）The magnetic hollow single hole nano silicon spheres of middle preparation, Copper dichloride dihydrate and N, N, N', N, ' the sub- second of N''- pentamethyls two
Base triamine, is added ascorbic acid under a nitrogen atmosphere, and after room temperature magnetic agitation, product uses ethyl alcohol, water washing respectively, then with methanol
It is that eluent soxhlet extraction removes template molecule cyanidenon with acetic acid mixed liquor（The volume ratio of methanol and acetic acid is 9:1）.Most
40 DEG C of vacuum drying of product SHH-MMIPs afterwards are kept in dark place.
Wherein, the cyanidenon and the mass ratio of 4- vinylphenylboronic acids are 5-20：10-25；First alcohol and water mixes
The volume ratio for closing first alcohol and water in solution is 1:1-3.
The time for being protected from light standing is 3-8h.
The amount of the magnetic hollow single hole nano silicon spheres of the addition is that magnetic hollow single hole is added per 5mg cyanidenons to receive
Rice silicon ball 50-100mg.
The cyanidenon of the addition, Copper dichloride dihydrate and N, N, N', N, ' the use of N''- five methyl diethylentriamines
Amount is 5-20 mg：5-50 mg：5-20 mL.
The mass ratio of the cyanidenon and ascorbic acid is 5-20：10-30.
The greenhouse magnetic agitation time is 2-5h.
The simultaneously synthesizing non-trace adsorbent of Ianus type single hole hollow magnetic（SHH-MNIPs）, step and SHH-MMIPs's
It prepares unanimously, is only not added with template molecule cyanidenon.
Compared with prior art, technical advantage of the invention embodies as follows：
The present invention uses emulsion template method combination Magnetic Isolation and molecular imprinting technology, and it is poly- successfully to prepare hollow single hole magnetic blotting
Close object（SHH-MMIPs）, in the preparation of the hollow silicon ball of single hole, pass through variety classes silane coupling agent（Tetraethyl orthosilicate,
Gamma-aminopropyl-triethoxy-silane and r-chloropropyl trimethoxyl silane）Addition realize the two-sidedness of Ianus particle.In height
Ferric acetyl acetonade is decomposed under the conditions of temperature, input amount is unstable when improving original ultrasonic method introducing magnetic particle, and binding ability is not
The problem of securely and the follow-up imprinted sites of indefinite position modification initiation cover.In imprinted layer modification, reversed atom turns
The application for moving radical polymerization, reduces the addition of metal ion, is more advantageous to environmental protection.It is magnetic by emulsion template method
Separation and three kinds of technologies of molecular engram are combined in the method for Selective recognition cyanidenon, are that the present invention is pioneering.
Description of the drawings
Fig. 1 is the hollow single hole nano silicon spheres prepared in embodiment 1（A）, magnetic hollow single hole nano silicon spheres（B）With it is refined
Exert this type single hole hollow magnetic trace adsorbent（C）Scanning electron microscope (SEM) photograph.
Fig. 2 is the hollow single hole nano silicon spheres prepared in embodiment 1（a）, magnetic hollow single hole nano silicon spheres（b）With it is refined
Exert this type single hole hollow magnetic trace adsorbent（c）Transmission electron microscope picture.
Fig. 3 is the hollow single hole nano silicon spheres prepared in embodiment 1（SHH-Si）, magnetic hollow single hole nano silicon spheres
（MSHH-Si）With Ianus type single hole hollow magnetic trace adsorbent（SHH-MMIPs）FTIR spectrum figure.
Fig. 4 is the hollow single hole nano silicon spheres prepared in embodiment 1（SHH-Si）, magnetic hollow single hole nano silicon spheres
（MSHH-Si）With Ianus type single hole hollow magnetic trace adsorbent（SHH-MMIPs）Hysteresis loop.
Fig. 5 is that the Ianus type single hole hollow magnetic trace before magnet attracts adsorbs agent dispersing liquid（a）After attracting with magnet
Ianus type single hole hollow magnetic trace adsorb agent dispersing liquid（b）.
Fig. 6 is that the curve of adsorption kinetics of the Ianus type single hole hollow magnetic trace adsorbent obtained in embodiment 1 is quasi-
It closes.
Fig. 7 is that the adsorption equilibrium thermoisopleth of the Ianus type single hole hollow magnetic trace adsorbent obtained in embodiment 1 is quasi-
It closes（Wherein left figure is SHH-MMIPs, right figure SHH-MNIPs）.
Fig. 8 is the selective absorption experiment knot of the Ianus type single hole hollow magnetic trace adsorbent obtained in embodiment 1
Fruit.
Specific implementation mode
Preferably to make those skilled in the art understand that technical scheme of the present invention, with reference to specific embodiments and the drawings
The present invention will be further described.
Recognition performance evaluation carries out by the following method in the specific embodiment of the invention：Utilize Staticadsorption experiment and choosing
The adsorption test of selecting property is completed.By the certain density cyanidenons of 10mL（LTL）Solution is added in centrifuge tube, adjusts pH=7.0,
A certain amount of Ianus type single hole hollow magnetic trace adsorbent is added（SHH-MMIPs）, it is placed in 25 DEG C of waters bath with thermostatic control and stands
Several hours, cyanidenon after absorption（LTL）Content is measured with ultraviolet-uisible spectrophotometer, and calculates absorption according to result
Capacity；Select several structures and kin hydroxy compounds, such as Quercetin（QRT）, hydroquinone and 2,4,6- trichlorines
Phenol（TCP）The recognition performance of adsorbent is studied Deng competitive Adsorption object, participation is used as.
Embodiment 1：
(1) preparation of hollow single hole nano-particle：
First, 2.0g polyvinylpyrrolidones is taken to be dissolved in 20mL n-amyl alcohols；Allocation ratio is 2 mL：0.1 g：The second of 5 mL
The ammonium hydroxide mixed solution of alcohol and sodium citrate；Above two solution is mixed and is placed in mechanical agitation in three-necked flask, is added simultaneously
0.1mL tetraethyl orthosilicates, 0.02mL gamma-aminopropyl-triethoxy-silanes and 0.01mL r-chloropropyl trimethoxyl silanes, after 2h
Stop stirring, using second alcohol and water respectively, respectively washing three times, is centrifuged and is dried in vacuo at 40 DEG C.Obtain hollow single hole nano-particle
Scanning electron microscope such as Figure 1A and transmission electron microscope such as Fig. 2 a, it is known that the radius size of hollow single hole nano material is 300nm or so.
(2) preparation of magnetic hollow single hole nano-particle：
0.1g succinic anhydrides are dissolved in 10mL dimethylformamides, above-mentioned steps are added（1）The hollow single hole nanometer of middle preparation
For 24 hours, three times through dimethylformamide washing, 40 DEG C are dried in vacuo for particulate material 50mg stirrings.Again by its ultrasonic disperse in 20mL
In N-Methyl pyrrolidone, it is warming up to 150 DEG C under nitrogen protection, 0.1g ferric acetyl acetonades are added, magneton stirs 1h, is cooled to
It is washed three times with ethyl alcohol after room temperature, magnet is collected and the drying in 40 DEG C of baking ovens.The scanning electricity of magnetic hollow single hole nano-particle
Mirror such as Figure 1B and transmission electron microscope such as Fig. 2 b realize the inner surface modified magnetic particle in hollow single hole nano material.
(3) preparation of magnetic hollow single hole imprinted polymer：
Weigh 5mg cyanidenons（LTL）It is 1 to be dissolved in volume ratio with 10mg 4- vinylphenylboronic acids：The mixing of 1 first alcohol and water
In solution, it is protected from light and stands 3h.It is separately added into step（2）MSHH-Si materials 50mg, the 5mg Copper dichloride dihydrate of middle preparation, 5mL
N, N, N', N, ' N''- five methyl diethylentriamines, under a nitrogen atmosphere be added 10mg ascorbic acid, room temperature magnetic agitation 2h,
Each three times of ethyl alcohol, washing, last 40 DEG C of vacuum drying are kept in dark place.The scanning electron microscope of magnetic hollow single hole imprinted polymer is as schemed
1C and transmission electron microscope such as Fig. 2 c realizes the outer surface trace in the hollow single hole nano material of modified magnetic as seen from the figure
Modification.As seen from the figure, the adsorbent shell thickness obtained is（35±10）Nanometer, opening size are（150-250）Nanometer.It is magnetic
Particle diameter is uniform, is distributed in material inner surface, realizes the advantage for not covering outer surface group.
In addition, by the characterization method of FTIR spectrum, the introducing of imprinted polymer in modifying process is illustrated, such as
Fig. 3.The magnetic of hollow single hole nano silicon spheres, magnetic hollow single hole nano silicon spheres and Ianus type single hole hollow magnetic trace adsorbent
Property size, by the hysteresis loop of Fig. 4, the saturation magnetic of magnetic hollow single hole nano-particle and magnetic hollow single hole imprinted polymer
It is respectively 1.82 gaussian sum, 1.29 Gauss to change intensity value.Ianus type single hole hollow magnetic trace before magnet attracts in Fig. 5 is inhaled
Attached agent dispersing liquid（a）Ianus type single hole hollow magnetic trace after attracting with magnet adsorbs agent dispersing liquid（b）Comparative illustration, material
Material has good magnetic and Magneto separate effect.
Embodiment 2：
(1) preparation of hollow single hole nano-particle：
First, 4.0g polyvinylpyrrolidones is taken to be dissolved in 30mL n-amyl alcohols；Allocation ratio is 5 mL：0.5 g：The second of 10mL
The ammonium hydroxide mixed solution of alcohol and sodium citrate；Above two solution is mixed and is placed in mechanical agitation in three-necked flask, is added simultaneously
0.35mL tetraethyl orthosilicates, 0.06mL gamma-aminopropyl-triethoxy-silanes and 0.05mL r-chloropropyl trimethoxyl silanes,
Stop stirring after 2.5h, three times with ethyl alcohol and water washing, centrifuges and be simultaneously dried in vacuo at 40 DEG C.
(2) preparation of magnetic hollow single hole nano-particle：
1g succinic anhydrides are dissolved in 100mL dimethylformamides, above-mentioned steps are added（1）The nano material 500mg of middle preparation
Stirring is for 24 hours.Three times through dimethylformamide washing, 40 DEG C of vacuum drying.Again by its ultrasonic disperse in 50mL N- crassitudes
In ketone, it is warming up to 200 DEG C under nitrogen protection, 0.5g ferric acetyl acetonades are added, magneton stirs 3h, ethyl alcohol is used after being cooled to room temperature
Three times, magnet is collected and the drying in 40 DEG C of baking ovens for washing.
(3) preparation of magnetic hollow single hole imprinted polymer：
Weigh 20mg cyanidenons（LTL）It is 1 to be dissolved in volume ratio with 25mg 4- vinylphenylboronic acids：The mixing of 3 first alcohol and water
In solution, it is protected from light and stands 8h.It is separately added into step（2）Bis- chloride hydrate of material MSHH-Si materials 200mg, 50mg of middle preparation
Copper, 20mL N, N, N', N, ' N''- five methyl diethylentriamines, 30mg ascorbic acid, room temperature magnetic are added under a nitrogen atmosphere
Power stirs 5h, and each three times of ethyl alcohol, washing, last 40 DEG C of vacuum drying are kept in dark place.
Embodiment 3：
(1) preparation of hollow single hole nano-particle：
First, 3.0g polyvinylpyrrolidones is taken to be dissolved in 25mL n-amyl alcohols；Allocation ratio is 3mL：0.3g：The ethyl alcohol of 8mL
With the ammonium hydroxide mixed solution of sodium citrate；Above two solution is mixed and is placed in mechanical agitation in three-necked flask, is added simultaneously
0.25mL tetraethyl orthosilicates, 0.04mL gamma-aminopropyl-triethoxy-silanes and 0.03mL r-chloropropyl trimethoxyl silanes,
Stop stirring after 2.5h, three times with ethyl alcohol and water washing, centrifuges and be simultaneously dried in vacuo at 40 DEG C.
(2) preparation of magnetic hollow single hole nano-particle：
0.5g succinic anhydrides are dissolved in 50mL dimethylformamides, above-mentioned steps are added（1）The nano material 250mg of middle preparation
Stirring is for 24 hours.Three times through dimethylformamide washing, 40 DEG C of vacuum drying.Again by its ultrasonic disperse in 35mL N- crassitudes
In ketone, it is warming up to 180 DEG C under nitrogen protection, 0.4g ferric acetyl acetonades are added, magneton stirs 2h, ethyl alcohol is used after being cooled to room temperature
Three times, magnet is collected and the drying in 40 DEG C of baking ovens for washing.
(3) preparation of magnetic hollow single hole imprinted polymer：
Weigh 15mg cyanidenons（LTL）It is dissolved in 1 with 20mg 4- vinylphenylboronic acids：In the mixed solution of 2 first alcohol and waters, keep away
Light stands 4h.It is separately added into step（2）Material MSHH-Si materials 150mg, the 35mg Copper dichloride dihydrate of middle preparation, 15mL N,
N, N', N, ' N''- five methyl diethylentriamines, 20mg ascorbic acid is added under a nitrogen atmosphere, room temperature magnetic agitation 3h divides
Not with each three times of ethyl alcohol, washing, last 40 DEG C of vacuum drying are kept in dark place.
Test example 1：
It is respectively the cyanidenon of 20 mg/L, 40 mg/L, 60 mg/L, 80 mg/L, 100 mg/L to take 10mL initial concentrations
（LTL）It is one group that solution, which is added in centrifuge tube, the Ianus type single hole hollow magnetic trace being separately added into 5mg embodiments 1
Adsorbent（SHH-MMIPs）, it is divided into three groups of test fluids and is respectively placed in temperature to stand 6h in 25 DEG C, 35 DEG C and 45 DEG C of water-bath
Afterwards, supernatant liquor is collected after magnet separation, unadsorbed LTL molecular concentrations are measured with ultraviolet-uisible spectrophotometer, absorption etc.
Warm line according to result as shown in fig. 7, calculate adsorption capacity, the results showed that, as initial a concentration of 80mg/L, Ianus type list
Hole hollow magnetic trace adsorbent（SHH-MMIPs）Absorption tend to balance, maximal absorptive capacity be 187.2 μm of ol/g.
Test example 2：
It is the cyanidenon of 100mg/L to take 10mL initial concentrations（LTL）Solution is added in centrifuge tube, is separately added into 5mg implementations
Ianus type single hole hollow magnetic trace adsorbent in example 1（SHH-MMIPs）, test fluid is placed on 25 DEG C of constant water bath box
In, it is taken out when 5min, 15min, 30min, 60min, 120 min, 240min, 360min and 720min respectively；Pass through
Magnet separates trace adsorbent and solution.LC concentration in filtrate is counted by ultraviolet specrophotometer under the wavelength of 353nm
It calculates and measures, and adsorption capacity is calculated according to result；Adsorption dynamics adsorption kinetics is as shown in Figure 6, the results showed that, the absorption of SHH-MMIPs
Process can be divided into fast phase（Preceding 60min）With the slow stage, and SHH-MMIPs reaches flat in the adsorption capacity of fast phase
It weighs the 80% of capacity, is slowly increase until balance later, it was demonstrated that boric acid binding site is to the influence of absorption and the absorption row
To belong to mono layer adsorption, in addition, microsphere possesses big adsorption equilibrium capacity and the fast rate of adsorption, in 60min interior suctions
It is attached to reach completion absorption in 89.58%, 120min.
Test example 3：
Select 2,4,6- trichlorophenol, 2,4,6,-Ts（TCP）, Quercetin（QRT）And hydroquinone（HDQ）For the hydroxy compounds of competitive Adsorption,
The solution of three of the above compound, a concentration of 100mg/L are prepared respectively.It takes 10mL to be added in centrifuge tube respectively, is separately added into
Test fluid, is placed on 12h in 25 DEG C of water bath chader by the trace adsorbent and non-trace adsorbent prepared in 5mg embodiments 1
Afterwards, supernatant is obtained by Magnetic Isolation.The concentration of TCP, QRT, HDQ solution in supernatant is respectively by ultraviolet specrophotometer
It calculates and measures at 291 nm, the wavelength of 291 nm and, 275 nm, and adsorption capacity is calculated according to result.Absorption selection
Property is as shown in Figure 8, the results showed that, SHH-MMIPs is smaller for the maximum adsorption capacity of TCP, QRT, HDQ.Illustrate relative to
TCP, QRT and HDQ, SHH-MMIPs have specific adsorption for LTL, have single-minded selectivity.
Claims (10)
1. a kind of magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type, the adsorbent is to be based on hollow single hole nano-particle
It is prepared, has magnetism.
2. a kind of preparation method of the magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type described in claim 1, feature
It is, includes the following steps：
（1）The preparation of hollow single hole nano silicon spheres：
Polyvinylpyrrolidone is dissolved in n-amyl alcohol, the ammonia spirit of ethyl alcohol and sodium citrate is added；By above-mentioned solution
Mixing is placed in mechanical agitation in three-necked flask, while sequentially adding tetraethyl orthosilicate, gamma-aminopropyl-triethoxy-silane and chlorine
Propyl trimethoxy silicane；Stop after stirring a period of time, after being washed successively with second alcohol and water, is dried in vacuo and hollow single hole is made
Nano silicon spheres；
（2）The preparation of magnetic hollow single hole nano silicon spheres：
First succinic anhydride is dissolved in dimethylformamide, hollow single hole nano silicon spheres stirring is added, through dimethylformamide
It is dried in vacuo after washing, then by its ultrasonic disperse in N-Methyl pyrrolidone, after being warming up to predetermined temperature under nitrogen protection,
Ferric acetyl acetonade is added to be washed with ethyl alcohol after being cooled to room temperature after magneton stirring, magnet is collected, dry in baking oven, and magnetic is made
The hollow single hole nano silicon spheres of property；
（3）The preparation of Ianus type single hole hollow magnetic trace adsorbent：
It weighs cyanidenon and 4- vinylphenylboronic acids is dissolved in the mixed solution of first alcohol and water, after being protected from light standing；It is separately added into
Step（2）The magnetic hollow single hole nano silicon spheres of middle preparation, Copper dichloride dihydrate and N, N, N', N, ' the sub- second of N''- pentamethyls two
Base triamine, is added ascorbic acid under a nitrogen atmosphere, and after room temperature magnetic agitation, product uses ethyl alcohol, water washing respectively, then with methanol
It is that eluent soxhlet extraction removes template molecule cyanidenon with acetic acid mixed liquor；Last product vacuum drying is kept in dark place.
3. a kind of preparation method of the magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type according to claim 2,
It is characterized in that, step（1）Described in polyvinylpyrrolidone and n-amyl alcohol dosage be 2.0-4.0g：20-30mL；The second
The dosage of alcohol, sodium citrate and ammonium hydroxide is 2-5 mL：0.1-0.5 g：5-10 mL；Tetraethyl orthosilicate, the γ-of the addition
The amount volume ratio of aminopropyl triethoxysilane and r-chloropropyl trimethoxyl silane is 0.10-0.35：0.02-0.06：0.01-
0.05。
4. a kind of preparation method of the magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type according to claim 2,
It is characterized in that, step（1）Described in hollow single hole nano silicon spheres are added after stir for 24 hours, the churned mechanically time is 2-
2.5h。
5. a kind of preparation method of the magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type according to claim 2,
It is characterized in that, step（2）Described in every 0.1 gram of succinic anhydride hollow single hole nano silicon spheres 50-100mg is added；Described
0.1-1g succinic anhydrides are dissolved in the dimethylformamide of 10-100mL；The succinic anhydride, N-Methyl pyrrolidone, levulinic
The dosage of ketone iron is 0.1-1g：20-50mL：0.1-0.5g.
6. a kind of preparation method of the magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type according to claim 2,
It is characterized in that, step（2）Described in be warming up to 150-200 DEG C under nitrogen protection；The magneton mixing time is 1-3h.
7. a kind of preparation method of the magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type according to claim 2,
It is characterized in that, step（3）Described in cyanidenon and 4- vinylphenylboronic acids mass ratio be 5-20：10-25；First alcohol and water
Mixed solution in first alcohol and water volume ratio be 1:1-3；The time for being protected from light standing is 3-8h.
8. a kind of preparation method of the magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type according to claim 2,
It is characterized in that, step（3）Described in addition magnetic hollow single hole nano silicon spheres amount be added per 5mg cyanidenons it is magnetic
Hollow single hole nano silicon spheres 50-100mg；The cyanidenon of the addition, Copper dichloride dihydrate and N, N, N', N, ' five first of N''-
The dosage of base diethylenetriamines is 5-20 mg：5-50 mg：5-20 mL.
9. a kind of preparation side of the magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type according to claim 2
Method, which is characterized in that step（3）Described in the mass ratio of cyanidenon and ascorbic acid be 5-20：10-30；Described
The greenhouse magnetic agitation time is 2-5h.
10. a kind of magnetic molecularly imprinted adsorbent of hollow single hole of Ianus type described in claim 1 is applied to Selective recognition
Cyanidenon.
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