CN104698051A - O-tolidine imprinted polymer film electrode and preparation method and application thereof - Google Patents
O-tolidine imprinted polymer film electrode and preparation method and application thereof Download PDFInfo
- Publication number
- CN104698051A CN104698051A CN201510069879.XA CN201510069879A CN104698051A CN 104698051 A CN104698051 A CN 104698051A CN 201510069879 A CN201510069879 A CN 201510069879A CN 104698051 A CN104698051 A CN 104698051A
- Authority
- CN
- China
- Prior art keywords
- tolidine
- electrode
- imprinted polymer
- solution
- graphene
- 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.)
- Pending
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an o-tolidine imprinted polymer film electrode. The electrode comprises a graphite rod, of which the two ends are wound with copper wires, wherein the two ends of each copper wire are fixed by rubber sleeve chucks, a surface layer of the graphite rod is made from a doped mixture of graphene and graphite, and an o-tolidine molecularly-imprinted polymer film is arranged outside a mixture layer. The electrode has the advantage that the defects of the existing chromatographic analysis techniques that the selectivity is not high, the operation is tedious and the detection period is long are overcome. The invention further discloses a preparation method of the imprinted polymer film electrode, wherein the preparation method comprises the specific steps of firstly preparing a graphene-graphite electrode, carrying out pretreatment, then, preparing the o-tolidine imprinted polymer film on the graphene-graphite electrode, and finally, carrying out eluting treatment, thereby obtaining the imprinted polymer film electrode. The invention further discloses a method for detecting by using the imprinted polymer film electrode, wherein the method comprises the specific steps of firstly connecting the o-tolidine imprinted polymer film electrode according to a zero-current potential system device, and then, testing by using a relationship formula between a zero-current potential and the concentration of o-tolidine.
Description
Technical field
The invention belongs to and analyze test material technical field, relate to a kind of imprinted polymer membrane electrode of o-tolidine, the invention still further relates to the preparation of this electrode.The invention still further relates to the new technology that the o-tolidine imprinted polymer membrane electrode applied and prepare detects o-tolidine under zero stream positioning system.
Background technology
O-tolidine, also known as 3,3 '-dimethylbenzidine (being called for short o-TD), because it has good spectroelectrochemistry character, is often used as the material of spectroelectrochemistry research.In addition, o-tolidine is also used as dyestuff, the crosslinking chemical etc. of Ethylurethanm resin and animal and feeds feed addictive.Food containing o-tolidine can cause renal damage even renal failure etc., there is very large carcinogenic risk.O-tolidine is classified as industrial banned substance by current Countries.Present analysis detects o-tolidine and adopts high performance liquid chromatography (HPLC) technology.But there is following wretched insufficiency in the method: (1) expensive cost of high performance liquid chromatograph used itself is high, and (2), in order to protect chromatographic column sample pre-treatments program loaded down with trivial details, high to human users's skill set requirements, the running time is long; (3) sensitivity is low, and selectivity is not high, easily produces false differentiation, needs to carry out secondary qualification in conjunction with other detection techniques.
Traditional imprinted polymer preparation method must have the participation such as chemical initiator, crosslinking chemical costly, and polymerization reaction time is long, and the imprinted polymer actual application value prepared is little.Therefore select the novel method preparing imprinted polymer just imperative.
Zero stream potential method is a kind of novel interfacial potentiometric sensors technology, do not need system to be checked must containing the material with volt-ampere response signal, the size of transducing signal (zero stream current potential) depends primarily on the interaction of electrode interface membrane material and thing to be checked and the membrane interface potential change that causes, is therefore applicable to very much the Detection results of the polymer film that assessment employing galvanochemistry is prepared.
Summary of the invention
The object of this invention is to provide a kind of imprinted polymer membrane electrode of o-tolidine, can be used for fast and convenient detection o-tolidine, solve existing chromatographic technique selectivity not high, complex operation, the defect that sense cycle is long.
The technical solution adopted in the present invention is, a kind of imprinted polymer membrane electrode of o-tolidine comprises the graphite rod that two ends are wound with copper wire, copper wire two ends rubber cutting ferrule is fixed, described graphite rod top layer is the potpourri of Graphene and graphite dopping, is the molecular imprinted polymer membrane of o-tolidine in the outside of this mixture layer.
Another object of the present invention is to provide a kind of preparation method of imprinted polymer membrane electrode of o-tolidine.
Another technical scheme of the present invention is: the preparation method of the imprinted polymer membrane electrode of the o-tolidine described in a kind of claim 1, specifically implements according to following steps:
Step 1, prepares Graphene-graphite electrode and carries out pre-service;
Step 2, Graphene-graphite electrode is prepared o-tolidine imprinted polymer film, obtains the semi-manufacture of imprinted polymer membrane electrode;
Step 3, carries out wash-out process, obtained o-tolidine imprinted polymer electrode.
Feature of the present invention is also,
Wherein, step 1 is specially:
Step 1.1, is cut into the segment of 2 ~ 4cm by graphite rod, in paraffin solution, boil 30 ~ 50min;
Step 1.2, cuts the copper wire of 5 ~ 10cm, two copper wires is wrapped in respectively the two ends of graphite rod, and copper wire and graphite rod is fixed together, make graphite carbon modified electrode;
Step 1.3, by the graphite electrode pan paper polishing of preparation in step 1.2, after then using absolute ethyl alcohol and each supersound washing 5 ~ 10min of redistilled water, dries for subsequent use;
Step 1.4, adds in the redistilled water of 10 ~ 20mL by the graphene powder of 5 ~ 10mg, in ultrasonic middle dispersion, until obtain even graphene aqueous solution; The graphene powder of 5 ~ 10mg is added ultrasonic disperse in the melt paraffin solution of 10 ~ 20mL until obtain even Graphene paraffin solution, and then the graphite electrode of preparation in step 1.3 is placed in graphene aqueous solution 10 ~ 15min post-drying, be placed in Graphene paraffin solution 10 ~ 15min again, dry for standby.
Wherein, step 2 is specially:
Step 2.1, is placed in PBS buffer solution by the Graphene-graphite electrode processed and carries out deoxygenation process 8min ~ 15min, and the concentration containing o-tolidine solution in described PBS buffer solution is 0.02 ~ 0.1molL
-1, the concentration of acrylamide solution is 0.12 ~ 0.6molL
-1, the two ratio is 1:6; The pH of described PBS buffer solution is 5.59 ~ 8.04;
Step 2.2, by the electrifying electrodes after step 2.1 deoxygenation, scans in potential range, to sweep speed for 0.1 ~ 0.3Vs at-1.0V ~ 1.0V
-1scan round 6 ~ 26 is enclosed, and prepares o-tolidine imprinted polymer film at electrode surface;
Wherein, step 3 is specially: the semi-manufacture of the o-tolidine imprinted polymer electrode of preparation in step 2 are carried out wash-out process, and concrete steps are, are taken out by electrode from damping fluid, be placed in clear water after ultrasonic cleaning 5 ~ 10min again, i.e. the imprinted polymer membrane electrode of obtained o-tolidine.
3rd object of the present invention is to provide the method that the imprinted polymer electrode applying the o-tolidine prepared carries out o-tolidine detection, specifically implements according to following steps:
Step 1, by the o-tolidine imprinted polymer membrane electrode prepared, namely surface has the imprinted polymer electrode of o-tolidine to connect according to zero stream positioning system device;
Step 2, utilizes zero stream current potential E
zCPand the relation formula between o-tolidine log concentration
E
zCP=-0.00715log [o-TD]+0.08951 (1) tests sample solution to be detected.
Feature of the present invention is also,
Wherein, zero stream positioning system device described in step 1, its structure is: the imprinted polymer membrane electrode and the CHI660 electrochemical workstation that comprise o-tolidine, CHI660 electrochemical workstation is provided with 3 electrode interfaces, contrast electrode interface respectively, working electrode interface and auxiliary electrode interface, contrast electrode interface is connected with saturated calomel electrode, CHI660 electrochemical workstation is connected with computing machine, computing machine is for control CHI660 electrochemical workstation, the two ends of the imprinted polymer membrane electrode of o-tolidine are connected with working electrode interface and auxiliary electrode interface respectively by copper wire, the imprinted polymer membrane electrode of saturated calomel electrode and o-tolidine is all dipped in solution, and solution is PBS solution or the o-tolidine solution to be measured of normal concentration o-tolidine sample.
Wherein, the formula (1) in step 2 obtains in accordance with the following steps:
First, by the electrode connected, it puts into the PBS sample solution containing standard o-tolidine; Scanning current potential be-0.6 ~ 0.6V, sweeping speed is 0.1 ~ 0.3Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Wherein, described o-tolidine concentration is 1 × 10
-9~ 1 × 10
-6molL
-1;
Then, by analyzing zero stream current potential E of the o-tolidine imprinted polymer membrane electrode recorded
zCPdata, zero stream current potential E
zCPfollowing relational expression is met between o-tolidine concentration value in (current potential of I=0) and solution:
E
ZCP＝-0.00715log[o-TD]+0.08951 (1)
Wherein, the concrete steps of step 2 are:
Step 2.1, puts into solution to be measured by the o-tolidine molecular imprinted polymer membrane electrode connected, switches on power;
Step 2.2, be-0.6 ~ 0.6V at scanning current potential, sweeping speed is 0.1 ~ 0.3Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Step 2.3, flows current potential E by zero of the testing sample solution recorded
zCPvalue substitutes in formula (1), can calculate the concentration of o-tolidine in testing sample solution, thus draw the content of o-tolidine in testing liquid.
The invention has the beneficial effects as follows, method of the present invention is directly at the imprinted polymer of Graphene composite graphite electrode surface by electrochemical method synthesis o-tolidine, and simply and easily zero stream positioning system under detect o-tolidine, detectability reaches 8.07 × 10
-10molL
-1, more highly sensitive than chromatography.
Accompanying drawing explanation
Fig. 1 is the electropolymerization curve map of o-tolidine and acrylic acid mixed solution during the present invention prepares to o-tolidine imprinted polymer membrane electrode method;
Fig. 2-1 is the structural representation of the zero stream positioning system device that the present invention utilizes o-tolidine imprinted polymer membrane electrode to carry out using in the method for o-tolidine detection;
Fig. 2-2 is that the present invention utilizes o-tolidine imprinted polymer membrane electrode to carry out the structural representation of the imprinted polymer membrane electrode used in zero stream positioning system device in the method for o-tolidine detection;
Fig. 3 is the linear sweep voltammetry curve map that the present invention utilizes o-tolidine imprinted polymer membrane electrode to carry out in the method for o-tolidine detection under zero stream positioning system in the o-tolidine solution of o-tolidine imprinted polymer film Graphene-graphite electrode at variable concentrations;
Fig. 4 is that the present invention utilizes o-tolidine imprinted polymer membrane electrode to carry out E in the method for o-tolidine detection
zCPand the graph of a relation between log [o-TD];
Fig. 5 is that the present invention utilizes o-tolidine imprinted polymer membrane electrode to carry out the cyclic voltammogram of Different electrodes in o-tolidine solution in the method for o-tolidine detection;
Fig. 6 be under the present invention utilizes o-tolidine imprinted polymer membrane electrode to carry out in the method for o-tolidine detection zero stream positioning system o-tolidine imprinted polymer to the trace capacity of several aromatic amine.
In figure, 1. imprinted polymer membrane electrode, 2. copper wire, 3. contrast electrode interface, 4. working electrode interface, 5. auxiliary electrode interface, 6. saturated calomel electrode, 7. computing machine, 8.CHI660 electrochemical workstation, 9. Graphene-graphite electrode, 10. imprinted polymer film, 11. rubber cutting ferrules, 12. solution.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
O-tolidine imprinted polymer membrane electrode of the present invention, as shown in Fig. 2-2, comprise the graphite rod 9 that two ends are wound with copper wire 2, copper wire 2 two ends rubber cutting ferrule 11 is fixed, described graphite rod top layer is the potpourri of the doping of Graphene and graphite, is the molecular imprinted polymer membrane 10 of o-tolidine in the outside of this mixture layer.
The preparation method of the imprinted polymer membrane electrode of o-tolidine of the present invention, specifically implements according to following steps:
Step 1, prepares Graphene-graphite electrode and carries out pre-service,
Step 1.1, is cut into the segment of 2 ~ 4cm by graphite rod, in paraffin solution, boil 30 ~ 50min;
Step 1.2, cuts the copper wire of 5 ~ 10cm, by clean for the polishing of 1 ~ 3cm place, copper wire two ends, two copper wires be wrapped in respectively the two ends of graphite rod, and copper wire and graphite rod be fixed together, make graphite carbon modified electrode;
Step 1.3, by the graphite electrode pan paper polishing of preparation in step 1.2, after then using absolute ethyl alcohol and each supersound washing 5 ~ 10min of redistilled water, dries for subsequent use;
Step 1.4, adds in the redistilled water of 10 ~ 20mL by the graphene powder of 5 ~ 10mg, in ultrasonic middle dispersion, until obtain even graphene aqueous solution; The graphene powder of 5 ~ 10mg is added ultrasonic disperse in the melt paraffin solution of 10 ~ 20mL until obtain even Graphene paraffin solution, the particle diameter of described Graphene 0.5 ~ 2 μm, thickness 0.8 ~ 1.2nm; And then the graphite electrode of preparation in step 1.3 is placed in graphene aqueous solution 10 ~ 15min post-drying, then be placed in Graphene paraffin solution 10 ~ 15min, dry for standby.
The graphene powder used in above-mentioned steps, its particle size distribution range is 0.5 ~ 2 μm, and thickness distribution scope is 0.8 ~ 1.2nm;
Step 2, Graphene-graphite electrode is prepared o-tolidine imprinted polymer film,
Step 2.1, is placed in PBS buffer solution by the Graphene-graphite electrode processed and carries out deoxygenation process 8 ~ 15min, and the concentration containing o-tolidine in described PBS buffer solution is 0.02 ~ 0.1molL
-1, the concentration of acrylamide is 0.12 ~ 0.6molL
-1, the two ratio is 1:6; The pH of described PBS buffer solution is 5.59 ~ 8.04.
Step 2.2, by the electrifying electrodes after step 2.1 deoxygenation ,-0.6 ~ 0.6V ,-0.8 ~ 0.8 ,-1.0 ~ 1.0 ,-1.2 ~ 1.2 ,-1.4 ~ 1.4 and-1.6 ~ 1.6V scans in potential range, to sweep speed for 0.1 ~ 0.3Vs
-1scan round 6 ~ 26 is enclosed, and prepares o-tolidine imprinted polymer film at electrode surface.
The semi-manufacture of the o-tolidine imprinted polymer electrode of preparation in step 2 are carried out wash-out process by step 3,
Concrete steps are, are taken out by electrode from damping fluid, then are placed in clear water after ultrasonic cleaning 5 ~ 10min, and namely obtained surface is the electrode of o-tolidine imprinted polymer film.
Fig. 1 is the electropolymerization curve map of o-tolidine solution when preparing o-tolidine imprinted polymer membrane electrode and acrylamide mixed solution; As seen from Figure 1, because o-tolidine is electroactive substance, along with the increase of the scanning number of turns, the a pair redox peak to peak current can observing o-tolidine increases gradually, spike potential is substantially constant, illustrate except being combined into except o-tolidine molecularly imprinted polymer with acrylamide copolymerization, o-tolidine redox products constantly deposits at electrode surface, but this unstable products, cannot generate poly-o-tolidine, what therefore electrode surface generated is o-tolidine imprinted polymer.
The present invention utilizes o-tolidine imprinted polymer membrane electrode to carry out the method for o-tolidine detection, specifically implements according to following steps:
Step 1, by the o-tolidine imprinted polymer membrane electrode prepared, namely surface has the Graphene-graphite electrode of o-tolidine imprinted polymer film to connect according to zero stream positioning system device;
Step 2, utilizes the relation formula between zero stream current potential EZCP and o-tolidine log concentration
E
ZCP＝-0.00715log[o-TD]+0.08951 (1)
Test sample solution to be detected, concrete steps are:
Step 2.1, puts into solution to be measured by the o-tolidine molecular imprinted polymer membrane electrode connected, switches on power;
Step 2.2, be-0.6 ~ 0.6V at scanning current potential, sweeping speed is 0.1 ~ 0.3Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Step 2.3, flows current potential E by zero of the testing sample solution recorded
zCPvalue substitutes in formula (1), can calculate the concentration of o-tolidine in testing sample solution, thus draw the content of o-tolidine in testing liquid.
Formula (1) in step 2 obtains in accordance with the following steps:
First, by the electrode connected, it puts into the PBS sample solution containing standard o-tolidine; Scanning current potential be-0.6 ~ 0.6V, sweeping speed is 0.1 ~ 0.3Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Wherein, described o-tolidine concentration is 1 × 10
-9~ 1 × 10
-6molL
-1;
Then, by analyzing zero stream current potential E of the o-tolidine imprinted polymer membrane electrode recorded
zCPdata, zero stream current potential E
zCPfollowing relational expression is met between o-tolidine concentration value in (current potential of I=0) and solution:
E
ZCP＝-0.00715log[o-TD]+0.08951 (1)
Wherein, E
zCPrepresent zero stream current potential; [o-TD] represents the concentration of o-tolidine.
Wherein, zero stream positioning system device described in step 1, its structure is: the imprinted polymer membrane electrode 1 and the CHI660 electrochemical workstation 8 that comprise o-tolidine, CHI660 electrochemical workstation 8 is provided with 3 electrode interfaces, contrast electrode interface 3 respectively, working electrode interface 4 and auxiliary electrode interface 5, contrast electrode interface 3 is connected with saturated calomel electrode, CHI660 electrochemical workstation 8 is connected with computing machine 7, computing machine 7 is for control CHI660 electrochemical workstation, the two ends of the imprinted polymer membrane electrode 1 of o-tolidine are connected with working electrode interface 4 and auxiliary electrode interface 5 respectively by copper wire 2, the imprinted polymer membrane electrode 1 of saturated calomel electrode 6 and o-tolidine is all dipped in solution 12, and solution 12 is PBS solution or the o-tolidine solution to be measured of normal concentration o-tolidine sample.
Saturated calomel electrode and imprinted polymer electrode are all dipped in solution, and described solution is the PBS sample solution containing standard o-tolidine in step 1 or the solution to be measured in step 3.
Different from traditional three-electrode system, working electrode and auxiliary electrode connect together by it, form two electrode systems, can detect the change of phase boundary potential.
Utilize the zero stream positioning system device of Fig. 2-1, known after adopting method of the present invention to carry out test, method of testing of the present invention is limited to 8.07 × 10 for the detection of o-tolidine
-10molL
-1, can find out that the detection sensitivity of detection method is high.
The o-tolidine solution of the electrode pair variable concentrations using the present invention to prepare detects, and is respectively 1 × 10 in o-tolidine concentration
-6molL
-1; 5 × 10
-6molL
-1; 1 × 10
-7molL
-1; 5 × 10
-7molL
-1; 1 × 10
-8molL
-1; 5 × 10
-8molL
-1; 1 × 10
-9molL
-1time, obtain different curve (1) ~ (7) in Fig. 3.The curve 1 to 7 be from left to right arranged in order in Fig. 3, represents that o-tolidine concentration is 1 × 10 respectively
-6molL
-1; 5 × 10
-6molL
-1; 1 × 10
-7molL
-1; 5 × 10
-7molL
-1; 1 × 10
-8molL
-1; 5 × 10
-8molL
-1; 1 × 10
-9molL
-1time linear sweep voltammetry curve; The curve 1 to 7 be from left to right arranged in order in Fig. 4, represents that o-tolidine concentration is 1 × 10-6molL-1 respectively; 5 × 10-6molL-1; 1 × 10-7molL-1; 5 × 10-7molL-1; 1 × 10-8molL-1; 5 × 10-8molL-1; Log concentration during 1 × 10-9molL-1 and zero flows the linear relationship of current potential, and data are as shown in table 1 below,
The zero stream potential value of table 1 o-tolidine molecularly imprinted polymer Graphene-graphite electrode in variable concentrations o-tolidine solution
As shown in table 1, when the PBS sample solution of the standard o-tolidine of variable concentrations is tested, its E relatively recorded
zCPcertain rule is there is, with E between numerical value
zCPfor ordinate, log [o-TD] is horizontal ordinate, can obtain concentration [o-TD] and zero stream potential value E by mapping
zCPcorresponding relation as shown in Figure 4, wherein, log [o-TD] is horizontal ordinate, E
zCPfor ordinate, as can be seen from curve in figure, E
zCPwith the relation between log [o-TD] meets formula (1), coefficient R=0.991 of curve, n=7.
The o-tolidine recovery is tested:
Collect the sample containing o-tolidine, according to experimental technique, polymer membrane electrode is put into actual sample solution, measure zero stream current potential of polymer film, according to formula (1), in calculation sample, the content of o-tolidine, the results are shown in Table 2.
The recovery of table 2 synthetic sample
As can be seen from Table 2, when the imprinted polymer electrode utilizing method of the present invention to prepare carries out o-tolidine test, its recovery meets the requirements.
The selectivity checking of o-tolidine imprinted polymer electrode:
The optionally verification method of o-tolidine imprinted polymer membrane electrode prepared by method of the present invention is as follows, interfering material in table 3 listed by first row is added respectively in o-tolidine solution, then test according to each step utilizing o-tolidine imprinted polymer electrode to carry out in the method for o-tolidine detection, and recording zero stream current potential of polymer film, experimental result is as shown in table 3 below.
The impact of table 3 interfering material
As shown in Table 3, above-mentioned substance to zero of o-tolidine stream potential measurement relative standard deviation be all no more than ± 5%, illustrate that o-tolidine imprinted polymer membrane electrode selectivity is good.
Respectively bare electrode, o-tolidine imprinted polymer membrane electrode (namely for measuring the imprinted polymer membrane electrode of o-tolidine concentration) three kinds of electrodes of not preparing for the imprinted polymer membrane electrode of wash-out and method of the present invention are put into o-tolidine solution respectively and carried out cyclic voltammetry scan, its result as shown in Figure 5.As can be seen from Figure 5, the curve utilizing bare electrode to carry out scanning is curve c, and the curve that non-wash-out imprinted polymer membrane electrode carries out scanning is curve b, and these two curves are few in electrode surface distribution due to o-tolidine molecule, therefore respond without volt-ampere; And the polymkeric substance blotting membrane electrode for measuring o-tolidine prepared in the present invention, its scan after result be curve a, because of the hole matched containing a large amount of and o-tolidine, o-tolidine molecule in adsorbable solution, membrane electrode surface is made to be full of o-tolidine molecule, thus there is the redox reaction of o-tolidine, illustrate that the o-tolidine imprinted polymer print identification prepared is good.
In addition, in order to verify that imprinted polymer membrane electrode prepared by the present invention is to the trace selectivity efficiency of o-tolidine, o-tolidine and azo material are compared at zero stream potential response of o-tolidine imprinted polymer membrane electrode, its result as shown in Figure 6.Horizontal ordinate 1 ~ 6 from left to right in Fig. 6 represents respectively: o-tolidine; Biphenylamine; Amino toluene; 4-chloroaniline; P-aminoazobenzene; Ortho-aminotoluene.As can be seen from Figure 6, the trace capacity of o-tolidine on trace electrode is maximum, illustrates that the trace selectivity efficiency of imprinted polymer to o-tolidine is high.
Table 4 imprinted polymer electrode is 1 × 10
-7molL
-1the zero stream current potential potential value of 10 times is repeated in o-TD solution
Have employed Graphene and graphite rod in method of the present invention to react and prepared the surface doping electrode of Graphene, Graphene is novel nano-material, and electronic conduction speed is excellent, and specific surface area is large, better than traditional graphitic conductive, easier enrichment of analyte.Therefore the electric conductivity of graphite is improved by the infiltration of graphene nano molecule.
The preparation of o-tolidine imprinted polymer membrane electrode is carried out according to the parameter selected in method of the present invention, prepared molecular imprinted polymer membrane can be made very large in conjunction with zero stream potential change amount of film before and after o-tolidine in absorption, the imprinted polymer trace selectivity prepared like this and trace associativity good.
The reappearance of o-tolidine imprinted polymer membrane electrode prepared by the present invention is fine, and long service life.In redistilled water, can initial conditions be returned to after supersound washing 5min by with the membrane electrode crossed after each mensuration.Membrane electrode is to 5 × 10
-7molL
-1o-tolidine solution carries out 10 replicate determinations, and measurement result is in table 4.It is 4.39% that 10 times zero stream potential values obtain relative standard deviation, shows good reappearance.
Embodiment 1
The preparation method of the imprinted polymer membrane electrode of a kind of o-tolidine chloroaniline of the present invention, specifically implements according to following steps:
Step 1, prepares Graphene-graphite electrode and carries out pre-service,
Step 1.1, is cut into the segment of 2cm by graphite rod, in paraffin solution, boil 30min;
Step 1.2, cuts the copper wire of 5cm, two copper wires is wrapped in respectively the two ends of graphite rod, and copper wire and graphite rod is fixed together, make graphite carbon modified electrode;
Step 1.3, by the graphite electrode pan paper polishing of preparation in step 1.2, after then using absolute ethyl alcohol and each supersound washing 5min of redistilled water, dries for subsequent use;
Step 1.4, adds in the redistilled water of 10mL by the graphene powder of 5mg, in ultrasonic middle dispersion, until obtain even graphene aqueous solution; The graphene powder of 5mg is added ultrasonic disperse in the melt paraffin solution of 10mL until obtain even Graphene paraffin solution; And then the graphite electrode of preparation in step 1.3 is placed in graphene aqueous solution 10min post-drying, then be placed in Graphene paraffin solution 10min, dry for standby.
Step 2, Graphene-graphite electrode is prepared o-tolidine imprinted polymer film,
Step 2.1, is placed in PBS buffer solution by the Graphene-graphite electrode processed and carries out deoxygenation process 8min, and the concentration containing o-tolidine in described PBS buffer solution is 0.02molL
-1, the concentration of acrylamide is 0.12molL
-1, the two ratio is 1:6; The pH of described PBS buffer solution is 5.59.
Step 2.2, by the electrifying electrodes after step 2.1 deoxygenation, scans in potential range at-1.0 ~ 1.0V, to sweep speed for 0.1Vs
-1scan round 6 is enclosed, and prepares o-tolidine imprinted polymer film at electrode surface.
The semi-manufacture of the o-tolidine imprinted polymer electrode of preparation in step 2 are carried out wash-out process by step 3,
Concrete steps are, are taken out by electrode from damping fluid, then are placed in clear water after ultrasonic cleaning 5min, and namely obtained surface is the electrode of o-tolidine imprinted polymer film.
Utilize above-mentioned o-tolidine imprinted polymer membrane electrode to carry out the method for o-tolidine detection, specifically implement according to following steps:
Step 1, by the o-tolidine imprinted polymer membrane electrode prepared, namely surface has the imprinted polymer electrode of o-tolidine to connect according to zero stream positioning system device;
Step 2, utilizes zero stream current potential E
zCPand the relation formula between o-tolidine log concentration
E
ZCP＝-0.00715log[o-TD]+0.08951 (1)
Sample solution to be detected is tested.
Be specially: step 2.1, the o-tolidine molecularly imprinted polymer electrode connected put into solution to be measured, switches on power;
Step 2.2, be-0.6 ~ 0.6V at scanning current potential, sweeping speed is 0.1Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Step 2.3, flows current potential E by zero of the testing sample solution recorded
zCPin the formula (1) that value substitution step 2 draws, the concentration of o-tolidine in testing sample solution can be calculated, thus draw the content of o-tolidine in testing liquid.
Embodiment 2
The preparation method of the imprinted polymer membrane electrode of a kind of o-tolidine of the present invention, specifically implements according to following steps:
Step 1, prepares Graphene-graphite electrode and carries out pre-service,
Step 1.1, is cut into the segment of 4cm by graphite rod, in paraffin solution, boil 50min;
Step 1.2, is wrapped in the two ends of graphite rod respectively by the copper wire of two 10cm, and copper wire and graphite rod is fixed together, and makes graphite carbon modified electrode;
Step 1.3, by the graphite electrode pan paper polishing of preparation in step 1.2, after then using absolute ethyl alcohol and each supersound washing 10min of redistilled water, dries for subsequent use;
Step 1.4, adds in the redistilled water of 20mL by the graphene powder of 10mg, in ultrasonic middle dispersion, until obtain even graphene aqueous solution; The graphene powder of 10mg is added ultrasonic disperse in the melt paraffin solution of 20mL until obtain even Graphene paraffin solution; And then the graphite electrode of preparation in step 1.3 is placed in graphene aqueous solution 15min post-drying, then be placed in Graphene paraffin solution 15min, dry for standby.
Step 2, Graphene-graphite electrode is prepared o-tolidine imprinted polymer film,
Step 2.1, is placed in PBS buffer solution by the Graphene-graphite electrode processed and carries out deoxygenation process 15min, and the concentration containing o-tolidine in described PBS buffer solution is 0.1molL
-1, the concentration of acrylamide is 0.6molL
-1, the two ratio is 1:6; The pH of described PBS buffer solution is 8.04.
Step 2.2, by the electrifying electrodes after step 2.1 deoxygenation, scans in potential range at-1.0 ~ 1.0V, to sweep speed for 0.3Vs
-1scan round 26 is enclosed, and prepares o-tolidine imprinted polymer film at electrode surface.
The semi-manufacture of the o-tolidine imprinted polymer electrode of preparation in step 2 are carried out wash-out process by step 3,
Concrete steps are, are taken out by electrode from damping fluid, then are placed in clear water after ultrasonic cleaning 10min, and namely obtained surface is the electrode of o-tolidine imprinted polymer film.
Utilize above-mentioned o-tolidine imprinted polymer membrane electrode to carry out the method for o-tolidine detection, specifically implement according to following steps:
Step 1, by the o-tolidine imprinted polymer membrane electrode prepared, namely surface has the imprinted polymer electrode of o-tolidine to connect according to zero stream positioning system device;
Step 2, utilizes zero stream current potential E
zCPand the relation formula between o-tolidine log concentration
E
ZCP＝-0.00715log[o-TD]+0.08951 (1)
Sample solution to be detected is tested.
Be specially: step 2.1, the o-tolidine molecularly imprinted polymer electrode connected put into solution to be measured, switches on power;
Step 2.2, be-0.6 ~ 0.6V at scanning current potential, sweeping speed is 0.3Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Step 2.3, flows current potential E by zero of the testing sample solution recorded
zCPin the formula (1) that value substitution step 2 draws, the concentration of o-tolidine in testing sample solution can be calculated, thus draw the content of o-tolidine in testing liquid.
Embodiment 3
The preparation method of the imprinted polymer membrane electrode of a kind of o-tolidine of the present invention, specifically implements according to following steps:
Step 1, prepares Graphene-graphite electrode and carries out pre-service,
Step 1.1, is cut into the segment of 3cm by graphite rod, in paraffin solution, boil 40min;
Step 1.2, is wrapped in the two ends of graphite rod respectively by the copper wire of two 7cm, and copper wire and graphite rod is fixed together, and makes graphite carbon modified electrode;
Step 1.3, by the graphite electrode pan paper polishing of preparation in step 1.2, after then using absolute ethyl alcohol and each supersound washing 6min of redistilled water, dries for subsequent use;
Step 1.4, adds in the redistilled water of 11.5mL by the graphene powder of 5.5mg, in ultrasonic middle dispersion, until obtain even graphene aqueous solution; The graphene powder of 5.5mg is added ultrasonic disperse in the melt paraffin solution of 10.5mL until obtain even Graphene paraffin solution; And then the graphite electrode of preparation in step 1.3 is placed in graphene aqueous solution 11min post-drying, then be placed in Graphene paraffin solution 11.5min, dry for standby.
Step 2, Graphene-graphite electrode is prepared o-tolidine imprinted polymer film,
Step 2.1, is placed in PBS buffer solution by the Graphene-graphite electrode processed and carries out deoxygenation process 8.95min, and the concentration containing o-tolidine in described PBS buffer solution is 0.03molL
-1, the concentration of acrylamide is 0.18molL
-1, the two ratio is 1:6; The pH of described PBS buffer solution is 6.5.
Step 2.2, by the electrifying electrodes after step 2.1 deoxygenation, scans in potential range at-1.0 ~ 1.0V, to sweep speed for 0.15Vs
-1scan round 10 is enclosed, and prepares o-tolidine imprinted polymer film at electrode surface.
The semi-manufacture of the o-tolidine imprinted polymer electrode of preparation in step 2 are carried out wash-out process by step 3,
Concrete steps are, are taken out by electrode from damping fluid, then are placed in clear water after ultrasonic cleaning 6min, and namely obtained surface is the electrode of o-tolidine imprinted polymer film.
Utilize above-mentioned o-tolidine imprinted polymer membrane electrode to carry out the method for o-tolidine detection, specifically implement according to following steps:
Step 1, by the o-tolidine imprinted polymer membrane electrode prepared, namely surface has the imprinted polymer electrode of o-tolidine to connect according to zero stream positioning system device;
Step 2, utilizes zero stream current potential E
zCPand the relation formula between o-tolidine log concentration
E
ZCP＝-0.00715log[o-TD]+0.08951 (1)
Sample solution to be detected is tested.
Be specially: step 2.1, the o-tolidine molecularly imprinted polymer electrode connected put into solution to be measured, switches on power;
Step 2.2, be-0.6 ~ 0.6V at scanning current potential, sweeping speed is 0.15Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Step 2.3, flows current potential E by zero of the testing sample solution recorded
zCPin the formula (1) that value substitution step 2 draws, the concentration of o-tolidine in testing sample solution can be calculated, thus draw the content of o-tolidine in testing liquid.
Embodiment 4
The preparation method of the imprinted polymer membrane electrode of a kind of o-tolidine of the present invention, specifically implements according to following steps:
Step 1, prepares Graphene-graphite electrode and carries out pre-service,
Step 1.1, is cut into the segment of 3.5cm by graphite rod, in paraffin solution, boil 48min;
Two 8.5cm copper wires are wrapped in the two ends of graphite rod, and copper wire and graphite rod are fixed together, make graphite carbon modified electrode by step 1.2 respectively;
Step 1.3, by the graphite electrode pan paper polishing of preparation in step 1.2, after then using absolute ethyl alcohol and each supersound washing 8.9min of redistilled water, dries for subsequent use;
Step 1.4, adds in the redistilled water of 17.5mL by the graphene powder of 8.5mg, in ultrasonic middle dispersion, until obtain even graphene aqueous solution; The graphene powder of 7.25mg is added ultrasonic disperse in the melt paraffin solution of 16.5mL until obtain even Graphene paraffin solution; And then the graphite electrode of preparation in step 1.3 is placed in graphene aqueous solution 13.5min post-drying, then be placed in Graphene paraffin solution 14.5min, dry for standby.
Step 2, Graphene-graphite electrode is prepared o-tolidine imprinted polymer film,
Step 2.1, is placed in PBS buffer solution by the Graphene-graphite electrode processed and carries out deoxygenation process 14.5min, and the concentration containing o-tolidine in described PBS buffer solution is 0.08molL
-1, the concentration of acrylamide is 0.48molL
-1, the two ratio is 1:6; The pH of described PBS buffer solution is 7.9.
Step 2.2, by the electrifying electrodes after step 2.1 deoxygenation, scans in potential range at-1.0-1.0V, to sweep speed for 0.25Vs
-1scan round 18 is enclosed, and prepares o-tolidine imprinted polymer film at electrode surface.
The semi-manufacture of the o-tolidine imprinted polymer electrode of preparation in step 2 are carried out wash-out process by step 3,
Concrete steps are, are taken out by electrode from damping fluid, then are placed in clear water after ultrasonic cleaning 7min, and namely obtained surface is the electrode of o-tolidine imprinted polymer film.
Utilize above-mentioned o-tolidine imprinted polymer membrane electrode to carry out the method for o-tolidine detection, specifically implement according to following steps:
Step 1, by the o-tolidine imprinted polymer membrane electrode prepared, namely surface has the imprinted polymer electrode of o-tolidine to connect according to zero stream positioning system device;
Step 2, utilizes zero stream current potential E
zCPand the relation formula between o-tolidine log concentration
E
ZCP＝-0.00715log[o-TD]+0.08951 (1)
Sample solution to be detected is tested.
Be specially: step 2.1, the o-tolidine molecularly imprinted polymer electrode connected put into solution to be measured, switches on power;
Step 2.2, be-0.6 ~ 0.6V at scanning current potential, sweeping speed is 0.25Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Step 2.3, flows current potential E by zero of the testing sample solution recorded
zCPin the formula (1) that value substitution step 2 draws, the concentration of o-tolidine in testing sample solution can be calculated, thus draw the content of o-tolidine in testing liquid.
Embodiment 5
The preparation method of the imprinted polymer membrane electrode of a kind of o-tolidine of the present invention, specifically implements according to following steps:
Step 1, prepares Graphene-graphite electrode and carries out pre-service,
Step 1.1, is cut into the segment of 2.8cm by graphite rod, in paraffin solution, boil 42min;
Step 1.2, is wrapped in the two ends of graphite rod respectively by the copper wire of two 6.6cm, and copper wire and graphite rod is fixed together, and makes graphite carbon modified electrode;
Step 1.3, by the graphite electrode pan paper polishing of preparation in step 1.2, after then using absolute ethyl alcohol and each supersound washing 6.7min of redistilled water, dries for subsequent use;
Step 1.4, adds in the redistilled water of 15.5mL by the graphene powder of 7mg, in ultrasonic middle dispersion, until obtain even graphene aqueous solution; The graphene powder of 5.5mg is added ultrasonic disperse in the melt paraffin solution of 13.5mL until obtain even Graphene paraffin solution; And then the graphite electrode of preparation in step 1.3 is placed in graphene aqueous solution 12.5min post-drying, then be placed in Graphene paraffin solution 13.5min, dry for standby.
Step 2, Graphene-graphite electrode is prepared o-tolidine imprinted polymer film,
Step 2.1, is placed in PBS buffer solution by the Graphene-graphite electrode processed and carries out deoxygenation process 12min, and the concentration containing o-tolidine in described PBS buffer solution is 0.06molL
-1, the concentration of acrylamide is 0.36molL
-1, the two ratio is 1:6; The pH of described PBS buffer solution is 7.
Step 2.2, by the electrifying electrodes after step 2.1 deoxygenation, scans in potential range at-1.0-1.0V, to sweep speed for 0.18Vs
-1scan round 12 is enclosed, and prepares o-tolidine imprinted polymer film at electrode surface.
The semi-manufacture of the o-tolidine imprinted polymer electrode of preparation in step 2 are carried out wash-out process by step 3,
Concrete steps are, are taken out by electrode from damping fluid, then are placed in clear water after ultrasonic cleaning 8min, and namely obtained surface is the electrode of o-tolidine imprinted polymer film.
Utilize above-mentioned o-tolidine imprinted polymer membrane electrode to carry out the method for o-tolidine detection, specifically implement according to following steps:
Step 1, by the o-tolidine imprinted polymer membrane electrode prepared, namely surface has the imprinted polymer electrode of o-tolidine to connect according to zero stream positioning system device;
Step 2, utilizes zero stream current potential E
zCPand the relation formula between o-tolidine log concentration
E
ZCP＝-0.00715log[o-TD]+0.08951 (1)
Sample solution to be detected is tested.
Be specially: step 2.1, the o-tolidine molecularly imprinted polymer electrode connected put into solution to be measured, switches on power;
Step 2.2, be-0.6 ~ 0.6V at scanning current potential, sweeping speed is 0.18Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Step 2.3, flows current potential E by zero of the testing sample solution recorded
zCPin the formula (1) that value substitution step 2 draws, the concentration of o-tolidine in testing sample solution can be calculated, thus draw the content of o-tolidine in testing liquid.
Claims (9)
1. the imprinted polymer membrane electrode of an o-tolidine, it is characterized in that, comprise the graphite rod (9) that two ends are wound with copper wire (2), copper wire two ends rubber cutting ferrule (11) are fixed, described graphite rod top layer is the potpourri of the doping of Graphene and graphite, is the molecular imprinted polymer membrane (10) of o-tolidine in the outside of this mixture layer.
2. a preparation method for the imprinted polymer membrane electrode of the o-tolidine described in claim 1, is characterized in that, specifically implements according to following steps:
Step 1, prepares Graphene-graphite electrode and carries out pre-service;
Step 2, Graphene-graphite electrode is prepared o-tolidine imprinted polymer film, obtains trace
The semi-manufacture of polymer membrane electrode;
Step 3, carries out wash-out process, obtained o-tolidine imprinted polymer electrode.
3. the preparation method of the imprinted polymer electrode of o-tolidine according to claim 2, it is characterized in that, described step 1 is specially:
Step 1.1, is cut into the segment of 2 ~ 4cm by graphite rod, in paraffin solution, boil 30 ~ 50min;
Step 1.2, cuts the copper wire of 5 ~ 10cm, two copper wires is wrapped in respectively the two ends of graphite rod, and copper wire and graphite rod is fixed together, make graphite carbon modified electrode;
Step 1.3, by the graphite electrode pan paper polishing of preparation in step 1.2, after then using absolute ethyl alcohol and each supersound washing 5 ~ 10min of redistilled water, dries for subsequent use;
Step 1.4, adds in the redistilled water of 10 ~ 20mL by the graphene powder of 5 ~ 10mg, in ultrasonic middle dispersion, until obtain even graphene aqueous solution; The graphene powder of 5 ~ 10mg is added ultrasonic disperse in the melt paraffin solution of 10 ~ 20mL until obtain even Graphene paraffin solution; And then the graphite electrode of preparation in step 1.3 is placed in graphene aqueous solution 10 ~ 15min post-drying, then be placed in Graphene paraffin solution 10 ~ 15min, dry for standby.
4. the preparation method of the imprinted polymer electrode of o-tolidine according to claim 2, it is characterized in that, described step 2 is specially:
Step 2.1, is placed in PBS buffer solution by the Graphene-graphite electrode processed and carries out deoxygenation process 8min ~ 15min, and the concentration containing o-tolidine solution in described PBS buffer solution is 0.02 ~ 0.1molL
-1, the concentration of acrylamide solution is 0.12 ~ 0.6molL
-1, the two ratio is 1:6; The pH of described PBS buffer solution is 5.59 ~ 8.04;
Step 2.2, by the electrifying electrodes after step 2.1 deoxygenation, scans in potential range, to sweep speed for 0.1 ~ 0.3Vs at-1.0V ~ 1.0V
-1scan round 6 ~ 26 is enclosed, and prepares o-tolidine imprinted polymer film at electrode surface.
5., according to the imprinted polymer electrode preparation method of claim 4 o-tolidine, it is characterized in that, described step 3 is specially:
The semi-manufacture of the o-tolidine imprinted polymer electrode of preparation in step 2 are carried out wash-out process, and concrete steps are, are taken out by electrode from damping fluid, then are placed in clear water after ultrasonic cleaning 5 ~ 10min, i.e. the imprinted polymer membrane electrode of obtained o-tolidine.
6. utilize the imprinted polymer electrode of the o-tolidine described in claim 1 to carry out a method for o-tolidine detection, it is characterized in that, specifically implement according to following steps:
Step 1, by the o-tolidine imprinted polymer membrane electrode prepared, namely surface has the imprinted polymer electrode of o-tolidine to connect according to zero stream positioning system device;
Step 2, utilizes zero stream current potential E
zCPand the relation formula between o-tolidine log concentration
E
ZCP＝-0.00715log[o-TD]+0.08951 (1)
Sample solution to be detected is tested.
7. o-tolidine detection method according to claim 6, it is characterized in that, zero stream positioning system device described in described step 1, its structure is: the imprinted polymer membrane electrode (1) and the CHI660 electrochemical workstation (8) that comprise o-tolidine, CHI660 electrochemical workstation (8) is provided with 3 electrode interfaces, contrast electrode interface (3) respectively, working electrode interface (4) and auxiliary electrode interface (5), contrast electrode interface (3) is connected with saturated calomel electrode, CHI660 electrochemical workstation (8) is connected with computing machine (7), computing machine (7) is for control CHI660 electrochemical workstation, the two ends of the imprinted polymer membrane electrode (1) of o-tolidine are connected with working electrode interface (4) and auxiliary electrode interface (5) respectively by copper wire (2), the imprinted polymer membrane electrode (1) of saturated calomel electrode (6) and o-tolidine is all dipped in solution (12), the PBS solution that solution (12) is normal concentration o-tolidine sample or o-tolidine solution to be measured.
8. according to claim 6 o-tolidine detection method, it is characterized in that, the formula (1) in described step 2 obtains in accordance with the following steps:
First, by the electrode connected, it puts into the PBS sample solution containing standard o-tolidine; Scanning current potential be-0.6 ~ 0.6V, sweeping speed is 0.1 ~ 0.3Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Wherein, described o-tolidine concentration is 1 × 10
-9~ 1 × 10
-6molL
-1;
Then, by analyzing zero stream current potential E of the o-tolidine imprinted polymer membrane electrode recorded
zCPdata, zero stream current potential E
zCP, the current potential namely during I=0, and meet following relational expression between o-tolidine concentration value in solution:
E
ZCP＝-0.00715log[o-TD]+0.08951 (1)
Wherein, E
zCPrepresent zero stream current potential; [o-TD] represents the concentration of o-tolidine.
9. o-tolidine detection method according to claim 6, is characterized in that, the concrete steps of described step 2 are:
Step 2.1, puts into solution to be measured by the o-tolidine molecular imprinted polymer membrane electrode connected, switches on power;
Step 2.2, be-0.6 ~ 0.6V at scanning current potential, sweeping speed is 0.1 ~ 0.3Vs
-1condition under carry out linear voltammetric scan, record I=0 time current potential zero stream current potential E
zCP;
Step 2.3, flows current potential E by zero of the testing sample solution recorded
zCPvalue substitutes in formula (1), can calculate the concentration of o-tolidine in testing sample solution, thus draw the content of o-tolidine in testing liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510069879.XA CN104698051A (en) | 2015-02-10 | 2015-02-10 | O-tolidine imprinted polymer film electrode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510069879.XA CN104698051A (en) | 2015-02-10 | 2015-02-10 | O-tolidine imprinted polymer film electrode and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104698051A true CN104698051A (en) | 2015-06-10 |
Family
ID=53345398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510069879.XA Pending CN104698051A (en) | 2015-02-10 | 2015-02-10 | O-tolidine imprinted polymer film electrode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104698051A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113504278A (en) * | 2021-06-04 | 2021-10-15 | 西安工程大学 | CPPU molecularly imprinted polymer membrane electrode and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080100645A (en) * | 2007-05-14 | 2008-11-19 | 한국식품연구원 | Surface plasmon resonance sensor chip using molecular imprinting technique for detecting the mycotoxins zearalenone and its derivatives, and method of the same, and detecting method of the mycotoxins zearalenone and its derivatives using the same |
| US20110024302A1 (en) * | 2009-07-28 | 2011-02-03 | Polestar Technologies, Inc. | Molecular Imprinted Nanosensors And Process For Producing Same |
| CN103115914A (en) * | 2013-01-31 | 2013-05-22 | 济南大学 | Preparation method and application of molecular imprinting electroluminescent sensor for detecting trace veterinary drug residue by taking battery as power |
| CN103868966A (en) * | 2014-03-21 | 2014-06-18 | 上海出入境检验检疫局工业品与原材料检测技术中心 | Molecularly-imprinted polymer-graphene composite material modified electrode as well as preparation method and application thereof |
| CN104020205A (en) * | 2014-06-26 | 2014-09-03 | 西安工程大学 | Parachloroaniline imprinted polymer membrane electrode, and preparation method and application method thereof |
-
2015
- 2015-02-10 CN CN201510069879.XA patent/CN104698051A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080100645A (en) * | 2007-05-14 | 2008-11-19 | 한국식품연구원 | Surface plasmon resonance sensor chip using molecular imprinting technique for detecting the mycotoxins zearalenone and its derivatives, and method of the same, and detecting method of the mycotoxins zearalenone and its derivatives using the same |
| US20110024302A1 (en) * | 2009-07-28 | 2011-02-03 | Polestar Technologies, Inc. | Molecular Imprinted Nanosensors And Process For Producing Same |
| US20130092547A1 (en) * | 2009-07-28 | 2013-04-18 | Polestar Technologies, Inc. | Molecular imprinted nanosensors |
| CN103115914A (en) * | 2013-01-31 | 2013-05-22 | 济南大学 | Preparation method and application of molecular imprinting electroluminescent sensor for detecting trace veterinary drug residue by taking battery as power |
| CN103868966A (en) * | 2014-03-21 | 2014-06-18 | 上海出入境检验检疫局工业品与原材料检测技术中心 | Molecularly-imprinted polymer-graphene composite material modified electrode as well as preparation method and application thereof |
| CN104020205A (en) * | 2014-06-26 | 2014-09-03 | 西安工程大学 | Parachloroaniline imprinted polymer membrane electrode, and preparation method and application method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN113504278A (en) * | 2021-06-04 | 2021-10-15 | 西安工程大学 | CPPU molecularly imprinted polymer membrane electrode and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Electrospun template directed molecularly imprinted nanofibers incorporated with BiOI nanoflake arrays as photoactive electrode for photoelectrochemical detection of triphenyl phosphate | |
| CN104807874A (en) | Preparation and application method of molecular imprinting electrochemical sensor | |
| CN103913499B (en) | A kind of preparation method of the molecular imprinting electrochemical sensor for bovine hemoglobin detection | |
| CN102879588A (en) | Method for detecting estrogens through graphene-nanogold biomimetic immunosensor | |
| Nie et al. | Simultaneous determination of nitroaromatic compounds in water using capillary electrophoresis with amperometric detection on an electrode modified with a mesoporous nano‐structured carbon material | |
| CN108732218B (en) | Electrochemical sensor for measuring 2,4, 6-trichlorophenol and preparation and application thereof | |
| Kim et al. | Subnanomolar ion detection by stripping voltammetry with solid-supported thin polymeric membrane | |
| CN104359996B (en) | Modifying carbon fibers fills polyetheretherketone pipe solid-phase microextraction post and preparation method thereof | |
| CN102735729A (en) | Electrochemical paracetamol molecular imprinting transducer and manufacturing method thereof | |
| CN109781815A (en) | A kind of preparation method of olaquindox molecular engram film electrochemical sensor | |
| CN103575783A (en) | Preparation method of molecularly-imprinted electrochemical transducer for detecting propylgallate as well as application thereof | |
| CN110501398B (en) | Beta-cyclodextrin modified graphite electrode, preparation method and application | |
| Ma et al. | An impedance molecularly imprinted sensor for the detection of bovine serum albumin (BSA) using the dynamic electrochemical impedance spectroscopy | |
| CN102169105A (en) | Graphene-based nano-pore monomolecular sensor and medium identification method thereof | |
| CN104569121B (en) | Method for detecting lead ion concentration in solution | |
| CN102128867A (en) | Method for detecting paracetanol with para aminobenzoic acid/nanometer gold modified carbon electrode | |
| CN102680549A (en) | Method for measuring 9-hydroxy fluorine based on electrochemistry hairpin DNA biosensor | |
| CN104698051A (en) | O-tolidine imprinted polymer film electrode and preparation method and application thereof | |
| CN104020205B (en) | The imprinted polymer membrane electrode of parachloroanilinum, its preparation method and application process | |
| AU2022432797A1 (en) | Soil parameter sensor system | |
| CN108287188B (en) | A kind of bionical electrochemical probe of electrochemical polymerization molecular engram, its preparation and application | |
| CN104698050B (en) | 2,4 diaminotoluene imprinted polymer electrodes, its preparation method and application | |
| CN103852642A (en) | Method for detecting electrical conductivity of small number of solids | |
| CN105158318B (en) | A kind of preparation method for the electrochemical sensor for detecting polycyclic aromatic hydrocarbon | |
| CN103543188A (en) | Electrochemical sensor for determining o-phenylenediamine with high flexibility as well as determining method of sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150610 |
|
| RJ01 | Rejection of invention patent application after publication |