CN103626906A - Synthetic method of hydrophilic polymeric microspheres capable of selectively identifying tetracycline - Google Patents
Synthetic method of hydrophilic polymeric microspheres capable of selectively identifying tetracycline Download PDFInfo
- Publication number
- CN103626906A CN103626906A CN201310511087.4A CN201310511087A CN103626906A CN 103626906 A CN103626906 A CN 103626906A CN 201310511087 A CN201310511087 A CN 201310511087A CN 103626906 A CN103626906 A CN 103626906A
- Authority
- CN
- China
- Prior art keywords
- tsiklomitsin
- ethanol
- mmol
- hydrophilic
- synthetic method
- 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.)
- Granted
Links
Images
Landscapes
- Materials For Medical Uses (AREA)
- Medicinal Preparation (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention relates to a synthetic method of hydrophilic polymeric microspheres capable of selectively identifying tetracycline, belonging to the technical field of environment function materials. The synthetic method provided by the invention prepares the hydrophilic molecularly imprinted polymer microspheres by a one-pot method by taking non-toxic and pollution-free ethanol as a green solvent, tetracycline as a template molecule, methacrylic acid as a functional monomer, styrene and trihydroxymethyl acrylate as cross-linking polymerization monomers and azodiisobutyronitrile as an initiator to imitate precipitation polymerization by means of adding a hydrophilic polymeric monomer hydroxyethyl methylacrylate in a delay manner. The invention provides a simple one-pot method to synthesize the hydrophilic molecularly imprinted polymer microspheres with excellent performances, thereby providing a novel material and a green preparation method for selectively removing tetracycline residues in a water environment.
Description
Technical field
The synthetic method that the present invention relates to a kind of hydrophilic polymer microballoon of alternative identification tsiklomitsin, belongs to environmentally conscious materials preparing technical field.
Background technology
Tetracycline antibiotics is disease prevention and the treatment that is widely used in human and animal, it is poor to digest and assimilate in vivo, major part does not participate in metabolism and gets rid of external, cause it in environment, to accumulate and enrichment, people take in after the residual water and food exceeding standard of tsiklomitsin for a long time, tsiklomitsin can slowly be accumulated in human body, and human body is produced to toxic side effect, causes the pathology of the multiple organ of human body.In ecotope, tsiklomitsin is residual be studies confirm that by Chinese scholars.Dimension, development and application is removed the residual efficient means of tsiklomitsin in environment and is just become particularly important.Adsorption method of separation is the most frequently used method, and adsorptive capacity is large, rate of adsorption is fast, adsorption selectivity is high, equipment is simple, easy to operate etc.
Molecular imprinting is that preparation has the method for single-minded recognition capability polymkeric substance to a certain specific molecular, and the polymkeric substance of preparation is called molecularly imprinted polymer.The preparation process of polymkeric substance is generally: template molecule and function monomer form the mixture with certain space structure by key covalently or non-covalently, under the effect of initiator and linking agent, there is subsequently trace polymerization, finally by template molecule wash-out from highly cross-linked converging network, in imprinted polymer, leave binding site template molecule to single-minded recognition reaction, this site has special affinity and selectivity to template molecule.Molecularly imprinted polymer has been widely used in the selective removal of pollutent in water surrounding.
Tradition molecularly imprinted polymer is made by mass polymerization mostly, must be through pulverizing, grind and screening obtaining the particle of wanting, the loaded down with trivial details and particle that obtains of this method process is pattern and size is irregular, loading capacity is low and template molecule is difficult to approach usually.Adopt suspension polymerization, two step swelling methods and precipitation polymerization method can access the uniform molecular imprinting polymerization of relative particle size ball.Wherein precipitation polymerization method, because not adding any stablizer in reaction system, has been avoided the impact on trace of stablizer or tensio-active agent; Component is simple, processing ease; Not only can avoid numerous and diverse aftertreatment, size distribution is more even, good dispersity, and adhesion phenomenon is less, and trace hole is exposed to the advantages such as the probability of microsphere surface is large.Therefore, precipitation polymerization method has been applied to the preparation of molecular blotting polymer microsphere.Yet precipitation polymerization mainly carries out polymerization in the toxic solvents such as acetonitrile, toluene at present, and studies less in innoxious solvent second alcohol and water.Therefore the green solvent system that, exploitation is applicable to prepare molecularly imprinted polymer has great Research Significance.Most of pollutents are extensively present in water surrounding, how in water surrounding, to carry out effectively identification with separated be problem urgently to be resolved hurrily.Hydrophilic molecular imprinting polymkeric substance can address this problem preferably.
Summary of the invention
The synthetic method that the object of this invention is to provide a kind of hydrophilic polymer microballoon of alternative identification tsiklomitsin, the hydrophilic molecular imprinting polymer microballoon of preparing by the method is identified with separated the selectivity of tsiklomitsin in water surrounding.
The synthetic method that the present invention relates to a kind of hydrophilic polymer microballoon of alternative identification tsiklomitsin, belongs to environment functional material technical field.The present invention be take, and nontoxic, free of contamination ethanol is green solvent, tsiklomitsin is template molecule, methacrylic acid is function monomer, vinylbenzene and trimethylolpropene acid esters are crosslinking polymerization monomer, Diisopropyl azodicarboxylate is for causing precipitation polymerization, postpone to add hydrophilic polymeric monomers hydroxyethyl methylacrylate, one kettle way is prepared hydrophilic molecular imprinting polymer microballoon.By the physicochemical property of the instrumental characterizing hydrophilic molecular imprinting polymer microballoons such as infrared spectrometer, field emission scanning electron microscope, size distribution instrument and contact angle measurement.Utilize adsorption experiment come institute system for hydrophilic molecular imprinting polymer microballoon to the adsorption equilibrium of tsiklomitsin, kinetics and adsorption selectivity performance.
the technical solution used in the present invention is:
A synthetic method for the hydrophilic polymer microballoon of alternative identification tsiklomitsin, according to following step, carry out:
According to tsiklomitsin (TC): methacrylic acid (MAA): trimethylolpropane trimethacrylate (TMPTMA): the mol ratio of vinylbenzene (St) is 1:(3-6): (24-48): (40-50) ratio of (mmol/mmol/mmol/mmol) adds tsiklomitsin, methacrylic acid, vinylbenzene and trimethylolpropane trimethacrylate successively in round-bottomed flask.According to vinylbenzene: the mass ratio of ethanol is 1:(50-100) ratio (g/g), in flask, add ethanol, ultrasonic dispersion, forms homogeneous phase solution.Under room temperature, the pre-assembled 12-24 hour of lucifuge; Ultrasonic degas, logical nitrogen 20-30 min, according to Diisopropyl azodicarboxylate (AIBN): the mass ratio of ethanol is (0.02-0.04): the ratio of 100 (g/g), in solution, add Diisopropyl azodicarboxylate as initiator, flask is placed in to water bath with thermostatic control vibrator, rotating speed is 100-200 r/min, and 1.0 h are interior from 25
oc is warming up to 60
oc, precipitation polymerization reacts 12 h; According to hydroxyethyl methylacrylate (HEMA): the mass ratio of ethanol is (0.01-0.03): the ratio of 100 (g/g) adds hydroxyethyl methylacrylate, 60 in system
oc continues oscillatory reaction 12 h.After reaction finishes, be cooled to room temperature, by acetone, ethanol and distilled water repetitive scrubbing reaction product, be dried to constant weight; The methyl alcohol that is 9:1 by volume ratio: acetic acid mixed solution Soxhlet is extracted 6 h, repeatedly, wash-out template molecule, till can't detect tsiklomitsin to elutriant with ultraviolet-visible pectrophotometer, with ethanol and distilled water, product washing is extremely neutral, 60
ounder C, vacuum-drying, to constant weight, obtains hydrophilic molecular imprinting polymer microballoon (HMIMs).Take same preparation method, but in process, do not add tsiklomitsin as template molecule, obtain the non-imprinted polymer microballoon of wetting ability (HNIMs).If in polymerization process, do not add hydroxyethyl methylacrylate to participate in polymerization, obtain molecular blotting polymer microsphere (MIMs); If methylate Hydroxyethyl acrylate and tsiklomitsin, do not obtain non-imprinted polymer microballoon (NIMs).
Technological merit of the present invention: ethanol is as polymer solvent, nontoxic, pollution-free is green polymerization system; Polymer microballoon prepared by precipitation polymerization does not need loaded down with trivial details last handling process, can directly use; The method that adds hydroxyethyl methylacrylate by delay, realize the wetting ability of imprinted polymer microballoon, and imprinted sites is not destroyed; Hydrophilic molecular imprinting polymer microballoon has good selectivity to tsiklomitsin in water surrounding, can be applied to the residual selective removal of tsiklomitsin in actual water sample.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of Fig. 1 MIMs (a), HMIMs (b), NIMs (c) and HNIMs (d).As can be known from Fig. 1: what NIMs particle was monodispersity is spherical, the relative homogeneous of size, is about 2.1 um, and HNIMs size slightly increases, and keeps spherical; MIMs and HMIMs particle present irregular form, and agglomeration is serious, infer thus, and in polymerization process, adding of template molecule produced larger impact to the pattern of polymer particle.
The infrared spectrogram of Fig. 2 HMIMs and HNIMs.As can be known from Fig. 2: 1730 cm
-1the stretching vibration peak of C=O, 2940 cm
-1with 2981 cm
-1for-CH
2with-CH
3stretching vibration peak, 3544 cm
-1broad peak and 1223 cm at place
-1the weak peak at place, illustrates that HEMA is successfully incorporated into the extexine of polymkeric substance.
The size distribution figure of Fig. 3 HMIMs and HNIMs.As can be known from Fig. 3: HMIMs size distribution is wider, HNIMs narrow diameter distribution, major part concentrates on 2.1 about um, and this result is with to obtain conclusion in Fig. 1 consistent.
The water contact angle figure (A) of Fig. 4 MIMs (a) and HMIMs (b); Scatter diagram (B) in the water of MIMs (a), HMIMs (b), NIMs (c) and HNIMs (d).Known from Fig. 4 A: the water contact angle of MIMs and HMIMs is respectively 149.92 ± 0.1 ° and 59.58 ± 0.2 °, illustrate and postpone to add hydroxyethyl methylacrylate to participate in polymerization, the HMIMs preparing has good wetting ability; In Fig. 4 B, HMIMs and HNIMs have good dispersed proving again HEMA and are successfully incorporated into polymkeric substance outside surface in water.
The impact of Fig. 5 pH on HMIMs and HNIMs absorption tsiklomitsin.As can be seen from Figure 5: when pH value is 5.0, adsorptive capacity reaches maximum value, therefore, the optimal ph of solution is 5.0.
Fig. 6 HMIMs and the HNIMs adsorption isothermal line matched curve figure to tsiklomitsin.As can be known from Fig. 6: under normal temperature, HMIMs and HNIMs are respectively 20.15 μ mol g to the maximum adsorption capacity of tsiklomitsin
-1with 12.10 μ mol g
-1, demonstrating good selective adsorption effect, both adsorption test data meet Freundlich Isothermal Model well simultaneously,
The kinetics matched curve of Fig. 7 HMIMs and HNIMs absorption tsiklomitsin.As can be seen from Figure 7: adsorption equilibrium reaches very soon, experimental data well matching accurate second-order kinetic equation.In whole time range, HMIMs is greater than the adsorptive capacity of HNIMs to the adsorptive capacity of tsiklomitsin, has shown good specific recognition performance, illustrates in imprinted polymer and to have the avtive spot matching with tsiklomitsin molecule.
Fig. 8 imprinted polymer and the adsorption selectivity of non-imprinted polymer to tsiklomitsin.As can be known from Fig. 8: imprinted polymer is maximum to the adsorptive capacity of tsiklomitsin, good selectivity identification and absorption property have been shown.
Embodiment
1, below in conjunction with concrete embodiment, the present invention will be further described:
According to tsiklomitsin (TC): methacrylic acid (MAA): trimethylolpropane trimethacrylate (TMPTMA): the mol ratio of vinylbenzene (St) is the ratio of 1:3:24:40 (mmol/mmol/mmol/mmol) adds tsiklomitsin, methacrylic acid, vinylbenzene and trimethylolpropane trimethacrylate successively in round-bottomed flask.According to vinylbenzene: the mass ratio of ethanol is the ratio of 1:50 (g/g), adds ethanol in flask, ultrasonic dispersion, forms homogeneous phase solution.Under room temperature, pre-assembled 12 hours of lucifuge; Ultrasonic degas, logical nitrogen 20 min, according to Diisopropyl azodicarboxylate (AIBN): the mass ratio of ethanol is the ratio of 0.02:100 (g/g), in solution, add Diisopropyl azodicarboxylate as initiator, flask is placed in to water bath with thermostatic control vibrator, rotating speed is 100 r/min, and 1.0 h are interior from 25
oc is warming up to 60
oc, precipitation polymerization reacts 12 h; According to hydroxyethyl methylacrylate (HEMA): the mass ratio of ethanol is the ratio of 0.01:100 (g/g), adds hydroxyethyl methylacrylate, 60 in system
oc continues oscillatory reaction 12 h.After reaction finishes, be cooled to room temperature, by acetone, ethanol and distilled water repetitive scrubbing reaction product, be dried to constant weight; The methyl alcohol that is 9:1 by volume ratio: acetic acid mixed solution Soxhlet is extracted 6 h, repeatedly, wash-out template molecule, till can't detect tsiklomitsin to elutriant with ultraviolet-visible pectrophotometer, with ethanol and distilled water, product washing is extremely neutral, 60
ounder C, vacuum-drying, to constant weight, obtains hydrophilic molecular imprinting polymer microballoon (HMIMs).Take same preparation method, but in process, do not add tsiklomitsin as template molecule, obtain the non-imprinted polymer microballoon of wetting ability (HNIMs).If in polymerization process, do not add hydroxyethyl methylacrylate to participate in polymerization, obtain molecular blotting polymer microsphere (MIMs); If methylate Hydroxyethyl acrylate and tsiklomitsin, do not obtain non-imprinted polymer microballoon (NIMs).
2, below in conjunction with concrete embodiment, the present invention will be further described:
According to tsiklomitsin (TC): methacrylic acid (MAA): trimethylolpropane trimethacrylate (TMPTMA): the mol ratio of vinylbenzene (St) is the ratio of 1:6:48:50 (mmol/mmol/mmol/mmol) adds tsiklomitsin, methacrylic acid, vinylbenzene and trimethylolpropane trimethacrylate successively in round-bottomed flask.According to vinylbenzene: the mass ratio of ethanol is the ratio of 1:100 (g/g), adds ethanol in flask, ultrasonic dispersion, forms homogeneous phase solution.Under room temperature, the pre-assembled 12-24 hour of lucifuge; Ultrasonic degas, logical nitrogen 30 min, according to Diisopropyl azodicarboxylate (AIBN): the mass ratio of ethanol is the ratio of 0.04:100 (g/g), in solution, add Diisopropyl azodicarboxylate as initiator, flask is placed in to water bath with thermostatic control vibrator, rotating speed is 200 r/min, and 1.0 h are interior from 25
oc is warming up to 60
oc, precipitation polymerization reacts 12 h; According to hydroxyethyl methylacrylate (HEMA): the mass ratio of ethanol is the ratio of 0.03:100 (g/g), adds hydroxyethyl methylacrylate, 60 in system
oc continues oscillatory reaction 12 h.After reaction finishes, be cooled to room temperature, by acetone, ethanol and distilled water repetitive scrubbing reaction product, be dried to constant weight; The methyl alcohol that is 9:1 by volume ratio: acetic acid mixed solution Soxhlet is extracted 6 h, repeatedly, wash-out template molecule, till can't detect tsiklomitsin to elutriant with ultraviolet-visible pectrophotometer, with ethanol and distilled water, product washing is extremely neutral, 60
ounder C, vacuum-drying, to constant weight, obtains hydrophilic molecular imprinting polymer microballoon (HMIMs).Take same preparation method, but in process, do not add tsiklomitsin as template molecule, obtain the non-imprinted polymer microballoon of wetting ability (HNIMs).If in polymerization process, do not add hydroxyethyl methylacrylate to participate in polymerization, obtain molecular blotting polymer microsphere (MIMs); If methylate Hydroxyethyl acrylate and tsiklomitsin, do not obtain non-imprinted polymer microballoon (NIMs).
2, below in conjunction with concrete embodiment, the present invention will be further described:
In the present invention, in specific embodiments, absorption property evaluation is carried out by the following method: utilize Staticadsorption experiment to complete.The certain density tetracycline of 10 ml is joined in centrifuge tube, add wherein respectively 10 mg HMIMs and HNIMs, be placed on standing 12 h in water bath with thermostatic control, investigate pH, time of repose, the impact of temperature on sorbent material absorption tsiklomitsin molecule.After absorption, by centrifugal collection, obtain clear liquid at the middle and upper levels, absorption tsiklomitsin molecular conecentration with uv-vis spectra, do not record, and according to result calculate loading capacity (
q e, μ mol/g).
Wherein
c 0(μ mol/L) and
c e(μ mol/L) is respectively the concentration of tsiklomitsin before and after absorption,
w(g) be sorbent material consumption,
v(mL) be test fluid volume.
Experiment examination example 1: get respectively 10 mg HMIMs and HNIMs and join in the centrifuge tube of 10ml, then getting respectively the tetracycline that 10 ml starting point concentrations are respectively 10,30,50,80,100,120,150,180 μ mol/L joins in centrifuge tube, centrifuge tube is placed on to standing 12.0 h in three differing tempss (298K, 308K and 318K) water-bath.After absorption, centrifugal collection supernatant liquid, the tsiklomitsin molecular conecentration not being adsorbed is measured with ultraviolet-visible pectrophotometer, and calculates loading capacity.Fig. 6 result shows: along with the rising of temperature and concentration, adsorptive capacity increases gradually, finally reaches adsorption equilibrium, and wetting ability imprinted polymer is greater than the non-imprinted polymer of wetting ability all the time to the adsorptive capacity of tsiklomitsin, proves and has a large amount of trace holes.
Experiment examination example 2: the tetracycline of getting 10 ml starting point concentrations and be 80 μ mol/L joins in centrifuge tube, add respectively 10 mg HMIMs and HNIMs, centrifuge tube is placed in the water-bath of 298 K to standing 10,20,30,45,60,90,120,150,180 and 240 minutes respectively.After standing completing, centrifugal collection supernatant liquid, the tsiklomitsin molecular conecentration not being adsorbed is measured with ultraviolet-visible pectrophotometer, and calculates loading capacity according to result.Fig. 7 result shows: HMIMs and HNIMs have good kinetics of adsorption performance to Fourth Ring, substantially reaches adsorption equilibrium in 3.0 h.
Experiment examination example 3: select the antibiotic compound that duomycin, Cephalexin Monohydrate Micro/Compacted and Ciprofloxacin are competitive adsorption.Configuring respectively solubility is the above-mentioned three kinds of microbiotic of 100 μ mol/L.Get the solution that 10 ml prepare and join in centrifuge tube, add respectively 10 mg HMIMs and HNIMs, centrifuge tube is placed in the water-bath of 298 K to standing 12 h respectively.After absorption, centrifugal collection supernatant liquid, the various competitive adsorption antibiotic concentrations that are not adsorbed are measured with ultraviolet-visible pectrophotometer.Fig. 8 result shows, wetting ability imprinted polymer has significant specific recognition to tsiklomitsin, and loading capacity is apparently higher than other microbiotic.
Claims (2)
1. alternative is identified a synthetic method for the hydrophilic polymer microballoon of tsiklomitsin, it is characterized in that carrying out according to following step:
In round-bottomed flask, add tsiklomitsin, methacrylic acid, vinylbenzene and trimethylolpropane trimethacrylate; In flask, add ethanol, ultrasonic dispersion, forms homogeneous phase solution;
Under room temperature, the pre-assembled 12-24 hour of lucifuge; Ultrasonic degas, logical nitrogen 20-30 min adds Diisopropyl azodicarboxylate as initiator in solution, and flask is placed in to water bath with thermostatic control vibrator, and rotating speed is 100-200 r/min, and 1.0 h are interior from 25
oc is warming up to 60
oc, precipitation polymerization reacts 12 h; In system, add hydroxyethyl methylacrylate, 60
oc continues oscillatory reaction 12 h; After reaction finishes, be cooled to room temperature, by acetone, ethanol and distilled water repetitive scrubbing reaction product, be dried to constant weight; The methyl alcohol that is 9:1 by volume ratio: acetic acid mixed solution Soxhlet is extracted 6.0 h, repeatedly, wash-out template molecule, till can't detect tsiklomitsin to elutriant with ultraviolet-visible pectrophotometer, with ethanol and distilled water, product washing is extremely neutral, 60
ounder C, vacuum-drying, to constant weight, obtains hydrophilic molecular imprinting polymer microballoon.
2. a kind of synthetic method of hydrophilic polymer microballoon of alternative identification tsiklomitsin according to claim 1, is characterized in that tsiklomitsin in step: methacrylic acid: trimethylolpropane trimethacrylate: the mol ratio of vinylbenzene (St) is 1:(3-6): (24-48): (40-50) (mmol/mmol/mmol/mmol); Vinylbenzene: the mass ratio of ethanol is 1:(50-100) (g/g); Diisopropyl azodicarboxylate: the mass ratio of ethanol is (0.02-0.04): 100 (g/g); Hydroxyethyl methylacrylate: the mass ratio of ethanol is (0.01-0.03): 100 (g/g).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310511087.4A CN103626906B (en) | 2013-10-25 | 2013-10-25 | A kind of alternative identifies the synthetic method of the hydrophilic polymer microballoon of tsiklomitsin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310511087.4A CN103626906B (en) | 2013-10-25 | 2013-10-25 | A kind of alternative identifies the synthetic method of the hydrophilic polymer microballoon of tsiklomitsin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103626906A true CN103626906A (en) | 2014-03-12 |
| CN103626906B CN103626906B (en) | 2016-04-06 |
Family
ID=50208379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310511087.4A Expired - Fee Related CN103626906B (en) | 2013-10-25 | 2013-10-25 | A kind of alternative identifies the synthetic method of the hydrophilic polymer microballoon of tsiklomitsin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103626906B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311109A (en) * | 2016-08-26 | 2017-01-11 | 江苏大学 | Embedded hollow magnetic imprinted photocatalytic nanoreactor and preparation method thereof |
| CN107913682A (en) * | 2017-11-08 | 2018-04-17 | 常州大学 | A kind of method for preparing porous temperature sensitive molecular imprinting adsorbing agent |
| CN109012587A (en) * | 2018-08-21 | 2018-12-18 | 齐鲁工业大学 | The preparation method of Tetracyclines hydrophily carbon compound adsorbent |
| CN109704432A (en) * | 2019-01-23 | 2019-05-03 | 河南师范大学 | One kettle way prepares UIO-66-NH2The method of/functional monomer composite material and its application in absorption antibiotic |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006069449A1 (en) * | 2004-12-29 | 2006-07-06 | The University Of British Columbia | Chemokine receptor-independent immunomodulatory and anti-proliferative activity |
| CN102059104A (en) * | 2009-11-17 | 2011-05-18 | 南开大学 | Surface-hydrophilic molecularly imprinted polymer microsphere and preparation method thereof |
| CN102952236A (en) * | 2011-08-29 | 2013-03-06 | 南开大学 | Molecularly imprinted polymeric microsphere resin applicable to aqueous solution system and preparing method thereof |
| CN103304723A (en) * | 2013-07-01 | 2013-09-18 | 江苏大学 | Green preparation method of hydrophilic molecular engram polymer |
-
2013
- 2013-10-25 CN CN201310511087.4A patent/CN103626906B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006069449A1 (en) * | 2004-12-29 | 2006-07-06 | The University Of British Columbia | Chemokine receptor-independent immunomodulatory and anti-proliferative activity |
| CN102059104A (en) * | 2009-11-17 | 2011-05-18 | 南开大学 | Surface-hydrophilic molecularly imprinted polymer microsphere and preparation method thereof |
| CN102952236A (en) * | 2011-08-29 | 2013-03-06 | 南开大学 | Molecularly imprinted polymeric microsphere resin applicable to aqueous solution system and preparing method thereof |
| CN103304723A (en) * | 2013-07-01 | 2013-09-18 | 江苏大学 | Green preparation method of hydrophilic molecular engram polymer |
Non-Patent Citations (1)
| Title |
|---|
| BEATE DIRION等: "Water-Compatible Molecularly Imprinted Polymers Obtained via High-Throughput Synthesis and Experimental Design", 《JOURNAL OF AMERICAN CHEMISTRY SOCIETY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311109A (en) * | 2016-08-26 | 2017-01-11 | 江苏大学 | Embedded hollow magnetic imprinted photocatalytic nanoreactor and preparation method thereof |
| CN107913682A (en) * | 2017-11-08 | 2018-04-17 | 常州大学 | A kind of method for preparing porous temperature sensitive molecular imprinting adsorbing agent |
| CN109012587A (en) * | 2018-08-21 | 2018-12-18 | 齐鲁工业大学 | The preparation method of Tetracyclines hydrophily carbon compound adsorbent |
| CN109012587B (en) * | 2018-08-21 | 2021-03-23 | 齐鲁工业大学 | Preparation method of tetracycline hydrophilic carbon composite adsorbent |
| CN109704432A (en) * | 2019-01-23 | 2019-05-03 | 河南师范大学 | One kettle way prepares UIO-66-NH2The method of/functional monomer composite material and its application in absorption antibiotic |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103626906B (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pardeshi et al. | Precipitation polymerization: a versatile tool for preparing molecularly imprinted polymer beads for chromatography applications | |
| Puoci et al. | New restricted access materials combined to molecularly imprinted polymers for selective recognition/release in water media | |
| Dai et al. | Preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization for the selective recognition of tetracycline from aqueous medium | |
| CN103601847B (en) | A kind of preparation method of Core-shell type magnetic surface trace nano composite material | |
| CN101333273B (en) | Method for preparing high molecular fluorescent microballoons | |
| Wang et al. | The preparation of high-capacity boronate affinity adsorbents by surface initiated reversible addition fragmentation chain transfer polymerization for the enrichment of ribonucleosides in serum | |
| CN103509161A (en) | Preparation method of hydrophilic magnetic halloysite surface molecularly-imprinted nano composite material | |
| CN101045755A (en) | Preparation method of non-porous or porous polymer microsphere of surface function | |
| CN103626906A (en) | Synthetic method of hydrophilic polymeric microspheres capable of selectively identifying tetracycline | |
| Qian et al. | Zwitterionic polymer chain-assisted lysozyme imprinted core-shell carbon microspheres with enhanced recognition and selectivity | |
| CN103613758B (en) | Self-assembly method is prepared molecular engram polyaniline nano compound | |
| Abouzarzadeh et al. | Synthesis and evaluation of uniformly sized nalidixic acid–imprinted nanospheres based on precipitation polymerization method for analytical and biomedical applications | |
| CN102532408B (en) | Preparation method of temperature sensitive magnetic western-blotting nanosphere | |
| CN104587970A (en) | Magnetic chitosan composite microsphere surface imprinted adsorbent and preparation method thereof | |
| CN101733081A (en) | Method for preparing molecularly imprinted microspheres on surface of polymer carrier | |
| Asadi et al. | Synthesis, recognition and evaluation of molecularly imprinted polymer nanoparticle using miniemulsion polymerization for controlled release and analysis of risperidone in human plasma samples | |
| CN103613719A (en) | Controllable preparation method of magnetic halloysite surface nano imprinting composite material | |
| CN105153367A (en) | Preparation method of dicyandiamide mesoporous surface molecularly imprinted polymer microspheres | |
| Kou et al. | Preparation of molecularly imprinted nanospheres by premix membrane emulsification technique | |
| Yang et al. | Hollow-structured molecularly imprinted polymers enabled specific enrichment and highly sensitive determination of aflatoxin B1 and sterigmatocystin against complex sample matrix | |
| CN106565908B (en) | A kind of preparation method of monodispersed large grain-size polymer microballoon | |
| Huang et al. | Thermosensitive molecularly imprinted polymers based on magnetic nanoparticles for the recognition of sulfamethazine | |
| CN105044254B (en) | The preparation method and application of itrofurans molecular blotting polymer microsphere | |
| Kou et al. | Synthesis, characterization and adsorption behavior of molecularly imprinted nanospheres for erythromycin using precipitation polymerization | |
| Zhu et al. | Dual-responsive copolymer hydrogel as broad-spectrum adsorbents for metal ions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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: 20160406 Termination date: 20161025 |