CN103497276A - Carbon nanotube-based magnetic organophosphorus molecularly-imprinted polymer and its preparation method and use - Google Patents
Carbon nanotube-based magnetic organophosphorus molecularly-imprinted polymer and its preparation method and use Download PDFInfo
- Publication number
- CN103497276A CN103497276A CN201310378769.2A CN201310378769A CN103497276A CN 103497276 A CN103497276 A CN 103497276A CN 201310378769 A CN201310378769 A CN 201310378769A CN 103497276 A CN103497276 A CN 103497276A
- Authority
- CN
- China
- Prior art keywords
- imprinted polymer
- carbon nanotube
- based magnetic
- organic phosphorous
- molecularly
- 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
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a carbon nanotube-based magnetic organophosphorus molecularly-imprinted polymer and its preparation method and use, and relates to a molecularly-imprinted polymer and its preparation method and use. The carbon nanotube-based magnetic organophosphorus molecularly-imprinted polymer and the preparation method solve the problem that the existing molecularly-imprinted polymers have poor dispersibility, the existing molecularly-imprinted polymer preparation method has poor applicability, and in use of the existing molecularly-imprinted polymers as adsorbents in sample pre-treatment in organophosphorus pesticide residue analysis, operation time is long and organic solvent consumption is large and selectivity is poor. The carbon nanotube-based magnetic organophosphorus molecularly-imprinted polymer comprises carbon nanotubes, FeCl3.6H2O, a cross-linking agent and a functional monomer. The preparation method comprises the following steps of 1, activating the carbon nanotubes, 2, adding FeCl3.6H2O into the activated carbon nanotubes, carrying out treatment and carrying out magnetic substance collection, 3, carrying out dispersion and adding tetraethyl orthosilicate into the dispersed system, 4, carrying out dispersion and carrying out magnetic substance collection, 5, preparing a magnetic molecularly-imprinted polymer having a template molecule, and 6, treating the magnetic molecularly-imprinted polymer to obtain the carbon nanotube-based magnetic organophosphorus molecularly-imprinted polymer. The carbon nanotube-based magnetic organophosphorus molecularly-imprinted polymer as an adsorbent can be used for selective extraction separation of organophosphorus pesticide residues in a complex sample.
Description
Technical field
The present invention relates to separate analytical technique field, particularly molecularly imprinted polymer and its preparation method and application.
Background technology
Organophosphorus insecticides, be widely used in the control of agricultural and city insect, have tag, stomach toxicity and fumigation action, can be effectively used to prevent and treat the over one hundred kind of insects such as snout moth's larva, tortrix moth, mythimna separata, scale insect, aphid, leafhopper and evil mite of the aspects such as vegetables, water paddy and wheat class, corn, cotton, sugarcane, tealeaves, fruit tree, flowers and livestock breeding,, in the registration of a lot of countries and regions, usage quantity and range of application are constantly increasing.Yet, eaten the food that contains organophosphorus pesticide, as after vegetables, brought harm to people healthy.Nowadays the food the Detection Technologies of Pesticide Residues improves constantly, and pretreatment technology is relatively backward, and common pre-treating process comprises liquid-liquid extraction, Solid-Phase Extraction, solid-phase microextraction, matrix solid phase dispersion etc.Wherein, liquid-liquid extraction need to consume a large amount of organic solvents, larger and time-consuming to operator's harm; The Solid-Phase Extraction troublesome poeration, need particular instrument; Solid-phase microextraction is difficult to the material of non-volatility the rate of recovery that reaches good; Matrix solid phase dispersion, owing to relating to manual operation, is difficult to its batch processing.Therefore, the quick sample preconditioning technique of setting up organophosphorus pesticide analysis in food is current problem demanding prompt solution.
Molecular imprinting (MIT) comes across 1931 first.MIT carries out polymerization by template molecule and linking agent to obtain solid dielectric in polymer monomer solution, then remove the template molecule in medium by physics or chemical process wash-out, obtaining " trace " has the space structure of target molecule and the molecularly imprinted polymer of binding site (MIPs).Yet, the conventional preparation method of MIPs is mass polymerization or precipitation polymerization method, remaining template molecule and recognition site are buried in body matrix, must can use through the loaded down with trivial details operation such as grinding and sieve, often because of the irregular size of particulate matter and shape and remaining template molecule thereof, cause the low extraction efficiency to target compound.In order to overcome the shortcoming of traditional MIPs, thereby people obtain molecular imprinted polymer on surface at the surface grafting MIPs of nano material.Trace hole in this imprinted polymer is located substantially on the surface of nano material, easily carries out mass transfer and can improve in medium the accessibility to specific compound.The nano materials such as silicon-dioxide, titanium dioxide, aluminum oxide have prepared molecularly imprinted polymer as carrier, but when application its disperse properties relatively poor.Carbon nanotube (CNTs) is a kind of nano material with high-specific surface area, high-ratio surface energy, high reaction activity, gap between its unique surface π-electron structure and multilayer carbon pipe, especially and containing the π between aromatic cycle compound-π interact, make it become the surface support material of molecularly imprinted polymer first-selection.Yet, if MIPs and CNTs combination are applied to traditional solid phase extraction techniques, also can there be some problems, as slow as processing sample speed, Chinese People's Anti-Japanese Military and Political College's molecule interference performance is poor, thereby causes poor selectivity, and the method applicability for preparing in addition this polymkeric substance is poor.Therefore, we introduce magneticsubstance, do not need to carry out the post mode of crossing that similar traditional Solid-Phase Extraction is the same.
Summary of the invention
To the objective of the invention is that the Sample Pretreatment Technique Used that existing molecularly imprinted polymer disperse properties method applicability relatively poor, that prepare polymkeric substance is poor, this polymkeric substance is analyzed for organophosphorus pesticide as sorbent material is time-consuming, organic solvent consumption large and the problem of poor selectivity in order solving, a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer and its preparation method and application to be provided.
Carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of the present invention comprises carbon nanotube, FeCl
36H
2o, linking agent and function monomer.
The preparation method of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of the present invention comprises following step:
One, the ratio that is 0.8g:100～200mL in quality with volume ratio by carbon nanotube and concentrated nitric acid mixes, oil bath lower magnetic force stirring 5～7h by mixture in 80～90 ℃, activated, and then the carbon nanotube of activation is washed till to neutrality, in 50～70 ℃ of oven dry, obtain powdery substance;
Two, the powdery substance 0.3～0.6g step 1 obtained and the FeCl of 1.0～1.8g
36H
2o mixes, and obtains mixture, in mixture, adds 60～100mL ethylene glycol solvent, in 80～90 ℃ of oil bath pans, is stirred to FeCl
36H
2after O dissolves fully, add 3.4～3.8g sodium acetate, be stirred to after sodium acetate dissolves fully and stir again 2～3min, then be transferred in reactor, it is, after 180～220 ℃ of baking ovens react 8～15h, reactor to be taken out standing that reactor is placed in to temperature, the question response still is opened after being cooled to room temperature, with utilizing powerful magnet for adsorption and collect magnetic substance, more alternately clean 3～5 times with dehydrated alcohol and water, dry and obtain product;
Three, the product 0.2～0.6g that gets the step 2 gained is scattered in the ethanol that 100～150mL volumn concentration is 10%～30%, then the ammonia soln that the quality percentage composition that adds 1～3mL is 25%～28%, stir 3～5min under 280～320rpm, add again 0.4～0.6mL tetraethyl orthosilicate, stir 20～30h under room temperature, obtain mixture;
Four, the volumn concentration that the mixture of getting the step 3 gained is scattered in 100～150mL is in 5%～10% acetic acid solution, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane that adds again 0.1～0.2mL, stir 3～5h under 60～80 ℃ after, with utilizing powerful magnet for adsorption and collect magnetic substance, magnetic substance is washed till to the pH value for neutral, obtains product;
Five, taking 1～2mmol template molecule and 4～8mmol function monomer is dissolved in 5～30mL dispersion agent, in lucifuge place stirred overnight, obtain mixture, getting the product that step 4 obtains joins in this mixture, add again Aqueous Solutions of Polyethylene Glycol, 20～40mmol linking agent and 70～180mg Diisopropyl azodicarboxylate that 100～300mL quality percentage composition is 10%～30%, after ultrasonic 3～5min, in 60～80 ℃ of stirred in water bath 20～24h, obtain having the magnetic molecularly imprinted polymer of template molecule;
Six, solvent cleaning 3～5 times of the magnetic molecularly imprinted polymer with template molecule that step 5 obtained, the acetic acid methanol solution that is 10%～20% with volumn concentration again carries out the Soxhlet extraction as extracting solution, obtains carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer.
As sorbent material, the selective extraction for the sample organophosphorus pesticide separates carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of the present invention.
The step schematic diagram that carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer prepared by the present invention is applied to sample pre-treatments as shown in Figure 1.
The present invention comprises following beneficial effect:
1, the present invention selects this material of carbon nanotube as carrier, makes final magnetic molecularly imprinted polymer have good disperse properties;
2, the preparation method of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer provided by the invention, suitability is wide;
3, because final product of the present invention has magnetic, when being applied to the actual sample analysis, can very simply from matrix, separate, the agricultural chemicals that can come simple dynamic separation to adsorb by magneticsubstance, make separation and purification complete rapidly a step, shorten the extracting and purifying time, also can reuse prepared magnetic adsorbent;
4, the present invention is owing to having adopted molecular imprinting, there is good selectivity, can the specific adsorption isolation of target substances, effectively avoid the interference of matrix impurity, for example the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of embodiment mono-preparation is 1.63 to the relative selectivity coefficient of its template molecule Chlorpyrifos 94, shows that carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer has obvious selectivity to organophosphorus;
5, the present invention is by MIPs, CNTs and magneticsubstance combine, prepare carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer, and set up on its basis method for separating and analyzing, this material can make sample pre-treatments become simple greatly, reduce analysis time, be applied to complex sample, there is very wide application prospect while separating as the selective extraction of organophosphorus pesticide in vegetables, fruit or grain samples.
The accompanying drawing explanation
Fig. 1 is the step schematic diagram that carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer prepared by the present invention is applied to sample pre-treatments;
The transmission electron microscope picture that Fig. 2 is the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of preparation in embodiment mono-;
The Fourier infrared spectrum figure that Fig. 3 is the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of preparation in embodiment mono-;
The magnetic hysteresis loop that Fig. 4 is the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of preparation in embodiment mono-;
The carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer that Fig. 5 is preparation in embodiment mono-and the adsorption isothermal line of the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus, wherein
the adsorption isothermal line that means the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of preparation in embodiment mono-,
the adsorption isothermal line that means the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus of preparation in embodiment mono-;
The Scatchard curve that Fig. 6 is the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of preparation in embodiment mono-;
The Scatchard curve that Fig. 7 is the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus of preparation in embodiment mono-.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of present embodiment comprises carbon nanotube, FeCl
36H
2o, linking agent and function monomer.
The beneficial effect of present embodiment:
The present invention selects this material of carbon nanotube as carrier, makes final magnetic molecularly imprinted polymer have good disperse properties.
Embodiment two: present embodiment is different from embodiment one: described linking agent is Ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate; Described function monomer is methacrylic acid, acrylamide or 4-vinylpridine.Other is identical with embodiment one.
Embodiment three: the preparation method of a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of present embodiment, carry out according to the following steps:
One, the ratio that is 0.8g:100～200mL in quality with volume ratio by carbon nanotube and concentrated nitric acid mixes, oil bath lower magnetic force stirring 5～7h by mixture in 80～90 ℃, activated, and then the carbon nanotube of activation is washed till to neutrality, in 50～70 ℃ of oven dry, obtain powdery substance;
Two, the powdery substance 0.3～0.6g step 1 obtained and the FeCl of 1.0～1.8g
36H
2o mixes, and obtains mixture, in mixture, adds 60～100mL ethylene glycol solvent, in 80～90 ℃ of oil bath pans, is stirred to FeCl
36H
2after O dissolves fully, add 3.4～3.8g sodium acetate, be stirred to after sodium acetate dissolves fully and stir again 2～3min, then be transferred in reactor, it is, after 180～220 ℃ of baking ovens react 8～15h, reactor to be taken out standing that reactor is placed in to temperature, the question response still is opened after being cooled to room temperature, with utilizing powerful magnet for adsorption and collect magnetic substance, more alternately clean 3～5 times with dehydrated alcohol and water, dry and obtain product;
Three, the product 0.2～0.6g that gets the step 2 gained is scattered in the ethanol that 100～150mL volumn concentration is 10%～30%, then the ammonia soln that the quality percentage composition that adds 1～3mL is 25%～28%, stir 3～5min under 280～320rpm, add again 0.4～0.6mL tetraethyl orthosilicate, stir 20～30h under room temperature, obtain mixture;
Four, the volumn concentration that the mixture of getting the step 3 gained is scattered in 100～150mL is in 5%～10% acetic acid solution, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane that adds again 0.1～0.2mL, stir 3～5h under 60～80 ℃ after, with utilizing powerful magnet for adsorption and collect magnetic substance, magnetic substance is washed till to the pH value for neutral, obtains product;
Five, taking 1～2mmol template molecule and 4～8mmol function monomer is dissolved in 5～30mL dispersion agent, in lucifuge place stirred overnight, obtain mixture, getting the product that step 4 obtains joins in this mixture, add again Aqueous Solutions of Polyethylene Glycol, 20～40mmol linking agent and 70～180mg Diisopropyl azodicarboxylate that 100～300mL quality percentage composition is 10%～30%, after ultrasonic 3～5min, in 60～80 ℃ of stirred in water bath 20～24h, obtain having the magnetic molecularly imprinted polymer of template molecule;
Six, solvent cleaning 3～5 times of the magnetic molecularly imprinted polymer with template molecule that step 5 obtained, the acetic acid methanol solution that is 10%～20% with volumn concentration again carries out the Soxhlet extraction as extracting solution, obtains carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer.
The beneficial effect of present embodiment:
The preparation method of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer provided by the invention, suitability is wide.
Embodiment four: present embodiment is different from embodiment three: the template molecule described in step 5 is Chlorpyrifos 94, acephate, Trichlorphon or Rogor; Described function monomer is methacrylic acid, acrylamide or 4-vinylpridine; Described dispersion agent is dehydrated alcohol or methyl alcohol; Described linking agent is Ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate.Other is identical with embodiment three.
Embodiment five: present embodiment is different from embodiment three or four: the solvent described in step 6 is dehydrated alcohol or methyl alcohol.Other is identical with embodiment three or four.
Embodiment six: the application of a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of present embodiment is characterized in that the selective extraction for the sample organophosphorus pesticide separates carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer as sorbent material.
The beneficial effect of present embodiment:
1, because final product of the present invention has magnetic, when being applied to the actual sample analysis, can very simply from matrix, separate, the agricultural chemicals that can come simple dynamic separation to adsorb by magneticsubstance, make separation and purification complete rapidly a step, shorten the extracting and purifying time, also can reuse prepared magnetic adsorbent;
2, the present invention is owing to having adopted molecular imprinting, there is good selectivity, can the specific adsorption isolation of target substances, effectively avoid the interference of matrix impurity, for example the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of embodiment mono-preparation is 1.63 to the relative selectivity coefficient of its template molecule Chlorpyrifos 94, shows that carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer has obvious selectivity to organophosphorus;
3, the present invention is by MIPs, CNTs and magneticsubstance combine, prepare carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer, and set up on its basis method for separating and analyzing, this material can make sample pre-treatments become simple greatly, reduce analysis time, be applied to complex sample, there is very wide application prospect while separating as the selective extraction of organophosphorus pesticide in vegetables, fruit or grain samples.
Embodiment seven: present embodiment is different from embodiment six: as sorbent material, the selective extraction for the sample organophosphorus pesticide separates described carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer, according to following steps, carries out:
One, extraction organophosphorus pesticide: get sample 0.5～5g to be determined, add extraction solvent 5～20mL, mixture is transferred to ultrasonic 10～30min in ultrasonic instrument, then, with 4000～6000rpm rotating speed centrifugation, 5～15min, then collects and separate the extraction liquid obtained;
Two, separation of organic phosphorous agricultural chemicals: add the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of 10～80mg in the extraction liquid obtained to step 1, 10～30min is adsorbed in speed oscillation with 180～220rpm on shaking table, utilize magnet to separate and collect magnetic substance, obtain adsorbing the polymkeric substance of organophosphorus pesticide, then add eluent 1～3mL in this polymkeric substance, ultrasonic 5～10s after mixing, again with utilizing powerful magnet for adsorption and collect magnetic substance, dry up the magnetic substance after drip washing, add elutriant 1～3mL ultrasonic 10～40s, after wash-out 2～5 times, merge resulting elutriant, be about to organophosphorus pesticide separates from sample solution.
Other is identical with embodiment six.
Embodiment eight: present embodiment is different from embodiment six or seven: the sample described in step 1 is vegetables, fruit or grain.Other is identical with embodiment six or seven.
Embodiment nine: present embodiment is different from one of embodiment six to eight: the extraction solvent described in step 1 is normal hexane or acetone.Other is identical with one of embodiment six to eight.
Embodiment ten: present embodiment is different from one of embodiment six to nine: the eluent described in step 2 is the methyl alcohol that volumn concentration is 3%～10%; Described elutriant is the acetic acid acetonitrile that volumn concentration is 1%～5%.Other is identical with one of embodiment six to nine.
Embodiment mono-:
The preparation method of the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of the present embodiment, carry out according to following steps:
One, the ratio that is 0.8g:150mL in quality with volume ratio by carbon nanotube and concentrated nitric acid mixes, oil bath lower magnetic force stirring 6h by mixture in 85 ℃, activated, and then the carbon nanotube of activation is washed till to neutrality, in 60 ℃ of oven dry, obtain black powder shape material;
Two, the black powder shape material 0.4g step 1 obtained and the FeCl of 1.4g
36H
2o mixes, and obtains mixture, in mixture, adds the 80mL ethylene glycol solvent, in 90 ℃ of oil bath pans, is stirred to FeCl
36H
2after O dissolves fully, add the 3.6g sodium acetate, be stirred to after sodium acetate dissolves fully and stir again 2min, then be transferred in reactor, it is, after 200 ℃ of baking ovens react 12h, reactor to be taken out standing that reactor is placed in to temperature, the question response still is opened after being cooled to room temperature, with utilizing powerful magnet for adsorption and collect magnetic substance, more alternately clean 3 times with dehydrated alcohol and water, dry and obtain product;
Three, the product 0.4g that gets the step 2 gained is scattered in the ethanol that the 100mL volumn concentration is 20%, then the ammonia soln that the quality percentage composition that adds 2mL is 28% stirs 3min under 300rpm, then adds the 0.5mL tetraethyl orthosilicate, stir 24h under room temperature, obtain mixture;
Four, the volumn concentration that the mixture of getting the step 3 gained is scattered in 150mL is in 10% acetic acid solution, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane that adds again 0.15mL, stir 5h under 60 ℃ after, with utilizing powerful magnet for adsorption and collect magnetic substance, magnetic substance is washed till to the pH value for neutral, obtains product;
Five, taking 1mmol Chlorpyrifos 94 and 4mmol methacrylic acid is dissolved in the 10mL dehydrated alcohol, in lucifuge place stirred overnight, obtain mixture, getting the product that step 4 obtains joins in this mixture, add again Aqueous Solutions of Polyethylene Glycol, 20mmol Ethylene glycol dimethacrylate and 80mg Diisopropyl azodicarboxylate (initiator) that 150mL quality percentage composition is 20%, after ultrasonic 3min, in 60 ℃ of stirred in water bath 24h, obtain having the magnetic molecularly imprinted polymer of template molecule;
Six, the magnetic molecularly imprinted polymer with template molecule step 5 obtained cleans 3 times with dehydrated alcohol, the acetic acid methanol solution that is 10% with volumn concentration again carries out the Soxhlet extraction as extracting solution, obtains slightly browny carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer.
The present embodiment adopts a kind of simple method to prepare the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer that Chlorpyrifos 94 is had to specific adsorption.
In order to investigate the selectivity of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer, the present embodiment has prepared the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus simultaneously, its preparation method is identical with the preparation method of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer, and different from it is not add the template molecule Chlorpyrifos 94 in step 5.
Carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer prepared by the present embodiment adopts transmission electron microscope to detect its microscopic appearance, transmission electron microscope picture as shown in Figure 2, result shows that carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer prepared by the present embodiment successfully combines carbon nanotube and molecularly imprinted polymer, and reached Nano grade, and there is good dispersiveness.
Carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer prepared by the present embodiment adopts Fourier infrared spectrograph to be detected, Fourier infrared spectrum figure as shown in Figure 3, as shown in Figure 3,3440cm in carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer
-1the stretching vibration absorption peak of O-H, 2921cm
-1cH
3the stretching vibration absorption peak, 1731cm
-1the vibration absorption peak of C=O, 1621cm
-1the charateristic avsorption band of carbon nanotube, 1381cm
-1the flexural vibration absorption peak of O-H, 1091cm
-1the characteristic peak of Si-O-Si, 591cm
-1be the absorption peak of Fe-O, result shows that carbon nanotube successfully synthesizes molecularly imprinted polymer and Fe
3o
4, therefore carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer possesses Fe
3o
4magnetic, and comprised Fe
3o
4, carbon nanotube and molecularly imprinted polymer.
Carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer prepared by the present embodiment adopts vibrating sample magnetometer to be detected, magnetic hysteresis loop as shown in Figure 4, the saturation magnetization of the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer that as shown in Figure 4, prepared by the present embodiment is 23.29emug
-1, result shows that carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer prepared by the present embodiment has very strong magnetic, can well realize magnetic resolution.
The preparation method of the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer that the present embodiment provides, suitability is wide.
Embodiment bis-:
As sorbent material, the selective extraction for the sample organophosphorus pesticide separates the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of the present embodiment, according to following steps, carries out:
One, extraction organophosphorus pesticide: get Chinese cabbage 1.0g to be determined, add acetone 10mL, mixture is transferred to ultrasonic 15min in ultrasonic instrument, then, with 5000rpm rotating speed centrifugation 5min, then collect and separate the extraction liquid obtained;
Two, separation of organic phosphorous agricultural chemicals: add the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of 40mg in the extraction liquid obtained to step 1, 15min is adsorbed in speed oscillation with 200rpm on shaking table, utilize magnet to separate and collect magnetic substance, obtain adsorbing the polymkeric substance of organophosphorus pesticide, then add methyl alcohol (eluent) 1mL that volumn concentration is 5% in this polymkeric substance, ultrasonic 5s after mixing, again with utilizing powerful magnet for adsorption and collect magnetic substance, dry up the magnetic substance after drip washing, add acetic acid acetonitrile (elutriant) 2mL ultrasonic 30s that volumn concentration is 5%, after wash-out 3 times, merge resulting elutriant, be about to organophosphorus pesticide separates from sample solution.
The carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of embodiment mono-preparation and the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus are to the adsorption isothermal line of target compound Chlorpyrifos 94 as shown in Figure 5, adopt the Scatchard analysis test method to be analyzed, the method concrete steps are as follows:
At first carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer and the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus of 25mg embodiment mono-preparation are joined to 5mL Chlorpyrifos 94 starting point concentration (μ gmL
-1) be respectively in 1,5,10,20,50,100,150,200,250,500 standard solution, then be transferred on vibrator, and be oscillatory reaction 12h under 200rpm at the vibration rotating speed, then utilize magnet to carry out magnetic resolution, get supernatant liquid filtering, adopt liquid chromatography to be detected it, obtain the equilibrium concentration of Chlorpyrifos 94, then draw adsorption isothermal line as shown in Figure 5.
Then, according to formula
calculate Q
max.Wherein Q is the adsorptive capacity that is attached to the Chlorpyrifos 94 on carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer or the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus, is that starting point concentration by Chlorpyrifos 94 deducts the quality divided by polymkeric substance after equilibrium concentration and obtains; C
eequilibrium concentration for Chlorpyrifos 94; K
ddissociation constant for binding site; Q
maxfor the apparent binding capacity of maximum.Carry out matching by the Origin8.0 mapping software, result as shown in Figure 6,7.
As shown in Figure 6, there are two kinds of forms in the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of embodiment mono-preparation to the absorption of Chlorpyrifos 94 to the Scatchard analytic curve of the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of embodiment mono-preparation as shown in Figure 6.Can obtain K as calculated
the d1(molecular imprinting)=1.14 μ gmL
-1, Q
max1 (molecular imprinting)=2.85mgg
-1; K
the d2(molecular imprinting)=35.82 μ gmL
-1, Q
max2 (molecular imprinting)=26.34mgg
-1.
The Scatchard analytic curve of the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus of embodiment mono-preparation as shown in Figure 7, as shown in Figure 7, only there is a kind of form in the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus of embodiment mono-preparation to the absorption of Chlorpyrifos 94, can obtain K as calculated
the non-molecular imprinting of d()=104.29 μ gmL
-1, Q
max (non-molecular imprinting)=14.61mgg
-1.
Result shows that the adsorptive capacity of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer is greater than the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus, carrys out agricultural chemicals residual in adsorption sample thereby more be suitable as sorbent material.
Carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer to embodiment mono-preparation carries out the selectivity analysis, by selecting cyhalofop-butyl as object of reference, compare the selectivity of prepared polymkeric substance to organophosphorus, these selective test method concrete steps are as follows:
At first carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer or the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus of 20mg embodiment mono-preparation are joined in the standardized solution of 5mL Chlorpyrifos 94 or cyhalofop-butyl, and be oscillatory reaction 12h under 200rmp at the vibration rotating speed, then utilize magnet to carry out magnetic resolution, get supernatant liquid filtering, adopt liquid chromatography to be detected it, obtain the equilibrium concentration of Chlorpyrifos 94 or cyhalofop-butyl, complete the analysis of molecular imprinting selectivity.
Account form is as follows:
The static allocation coefficient:
Selectivity coefficient:
The relative selectivity coefficient:
Wherein, static allocation coefficient δ, selectivity coefficient α, relative selectivity factor beta are and weigh optionally index of molecular imprinting; Q is attached to Chlorpyrifos 94 on carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer or the non-molecularly imprinted polymer of carbon nanotube-based magnetic organophosphorus or the adsorptive capacity of cyhalofop-butyl, is that starting point concentration by Chlorpyrifos 94 or cyhalofop-butyl deducts the quality divided by polymkeric substance after equilibrium concentration and obtains; The starting point concentration that C is Chlorpyrifos 94 or cyhalofop-butyl; α
chlorpyrifos 94and α
cyhalofop-butylbe respectively the selectivity coefficient of Chlorpyrifos 94 and cyhalofop-butyl; β is the relative selectivity coefficient.
The selectivity analysis of the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of table 1 embodiment mono-preparation
The selectivity analytical results of the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of embodiment mono-preparation is as shown in table 1, by optionally analyzing, the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer that finally obtains embodiment mono-preparation is 1.63 to the relative selectivity coefficient of its template molecule Chlorpyrifos 94, and result shows that the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of embodiment mono-preparation has obvious selectivity to organophosphorus.
Claims (10)
1. a carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer, is characterized in that carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer comprises carbon nanotube, FeCl
36H
2o, linking agent and function monomer.
2. a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer according to claim 1, is characterized in that described linking agent is Ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate; Described function monomer is methacrylic acid, acrylamide or 4-vinylpridine.
3. the preparation method of a carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer is characterized in that it carries out according to following steps:
One, the ratio that is 0.8g:100～200mL in quality with volume ratio by carbon nanotube and concentrated nitric acid mixes, oil bath lower magnetic force stirring 5～7h by mixture in 80～90 ℃, activated, and then the carbon nanotube of activation is washed till to neutrality, in 50～70 ℃ of oven dry, obtain powdery substance;
Two, the powdery substance 0.3～0.6g step 1 obtained and the FeCl of 1.0～1.8g
36H
2o mixes, and obtains mixture, in mixture, adds 60～100mL ethylene glycol solvent, in 80～90 ℃ of oil bath pans, is stirred to FeCl
36H
2after O dissolves fully, add 3.4～3.8g sodium acetate, be stirred to after sodium acetate dissolves fully and stir again 2～3min, then be transferred in reactor, it is, after 180～220 ℃ of baking ovens react 8～15h, reactor to be taken out standing that reactor is placed in to temperature, the question response still is opened after being cooled to room temperature, with utilizing powerful magnet for adsorption and collect magnetic substance, more alternately clean 3～5 times with dehydrated alcohol and water, dry and obtain product;
Three, the product 0.2～0.6g that gets the step 2 gained is scattered in the ethanol that 100～150mL volumn concentration is 10%～30%, then the ammonia soln that the quality percentage composition that adds 1～3mL is 25%～28%, stir 3～5min under 280～320rpm, add again 0.4～0.6mL tetraethyl orthosilicate, stir 20～30h under room temperature, obtain mixture;
Four, the volumn concentration that the mixture of getting the step 3 gained is scattered in 100～150mL is in 5%～10% acetic acid solution, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane that adds again 0.1～0.2mL, stir 3～5h under 60～80 ℃ after, with utilizing powerful magnet for adsorption and collect magnetic substance, magnetic substance is washed till to the pH value for neutral, obtains product;
Five, taking 1～2mmol template molecule and 4～8mmol function monomer is dissolved in 5～30mL dispersion agent, in lucifuge place stirred overnight, obtain mixture, getting the product that step 4 obtains joins in this mixture, add again Aqueous Solutions of Polyethylene Glycol, 20～40mmol linking agent and 70～180mg Diisopropyl azodicarboxylate that 100～300mL quality percentage composition is 10%～30%, after ultrasonic 3～5min, in 60～80 ℃ of stirred in water bath 20～24h, obtain having the magnetic molecularly imprinted polymer of template molecule;
Six, solvent cleaning 3～5 times of the magnetic molecularly imprinted polymer with template molecule that step 5 obtained, the acetic acid methanol solution that is 10%～20% with volumn concentration again carries out the Soxhlet extraction as extracting solution, obtains carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer.
4. the preparation method of a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer according to claim 3, is characterized in that the template molecule described in step 5 is Chlorpyrifos 94, acephate, Trichlorphon or Rogor; Described function monomer is methacrylic acid, acrylamide or 4-vinylpridine; Described dispersion agent is dehydrated alcohol or methyl alcohol; Described linking agent is Ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate.
5. the preparation method of a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer according to claim 3, is characterized in that the solvent described in step 6 is dehydrated alcohol or methyl alcohol.
6. the application of a carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer, is characterized in that the selective extraction for the sample organophosphorus pesticide separates carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer as sorbent material.
7. the application of a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer according to claim 6, it is characterized in that the selective extraction for the sample organophosphorus pesticide separates carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer as sorbent material, carries out according to following steps:
One, extraction organophosphorus pesticide: get sample 0.5～5g to be determined, add extraction solvent 5～20mL, mixture is transferred to ultrasonic 10～30min in ultrasonic instrument, then, with 4000～6000rpm rotating speed centrifugation, 5～15min, then collects and separate the extraction liquid obtained;
Two, separation of organic phosphorous agricultural chemicals: add the carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer of 10～80mg in the extraction liquid obtained to step 1, 10～30min is adsorbed in speed oscillation with 180～220rpm on shaking table, utilize magnet to separate and collect magnetic substance, obtain adsorbing the polymkeric substance of organophosphorus pesticide, then add eluent 1～3mL in this polymkeric substance, ultrasonic 5～10s after mixing, again with utilizing powerful magnet for adsorption and collect magnetic substance, dry up the magnetic substance after drip washing, add elutriant 1～3mL ultrasonic 10～40s, after wash-out 2～5 times, merge resulting elutriant, be about to organophosphorus pesticide separates from sample solution.
8. the application of a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer according to claim 7, is characterized in that the sample described in step 1 is vegetables, fruit or grain.
9. the application of a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer according to claim 7, is characterized in that the extraction solvent described in step 1 is normal hexane or acetone.
10. the application of a kind of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer according to claim 7, is characterized in that the eluent described in step 2 is the methyl alcohol that volumn concentration is 3%～10%; Described elutriant is the acetic acid acetonitrile that volumn concentration is 1%～5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310378769.2A CN103497276B (en) | 2013-08-27 | 2013-08-27 | A kind of preparation method and application of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310378769.2A CN103497276B (en) | 2013-08-27 | 2013-08-27 | A kind of preparation method and application of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103497276A true CN103497276A (en) | 2014-01-08 |
| CN103497276B CN103497276B (en) | 2015-10-21 |
Family
ID=49862547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310378769.2A Expired - Fee Related CN103497276B (en) | 2013-08-27 | 2013-08-27 | A kind of preparation method and application of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103497276B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693961A (en) * | 2016-04-08 | 2016-06-22 | 东北林业大学 | Preparation and application methods of carbon-nanotube-base magnetic bactericide molecularly-imprinted polymer |
| CN106046279A (en) * | 2016-05-23 | 2016-10-26 | 中国环境科学研究院 | Preparation method for perfluorocaprylic acid molecular imprinting polymer on surfaces of multi-walled carbon nanotubes |
| CN106215905A (en) * | 2016-09-29 | 2016-12-14 | 安徽出入境检验检疫局检验检疫技术中心 | A kind of preparation method of magnetic fullerene molecule trace nano composite material |
| CN106732437A (en) * | 2017-03-10 | 2017-05-31 | 深圳市瑞赛生物技术有限公司 | A kind of affine magnetic microsphere and its preparation and application for purifying and detecting carbamate and organophosphorus pesticide |
| CN107033302A (en) * | 2017-04-18 | 2017-08-11 | 南开大学 | A kind of preparation method of double-template epitope magnetic imprinted polymer |
| CN107413307A (en) * | 2017-05-31 | 2017-12-01 | 常熟理工学院 | A kind of diflubenzuron magnetic double-helix carbon nanotube surface imprinted material and its preparation method and application |
| CN110961086A (en) * | 2019-12-15 | 2020-04-07 | 江西理工大学 | Extractant functionalized magnetic nano-adsorption material, preparation method and application |
| CN111393577A (en) * | 2020-05-23 | 2020-07-10 | 中国检验检疫科学研究院 | Compound extraction particle and preparation method and application thereof |
| CN113087842A (en) * | 2021-04-27 | 2021-07-09 | 浙江工业大学 | Preparation method and application of ferulic acid molecularly imprinted polymer |
| CN114436676A (en) * | 2022-01-29 | 2022-05-06 | 深圳市中科纳米科技有限公司 | Production method of carbon nano tube composite porous ceramic capable of adsorbing toxic substances |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044639A (en) * | 2011-10-14 | 2013-04-17 | 中国药科大学 | Novel carbon nanotube surface molecularly imprinted polymer and preparation method thereof |
| CN103059206A (en) * | 2013-01-24 | 2013-04-24 | 东北林业大学 | Methods for preparing and using sudan red magnetic molecularly imprinted polymer |
-
2013
- 2013-08-27 CN CN201310378769.2A patent/CN103497276B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044639A (en) * | 2011-10-14 | 2013-04-17 | 中国药科大学 | Novel carbon nanotube surface molecularly imprinted polymer and preparation method thereof |
| CN103059206A (en) * | 2013-01-24 | 2013-04-24 | 东北林业大学 | Methods for preparing and using sudan red magnetic molecularly imprinted polymer |
Non-Patent Citations (1)
| Title |
|---|
| 苏晓倩: "有机磷农经类分子印迹聚合物材料的制备及其应用", 《万方数据知识服务平台》, 29 December 2011 (2011-12-29), pages 46 - 49 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693961A (en) * | 2016-04-08 | 2016-06-22 | 东北林业大学 | Preparation and application methods of carbon-nanotube-base magnetic bactericide molecularly-imprinted polymer |
| CN106046279B (en) * | 2016-05-23 | 2018-03-09 | 中国环境科学研究院 | The preparation method of multi-wall carbon nano-tube pipe surface perfluoro caprylic acid molecularly imprinted polymer |
| CN106046279A (en) * | 2016-05-23 | 2016-10-26 | 中国环境科学研究院 | Preparation method for perfluorocaprylic acid molecular imprinting polymer on surfaces of multi-walled carbon nanotubes |
| CN106215905A (en) * | 2016-09-29 | 2016-12-14 | 安徽出入境检验检疫局检验检疫技术中心 | A kind of preparation method of magnetic fullerene molecule trace nano composite material |
| CN106732437A (en) * | 2017-03-10 | 2017-05-31 | 深圳市瑞赛生物技术有限公司 | A kind of affine magnetic microsphere and its preparation and application for purifying and detecting carbamate and organophosphorus pesticide |
| CN107033302A (en) * | 2017-04-18 | 2017-08-11 | 南开大学 | A kind of preparation method of double-template epitope magnetic imprinted polymer |
| CN107413307A (en) * | 2017-05-31 | 2017-12-01 | 常熟理工学院 | A kind of diflubenzuron magnetic double-helix carbon nanotube surface imprinted material and its preparation method and application |
| CN107413307B (en) * | 2017-05-31 | 2020-04-21 | 常熟理工学院 | Diflubenzuron magnetic double-helix carbon nanotube surface imprinting material and preparation method and application thereof |
| CN110961086A (en) * | 2019-12-15 | 2020-04-07 | 江西理工大学 | Extractant functionalized magnetic nano-adsorption material, preparation method and application |
| CN110961086B (en) * | 2019-12-15 | 2021-12-03 | 江西理工大学 | Extractant functionalized magnetic nano-adsorption material, preparation method and application |
| CN111393577A (en) * | 2020-05-23 | 2020-07-10 | 中国检验检疫科学研究院 | Compound extraction particle and preparation method and application thereof |
| CN113087842A (en) * | 2021-04-27 | 2021-07-09 | 浙江工业大学 | Preparation method and application of ferulic acid molecularly imprinted polymer |
| CN113087842B (en) * | 2021-04-27 | 2022-07-26 | 浙江工业大学 | Preparation method and application of ferulic acid molecularly imprinted polymer |
| CN114436676A (en) * | 2022-01-29 | 2022-05-06 | 深圳市中科纳米科技有限公司 | Production method of carbon nano tube composite porous ceramic capable of adsorbing toxic substances |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103497276B (en) | 2015-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103497276B (en) | A kind of preparation method and application of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer | |
| Zhang et al. | Preparation of core–shell magnetic ion-imprinted polymer for selective extraction of Pb (II) from environmental samples | |
| Sun et al. | Preparation and adsorption property of xylan/poly (acrylic acid) magnetic nanocomposite hydrogel adsorbent | |
| Yuan et al. | Selective extraction and detection of β-agonists in swine urine for monitoring illegal use in livestock breeding | |
| Xiao et al. | Preparation of molecularly imprinted polymers on the surface of magnetic carbon nanotubes with a pseudo template for rapid simultaneous extraction of four fluoroquinolones in egg samples | |
| Zhao et al. | Preparation of molecularly imprinted polymers based on magnetic carbon nanotubes for determination of sulfamethoxazole in food samples | |
| CN102532390B (en) | Triazine weedicide, and metabolite molecular engram polymer microspheres, preparation method and application thereof | |
| Ma et al. | Development of magnetic molecularly imprinted polymers based on carbon nanotubes–Application for trace analysis of pyrethroids in fruit matrices | |
| Zhao et al. | Magnetic molecular imprinting polymers based on three-dimensional (3D) graphene-carbon nanotube hybrid composites for analysis of melamine in milk powder | |
| Gao et al. | Selective extraction of sulfonamides from food by use of silica-coated molecularly imprinted polymer nanospheres | |
| Azodi-Deilami et al. | Magnetic molecularly imprinted polymer nanoparticles for the solid-phase extraction of paracetamol from plasma samples, followed its determination by HPLC | |
| Dramou et al. | Preparation of novel molecularly imprinted magnetic graphene oxide and their application for quercetin determination | |
| Tizro et al. | Preparation and application of grafted β‑cyclodextrin/thermo-sensitive polymer onto modified Fe3O4@ SiO2 nano-particles for fenitrothion elimination from aqueous solution | |
| CN108452784A (en) | Catecholamine Solid Phase Extraction functional composite material and its preparation method and application | |
| CN102070739A (en) | Method for preparing cyhalothrin molecular imprinting polymer microspheres | |
| CN104587970A (en) | Magnetic chitosan composite microsphere surface imprinted adsorbent and preparation method thereof | |
| Lian et al. | Selective extraction and concentration of mebendazole in seawater samples using molecularly imprinted polymer as sorbent | |
| Yang et al. | Dual‐template magnetic molecularly imprinted particles with multi‐hollow structure for the detection of dicofol and chlorpyrifos‐methyl | |
| CN107913682A (en) | A kind of method for preparing porous temperature sensitive molecular imprinting adsorbing agent | |
| CN102070750A (en) | Method for preparing sumicidin molecularly imprinted polymer microspheres | |
| CN104193875A (en) | Preparation method and application of magnetic diethylstilbestrol molecularly-imprinted polymer | |
| Yahaya et al. | Recent applications of electrospun nanofibres in microextraction based-sample preparation techniques for determination of environmental pollutants | |
| Li et al. | Selective solid-phase extraction of four phenylarsonic compounds from feeds, edible chicken and pork with tailoring imprinted polymer | |
| CN103301820A (en) | Core-shell type Rhodamine B molecular imprinting solid-phase extraction magnetic material, and preparation method and application thereof | |
| Semong | Development of an aflatoxin B1 specific molecularly imprinted solid phase extraction sorbent for the selective pre-concentration of toxic aflatoxin B1 from child weaning food, Tsabana |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151021 Termination date: 20160827 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |