CN108709922B - Polymer modified electrode for detecting superoxide dismutase with high sensitivity - Google Patents
Polymer modified electrode for detecting superoxide dismutase with high sensitivity Download PDFInfo
- Publication number
- CN108709922B CN108709922B CN201810446357.0A CN201810446357A CN108709922B CN 108709922 B CN108709922 B CN 108709922B CN 201810446357 A CN201810446357 A CN 201810446357A CN 108709922 B CN108709922 B CN 108709922B
- Authority
- CN
- China
- Prior art keywords
- electrode
- superoxide dismutase
- cys
- bromine
- containing compound
- 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.)
- Expired - Fee Related
Links
Images
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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Enzymes And Modification Thereof (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a polymer modified electrode for detecting superoxide dismutase with high sensitivity, which is prepared by modifying a polymer on the surface of the electrode in the presence of superoxide dismutase by utilizing an eATRP polymerization method, and then removing the superoxide dismutase. The modified electrode can be applied to an electrochemical sensor for detecting superoxide dismutase, has the advantages of high sensitivity, high detection speed and the like, and has the linear range of 1.0 multiplied by 10 for detecting the superoxide dismutase standard solution－7100mg/L, detection limit of 6.7802 multiplied by 10－8mg/L（LOD,S/N=3）。
Description
Technical Field
The invention discloses an electrochemical imprinting sensor, in particular to a polymer modified electrode which is simple to prepare, saves reagents and protects the environment and is used for detecting superoxide dismutase with high sensitivity.
Background
Superoxide Dismutase (SOD), also known as hepatic protein, is an active substance derived from living body, can eliminate harmful substances generated in the metabolism process of organisms, and has special effect of resisting aging. The conventional detection methods of superoxide dismutase comprise spectrophotometry, chemiluminescence, Electron Spin Resonance (ESR) spectroscopy, detection by using water-soluble tetrazolium salt and the like. However, the above methods have the disadvantages of low detection sensitivity, high detection limit, low specificity and the like.
Molecular imprinting is a unique replication-memory method that can be described vividly as a technique to make "artificial locks" that recognize "molecular keys". The core of the molecular imprinting technology is a molecular imprinting polymer, which is a polymer generated by copolymerizing a functional monomer and a target molecule in a non-covalent or covalent manner, and then eluting the target molecule through a solvent to leave a unique 'memory' hole in the polymer, wherein the hole can be reversibly and specifically combined with the target molecule in a mixture, and the molecular imprinting technology is widely applied to analysis.
There are many methods for preparing molecularly imprinted polymers, and Atom Transfer Radical Polymerization (ATRP) is a common method for achieving "living"/controlled polymerization, and is one of the effective means for preparing molecularly imprinted polymers. There are two major difficulties with the conventional ATRP method for the preparation of protein MIPs: (1) the low-valence metal catalyst required for polymerization is sensitive to air and the like and is not easy to store; (2) the catalyst has certain toxicity to protein and other biological macromolecules, and the common post-treatment process for removing the catalyst, the coordination agent and the like is complex. Various improved ATRP methods are continuously reported at present, for example, Matyjaszewski et al in 2011 propose a new eATRP method, which can reduce the content of a catalyst required by polymerization to 50 ppm and can realize more effective control on polymerization by adjusting conditions such as potential, current, electric quantity and the like; silva et al, added ascorbic acid reducing agent to hemoglobin (Hb) [ Fe (III) in Hb was reduced to Fe (II) ], found that Hb had ATRP catalytic activity, and succeeded in ATRP polymerization of N-isopropylacrylamide, (ethylene glycol) ethyl methacrylate, and (ethylene glycol) methyl ether methacrylate.
The electrochemical sensor is a three-electrode system consisting of a working electrode, a reference electrode and a counter electrode, is a device for detecting a detected sample by using the change of an electrochemical signal, has the characteristics of high sensitivity, simple and convenient preparation, low cost, easy miniaturization, suitability for field detection and the like, and is one of the most mature biosensing technologies so far. So far, there is no report on the application of polymer modified electrode with simple preparation, reagent saving and environmental protection to electrochemical sensor for detecting superoxide dismutase with high sensitivity.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a polymer modified electrode for detecting superoxide dismutase with high sensitivity.
The technical solution of the invention is as follows: a polymer modified electrode for detecting superoxide dismutase with high sensitivity is prepared by the following steps in sequence:
a. soaking the treated bare gold electrode in 1mM cysteine prepared by 0.1M PBS for 24 hours, then taking out the electrode, fully washing the electrode with ultrapure water, and removing the cysteine molecules physically adsorbed, thus obtaining the Au/Cys electrode;
b. placing Au/Cys electrode as working electrode, saturated calomel electrode as reference electrode, platinum wire as counter electrode in a system containing 5mM HAuCl4In the solution, under the constant potential of-0.9V, electrodepositing for 400s to prepare an Au/cys/Nano Au electrode;
c. modifying a clean gold electrode by using a mercapto-terminated bromine-containing compound to obtain a bromine-containing compound modified gold electrode; then putting a mixed solution containing 0.025-0.5 moL/L acrylamide, 1-20 mg/mL superoxide dismutase and 0.025-0.5 moL/LN, N-methylene bisacrylamide into an electrolytic cell, inserting a bromine-containing compound modified gold electrode into the mixed solution at room temperature, simultaneously inserting a three-electrode system with an Au/cys/Nano Au electrode as a working electrode, a platinum wire as a counter electrode and a saturated calomel electrode as a reference electrode, and applying a constant potential for 1.5h at a potential of 0.130V;
d. and taking out the bromine-containing compound modified gold electrode deposited with the polymer, cleaning the electrode by using ultrapure water, soaking the electrode in a 30% hydrogen peroxide solution for 2 hours, and then washing the electrode by using the ultrapure water, and naturally airing the electrode to obtain the electrode.
The SOD is used as a template molecule and a catalyst to carry out an eATRP reaction to prepare a polymer modified electrode for detecting the superoxide dismutase, the electrode is applied to an electrochemical imprinting sensor, the SOD can be detected quickly and highly sensitively, and the linear range of the detection of the standard solution of the superoxide dismutase is 1.0 multiplied by 10－7100mg/L, detection limit of 6.7802 multiplied by 10－8mg/L (LOD, S/N = 3), and has the advantages of simple preparation, reagent saving, environmental protection and the like.
Drawings
FIG. 1 shows the preparation of polymer modified electrode of example 1 of the present invention, the different modified electrodes containing 5mM [ Fe CN ]6]3-/4-+ 0.1M KCl (pH 7.0 PBS) solutionCyclic voltammogram of (a).
FIG. 2 is an X-ray photoelectron spectroscopy analysis chart of the polymer modified electrode of example 1 of the present invention.
FIG. 3 is a graph showing the effect of selectivity of the polymer-modified electrode according to example 1 of the present invention.
FIG. 4 is a differential pulse voltammetry curve (A) and a working curve (B) for detecting superoxide dismutase by the polymer modified electrode of example 1 of the present invention.
The specific implementation mode is as follows:
example 1:
the polymer modified electrode for detecting superoxide dismutase with high sensitivity is prepared by the following steps in sequence:
a. soaking the treated bare gold electrode in 1mM cysteine prepared by 0.1M PBS for 24 hours, then taking out the electrode, fully washing the electrode with ultrapure water, and removing the cysteine molecules physically adsorbed, thus obtaining the Au/Cys electrode;
b. placing Au/Cys electrode as working electrode, saturated calomel electrode as reference electrode, platinum wire as counter electrode in a system containing 5mM HAuCl4In the solution, under the constant potential of-0.9V, electrodepositing for 400s to prepare an Au/cys/Nano Au electrode;
c. modifying a clean gold electrode by utilizing a mercapto-terminated bromine-containing compound (initiator) to obtain a bromine-containing compound modified gold electrode; then putting a mixed solution containing 0.1 moL/L acrylamide (functional monomer), 4mg/mL superoxide dismutase and 0.1 moL/LN, N-methylene bisacrylamide (cross-linking agent) into an electrolytic cell, inserting a bromine-containing compound modified gold electrode into the mixed solution at room temperature, simultaneously inserting a three-electrode system which takes an Au/cys/Nano Au electrode as a working electrode, a platinum wire as a counter electrode and a saturated calomel electrode as a reference electrode, and applying a constant potential for 1.5h under the potential of 0.130V;
d. and taking out the bromine-containing compound modified gold electrode deposited with the polymer, cleaning the electrode by using ultrapure water, soaking the electrode in a 30% hydrogen peroxide solution for 2 hours, and then washing the electrode by using the ultrapure water, and naturally airing the electrode to obtain the electrode.
FIG. 1 shows the present inventionWhile the electrode of example 1 was prepared with a different modified electrode containing 5mM [ Fe CN ]6]3-/4-Cyclic voltammograms in + 0.1M KCl (pH 7.0 PBS) solution.
In FIG. 1, curve 1 is the CV curve of bare gold electrode in solution, which shows a pair of reversible [ Fe (CN) ]around 0.2V6]3-/4-Probe ion redox peak. Curve 2 is the CV curve of the gold electrode after modification with a bromine compound (initiator), and the peak current is lower than that of curve 1, which indicates that probe ions are prevented from reaching the electrode surface after the initiator is self-assembled on the surface of the gold electrode. The curve 3 shows that the peak current is significantly lower than that of the curve 2 after the acrylamide is polymerized, which indicates that after the acrylamide is polymerized, a thick polymer film which prevents the probe ions from reaching the electrode surface is formed on the electrode surface, so that the peak current is low. Curve 4 is the CV curve after elution of the template molecule (superoxide dismutase), the peak current is obviously higher than curve 3, and the peak current is increased because imprinted cavities appear on the surface of the electrode after removal of superoxide dismutase, which is beneficial for the probe ions to reach the surface of the electrode.
FIG. 2 is an X-ray photoelectron spectroscopy analysis chart of the polymer modified electrode of example 1 of the present invention. It can be seen from fig. 2 that the polymer modified electrode was successfully prepared.
To investigate the selectivity of the polymer modified electrode, Lysozyme (LYZ) (MW 14.4 kDa), carbonic anhydrase (CA, MW 29 kDa), pepsin (MW 35 kDa), hemoglobin (MW 65 kDa) were used as interferents in the experiment. The same concentration (1 mg. L.) was measured using Differential Pulse Voltammetry (DPV) using the polymer-modified electrode of example 1 of the present invention and a non-imprinted electrode (prepared in the same manner as in example 1 except that no superoxide dismutase was added during preparation)-1) The results are shown in FIG. 3, which shows the difference in response signals between the different proteins. From fig. 3, it can be seen that the response signal Δ I of superoxide dismutase detected by the polymer modified electrode of the present invention is 39.86 μ a, which is 5.84, 12.56,14.80 and 9.20 times that of CA, Hb, Lyz and PG, respectively. The results show that the selectivity for the target protein superoxide dismutase is better. The selectivity of the electrode can also be determined by the imprinting factor: (β) Evaluation was performed. It is composed ofThe calculation equation isβ=ΔI(MIP)/ΔI(NIP)Wherein Δ I(NIP)The response signal of non-imprinted electrode to protein, and Δ I(MIP)Is the response signal of the polymer modified electrode to the protein. As shown in FIG. 3, SOD, CA, Hb, Lyz and PG were calculated by the equationsβThe values are 6.087, 1.846, 2.160, 1.940 and 2.302, respectively. Of SODβThe maximum value shows that the SOD detection capability of the polymer modified electrode in the embodiment 1 is far higher than that of a non-imprinted electrode, and the polymer modified electrode in the embodiment 1 only has good selectivity on target protein.
FIG. 4 is a differential pulse voltammetry curve (A) and a working curve (B) for detecting superoxide dismutase by the polymer modified electrode of example 1 of the present invention.
In FIG. 4A, the concentrations of superoxide dismutase corresponding to curves 1-10 are 0 and 10, respectively-7，10－6，10－5， 10－4，10－3，10－2，10－11, 10, 100 mg/L. As can be seen from fig. 4A, the peak current of the differential pulse voltammogram decreased as the SOD concentration increased. This is because the polymer modified electrode of example 1 of the present invention, after binding superoxide dismutase, has imprinted holes occupied by SOD, which prevents probe ions from reaching the surface of the electrode, thereby reducing the peak current value of the differential pulse voltammetry curve of the electrode, and the higher the SOD concentration is, the more the imprinted holes are occupied, and the more the peak current value is reduced. FIG. 4B is a graph of peak current value decay (signal response,. DELTA.I) versus the logarithm of SOD concentration. As can be seen from FIG. 4B, the linear range of the concentration of superoxide dismutase detected by the polymer modified electrode after binding superoxide dismutase in example 1 of the present invention is 1.0X 10－7100 mg/L. Linear regression equation of ΔI（μA）=0.6563logC(mg/L) +35.386, correlation coefficient 0.9944. From the standard curve, the limit of detection is (LOD, S/N = 3) 6.7802 × 10－8mg/L。
Example 2:
the invention relates to a polymer modified electrode for detecting superoxide dismutase with high sensitivity, which is prepared by the following steps in sequence:
a. soaking the treated bare gold electrode in 1mM cysteine prepared by 0.1M PBS for 24 hours, then taking out the electrode, fully washing the electrode with ultrapure water, and removing the cysteine molecules physically adsorbed, thus obtaining the Au/Cys electrode;
b. placing Au/Cys electrode as working electrode, saturated calomel electrode as reference electrode, platinum wire as counter electrode in a system containing 5mM HAuCl4In the solution, under the constant potential of-0.9V, electrodepositing for 400s to prepare an Au/cys/Nano Au electrode;
c. modifying a clean gold electrode by utilizing a mercapto-terminated bromine-containing compound (initiator) to obtain a bromine-containing compound modified gold electrode; then putting a mixed solution containing 0.2 moL/L acrylamide (functional monomer), 8mg/mL superoxide dismutase and 0.2 moL/LN, N-methylene bisacrylamide (cross-linking agent) into an electrolytic cell, inserting a bromine-containing compound modified gold electrode into the mixed solution at room temperature, simultaneously inserting a three-electrode system which takes an Au/cys/Nano Au electrode as a working electrode, a platinum wire as a counter electrode and a saturated calomel electrode as a reference electrode, and applying a constant potential for 1.5h under the potential of 0.130V;
d. and taking out the bromine-containing compound modified gold electrode deposited with the polymer, cleaning the electrode by using ultrapure water, soaking the electrode in a 30% hydrogen peroxide solution for 2 hours, and then washing the electrode by using the ultrapure water, and naturally airing the electrode to obtain the electrode.
Example 3:
the polymer modified electrode for detecting superoxide dismutase with high sensitivity is prepared by the following steps in sequence:
a. soaking the treated bare gold electrode in 1mM cysteine prepared by 0.1M PBS for 24 hours, then taking out the electrode, fully washing the electrode with ultrapure water, and removing the cysteine molecules physically adsorbed, thus obtaining the Au/Cys electrode;
b. placing Au/Cys electrode as working electrode, saturated calomel electrode as reference electrode, platinum wire as counter electrode in a system containing 5mM HAuCl4In the solution, under the constant potential of-0.9V, electrodepositing for 400s to prepare an Au/cys/Nano Au electrode;
c. modifying a clean gold electrode by utilizing a mercapto-terminated bromine-containing compound (initiator) to obtain a bromine-containing compound modified gold electrode; then putting a mixed solution containing 0.4 moL/L acrylamide (functional monomer), 16mg/mL superoxide dismutase and 0.4 moL/LN, N-methylene bisacrylamide (cross-linking agent) into an electrolytic cell, inserting a bromine-containing compound modified gold electrode into the mixed solution at room temperature, simultaneously inserting a three-electrode system which takes an Au/cys/Nano Au electrode as a working electrode, a platinum wire as a counter electrode and a saturated calomel electrode as a reference electrode, and applying a constant potential for 1.5h under the potential of 0.130V;
d. and taking out the bromine-containing compound modified gold electrode deposited with the polymer, cleaning the electrode by using ultrapure water, soaking the electrode in a 30% hydrogen peroxide solution for 2 hours, and then washing the electrode by using the ultrapure water, and naturally airing the electrode to obtain the electrode.
Example 4:
the polymer modified electrode for detecting superoxide dismutase with high sensitivity is prepared by the following steps in sequence:
a. soaking the treated bare gold electrode in 1mM cysteine prepared by 0.1M PBS for 24 hours, then taking out the electrode, fully washing the electrode with ultrapure water, and removing the cysteine molecules physically adsorbed, thus obtaining the Au/Cys electrode;
b. placing Au/Cys electrode as working electrode, saturated calomel electrode as reference electrode, platinum wire as counter electrode in a system containing 5mM HAuCl4In the solution, under the constant potential of-0.9V, electrodepositing for 400s to prepare an Au/cys/Nano Au electrode;
c. modifying a clean gold electrode by utilizing a mercapto-terminated bromine-containing compound (initiator) to obtain a bromine-containing compound modified gold electrode; then putting a mixed solution containing 0.05moL/L acrylamide (functional monomer), 2mg/mL superoxide dismutase and 0.05moL/LN, N-methylene bisacrylamide (cross-linking agent) into an electrolytic cell, inserting a bromine-containing compound modified gold electrode into the mixed solution at room temperature, simultaneously inserting a three-electrode system which takes an Au/cys/Nano Au electrode as a working electrode, a platinum wire as a counter electrode and a saturated calomel electrode as a reference electrode, and applying a constant potential for 1.5h under the potential of 0.130V;
d. and taking out the bromine-containing compound modified gold electrode deposited with the polymer, cleaning the electrode by using ultrapure water, soaking the electrode in a 30% hydrogen peroxide solution for 2 hours, and then washing the electrode by using the ultrapure water, and naturally airing the electrode to obtain the electrode.
Example 5:
the polymer modified electrode for detecting superoxide dismutase with high sensitivity is prepared by the following steps in sequence:
a. soaking the treated bare gold electrode in 1mM cysteine prepared by 0.1M PBS for 24 hours, then taking out the electrode, fully washing the electrode with ultrapure water, and removing the cysteine molecules physically adsorbed, thus obtaining the Au/Cys electrode;
b. placing Au/Cys electrode as working electrode, saturated calomel electrode as reference electrode, platinum wire as counter electrode in a system containing 5mM HAuCl4In the solution, under the constant potential of-0.9V, electrodepositing for 400s to prepare an Au/cys/Nano Au electrode;
c. modifying a clean gold electrode by utilizing a mercapto-terminated bromine-containing compound (initiator) to obtain a bromine-containing compound modified gold electrode; then putting a mixed solution containing 0.025moL/L acrylamide (functional monomer), 1mg/mL superoxide dismutase and 0.025moL/L N, N-methylene bisacrylamide (cross-linking agent) into an electrolytic cell, inserting a bromine-containing compound modified gold electrode into the mixed solution at room temperature, simultaneously inserting a three-electrode system which takes an Au/cys/Nano Au electrode as a working electrode, a platinum wire as a counter electrode and a saturated calomel electrode as a reference electrode, and applying a constant potential for 1.5h at a potential of 0.130V;
d. and taking out the bromine-containing compound modified gold electrode deposited with the polymer, cleaning the electrode by using ultrapure water, soaking the electrode in a 30% hydrogen peroxide solution for 2 hours, and then washing the electrode by using the ultrapure water, and naturally airing the electrode to obtain the electrode.
The experimental results of examples 2 to 5 were the same as those of example 1.
Claims (1)
1. A polymer modified electrode for detecting superoxide dismutase with high sensitivity is prepared by the following steps in sequence:
a. soaking the treated bare gold electrode in 1mM cysteine prepared by 0.1M PBS for 24 hours, then taking out the electrode, fully washing the electrode with ultrapure water, and removing the cysteine molecules physically adsorbed, thus obtaining the Au/Cys electrode;
b. forming a three-electrode system by using an Au/Cys electrode as a working electrode, a saturated calomel electrode as a reference electrode and a platinum wire as a counter electrode, and placing the three-electrode system in a container containing 5mM HAuCl4In the solution, under the constant potential of-0.9V, electro-deposition is carried out for 400s, and an Au/Cys/Nano Au electrode is prepared;
c. modifying a clean gold electrode by using a mercapto-terminated bromine-containing compound to obtain a bromine-containing compound modified gold electrode; then putting a mixed solution containing 0.025-0.5 moL/L acrylamide, 1-20 mg/mL superoxide dismutase and 0.025-0.5 moL/L N, N-methylene bisacrylamide into an electrolytic cell, inserting a bromine-containing compound modified gold electrode into the mixed solution at room temperature, simultaneously inserting a three-electrode system with an Au/Cys/Nano Au electrode as a working electrode, a platinum wire as a counter electrode and a saturated calomel electrode as a reference electrode, and applying a constant potential for 1.5h at a potential of 0.130V;
d. and taking out the bromine-containing compound modified gold electrode deposited with the polymer, cleaning the electrode by using ultrapure water, soaking the electrode in a 30% hydrogen peroxide solution for 2 hours, and then washing the electrode by using the ultrapure water, and naturally airing the electrode to obtain the electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810446357.0A CN108709922B (en) | 2018-05-11 | 2018-05-11 | Polymer modified electrode for detecting superoxide dismutase with high sensitivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810446357.0A CN108709922B (en) | 2018-05-11 | 2018-05-11 | Polymer modified electrode for detecting superoxide dismutase with high sensitivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108709922A CN108709922A (en) | 2018-10-26 |
| CN108709922B true CN108709922B (en) | 2020-04-21 |
Family
ID=63867973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810446357.0A Expired - Fee Related CN108709922B (en) | 2018-05-11 | 2018-05-11 | Polymer modified electrode for detecting superoxide dismutase with high sensitivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108709922B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109490389B (en) * | 2018-11-28 | 2020-10-13 | 辽宁师范大学 | Preparation method of imprinted polymer modified electrode for detecting myoglobin with high sensitivity |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104142361A (en) * | 2014-07-31 | 2014-11-12 | 中南民族大学 | Protein molecular imprinting polyion liquid membrane electrochemical transducer |
| CN105859988A (en) * | 2016-05-04 | 2016-08-17 | 嘉兴学院 | Molecularly imprinted polymer for detecting ofloxacin and preparing method and application thereof |
| CN108007992A (en) * | 2017-12-04 | 2018-05-08 | 辽宁师范大学 | Detect the preparation method of the poly ion liquid@3D nanogold cluster modified electrodes of hemoglobin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018044806A1 (en) * | 2016-08-31 | 2018-03-08 | Empire Technology Development Llc | Food items and sensor devices |
| WO2018067521A1 (en) * | 2016-10-03 | 2018-04-12 | Eccrine Systems, Inc. | Biosensors with ph-independent redox moieties |
-
2018
- 2018-05-11 CN CN201810446357.0A patent/CN108709922B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104142361A (en) * | 2014-07-31 | 2014-11-12 | 中南民族大学 | Protein molecular imprinting polyion liquid membrane electrochemical transducer |
| CN105859988A (en) * | 2016-05-04 | 2016-08-17 | 嘉兴学院 | Molecularly imprinted polymer for detecting ofloxacin and preparing method and application thereof |
| CN108007992A (en) * | 2017-12-04 | 2018-05-08 | 辽宁师范大学 | Detect the preparation method of the poly ion liquid@3D nanogold cluster modified electrodes of hemoglobin |
Non-Patent Citations (1)
| Title |
|---|
| 超氧化物歧化酶在纳米金/L-半胱氨酸修饰金电极上的电化学行为;何晓英 等;《化学研究与应用》;20120831;第24卷(第8期);第1192-1193页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108709922A (en) | 2018-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Preparation of hemoglobin (Hb) imprinted polymer by Hb catalyzed eATRP and its application in biosensor | |
| JP6022480B2 (en) | Aqueous amino acid sensor with molecularly imprinted conductive polymer film | |
| Bagheri et al. | Fabrication of a novel electrochemical sensing platform based on a core–shell nano-structured/molecularly imprinted polymer for sensitive and selective determination of ephedrine | |
| Karimian et al. | Cefixime detection by a novel electrochemical sensor based on glassy carbon electrode modified with surface imprinted polymer/multiwall carbon nanotubes | |
| Lin et al. | Electrochemical analysis of copper ion using a Gly–Gly–His tripeptide modified poly (3-thiopheneacetic acid) biosensor | |
| KR101523428B1 (en) | GO-MIP composite, biosensor using the GO-MIP composite and method of fabrication of the same | |
| Raoof et al. | Fabrication of layer-by-layer deposited films containing carbon nanotubes and poly (malachite green) as a sensor for simultaneous determination of ascorbic acid, epinephrine, and uric acid | |
| CN109085225B (en) | Preparation method of western blot sensor with magnetic electrode modified by one-step deposition method | |
| CN108387632B (en) | Eu (Eu)3+Selective quantitative detection method | |
| Yan et al. | Selective recognition of ciprofloxacin hydrochloride based on molecular imprinted sensor via electrochemical copolymerization of pyrrole and o-phenylenediamine | |
| Sun et al. | Preparation of protein imprinted polymers via protein-catalyzed eATRP on 3D gold nanodendrites and their application in biosensors | |
| Sun et al. | Fabrication of a thermal responsive hemoglobin (Hb) biosensor via Hb-catalyzed eATRP on the surface of ZnO nanoflowers | |
| Gholivand et al. | Highly sensitive and selective determination methyldopa in the presence of ascorbic acid using OPPy/TY/Au modified electrode | |
| Thimoonnee et al. | Fast, sensitive and selective simultaneous determination of paraquat and glyphosate herbicides in water samples using a compact electrochemical sensor | |
| Mardani et al. | Preparation of molecularly imprinted magnetic graphene oxide-gold nanocomposite and its application to the design of electrochemical sensor for determination of epinephrine | |
| Zhang et al. | Covalent modification of glassy carbon electrodes with β-alanine for voltammetric separation of dopamine and ascorbic acid | |
| CN108709922B (en) | Polymer modified electrode for detecting superoxide dismutase with high sensitivity | |
| Zhang | Covalent modification of glassy carbon electrode with cysteine for the determination of dopamine in the presence of ascorbic acid | |
| Sun et al. | Preparation of hemoglobin imprinted polymers based on graphene and protein removal assisted by electric potential | |
| CN105866221A (en) | Catalytic reduction hemoglobin electrochemical sensor | |
| Trojanowicz et al. | A potentiometric polypyrrole‐based glucose biosensor | |
| Rastogi et al. | Ion exchange voltammetry at permselective copolymer modified electrode and its application for the determination of catecholamines | |
| Dias Filho et al. | Preconcentration and determination of mercury (II) at a chemically modified electrode containing 3-(2-thioimidazolyl) propyl silica gel | |
| Ramanaviciene et al. | Molecularly imprinted polypyrrole for sensor design | |
| WO2019175565A1 (en) | Electrochemical sensor |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200421 Termination date: 20210511 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |