CN103868966A - Molecularly-imprinted polymer-graphene composite material modified electrode as well as preparation method and application thereof - Google Patents
Molecularly-imprinted polymer-graphene composite material modified electrode as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN103868966A CN103868966A CN201410106920.1A CN201410106920A CN103868966A CN 103868966 A CN103868966 A CN 103868966A CN 201410106920 A CN201410106920 A CN 201410106920A CN 103868966 A CN103868966 A CN 103868966A
- Authority
- CN
- China
- Prior art keywords
- imprinted polymer
- composite material
- graphene composite
- molecularly imprinted
- mda
- 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
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a molecularly-imprinted polymer-graphene composite material modified electrode. The molecularly-imprinted polymer-graphene composite material modified electrode comprises a molecularly-imprinted polymer-graphene composite material and a glassy carbon electrode, wherein the glassy carbon electrode is used as a base body; the molecularly-imprinted polymer-graphene composite material is modified on the glassy carbon electrode. The invention further provides a preparation method of the molecularly-imprinted polymer-graphene composite material modified electrode and an application of the molecularly-imprinted polymer-graphene composite material modified electrode to detection of aniline and 4,4'-methylenedianiline (MDA). The molecularly-imprinted polymer-graphene composite material modified electrode has the advantages of high responding speed, good selectivity, high sensitivity and the like and is suitable for rapidly detecting the aniline and the MDA in food safety and environmental sanitation.
Description
Technical field
This technology relates to food safety monitoring technical field, is specifically related to a kind of molecularly imprinted polymer-graphene composite material modified electrode and its preparation method and application.
Background technology
Aromatic amine compounds is the poisonous and harmful substance of a quasi-representative, and by international cancer, mechanism is known as suspect carcinogen.The application of aromatic amine compounds in chemical industry is wider, is mainly used in the synthetic intermediate of dyestuff, cosmetics, medicine and rubber, and with industrial wastewater discharge, brings environmental pollution to water body, soil.Some plastic food packing materials are also one of sources of primary aromatic diamine.This plastic package material, for packaging for foodstuff, can migrate in food and pollutes, and carrys out serious future trouble to food securing band.Wherein 4, it is the food contact material defective main cause of being moved back fortune of current China's export to European Union that the migration amount of 4 '-methylene dianiline (MDA) and aniline exceeds standard.Therefore, set up quick, sensitive, accurately 4,4 '-methylene dianiline (MDA) and aniline detection method for protection of the environment, ensure food safety and promote foreign trade to develop in a healthy way, significant.
At present, the detection method of aromatic amine compounds mainly contains thin-layered chromatography, vapor-phase chromatography, high performance liquid chromatography, gas chromatography-mass spectrography, liquid chromatography-mass spectrography etc., and sample is mainly for water body, food, textile and leather etc.Although existing detection method sensitivity and degree of accuracy are high, but there is the shortcomings such as length analysis time, complicated operation, cost costliness, for example: gas chromatography-mass spectrography energy fast detecting aromatic amine, but because aromatic amine volatility and thermal stability in sample are lower, detect and have certain difficulty.Chemically modified electrode is development in recent years novel detection technique faster, and compared with classic method, it has the advantages such as quick, accurate, sensitive, has been widely used in the fields such as health care, food security and environmental science.Existing many reports adopt Electrochemical Modification electrode detection aromatic amine at present, but the electrode poor sensitivity that these methods adopt, serviceable life is short, and selectivity is not high, easily has interference in testing process.
Summary of the invention
The present invention has overcome the above defect of prior art, a kind of molecularly imprinted polymer-graphene composite material modified electrode and its preparation method and application is provided, can detect 4 simultaneously, 4 '-methylene dianiline (MDA) (hereinafter to be referred as MDA) and aniline, there is the advantages such as preparation is simple, selectivity is good, highly sensitive, good stability, be applicable to industrial application.
The invention provides a kind of molecularly imprinted polymer-graphene composite material modified electrode, comprise molecularly imprinted polymer-graphene composite material and glass-carbon electrode; Take described glass-carbon electrode as matrix; Described molecularly imprinted polymer-graphene composite material is modified on described glass-carbon electrode.In the present invention, molecularly imprinted polymer-graphene composite material is fixed on glass-carbon electrode surface by the adhesion of shitosan, and described shitosan has that adhesion is strong, physical strength advantages of higher.
In the present invention, described molecularly imprinted polymer-graphene composite material is the compound substance that molecularly imprinted polymer and Graphene form, the irregular Graphene surface that is covered in of molecularly imprinted polymer.Wherein, graphene-structured is scraps of paper shape, has fold in Graphene, and these folds can prevent that Graphene from producing reunion.
The present invention also provides a kind of preparation method of Graphene/modified by magnetic nanoparticles, its electrode, comprises the following steps successively:
Step 1: glass-carbon electrode carries out pre-service
With alumina powder, glass-carbon electrode is carried out to polishing, after redistilled water rinses, carry out ultrasonic cleaning in acetone, salpeter solution, NaOH solution and aqueous solution successively;
Step 2: molecularly imprinted polymer-graphene composite material preparation
The Graphene of 20mg is scattered in 20mL organic solvent, add 4, the ultrasonic 30min of 4 '-methylene dianiline (MDA) (MDA) is uniformly dispersed, then, 4-vinylpridine (hereinafter to be referred as 4-VP), ethylene glycol dimethacrylate (hereinafter to be referred as EGDMA) and 2,2 '-azobis isobutyronitrile (hereinafter to be referred as AIBN) adds in solution, and under nitrogen atmosphere, 60 ℃ are stirred 24 hours.Obtain described molecularly imprinted polymer-graphene composite material through centrifugal, separation, oven dry.Concrete for example compound substance is by centrifuging, and adopts washed with methanol 3 times, places 12h oven dry in 55 ℃ of vacuum drying ovens.
Step 3: prepare molecularly imprinted polymer-graphene composite material modified electrode
Described molecularly imprinted polymer-graphene composite material is added in acetum and (contains 0.5% shitosan), mix by ultrasonic; Get mixed liquor 3～8uL and be added drop-wise to through the pretreated glass-carbon electrode of step 1 surface, under infrared lamp, dry.In PBS solution, adopt linear sweep voltammetry to detect, until can't detect the electrochemical signals of MDA, in pattern of descriptive parts, MDA molecule is removed, and prepares described molecularly imprinted polymer-graphene composite material modified electrode.
In step 2, organic solvent is the mixed solution of trichloroethanes and acetonitrile, and volume ratio is 1: 2.0～4.0.The concentration of MDA is 0.01～0.02mol/L, and the concentration of 4-VP, EGDMA and AIBN is respectively 0.02～0.06mol/L, 0.1～0.3mol/L, 0.01～0.02mol/L.
The present invention also provides a kind of molecularly imprinted polymer-graphene composite material modified electrode 4, the application during 4 '-methylene dianiline (MDA) and aniline detect.In particular, molecularly imprinted polymer-graphene composite material modified electrode of the present invention can detect MDA in sample and aniline simultaneously.
With molecularly imprinted polymer-graphene composite material modified electrode in sample 4, the method that 4 '-methylene dianiline (MDA) and aniline detect is, reference substance MDA and aniline are disposed in substrate solution, adopt Differential Pulse Voltammetry record current response, set up reference substance current-responsive-MDA and current-responsive-concentration of aniline curve.Then, under the same conditions testing sample is placed in to substrate solution and measures and record current response, by this above-mentioned current-responsive-MDA of current-responsive value substitution and concentration of aniline curve, thereby determine MDA and the concentration of aniline in testing sample.The applicable testing sample of detection method of the present invention comprises food contact material (for example: plastic bowl, chopsticks, soup ladle) etc.
In the present invention's application, described substrate solution is phosphate buffer solution, and its pH value is 5-9.
In the present invention, after mixing with shitosan, modifies in described glass-carbon electrode surface by dripping to be coated with molecularly imprinted polymer-graphene composite material.
The present invention innovates and proposes a kind of molecularly imprinted polymer-graphene composite material modified electrode and its preparation method and application, to not yet there being so far other similar open reports.In the present invention, molecularly imprinted polymer-graphene composite material is modified on electrode, increases electrode specific surface area, not only can accelerate electronics transfer rate, improves MDA and aniline detection sensitivity.And described modified electrode has good selectivity for MDA and aniline, can get rid of the interference of other aromatic amine materials and metallic ion.The sample that molecularly imprinted polymer-graphene composite material modified electrode of the present invention can be realized containing MDA and aniline detects both under the condition without separating in advance simultaneously, has the advantages such as quick, efficient.
Molecularly imprinted polymer-graphene composite material modified electrode of the present invention, in the detection of MDA and aniline, has the advantages such as fast response time, highly sensitive, method is easy.The present invention utilizes the glass-carbon electrode of molecularly imprinted polymer-graphene composite material to utilize the application of ampere analytic approach fast detecting MDA and aniline, and the electrochemical detector of analyzing as ampere detects MDA and aniline in PBS.Environmental protection and economy of the present invention, method are simple, and condition is easy to control, has good sensitivity, convenience, are convenient to produce, and have a good application prospect, and are particularly useful for the fast detecting of aniline and MDA in food security and environmental health.
Compared with prior art, beneficial effect of the present invention comprises: molecularly imprinted polymer-graphene composite material modified electrode of the present invention has good response in MDA and aniline detection, can detect MDA and aniline simultaneously, and fine selectivity.Molecularly imprinted polymer-graphene composite material modified electrode of the present invention is in MDA and aniline detection, have the following advantages: detection time short (for example only needing for 3 seconds), simple to operate, selectivity is good, can get rid of the interference of other aromatic amine materials and metallic ion, highly sensitive, meet the demand of modern society's fast detecting, detect and have great importance for MDA in food security and environmental health and aniline.With the existing MDA of tradition and the comparison of aniline detecting electrode, the glass-carbon electrode that molecularly imprinted polymer of the present invention-graphene composite material is modified has the advantages such as selectivity is good, the range of linearity is wide, sensitivity is high.
Accompanying drawing explanation
Fig. 1 is SEM and the TEM figure of molecularly imprinted polymer-graphene composite material in the present invention.
Fig. 2 is the Raman spectrogram of Graphene in the present invention (a) and molecularly imprinted polymer-graphene composite material (b).
Fig. 3 is that molecularly imprinted polymer-graphene composite material modified electrode of the present invention is applied to while detecting MDA and aniline, the current-responsive curve synoptic diagram of different concentrations of MDA and aniline.
Fig. 4 is that molecularly imprinted polymer-graphene composite material modified electrode of the present invention is applied to while detecting MDA and aniline, the linear relationship schematic diagram between response current and MDA, response current and aniline.
Fig. 5 is that molecularly imprinted polymer-graphene composite material modified electrode of the present invention is at the cyclic voltammogram containing in MDA and aniline solution.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Do not deviating under the spirit and scope of inventive concept, variation and advantage that those skilled in the art can expect are all included in the present invention, and take appending claims as protection domain.Implement process of the present invention, condition, reagent, experimental technique etc., except the content of mentioning specially below, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
Adopt 0.5 μ m alumina powder to carry out sanding and polishing to glass-carbon electrode, then rinse out surperficial alumina powder with redistilled water, then successively at redistilled water, acetone (analyzing pure), HNO
3each ultrasonic 5min in solution (1.0mol/L), NaOH solution (1.0mol/L) and redistilled water, finally dries electrode at room temperature.
The Graphene of 20mg is scattered in the mixed solution (v/v of 20mL trichloroethanes and acetonitrile, 1: 3), add the ultrasonic 30min of MDA (0.01mol/L) to be uniformly dispersed, then, 0.04mol/L4-VP, 0.2mol/LEGDMA and 0.01mol/LAIBN add in solution, and under nitrogen atmosphere, 60 ℃ are stirred 24 hours.Product is by centrifuging, and adopts washed with methanol 3 times.Finally, compound substance is placed 12h oven dry in 55 ℃ of vacuum drying ovens.
As shown in Figure 1, the SEM of the Graphene (a, b) in the present invention and molecularly imprinted polymer-graphene composite material (b, d) and TEM figure.Molecularly imprinted polymer-graphene composite material that the present embodiment is prepared, by molecularly imprinted polymer with Graphene is compound forms, wherein, the irregular Graphene surface that is covered in of molecularly imprinted polymer.Wherein, graphene-structured is scraps of paper shape, has fold, and these folds can prevent that Graphene from producing reunion.
As shown in Figure 2, the Raman spectrogram of the Graphene in the present invention (a) and molecularly imprinted polymer-graphene composite material (b).Molecularly imprinted polymer-graphene composite material, its G band is absorbed as 1621cm-1 (b), compared with absorbing (1608cm-1) with the G band of Graphene, there is obvious blue shift, illustrated that between molecularly imprinted polymer and Graphene, stronger interaction and the electronics of existence shifts.
Embodiment 3 prepares molecularly imprinted polymer-graphene composite material modified electrode
Molecularly imprinted polymer-graphene composite material prepared by embodiment 2 adds in acetum and (contains 0.5% shitosan), mixes by ultrasonic; Get mixed liquor 5 μ L and be added drop-wise to through the pretreated glass-carbon electrode of embodiment 1 surface, under infrared lamp, dry.Electrode after oven dry is at phosphate buffered solution (PBS, pH7.0) in, do linear volt-ampere scanning 20 times, along with increasing of scanning times, in template molecule, the oxidation peak of MDA is more and more less, fade away, now MDA molecule is removed from template, prepares molecularly imprinted polymer-graphene composite material modified electrode of the present invention.
As shown in Figure 3, Fig. 3 a is that the present invention prepares molecularly imprinted polymer-graphene composite material modified electrode and containing MDA cyclic voltammetry scan figure, Fig. 3 b is that the present invention prepares molecularly imprinted polymer-graphene composite material modified electrode and containing MDA cyclic voltammetry scan figure, the oxidation peak of MDA is respectively at 0.496V and 0.108V, the oxidation peak of aniline and reduction peak current potential, respectively at 0.523V and 0.110V, illustrate that described molecularly imprinted polymer-graphene composite material modified electrode has good electrochemical response to MDA and aniline.
The current-responsive of embodiment 4 molecularly imprinted polymers-graphene composite material modified electrode to MDA and aniline
In the present embodiment, determine the relation of the glass-carbon electrode response current of MDA and concentration of aniline and Graphene/modified by magnetic nanoparticles, its: by Differential Pulse Voltammetry method fast detecting MDA and concentration of aniline, take glass-carbon electrode as working electrode, Ag/AgCl electrode is contrast electrode, platinum electrode is auxiliary electrode, substrate solution is the phosphate buffer solution of pH7.0, adopt Differential Pulse Voltammetry to record the response current of different concentrations of MDA and aniline, as shown in Figure 4, Fig. 4 a is the current-responsive curve of the MDA of variable concentrations, Fig. 4 b is the current-responsive curve of the aniline of variable concentrations.Take the concentration of MDA and aniline as horizontal ordinate, the response current recording using correspondence, as ordinate, is set up current-responsive-MDA and current-responsive-concentration of aniline working curve diagram.As shown in Figure 3, wherein Fig. 5 a is the working curve diagram of current-responsive-MDA concentration, and Fig. 5 b is the working curve diagram of current-responsive-concentration of aniline.
Utilize in Graphene/modified by magnetic nanoparticles, its electrode of the present invention and embodiment 4 establish-linear relationship of MDA and response current-concentration of aniline, the concentration of MDA and aniline in fast detecting testing sample.In the present embodiment, using packaging material for food as testing sample.Detecting step is as follows:
(1) distilled water according to the contact area 6mL/dm of packaging material for food
2calculate, packaging material for food is soaked to 2h in 100 ℃ of aqueous solution of temperature, measure the distilled water immersion liquid of 100mL, adopt the enrichment of EnviChrom P solid phase extraction column, add 5mL acetonitrile to carry out wash-out, collect eluent; After Nitrogen evaporator is concentrated, add 10mL PBS solution;
(2) utilize MDA and concentration of aniline in the glass-carbon electrode fast detecting packaging material for food of Graphene/modified by magnetic nanoparticles, its of the present invention, test experience condition is in the same manner as in Example 4;
(3) adopt Differential Pulse Voltammetry to detect, record its response current value, according to calculating MDA corresponding to this current-responsive value and concentration of aniline, obtain MDA and aniline content in testing sample wrappage.
Experimental result as shown in the following Table 1, sample 2 and sample 4 all detect MDA and aniline, MDA and aniline in sample 1 and sample 3 all do not detect, lower than the detection limit (conforming to traditional detection result) of method, Graphene/modified by magnetic nanoparticles, its electrode of the present invention can be realized the fast detecting of MDA and aniline in packaging material for food, has good actual application value.
Table 1: adopt the glass-carbon electrode of Graphene/modified by magnetic nanoparticles, its to detect MDA and aniline in packaging material for food
In the present embodiment, when the glass-carbon electrode of Graphene/modified by magnetic nanoparticles, its of the present invention detects MDA and aniline, selectivity is good, highly sensitive, easy and simple to handle.Need compare the analysis time of dozens of minutes with traditional vapor-phase chromatography with liquid phase chromatography, this method only needs can complete for 1 minute the detection of MDA and aniline in packaging material for food.And, also do not have report to adopt Electrochemical Modification electrode to detect the report of aniline and MDA at present simultaneously, and adopt the present invention to detect the sample that contains two kinds of compounds simultaneously very easily.
Claims (9)
1. molecularly imprinted polymer-graphene composite material modified electrode, is characterized in that, comprises molecularly imprinted polymer-graphene composite material and glass-carbon electrode; Take described glass-carbon electrode as matrix, described molecularly imprinted polymer-graphene composite material is modified on described glass-carbon electrode.
2. molecularly imprinted polymer-graphene composite material modified electrode as claimed in claim 1, it is characterized in that, described molecularly imprinted polymer-graphene composite material is the compound substance that molecularly imprinted polymer and Graphene form, and molecularly imprinted polymer is covered in Graphene surface with irregular mode.
3. molecularly imprinted polymer-graphene composite material modified electrode as claimed in claim 2, is characterized in that, described Graphene has scraps of paper shape.
4. a preparation method for molecularly imprinted polymer-graphene composite material modified electrode, is characterized in that, comprises the following steps:
Step 1: glass-carbon electrode carries out pre-service
With alumina powder, described glass-carbon electrode is carried out to polishing, after redistilled water rinses, carry out ultrasonic cleaning in acetone, salpeter solution, NaOH solution and aqueous solution successively;
Step 2: molecularly imprinted polymer-graphene composite material
Graphene is scattered in organic solvent, adds 4,4 '-methylene dianiline (MDA) is ultrasonic to being uniformly dispersed, and adds 4-vinylpridine, ethylene glycol dimethacrylate and 2,2 '-azobis isobutyronitrile, under nitrogen atmosphere, stirs; Obtain described molecularly imprinted polymer-graphene composite material through centrifugal, separation, oven dry;
Step 3: prepare molecularly imprinted polymer-graphene composite material modified electrode
Described molecularly imprinted polymer-graphene composite material is added in acetum, mix by ultrasonic; Mixed liquor is added drop-wise to pretreated glass-carbon electrode surface, under infrared lamp, dries; In PBS solution, adopt linear sweep voltammetry to detect, until can't detect 4, the electrochemical signals of 4 '-methylene dianiline (MDA), remove in template 4,4 '-methylene dianiline (MDA) molecule, prepares described molecularly imprinted polymer-graphene composite material modified electrode; Wherein, in described acetum, contain 0.5% shitosan.
5. preparation method as claimed in claim 4, is characterized in that, in described step 2, organic solvent is the mixed solution of trichloroethanes and acetonitrile, and volume ratio is 1: 2.0～4.0; 4, the concentration of 4 '-methylene dianiline (MDA) is 0.01～0.02mol/L, and the concentration of 4-vinylpridine is 0.02～0.06mol/L, and the concentration of ethylene glycol dimethacrylate is 0.1～0.3mol/L, concentration 0.01～the 0.02mol/L of 2,2 '-azobis isobutyronitrile.
6. molecularly imprinted polymer-graphene composite material modified electrode claimed in claim 1 is 4, the application during 4 '-methylene dianiline (MDA) and aniline detect.
7. application as claimed in claim 6, is characterized in that, described molecularly imprinted polymer-graphene composite material modified electrode is in sample 4, and 4 '-methylene dianiline (MDA) and aniline detect simultaneously.
8. application as claimed in claim 6, is characterized in that, by 4,4 '-methylene dianiline (MDA), aniline are disposed in substrate solution, measure and record initial current response, set up current-responsive-4,4 '-methylene dianiline (MDA) and current-responsive-concentration of aniline curve; Under the same conditions, sample is placed in to substrate solution to be measured and record current response, again respectively according to described current-responsive-4,4 '-methylene dianiline (MDA) and current-responsive-concentration of aniline curve obtain in described sample 4,4 '-methylene dianiline (MDA) and concentration of aniline.
9. application as claimed in claim 8, is characterized in that, described substrate solution is phosphate buffer solution, and its pH value is 5-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410106920.1A CN103868966B (en) | 2014-03-21 | 2014-03-21 | A kind of molecularly imprinted polymer-graphene composite material modified electrode and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410106920.1A CN103868966B (en) | 2014-03-21 | 2014-03-21 | A kind of molecularly imprinted polymer-graphene composite material modified electrode and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103868966A true CN103868966A (en) | 2014-06-18 |
| CN103868966B CN103868966B (en) | 2016-08-24 |
Family
ID=50907730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410106920.1A Expired - Fee Related CN103868966B (en) | 2014-03-21 | 2014-03-21 | A kind of molecularly imprinted polymer-graphene composite material modified electrode and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103868966B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104237333A (en) * | 2014-07-04 | 2014-12-24 | 山东大学 | Multi-hydrogen bond electrochemical sensor, preparation method of sensor and application of sensor to melamine detection |
| CN104374815A (en) * | 2014-09-16 | 2015-02-25 | 江南大学 | Electrochemical sensor based on graphene molecular imprinting material, and preparation method thereof |
| CN104698050A (en) * | 2015-02-10 | 2015-06-10 | 西安工程大学 | 2,4-diaminotoluene imprinted polymer film electrode and preparation method and application thereof |
| CN104698051A (en) * | 2015-02-10 | 2015-06-10 | 西安工程大学 | O-tolidine imprinted polymer film electrode and preparation method and application thereof |
| CN108084337A (en) * | 2017-12-06 | 2018-05-29 | 华中科技大学 | The double imprinted materials of the paper substrate of Selective recognition protein and preparation method and application |
| CN108586653A (en) * | 2018-04-24 | 2018-09-28 | 湖北出入境检验检疫局检验检疫技术中心 | A kind of two-dimensional graphene trace composite material and preparation method and application |
| CN108614021A (en) * | 2018-05-15 | 2018-10-02 | 云南大学 | A kind of electrochemical detection method of Capillary zone electropheresis |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633027B (en) * | 2016-10-10 | 2018-06-08 | 太原理工大学 | A kind of preparation method of aniline molecule imprinted polymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641944A (en) * | 2013-12-13 | 2014-03-19 | 天津工业大学 | Preparation and application of molecularly imprinted hybrid material of estrogenic endocrine disrupter |
-
2014
- 2014-03-21 CN CN201410106920.1A patent/CN103868966B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641944A (en) * | 2013-12-13 | 2014-03-19 | 天津工业大学 | Preparation and application of molecularly imprinted hybrid material of estrogenic endocrine disrupter |
Non-Patent Citations (2)
| Title |
|---|
| NINGNING CHEN 等: "《Molecularly imprinted polymer grafted graphene for simultaneous electrochemical sensing of 4,4-methylene diphenylamine and aniline by differential pulse voltammetry》", 《TALANTA》, no. 132, 16 September 2014 (2014-09-16) * |
| 王丹丹 等: "《石墨烯修饰电极分子印迹电化学传感器的研制及其对多巴胺的测定》", 《分析测试学报》, vol. 32, no. 5, 31 May 2013 (2013-05-31), pages 581 - 585 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104237333A (en) * | 2014-07-04 | 2014-12-24 | 山东大学 | Multi-hydrogen bond electrochemical sensor, preparation method of sensor and application of sensor to melamine detection |
| CN104237333B (en) * | 2014-07-04 | 2016-05-11 | 山东大学 | A kind of many hydrogen bonds electrochemical sensor and preparation method thereof and the application in melamine detects |
| CN104374815A (en) * | 2014-09-16 | 2015-02-25 | 江南大学 | Electrochemical sensor based on graphene molecular imprinting material, and preparation method thereof |
| CN104374815B (en) * | 2014-09-16 | 2017-06-06 | 江南大学 | A kind of electrochemical sensor based on graphene molecules imprinted material and preparation method thereof |
| CN104698050A (en) * | 2015-02-10 | 2015-06-10 | 西安工程大学 | 2,4-diaminotoluene imprinted polymer film electrode and preparation method and application thereof |
| CN104698051A (en) * | 2015-02-10 | 2015-06-10 | 西安工程大学 | O-tolidine imprinted polymer film electrode and preparation method and application thereof |
| CN104698050B (en) * | 2015-02-10 | 2018-03-23 | 西安工程大学 | 2,4 diaminotoluene imprinted polymer electrodes, its preparation method and application |
| CN108084337A (en) * | 2017-12-06 | 2018-05-29 | 华中科技大学 | The double imprinted materials of the paper substrate of Selective recognition protein and preparation method and application |
| CN108084337B (en) * | 2017-12-06 | 2019-06-07 | 华中科技大学 | The double imprinted materials of the paper base of Selective recognition protein and preparation method and application |
| CN108586653A (en) * | 2018-04-24 | 2018-09-28 | 湖北出入境检验检疫局检验检疫技术中心 | A kind of two-dimensional graphene trace composite material and preparation method and application |
| CN108586653B (en) * | 2018-04-24 | 2020-07-10 | 湖北出入境检验检疫局检验检疫技术中心 | Two-dimensional graphene imprinted composite material and preparation method and application thereof |
| CN108614021A (en) * | 2018-05-15 | 2018-10-02 | 云南大学 | A kind of electrochemical detection method of Capillary zone electropheresis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103868966B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103868966A (en) | Molecularly-imprinted polymer-graphene composite material modified electrode as well as preparation method and application thereof | |
| CN103278541B (en) | Electrochemical biosensor for detecting bisphenol-A, and preparation method and application thereof | |
| Yang et al. | Electrospun template directed molecularly imprinted nanofibers incorporated with BiOI nanoflake arrays as photoactive electrode for photoelectrochemical detection of triphenyl phosphate | |
| CN103604849B (en) | Electrochemical sensor capable of simultaneously detecting dopamine, ascorbic acid and uric acid | |
| CN108693229B (en) | It is a kind of for detecting the molecular imprinting electrochemical sensor and preparation method of patulin | |
| CN108732218B (en) | Electrochemical sensor for measuring 2,4, 6-trichlorophenol and preparation and application thereof | |
| CN103575783A (en) | Preparation method of molecularly-imprinted electrochemical transducer for detecting propylgallate as well as application thereof | |
| CN103308640A (en) | Gas chromatography-mass spectrometry detection method of 17 phthalate compounds in printing ink | |
| CN103675064A (en) | Preparation of EDTA (ethylene diamine tetraacetic acid) functionalized graphene modified electrode and heavy metal detection method thereof | |
| CN102507685B (en) | Funtionalized carbon nanotube modified electrode and its preparation method and uses | |
| CN101539525A (en) | Method for measuring formaldehyde in aqueous solution by electrochemical luminescence of terpyridyl ruthenium | |
| CN102213678A (en) | Sulfite detection test paper and preparation method thereof | |
| CN104165909B (en) | Biological electrochemical detection method of fumaric acid | |
| CN105954334B (en) | A kind of molecular imprinting electrochemical sensor and its application for detecting diphenylamines | |
| CN112684070B (en) | Method for measuring semi-volatile organic compounds in solid waste | |
| CN106053695A (en) | Method for detecting content of ethyl carbamate in soybean-flavor Baijiu | |
| CN105486741B (en) | For quickly detecting the preparation method and its detection method of the nano immune sensor of benzo (a) pyrene | |
| CN105334252A (en) | Molecular imprinting piezoelectric sensor for detecting trace citrinin and preparation method of molecular imprinting piezoelectric sensor | |
| CN105223260A (en) | Trace is electrochemical sensor detecting butyl p-hydroxybenzoate and preparation method thereof fast | |
| CN103424445A (en) | Graphene/magnetic nanoparticle-modified electrode and its preparation method and use | |
| CN103926303B (en) | A kind of method for Simultaneously test amino phenol isomeride | |
| CN107340324A (en) | Using the method for the glass-carbon electrode detection L tyrosine of aminated post [5] aromatic hydrocarbons reduced graphene composite modification | |
| CN109507306B (en) | Method for determining acetyl tributyl citrate in water-based adhesive | |
| CN106645324B (en) | A kind of microsphere polymer and molecular imprinting electrochemical sensor based on boric acid base group | |
| Xu et al. | An amperometric sensor for sunset yellow fcf detection based on molecularly imprinted polypyrrole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Cheng Yuxiao Inventor after: Shi Xinhao Inventor after: Zhao Kai Inventor after: Qiang Yin Inventor after: Fei Xudong Inventor after: Zhang Jidong Inventor after: Gu Zhongyi Inventor after: Jin Yinghua Inventor after: Xin Yue Zhong Inventor after: Chen Ningning Inventor after: Gu Wei Inventor before: Cheng Yuxiao Inventor before: Shi Xinhao Inventor before: Zhao Kai Inventor before: Gu Zhongyi Inventor before: Shen Jie Inventor before: Jin Yinghua Inventor before: Qiang Yin Inventor before: Zhou Yuyan Inventor before: Xin Yue Zhong Inventor before: Chen Ningning Inventor before: Gu Wei Inventor after: Cheng Yuxiao Inventor after: Shi Xinhao Inventor after: Zhao Kai Inventor after: Gu Zhongyi Inventor after: Shen Jie Inventor after: Jin Yinghua Inventor after: Qiang Yin Inventor after: Zhou Yuyan Inventor after: Xin Yue Zhong Inventor after: Chen Ningning Inventor after: Gu Wei Inventor before: Cheng Yuxiao Inventor before: Shi Xinhao Inventor before: Zhao Kai Inventor before: Gu Zhongyi Inventor before: Shen Jie Inventor before: Jin Yinghua Inventor before: Qiang Yin Inventor before: Zhou Yuyan Inventor before: Xin Yue Zhong Inventor before: Chen Ningning Inventor before: Gu Wei |
|
| COR | Change of bibliographic data | ||
| 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: 20160824 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |