CN110568038A - Application of thiamphenicol molecularly imprinted electrochemical sensor - Google Patents
Application of thiamphenicol molecularly imprinted electrochemical sensor Download PDFInfo
- Publication number
- CN110568038A CN110568038A CN201910836981.6A CN201910836981A CN110568038A CN 110568038 A CN110568038 A CN 110568038A CN 201910836981 A CN201910836981 A CN 201910836981A CN 110568038 A CN110568038 A CN 110568038A
- Authority
- CN
- China
- Prior art keywords
- thiamphenicol
- electrode
- molecularly imprinted
- porous
- modified
- 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
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Abstract
The invention discloses an application of a thiamphenicol molecular imprinting electrochemical sensor, wherein an L-shaped glassy carbon electrode modified by a molecular imprinting film is immersed into a sample containing thiamphenicol for identification, and then water is used for washing to remove non-specifically adsorbed molecules; then, the identified molecular imprinting membrane modified L-shaped glassy carbon electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode to form a three-electrode system, a 2cm cuvette is used as a photoelectric detection cell, and the three-electrode system is immersed into a solution containing 0.1mol L of the identified molecular imprinting membrane modified L-shaped glassy carbon electrode‑1Ascorbic acid in phosphate buffer at pH 7.0; and irradiating the surface of the working electrode by 405nm laser, wherein AA generates photocurrent, and a working curve is obtained according to the direct proportion of the variation of the photocurrent to the concentration of thiamphenicol. The sensor can quickly and accurately detect the thiamphenicol in meat samples and feed samples.
Description
The invention discloses a thiamphenicol molecularly imprinted electrochemical sensor with application number of 201610944433.1 and application date of 2016.11.02, and a preparation method and application thereof.
Technical Field
the invention belongs to the technical field of molecular imprinting, and particularly relates to an application of a thiamphenicol molecular imprinting electrochemical sensor.
Background
Thiamphenicol is a commonly used antibiotic, belongs to a broad-spectrum antibiotic with chloramphenicol and florfenicol, has good antibacterial effect, and is widely applied to human disease treatment and animal food production, and residues are formed. Meanwhile, in the background of the banned use of chloramphenicol in the production of animal-derived foods in countries such as china, canada, the united states and the european union, chloramphenicol is gradually becoming a substitute for chloramphenicol in the production of animal-derived foods. However, excessive intake can have a significant impact on human health. Therefore, countries such as the united states, canada, and china have prohibited their use in the production of animal-derived foods and set maximum residual amounts in food safety management systems. In view of this, the construction of the sensor for electrochemically detecting thiamphenicol has certain research work with practical significance.
In the construction of the molecular imprinting electrochemical sensor, the electropolymerization method is one of the common methods for preparing a Molecular Imprinting Polymer (MIP) modified electrode, realizes the simultaneous completion of the preparation and modification of the MIP film, and has the characteristics of controllable thickness, convenience, simplicity, practicability and the like. It is well known that the imprinted substrate is one of the important factors determining the performance of such electrochemical sensors. Meanwhile, the conductive nano material modified interface can improve the imprinting site number, the conductivity and the catalytic performance of the imprinting film, and the three-dimensional imprinting substrate can obviously improve the performances, is very beneficial to improving the sensitivity of the sensor, and is good for selecting the substrate for preparing the MIP film in situ by electropolymerization. Meanwhile, the detection of the non-electroactive target by combining photoelectric current is also one of the research hotspots of the current molecularly imprinted electrochemical sensor.
Disclosure of Invention
In view of the above, the invention provides a thiamphenicol molecularly imprinted electrochemical sensor, and a preparation method and application thereof, and the invention adopts porous graphene (P-r-GO-MoS)2) Nanoflower composite and aminated porous carbon Nanotube (NH)2MWCNTs) and porous Pt-Pd nanoparticles (Pt-Pd NPs) construct a three-dimensional porous imprinting substrate; then, o-phenylenediamine is used as a functional monomer, thiamphenicol is imprinted by cyclic voltammetry, and photocurrent generated by an Ascorbic Acid (AA) electrochemical probe is used as an electric signal to construct an electrochemical sensor for detecting electrochemical detection thiamphenicol. As far as we know, a method for electrochemically detecting thiamphenicol is not reported, and the method for applying the three-dimensional modified electrode to the technical field of molecular imprinting is not reported.
In order to solve the technical problem, the invention discloses a preparation method of a thiamphenicol molecularly imprinted electrochemical sensor, which comprises the following steps:
Step 1, preparing porous Pt-Pd nano particles;
Step 2, preparing a porous graphene-molybdenum disulfide nano flower-like compound;
Step 3, modifying the L-shaped glassy carbon electrode by using the porous graphene-molybdenum disulfide nano flower-shaped compound, the aminated multi-walled carbon nanotube and the porous Pt-Pd nano particles;
Step 4, preparing the modified L-shaped glassy carbon electrode into a molecularly imprinted modified electrode by using o-phenylenediamine as a functional monomer and thiamphenicol as a template molecule through cyclic voltammetry; and then washing to remove the template molecules in the polymeric membrane to obtain the thiamphenicol molecularly imprinted membrane modified electrode.
Further, the preparation of the porous Pt-Pd nanoparticles in step 1 is specifically as follows: mixing cetylpyridinium (HDPC) and Na2PdCl4And H2PtCl6Adding the mixture into a round-bottom flask according to the volume ratio of 3:1:1-8:1:1 to form uniform dispersion liquid; then, quickly adding a freshly prepared Ascorbic Acid (AA) solution into the solution, wherein the volume ratio of the AA solution to HDPC is 1:25-1:5, dispersing the AA solution uniformly by slight earthquake, and placing the round-bottom flask into an oil bath at the temperature of 80-90 ℃ for reacting for 2.5-3.5 h; then thecentrifuging the obtained sol, and washing with water for multiple times to obtain dendritic porous Pt-Pd nanoparticles; cetyl pyridine, Na2PdCl4、H2PtCl6The concentrations of (A) are as follows: 10mol L of-1。
Further, the preparation of the porous graphene-molybdenum disulfide nanoflower composite in the step 2 specifically comprises the following steps:
step 2.1, preparing porous graphene oxide:
KMnO was added under magnetic stirring4Adding the Graphene Oxide (GO) into the Graphene Oxide (GO) dispersion liquid to react for 12h, wherein KMnO4the mass ratio of the GO to the GO dispersion liquid is 8:1-15: 1; then, HCl and H are added2O2adding into the reaction solution, and continuing to react for 3H, wherein GO dispersion liquid, HCl and H2O2The volume ratio of (A) to (B) is 2:1-4: 1; after the reaction is finished, centrifugally separating and washing the obtained product, and drying the product in a vacuum drier at the temperature of 55-60 ℃; preparing a porous graphene oxide dispersion liquid;
Step 2.2, preparing the porous graphene-molybdenum disulfide nanoflower compound:
Will be (NH)4)6Mo7O2·4H2Dissolving O and thiourea in the porous graphene solution, transferring the mixed solution into a reaction kettle, and reacting for 12 hours at 210-230 ℃; wherein (NH)4)6Mo7O2·4H2The mass ratio of the O to the porous graphene oxide is 4:1-1: 1; the mass ratio of the thiourea to the porous graphene oxide is 50:1-30: 1; after the reaction is finished, centrifugally separating and washing the obtained product, and drying the product in a vacuum drier at the temperature of 55-65 ℃ to prepare the porous graphene-molybdenum disulfide nano flower-like compound (P-r-GO-MoS)2) (ii) a HCl and H2O2The mass percentage concentration of (A) is 36% and 30% respectively.
Further, the modification in step 3 employs the following steps: dropping DMF dispersed liquid of the porous graphene-molybdenum disulfide nanoflower composite onto the surface of an L-shaped GCE electrode, and drying at 80 ℃; then, multi-wall carbon nano-tube (NH) containing amino2-MWCNTs) with DMF dispersed droplets of porous Pt-Pd nanoparticlesdrying the surface of the electrode at 80 ℃;
The concentration of the N, N-dimethylformamide dispersion liquid of the porous graphene-molybdenum disulfide nano flower-like compound is 5mg mL-1(ii) a The concentration of the aminated multi-walled carbon nanotube in the DMF dispersion liquid containing the aminated multi-walled carbon nanotube and the porous Pt-Pd nano-particles is 0.2mg mu L-1The concentration of the porous Pt-Pd nanoparticles is 5mg mu L-1The volume ratio of the N, N-dimethylformamide dispersion liquid of the porous graphene-molybdenum disulfide nanoflower composite to the DMF dispersion liquid containing the aminated multiwalled carbon nanotube and the porous Pt-Pd nanoparticles is 1: 1.
Further, in the step 4, the modified L-shaped glassy carbon electrode takes o-phenylenediamine as a functional monomer and thiamphenicol as a template molecule, and a molecular imprinting modified electrode is prepared by cyclic voltammetry; and then washing to remove the template molecules in the polymeric membrane to obtain the thiamphenicol molecularly imprinted membrane modified electrode, which specifically comprises the following steps: immersing the modified L-shaped glassy carbon electrode into acetate buffer solution containing template molecules and imprinting monomers, wherein the template molecules are thiamphenicol, the functional monomers are o-phenylenediamine, and obtaining the molecularly imprinted modified electrode embedded with the thiamphenicol by cyclic voltammetry, wherein the scanning potential of the cyclic voltammetry is 0mV-1.2mV, the number of scanning cycles is 10, and the scanning speed is 100mV s-1。
Further, the molar concentration ratio of o-phenylenediamine to thiamphenicol in the acetic acid buffer solution is 2:1-8:1, the pH value of the acetic acid buffer solution is 5.2, the eluent is a methanol/acetic acid solution with the volume ratio of 9:1, and the elution time is 30 minutes.
the invention also provides the thiamphenicol molecularly imprinted electrochemical sensor obtained by the preparation method.
The invention also provides an application of the thiamphenicol molecularly imprinted electrochemical sensor in detecting thiamphenicol in meat samples and feed samples, which is implemented according to the following detection steps: immersing the L-shaped glassy carbon electrode modified by the molecularly imprinted membrane into a sample containing thiamphenicol for identification, and then washing with water to remove non-specifically adsorbed molecules; then working with the identified molecular engram film modified L-shaped glassy carbon electrodeAs an electrode, a saturated calomel electrode as a reference electrode, a platinum wire electrode as a counter electrode to form a three-electrode system, and a 2cm cuvette as a photoelectric detection cell immersed in a solution containing 0.1mol L of mercury-1Ascorbic Acid (AA) in Phosphate Buffered Saline (PBS) at pH 7.0; and irradiating the surface of the working electrode by 405nm laser, wherein AA generates photocurrent, and a working curve is obtained according to the direct proportion of the variation of the photocurrent to the concentration of thiamphenicol.
Further, a sample containing thiamphenicol was prepared by: accurately weighing 1.0000g of a sample containing thiamphenicol, adding 20mL of methanol, and swirling for 15min on a high-speed swirl mixer; subsequently, the resulting suspension was centrifuged at 10000r/min for 10min, and the supernatant was taken out and concentrated in a constant temperature water bath at 40 ℃. When the methanol was completely volatilized, the solution was dissolved in a small amount of PBS (pH 7.0), and then filtered through a 0.45 μm organic membrane, and the filtrate was transferred to a 10.0mL volumetric flask and subjected to constant volume.
Further, the linear range of detection of the molecularly imprinted electrochemical sensor on thiamphenicol is 1.0 multiplied by 10-9-3.5×10-6mol L-1regression equation is iΔ(μA)＝0.4981C(μmol L-1)+0.5012,(r20.9912), detection limit of 5.0 × 10-9mol L-1。
Compared with the prior art, the invention can obtain the following technical effects:
1) The sensor has good response to thiamphenicol, and the linear range of the sensor is 1.0 multiplied by 10-9-3.5×10-6mol L-1The lower detection limit is 5.0 × 10-9mol L-1。
2) the invention adopts MoS2、NH2The MWCNTs and the porous Pt-Pd NPs construct a three-dimensional porous imprinting substrate, and the electrochemical sensor for detecting thiamphenicol is prepared by combining the MIP technology and the photoelectric sensing technology. The three-dimensional porous imprinting substrate has a larger specific surface and a faster mass transfer speed, which is very beneficial to improving the sensitivity of the sensor, and the MIP improves the selectivity of the sensor.
3) The sensor can be used for detecting thiamphenicol in practical samples, particularly for detecting thiamphenicol in meat samples and feed samples, widens the detection channel, and has certain practical significance.
Of course, it is not necessary for any one product in which the invention is practiced to achieve all of the above-described technical effects simultaneously.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a technical flow chart of the sensor preparation of the present invention. Wherein, A is the preparation process of the imprinted sensor, and B is the electrochemical detection device of the sensor;
FIG. 2 is a representation of a microscopic material according to the present invention; wherein A represents a porous graphene-molybdenum disulfide projection electron microscope image; b represents a high-power projection electron microscope image of the porous graphene; c represents a high-power transmission electron microscope image of the molybdenum disulfide; d represents a projection electron micrograph of the porous Pt-Pd nanoparticles;
FIG. 3 is a microscopic representation of a scanning electron microscope during electrode modification according to the present invention; wherein A represents a scanning electron microscope image of a porous graphene-molybdenum disulfide modified L-glassy carbon electrode (L-GCE), and B represents a porous Pt-Pd-aminated multi-walled carbon nanotube modified interface; c represents a scanning electron microscope image after the molecularly imprinted polymer is polymerized on the modified interface;
FIG. 4 shows that the imprinted sensor and the non-imprinted sensor of the present invention contain 0.1mol L-1Comparison of photocurrent generated in phosphate buffered saline (PBS, pH 7.0) of Ascorbic Acid (AA); a and b represent photocurrent generated by AA when thiamphenicol (concentration) is not recognized by the imprinted electrode and the non-imprinted electrode respectively; a 'and b' represent the recognition of thiamphenicol by the imprinted electrode and the non-imprinted electrode respectively (1.75 multiplied by 10)-6mol L-1) The photocurrent generated by AA;
FIG. 5 shows a different blot sensor of the invention containing 0.1mol L-1comparison of photocurrent generated in phosphate buffered saline (PBS, pH 7.0) of Ascorbic Acid (AA). a. b, c and d respectively replace the imprinting sensor of the naked L-shaped glassy carbon electrode, porous graphene,The imprinting sensor prepared by using the electrode modified by the porous graphene-molybdenum disulfide and the aminated multi-walled carbon nanotube-porous graphene-molybdenum disulfide contains 0.1mol L of L-1Photocurrent generated in phosphate buffered saline (PBS, pH 7.0) of Ascorbic Acid (AA); a ', b', c 'and d' respectively represent a print sensor of a bare L-shaped glassy carbon electrode, porous graphene-molybdenum disulfide and an aminated multi-walled carbon nanotube-porous graphene-molybdenum disulfide modified electrode prepared print sensor enriched with 1.75 multiplied by 10-6mol L-1After thiamphenicol, in a solution containing 0.1mol L-1Photocurrent generated in phosphate buffered saline (PBS, pH 7.0) with Ascorbic Acid (AA);
FIG. 6 is a graph of the ratio of functional monomers to template molecules of the present invention as a function of the response current of the sensor;
FIG. 7 is a graph of the aggregate time versus response current of the sensor of the present invention;
FIG. 8 is a graph of enrichment time versus response current of a sensor according to the present invention;
FIG. 9 is a graph of the sensorlinear response of the present invention; the concentration of thiamphenicol is: 1.0X 10-9-3.5×10-6mol L-1The inset is a calibration curve, and the error bars represent standard deviations (n ═ 3);
FIG. 10 is an interference plot of a sensor of the present invention; wherein, a represents a sensing pair of 1.75 × 10-6mol L-1Photocurrent response value of thiamphenicol; b. c represents a sensor pair of 1.75X 10, respectively-6mol L-1+3.5×10-5mol L-1Chloramphenicol and 1.75X 10-6mol L-1+3.5×10-5mol L-1Photocurrent response values of florfenicol.
Detailed Description
The following embodiments are described in detail with reference to the accompanying drawings, so that how to implement the technical features of the present invention to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Example 1
(1) Preparation of porous Pt-Pd NPs: 5.0mL of cetylpyridine (HDPC) (4.0mg mL)-1)、0.40mL Na2PdCl4(10mmol L-1) And 0.40mL H2PtCl6(10mmol L-1) Adding the mixture into a round-bottom flask to form uniform dispersion liquid; then, 0.60mL of freshly prepared AA solution is rapidly added into the solution, the solution is uniformly dispersed by gentle seismic oscillation, and the round-bottom flask is placed in an oil bath at 85 ℃ for reaction for 3 hours; then, centrifuging the obtained sol, and washing with water for multiple times to obtain dendritic Pt-Pd NPs;
(2) Preparing porous graphene oxide: under magnetic stirring, 0.5g of KMnO4Adding 100mL of 0.5mg mL- 1GO dispersion was allowed to react for 12 h. Then, 30mL of HCl (36%, wt%) and 30mL of H2O2(30%, wt%) was added to the above reaction solution and the reaction was continued for 3 hours. After the reaction is finished, centrifugally separating and washing the obtained product, and drying the product in a vacuum drier at the temperature of 60 ℃; preparing a porous graphene oxide dispersion liquid;
(3) Porous graphene-molybdenum disulfide nanoflower (P-r-GO-MoS)2) The preparation of (1): 1mmol (NH)4)6Mo7O2·4H2O) and 30mmol of thiourea are dissolved in 50mL of graphene oxide dispersion liquid, and the mixed liquid is transferred to a 50mL reaction kettle to react for 12h at 220 ℃. After the reaction is finished, the obtained product is centrifugally separated, washed and dried in a vacuum drier at the temperature of 60 ℃.
(4) As shown in fig. 1-a, the L-shaped glassy carbon electrode is modified with an aminated multi-walled carbon nanotube, porous Pt-Pd nanoparticles, and a porous graphene-molybdenum disulfide nanoflower complex: 5mg mL of-1P-r-GO-MoS of2The DMF dispersion liquid is dripped on the surface of the modified electrode and is continuously dried at 80 ℃; then, 5. mu.L of NH was added2DMF dispersion of-MWC NTs with Pt-Pd NTs (containing 1mg NH)2MWCNTs and 25mg Pt-Pd NTs) on the electrode surface, and continuously drying at 80 ℃ to obtain the imprinting substrate.
(5) Immersing the electrode obtained by the modification into a solution containing 0.8mmol L-1O-phenylenediamine and 0.2mmol L-1Acetate buffer of thiamphenicol (pH 5.2) at a potential of 0mV to 1.2mV with 100mV s-1CV blot polymerization was performed at the same speed. When the number of polymerization cycles reaches 10 cycles, placing the obtained electrode at room temperature for airing, and eluting template molecules with methanol/acetic acid solution (9/1, V/V) for 30min to obtain the molecularly imprinted polymer MIP/Pt-Pd NPs-NH2-MWCNTs/P-r-GO-MoS2the/L-GCE is the thiamphenicol molecularly imprinted electrochemical sensor.
Example 2
(1) preparation of porous Pt-Pd NPs: mixing cetyl pyridine (HDPC,10mol L)-1)、Na2PdCl4(10molL-1) And H2PtCl6(10molL-1) Adding the mixture into a round-bottom flask according to the volume ratio of 3:1:1 to form uniform dispersion liquid; then, quickly adding a freshly prepared Ascorbic Acid (AA) solution into the solution, wherein the volume ratio of the AA solution to HDPC is 1:25, dispersing the AA solution uniformly by gentle earthquake, and placing the round-bottom flask into an oil bath at the temperature of 80 ℃ for reaction for 2.5 hours; then, centrifuging the obtained sol, and washing with water for multiple times to obtain dendritic Pt-Pd NPs;
(2) Preparing porous graphene oxide:
KMnO was added under magnetic stirring4Adding into GO dispersion, and reacting for 6h, wherein KMnO4The mass ratio of the GO to the GO dispersion is 8: 1; then, HCl (36%, wt%) and H were combined2O2(30 percent, wt%) is added into the reaction solution and the reaction is continued for 3 hours, wherein GO dispersion liquid, HCl and H2O2The volume ratio of (A) to (B) is 2: 1; after the reaction is finished, centrifugally separating and washing the obtained product, and drying the product in a vacuum drier at 55 ℃; preparing a porous graphene oxide dispersion liquid;
(3) Porous graphene-molybdenum disulfide nanoflower (P-r-GO-MoS)2) The preparation of (1): will be (NH)4)6Mo7O2·4H2Dissolving O and thiourea into the porous graphene oxide dispersion liquid, transferring the mixed liquid into a 50mL reaction kettle, and reacting for 12h at 210 ℃; wherein NH4)6Mo7O2·4H2the mass of O and P-r-GO is 4: 1; the mass ratio of the thiourea to the porous graphene oxide is 50: 1. After the reaction is finished, the reaction solution is added,Centrifugally separating the obtained product, washing with water, and drying in a vacuum drier at 55 ℃;
(4) Modifying an L-shaped glassy carbon electrode by using an aminated multi-walled carbon nanotube, porous Pt-Pd nanoparticles and a porous graphene-molybdenum disulfide nanoflower compound: 5mg mL of-1P-r-GO-MoS of2The DMF dispersion liquid is dripped on the surface of the modified electrode and is continuously dried at 80 ℃; then, 5. mu.L of NH was added2DMF Dispersion of-MWCNTs and Pt-Pd (containing 1mg NH)2MWCNTs and 25mg Pt-Pd) are dripped on the surface of the electrode, and the drying is continued at 80 ℃ to obtain the imprinting substrate.
(5) Immersing the electrode obtained by the modification into a solution containing 0.8mmol L-1O-phenylenediamine and 0.2mmol L-1Acetate buffer of thiamphenicol (pH 5.2) at a potential of 0mV-1.2mV, at 100mV s-1CV blot polymerization was performed at the same speed. When the number of polymerization cycles reaches 10 cycles, the obtained electrode is placed at room temperature for airing, and the template molecules are eluted for 30min by using methanol/acetic acid solution (9/1, V/V) to obtain MIP/Pt-Pd NPs-NH2-MWCNTs/P-r-GO-MoS2the/L-GCE is the thiamphenicol molecularly imprinted electrochemical sensor.
Example 3
(1) preparation of porous Pt-Pd NPs: mixing cetyl pyridine (HDPC,10mol L)-1)、Na2PdCl4(10molL-1) And H2PtCl6(10molL-1) Adding the mixture into a round-bottom flask according to the volume ratio of 8:1:1 to form uniform dispersion liquid; then, quickly adding a freshly prepared Ascorbic Acid (AA) solution into the solution, wherein the volume ratio of the AA solution to HDPC is 1:5, dispersing the AA solution uniformly by gentle earthquake, and placing the round-bottom flask into an oil bath at 90 ℃ for reaction for 3.5 hours; then, centrifuging the obtained sol, and washing with water for multiple times to obtain dendritic Pt-Pd NPs;
(2) Preparing porous graphene oxide:
KMnO was added under magnetic stirring4Adding into GO dispersion, and reacting for 12h, wherein KMnO4The mass ratio of the GO to the GO dispersion is 15: 1; then, HCl (36%, wt%) and H were combined2O2(30%, wt.%) toContinuously reacting the reaction solution for 3 hours, wherein the GO dispersion liquid, HCl and H2O2The volume ratio of (A) to (B) is 4: 1; after the reaction is finished, centrifugally separating and washing the obtained product, and drying the product in a vacuum drier at the temperature of 60 ℃; preparing a porous graphene oxide dispersion liquid;
(3) Porous graphene-molybdenum disulfide nanoflower (P-r-GO-MoS)2) The preparation of (1): will be (NH)4)6Mo7O2·4H2dissolving O and thiourea into the porous graphene dispersion liquid, transferring the mixed liquid into a 50mL reaction kettle, and reacting for 12h at 210-230 ℃; wherein NH4)6Mo7O2·4H2The mass of O and P-r-GO is 1: 1; the mass ratio of the thiourea to the porous graphene oxide is 30: 1. After the reaction is finished, centrifugally separating and washing the obtained product, and drying the product in a vacuum drier at 65 ℃;
(4) Modifying an L-shaped glassy carbon electrode by using an aminated multi-walled carbon nanotube, porous Pt-Pd nanoparticles and a porous graphene-molybdenum disulfide nanoflower compound: 5mg mL of-1P-r-GO-MoS of2The DMF dispersion liquid is dripped on the surface of the modified electrode and is continuously dried at 80 ℃; then, 5. mu.L of NH was added2DMF Dispersion of-MWCNTs and Pt-Pd (containing 1mg NH)2MWCNTs and 25mg Pt-Pd) are dripped on the surface of the electrode, and the drying is continued at 80 ℃ to obtain the imprinting substrate.
(5) Immersing the electrode obtained by the modification into a solution containing 0.8mmol L-1O-phenylenediamine and 0.2mmol L-1Acetate buffer of thiamphenicol (pH 5.2) at a potential of 0mV-1.2mV, at 100mV s-1CV blot polymerization was performed at the same speed. When the number of polymerization cycles reaches 10 cycles, the obtained electrode is placed at room temperature for airing, and the template molecules are eluted for 30min by using methanol/acetic acid solution (9/1, V/V) to obtain MIP/Pt-Pd NPs-NH2-MWCNTs/P-r-GO-MoS2the/L-GCE is the thiamphenicol molecularly imprinted electrochemical sensor.
example 4 comparative example:
Non-imprinted electrode NIP/Pt-Pd NPs-NH2-MWCNTs/P-r-GO-MoS2Preparation of/L-GCE: except that the polymerization liquid does not contain template moleculesThe remaining conditions are consistent with those of the MIP sensor.
MIP/L-GCE、MIP/P-r-GO-MoS2/L-GCE、MIP/NH2-MWCNTs/P-r-GO-MoS2(ii)/L-GCE and MIP/Pt-Pd NPs-NH2-MWCNTs/P-r-GO-MoS2preparation of/L-GCE: the same as above;
Example 5
The thiamphenicol molecularly imprinted electrochemical sensor prepared in the embodiment 1 is used for detecting thiamphenicol, and comprises the following steps:
The thiamphenicol molecularly imprinted electrochemical sensor is put into PBS buffer (pH 7) containing a certain concentration of thiamphenicol, and the target molecules are captured under gentle stirring. After 180s, the imprinted electrode was taken out, the non-specifically adsorbed molecules were washed with water, and the sensor was assembled into a three-electrode system (the imprinted electrode was a working electrode, the saturated calomel electrode was a reference electrode, and the platinum wire electrode was a counter electrode), and in 5mL PBS (pH 7) containing 0.1mol L-1AA, a current-time (i-t) experiment was performed with a potential of 0mV, and a blue-violet laser emitter was turned on to generate a photocurrent signal.
an electrochemical detection device of a thiamphenicol molecularly imprinted electrochemical sensor is shown in fig. 1-B, and the key of the design is an L-GCE electrode, the surface of the L-GCE electrode can be well irradiated by blue-violet light, and compared with common ITO, the L-GCE electrode is easier to modify, update and stabilize.
The technical effects of the invention are illustrated below with reference to specific experimental procedures:
1. Instrument and reagent
scanning Electron Microscope (SEM) images were taken at Zeiss (Germany) and the measurement voltage was 10 kV. Transmission Electron Microscopy (TEM) and EDS tests were carried out on JEM-2100 (Japan) at a voltage of 200 kV. The electrochemical experiment was performed on electrochemical workstation CHI660D, with the calomel electrode as the reference electrode, the Pt wire electrode as the counter electrode, and the modified L-glassy carbon electrode (L-GCE) as the working electrode. The photocurrent detection device is self-made in a laboratory.
n, N-Dimethylformamide (DMF), sodium tetrachloropalladate (Na)2PdCl4) And chloroplatinic acid (H)2PtCl6.6H2O), chloro-decaHexaalkylpyridines (HDPC), thiamphenicol, chloramphenicol, florfenicol, Ascorbic Acid (AA), and 3-propylamino-1-ethylimidazole chloride were all purchased from Sigma (St. Louis, MO, USA). Porous graphene (r-GO) was prepared according to literature. Aminated multi-walled carbon Nanotubes (NH)2MWCNTs) were purchased from nanjing piofeng nanomaterials technology ltd (nanjing, china). Feed samples were purchased from local supermarkets. Other reagents not mentioned were all analytically pure. The supporting electrolyte used for experimental determination is 0.1mol L-1Phosphate buffered saline (PBS, pH 7.0) from NaH2PO4And Na2HPO4and (4) preparing.
2. preparing an electrochemical sensor for detecting thiamphenicol: the same as in example 1.
3. Results and discussion
3.1 electrode interface Change during sensor preparation
First, porous graphene-MoS was characterized using TEM2The micro-morphology of (2). The two are shown as petals in the well of FIG. 2A, and the composite has two structures, MoS with wider interlayer spacing, as shown in the high resolution of FIG. 2B2The bending fold is graphene (r-GO), indicating that the two have better composite structures. Meanwhile, fig. 2C shows that graphene has a porous structure with a pore size of about 10-20 nm. Again, FIG. 2D shows MoS2Has a layer spacing of about 0.63nm and a crystal lattice of about 0.21 nm.
Secondly, as can be seen from fig. 2E, the Pt — Pd nanoparticles are spherical and porous with a diameter of about 80-90nm, and they have highly uniform pore channels with a diameter of about 1nm and branches with a diameter of about 1-2nm, consistent with literature reports. As can be seen from FIG. 2-B, P-r-GO has a three-dimensional porous structure with pore sizes ranging from about 20 to 30 nm.
Secondly, the fabrication process of the sensor was characterized by SEM. When the surface of the L-GCE electrode is modified with MoS2after-P-r-GO, the modified electrode shows a three-dimensional porous structure (FIG. 3-A). However, when Pt-Pd NPs-NH2MWCNTs are modified, a three-dimensional porous structure can be obtained, and Pt-Pd NPs are uniformly dispersed (FIG. 3-B), which is probably caused by the acting force between amino groups and the Pt-Pd NPs. When electropolymerization is used for printing hairAfter generation, a thin MIP layer was observed modifying the electrode surface (fig. 3-C).
3.2 different electrode photocurrent response
First, the imprint effect was compared using the change in photocurrent. As can be seen from fig. 4, the MIP sensor has a large photoelectric response before the template molecule is not recognized, and the response current after the MIP sensor captures the template molecule is significantly reduced, because the recognition of the template molecule reduces the photoelectric oxidation of AA by the polymeric membrane. Similarly, the photocurrent variation of the NIP sensor is small (fig. 5). It is speculated that the imprinting effect of MIP is more pronounced and allows more template molecules to be identified, while the reduction of current response for NIP sensors may be due to a small fraction of non-specific identification.
second, the response of different modified electrodes was compared using changes in photocurrent. From FIG. 5, it can be seen that the photocurrent variation of the P-r-GO modified electrode is significantly larger than that of the GCE electrode, probably because P-r-GO improves the MIP membrane area and the conduction of photoelectrons. Similarly, when in P-r-GO-MoS2After being dripped on the surface of the electrode, the photoelectric response change of the electrode is larger than MIP/P-r-GO/GCE, because of MoS2has good photoelectrocatalysis effect. When in MoS2Surface modification of NH2After MWCNTs, NH2The three-dimensional network structure of the MWCNTs increases the imprinting area and accelerates the mass transfer rate, thereby increasing the photocurrent. However, NH2porous Pt-Pd NPs are fixed in the MWCNTs network, the surface area and the electron transfer capacity of the imprinted membrane are further increased, and the response of the obtained MIP sensor is increased.
3.3 Condition optimization
3.3.1 ratio of template molecules to functional monomers
Experiments examined the effect of the time to polymerization on the photocurrent of MIP sensors. As shown in fig. 6, the change of the response current of the sensor increases as the ratio of the template molecules decreases, and the change of the response current is the largest when the ratio of the two is 1: 4; after that, the response current is gradually decreased again. This may be the ratio of the two correlated with the change in the number of imprinted sites in the MIP membrane. When the ratio of the two is larger, fewer template molecules can be fixed, so that the number of imprinting sites is reduced; on the contrary, too many functional monomers cause the embedding of the imprinted sites, which reduces the photocurrent. Therefore, the experiment employed preparing the sensor when the ratio of the two was 1: 4.
3.3.2 Effect of polymerization time
The experiment recorded the change in sensor photocurrent when the polymerization time was varied from 6 to 13 cycles (fig. 7). The results show that the variation of photocurrent of the resulting sensor is the largest when the polymerization time is 10 cycles. When the polymerization time is less than 10 cycles, the number of imprinted sites is small, and when the polymerization time is more than 10 cycles, the MIP too thick blocks conduction of photocurrent and imprinting site embedding, resulting in reduction of response current. Accordingly, the experiments employed MIP membrane layers prepared when the polymerization time was 10 cycles.
3.3.3 Effect of enrichment time
The experiment optimizes the enrichment time of the template molecules. As shown in fig. 8, the photocurrent variation increased with the increase of the enrichment time and then remained unchanged, indicating that the template molecules on the electrode surface reached a saturated state. However, for larger concentrations of thiamphenicol (1.75X 10)-6mol L-1) The MIP sensor has short time to reach adsorption equilibrium and lower concentration (2.0 multiplied by 10)-7mol L-1). Therefore, the experiment delayed the enrichment time to 180s in order to reach equilibrium for lower concentrations of thiamphenicol.
3.4 response Performance of the sensor
After optimized conditions, the photocurrent response curve of the sensor was recorded experimentally. As shown in fig. 9, the response current of the MIP sensor gradually decreases with the increase of the concentration of thiamphenicol, and the MIP sensor and the thiamphenicol have good linear relationship, and the range of the response current is 1.0 × 10-9-3.5×10-6mol L-1The linear relationship is iΔ(μA)＝0.4981C(μmol L-1)+0.5012,(r20.9912), the lower detection limit was 5.0 × 10-9mol L-1。
3.5 interference experiments
First, the experiment examined 100-fold of ceftriaxone, cefotaxime and amorelin versus 1.75X 10-6mol L-1The effect of the assay. The results show that the above antibiotics were tested forIs not interfered. Secondly, the effect of 20-fold chloramphenicol and florfenicol on their determination was investigated experimentally, and the results showed that the analogs were not substantially affected (fig. 10), indicating good selectivity of the sensor.
3.6 reproducibility and stability of the sensor
The obtained MIP sensor is 1.75 multiplied by 10-6The Relative Standard Deviation (RSD) of the photocurrent response values of 5 replicates of mol L-1 thiamphenicol was 0.34%. Next, the MIP sensor was paired with 1.75X 10 sensor 10 times in succession-6mol L-1The response of the thiamphenicol is measured to be 96.3% of the initial value, and the same concentration of thiamphenicol is measured again in 15 days, and the photocurrent response value is kept 95.2% of the initial value (RSD is 1.21%, and n is 3), which indicates that the sensor has good stability. Then, in order to examine the reproducibility of the sensor, 5 electrodes were prepared in parallel in the experiment, and the RSD value of the obtained photocurrent response value was 3.23% (n ═ 5), indicating that the sensor had good reproducibility.
3.7 determination of actual samples
The performance of the sensor is investigated by adopting a recovery rate method in the experiment. As shown in Table-1, the recovery rate was 90% -98%, indicating that the sensor has the detection of thiamphenicol applied to actual samples. In order to further examine the practicability of the sensor, the sensor is used for detecting thiamphenicol in actual sample feed. Firstly, accurately weighing 1.0000g of sample, adding 20mL of methanol, and swirling for 15min on a high-speed swirl mixer; subsequently, the resulting suspension was centrifuged at 10000r/min for 10min, and the supernatant was taken out and concentrated in a constant temperature water bath at 40 ℃. When the methanol was completely volatilized, the solution was dissolved in a small amount of PBS (pH 7.0), and then filtered through a 0.45 μm organic membrane, and the filtrate was transferred to a 10.0mL volumetric flask and subjected to constant volume. Finally, at each measurement, 1mL of the above-described fixative solution was removed and added to 4.0mL of PBS, and the sensor was enriched and measured. The results indicate that the recovery of the standard addition method of the sensor is between 90% and 95% (as in table-2), indicating that the sensor can be used for the assay with thiamphenicol in the actual sample.
TABLE 1 recovery of thiamphenicol
TABLE 2 recovery determination table of thiamphenicol in feed samples
While the foregoing description shows and describes several preferred embodiments of the invention, it is to be understood, as noted above, that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The application of the thiamphenicol molecularly imprinted electrochemical sensor is characterized by being implemented according to the following detection steps: immersing the L-shaped glassy carbon electrode modified by the molecularly imprinted membrane into a sample containing thiamphenicol for identification, and then washing with water to remove non-specifically adsorbed molecules; then, the identified molecular imprinting membrane modified L-shaped glassy carbon electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode to form a three-electrode system, a 2cm cuvette is used as a photoelectric detection cell, and the three-electrode system is immersed into a solution containing 0.1mol L of the identified molecular imprinting membrane modified L-shaped glassy carbon electrode-1Ascorbic acid in phosphate buffer at pH 7.0; irradiating the surface of the working electrode with 405nm laser, wherein AA generates photocurrent, and a working curve is obtained according to the direct proportion of the variation of the photocurrent to the concentration of thiamphenicol; wherein
The preparation method of the molecularly imprinted membrane modified L-shaped glassy carbon electrode comprises the following steps:
Step 1, preparing porous Pt-Pd nano particles;
Step 2, preparing a porous graphene-molybdenum disulfide nano flower-like compound;
Step 3, modifying the L-shaped glassy carbon electrode by using the porous graphene-molybdenum disulfide nano flower-shaped compound, the aminated multi-walled carbon nanotube and the porous Pt-Pd nano particles;
Step 4, preparing the modified L-shaped glassy carbon electrode into a molecularly imprinted modified electrode by using o-phenylenediamine as a functional monomer and thiamphenicol as a template molecule through cyclic voltammetry; and then washing to remove the template molecules in the polymeric membrane to obtain the thiamphenicol molecularly imprinted membrane modified electrode.
2. the application of the thiamphenicol molecularly imprinted electrochemical sensor according to claim 1, wherein the preparation of the porous Pt-Pd nanoparticles in step 1 is specifically as follows: mixing cetyl pyridine and Na2PdCl4and H2PtCl6Adding the mixture into a round-bottom flask according to the volume ratio of 3:1:1-8:1:1 to form uniform dispersion liquid; then, quickly adding a freshly prepared ascorbic acid solution into the solution, wherein the volume ratio of the ascorbic acid solution to the cetylpyridinium solution is 1:25-1:5, dispersing the ascorbic acid solution uniformly by slight earthquake, and placing the round-bottom flask into an oil bath at the temperature of 80-90 ℃ for reacting for 2.5-3.5 h; then, centrifuging the obtained sol, and washing with water for multiple times to obtain dendritic porous Pt-Pd nanoparticles; cetyl pyridine, Na2PdCl4、H2PtCl6The concentrations of (A) are as follows: 10mol L of-1。
3. The application of the thiamphenicol molecularly imprinted electrochemical sensor according to claim 1, characterized in that the modification in step 3 adopts the following steps: dripping N, N-dimethylformamide dispersed liquid of the porous graphene-molybdenum disulfide nanoflower composite on the surface of an L-shaped glassy carbon electrode, and drying at 80 ℃; then, the N, N-dimethylformamide dispersion liquid containing the aminated multi-walled carbon nanotube and the porous Pt-Pd nanoparticle is dripped on the surface of the electrode, and the drying is continued at 80 ℃.
4. The application of the thiamphenicol molecularly imprinted electrochemical sensor according to claim 3,
The concentration of the N, N-dimethylformamide dispersion liquid of the porous graphene-molybdenum disulfide nano flower-like compound is 5mg mL-1(ii) a The concentration of the aminated multi-walled carbon nanotube in the DMF dispersion liquid containing the aminated multi-walled carbon nanotube and the porous Pt-Pd nano-particles is 0.2mg mu L-1the concentration of the porous Pt-Pd nanoparticles is 5mg mu L-1The volume ratio of the N, N-dimethylformamide dispersion liquid of the porous graphene-molybdenum disulfide nanoflower composite to the N, N-dimethylformamide dispersion liquid containing the aminated multiwalled carbon nanotube and the porous Pt-Pd nanoparticle is 1: 1.
5. The application of the thiamphenicol molecularly imprinted electrochemical sensor according to claim 1, wherein in the step 4, the modified L-shaped glassy carbon electrode takes o-phenylenediamine as a functional monomer and thiamphenicol as a template molecule, and the molecularly imprinted modified electrode is prepared by cyclic voltammetry; and then washing to remove the template molecules in the polymeric membrane to obtain the thiamphenicol molecularly imprinted membrane modified electrode, which specifically comprises the following steps: immersing the modified L-shaped glassy carbon electrode into acetate buffer solution containing template molecules and functional monomers, wherein the template molecules are thiamphenicol, the functional monomers are o-phenylenediamine, and obtaining the molecularly imprinted modified electrode embedded with the thiamphenicol by cyclic voltammetry, wherein the scanning potential of the cyclic voltammetry is 0mV-1.2mV, the number of scanning cycles is 10, and the scanning speed is 100mV s-1。
6. The application of the thiamphenicol molecularly imprinted electrochemical sensor according to claim 5, wherein the molar concentration ratio of o-phenylenediamine to thiamphenicol in the acetic acid buffer solution is 2:1-8:1, the pH of the acetic acid buffer solution is 5.2, the eluent is a methanol/acetic acid solution with a volume ratio of 9:1, and the elution time is 30 minutes.
7. the application of the thiamphenicol molecularly imprinted electrochemical sensor according to claim 6, characterized in that the sample containing thiamphenicol is prepared by the following method: accurately weighing 1.0000g of a sample containing thiamphenicol, adding 20mL of methanol, and swirling for 15min on a high-speed swirl mixer; subsequently, the resulting suspension was centrifuged at 10000r/min for 10min, and the supernatant was taken out and concentrated in a constant temperature water bath at 40 ℃. When the methanol was completely volatilized, the solution was dissolved in a small amount of phosphate buffer solution having a pH of 7.0, and then filtered through a 0.45 μm organic membrane, and the filtrate was transferred to a 10.0mL volumetric flask and subjected to constant volume.
8. The application of the thiamphenicol molecularly imprinted electrochemical sensor in detecting thiamphenicol in meat samples and feed samples as claimed in claim 7, wherein the linear range of detection of the molecularly imprinted electrochemical sensor on the thiamphenicol is 1.0 x 10-9-3.5×10-6mol L-1regression equation is iΔ(μA)＝0.4981C(μmol L-1)+0.5012,(r20.9912), detection limit of 5.0 × 10-9mol L-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910836981.6A CN110568038B (en) | 2016-11-02 | 2016-11-02 | Application of thiamphenicol molecularly imprinted electrochemical sensor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610944433.1A CN106525932B (en) | 2016-11-02 | 2016-11-02 | Thiamphenicol molecular imprinting electrochemical sensor and the preparation method and application thereof |
| CN201910836981.6A CN110568038B (en) | 2016-11-02 | 2016-11-02 | Application of thiamphenicol molecularly imprinted electrochemical sensor |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610944433.1A Division CN106525932B (en) | 2016-11-02 | 2016-11-02 | Thiamphenicol molecular imprinting electrochemical sensor and the preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110568038A true CN110568038A (en) | 2019-12-13 |
| CN110568038B CN110568038B (en) | 2022-03-04 |
Family
ID=58292801
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610944433.1A Active CN106525932B (en) | 2016-11-02 | 2016-11-02 | Thiamphenicol molecular imprinting electrochemical sensor and the preparation method and application thereof |
| CN201910836981.6A Active CN110568038B (en) | 2016-11-02 | 2016-11-02 | Application of thiamphenicol molecularly imprinted electrochemical sensor |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610944433.1A Active CN106525932B (en) | 2016-11-02 | 2016-11-02 | Thiamphenicol molecular imprinting electrochemical sensor and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN106525932B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107271505A (en) * | 2017-06-01 | 2017-10-20 | 赵云飞 | Composite electrode and preparation method thereof, Quercetin sensor |
| CN107298442A (en) * | 2017-07-15 | 2017-10-27 | 中国海洋大学 | A kind of biomass carbon/molybdenum disulfide nano-composite material and preparation method thereof |
| CN107271518B (en) * | 2017-07-31 | 2019-05-07 | 首都师范大学 | A kind of amperometric electrochemical sensor and its preparation method and application |
| CN107585764B (en) * | 2017-09-07 | 2020-04-14 | 中国热带农业科学院南亚热带作物研究所 | Porous graphene oxide and preparation method thereof, and porous graphene oxide coated slow-release fertilizer and preparation method thereof |
| CN108828036B (en) * | 2018-06-12 | 2020-09-22 | 湖北大学 | Molecular imprinting photoelectrochemical sensor based on graphene oxide and cadmium sulfide quantum dot heterostructure and preparation method and application thereof |
| CN108862260A (en) * | 2018-07-19 | 2018-11-23 | 山东理工大学 | A kind of nontoxic preparation method of molybdenum disulfide cluster layer composite graphite alkene material |
| CN109908874B (en) * | 2019-03-25 | 2021-12-10 | 宁夏大学 | Novel MoS2QDs @ MIPs molecularly imprinted polymer and preparation method thereof |
| CN112305037B (en) * | 2020-09-24 | 2022-12-16 | 江苏大学 | Amino modified multi-walled carbon nanotube modified imprinted material, preparation method, sensor and application |
| CN113893833B (en) * | 2021-11-29 | 2024-03-05 | 北京普析通用仪器有限责任公司 | Preparation method and application of molecular imprinting composite two-dimensional material for high-throughput identification of aflatoxin |
| CN114778638A (en) * | 2022-04-24 | 2022-07-22 | 广西民族师范学院 | Photoelectric chemical sensor for detecting acrylamide and preparation method and application thereof |
| CN115784307B (en) * | 2022-09-08 | 2023-12-26 | 哈尔滨理工大学 | Preparation method and application of platinum or graphene-modified two-dimensional petal flaky molybdenum disulfide sensitive material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142551A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Graphene nano sheet/MoS2 composite nano material and synthesis method thereof |
| CN103243367A (en) * | 2013-05-17 | 2013-08-14 | 天津前方科技有限公司 | Producing method of streptomycin antibiotic molecular imprinting biosensor |
| CN104857976A (en) * | 2015-04-03 | 2015-08-26 | 浙江理工大学 | Three-dimensional molybdenum disulfide nanoflower-graphene composite material and application thereof |
| CN105891287A (en) * | 2016-06-06 | 2016-08-24 | 同济大学 | Microcystic toxin molecular imprinting functionalization TiO2@CNTs photoelectric sensor electrode and photoelectric analysis method with same |
-
2016
- 2016-11-02 CN CN201610944433.1A patent/CN106525932B/en active Active
- 2016-11-02 CN CN201910836981.6A patent/CN110568038B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142551A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Graphene nano sheet/MoS2 composite nano material and synthesis method thereof |
| CN103243367A (en) * | 2013-05-17 | 2013-08-14 | 天津前方科技有限公司 | Producing method of streptomycin antibiotic molecular imprinting biosensor |
| CN104857976A (en) * | 2015-04-03 | 2015-08-26 | 浙江理工大学 | Three-dimensional molybdenum disulfide nanoflower-graphene composite material and application thereof |
| CN105891287A (en) * | 2016-06-06 | 2016-08-24 | 同济大学 | Microcystic toxin molecular imprinting functionalization TiO2@CNTs photoelectric sensor electrode and photoelectric analysis method with same |
Non-Patent Citations (3)
| Title |
|---|
| GUANGMING YANG等: "A novel electrochemical sensor for the determination of lidocaine based on surfaceimprinting on porous three-dimensional film", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
| HAILONG YU等: "Three-Dimensional Hierarchical Architectures Constructed by Graphene/MoS2 Nanoflake Arrays and Their Rapid Charging/Discharging Properties as Lithium-Ion Battery Anodes", 《CHEMISTRY - A EUROPEAN JOURNAL》 * |
| 魏小平等: "镍配合物分子印迹光电流型传感器的研究", 《分析化学》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106525932B (en) | 2019-10-11 |
| CN106525932A (en) | 2017-03-22 |
| CN110568038B (en) | 2022-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110568038B (en) | Application of thiamphenicol molecularly imprinted electrochemical sensor | |
| Amatatongchai et al. | Highly sensitive and selective electrochemical paper-based device using a graphite screen-printed electrode modified with molecularly imprinted polymers coated Fe3O4@ Au@ SiO2 for serotonin determination | |
| Santana et al. | An original ferroferric oxide and gold nanoparticles-modified glassy carbon electrode for the determination of bisphenol A | |
| US10809215B2 (en) | Molecularly imprinted polymer sensors | |
| Dai et al. | Synthesis and analytical applications of molecularly imprinted polymers on the surface of carbon nanotubes: a review | |
| Shin et al. | Thin‐wall assembled SnO2 fibers functionalized by catalytic Pt nanoparticles and their superior exhaled‐breath‐sensing properties for the diagnosis of diabetes | |
| Luo et al. | A facile approach for synthesizing molecularly imprinted graphene for ultrasensitive and selective electrochemical detecting 4-nitrophenol | |
| US20140220706A1 (en) | Molecularly Imprinted Polymer for Detecting Waterborne Target Molecules and Improving Water Quality | |
| Mukdasai et al. | A highly sensitive electrochemical determination of l-tryptophan in the presence of ascorbic acid and uric acid using in situ addition of tetrabutylammonium bromide on the ß-cyclodextrin incorporated multi-walled carbon nanotubes modified electrode | |
| Li et al. | Green synthesis of monolithic column incorporated with graphene oxide using room temperature ionic liquid and eutectic solvents for capillary electrochromatography | |
| Cui et al. | An ultrasensitive electrochemical immunosensor for the detection of salbutamol based on Pd@ SBA-15 and ionic liquid | |
| Wang et al. | Pt‐Pd bimetallic nanoparticles decorated nanoporous graphene as a catalytic amplification platform for electrochemical detection of xanthine | |
| dos Santos Moretti et al. | Synthesis of surface molecularly imprinted poly (methacrylic acid-hemin) on carbon nanotubes for the voltammetric simultaneous determination of antioxidants from lipid matrices and biodiesel | |
| Wang et al. | Photoelectrochemical lab-on-paper device based on molecularly imprinted polymer and porous Au-paper electrode | |
| JPWO2019049693A1 (en) | Formaldehyde detection sensor and system using it | |
| Faradilla et al. | Electrochemical sensor based on screen printed carbon electrode–zinc oxide nano particles/molecularly imprinted-polymer (SPCE–ZnONPs/MIP) for detection of sodium dodecyl sulfate (SDS) | |
| Dai et al. | An electrochemical impedimetric sensor based on biomimetic electrospun nanofibers for formaldehyde | |
| Yang et al. | Voltammetric determination of 5-hydroxytryptamine based on the use of platinum nanoparticles coated with molecularly imprinted silica | |
| Motaharian et al. | Electrochemical sensor based on a carbon paste electrode modified by graphene nanosheets and molecularly imprinted polymer nanoparticles for determination of a chlordiazepoxide drug | |
| Dang et al. | Determination of norfloxacin using a tetraoxocalix [2] arene [2]-triazine covalently functionalized multi-walled carbon nanotubes modified electrode | |
| Zaidi | Effective imprinting of an anticancer drug, 6-thioguanine, via mussel-inspired self-polymerization of dopamine over reduced graphene oxide | |
| Tertis et al. | An innovative sensor based on chitosan and graphene oxide for selective and highly‐sensitive detection of serotonin | |
| Wang et al. | Polythionine-mediated AgNWs-AuNPs aggregation conductive network: Fabrication of molecularly imprinted electrochemiluminescence sensors for selective capture of kanamycin | |
| Yasri et al. | Azo dye functionalized graphene nanoplatelets for selective detection of bisphenol A and hydrogen peroxide | |
| Alizadeh | Application of electrochemical impedance spectroscopy and conventional rebinding experiments for the investigation of recognition characteristic of bulky and nano-sized imprinted polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |