CN110632146A - Enzyme-free glucose electrochemical sensor and detection method thereof - Google Patents
Enzyme-free glucose electrochemical sensor and detection method thereof Download PDFInfo
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Abstract
The invention discloses an enzyme-free glucose electrochemical sensor and a detection method thereof, wherein the sensor comprises a three-electrode system consisting of a reference electrode, a counter electrode and a working electrode, and is characterized in that the working electrode comprises a metal organic framework with electrochemical catalytic activity and a metal nanoparticle composite material coated with the metal organic framework; the metal organic framework and the metal nano particles are matched to generate a hydrogen overflow effect. The invention discloses a detection method of an enzyme-free glucose electrochemical sensor, which comprises the following steps: (1) electrochemical pretreatment of working electrode: applying a high negative potential; (2) electrochemical oxidation of glucose: applying a potential required for glucose oxidation; (3) electrochemical cleaning of the working electrode: a positive potential is applied. The enzyme-free glucose electrochemical sensor and the detection method can eliminate a large amount of bubbles generated near the working electrode in the detection process, and improve the accuracy and the sensitivity of the detection.
Description
Technical Field
The invention relates to an electrochemical sensor and a detection method thereof, in particular to an enzyme-free glucose electrochemical sensor and a detection method thereof.
Background
Glucose is a monosaccharide which is the most widely and important in nature, and has an important position in the field of biology. The development of highly sensitive glucose detection technology is of great significance for the research of biological metabolism and the diagnosis of diseases. The electrochemical detection method has the characteristics of high sensitivity, simple operation, easy miniaturization, real-time online and the like, and is receiving more and more attention, and the glucose detection based on the electrochemical technology also becomes a hot point for research of researchers. Traditional electrochemical methods for detecting glucose include both enzymatic and non-enzymatic detection. The enzyme detection is a main method for detecting glucose in vitro, and glucose oxidase or dehydrogenase with high specificity is added in the preparation process of an electrode to realize quantitative detection of glucose in a complex sample. However, the catalytic activity of the added enzyme is affected by the ambient temperature, humidity and pH, and although many methods have been reported to improve the stability of the enzyme, these operations are tedious and time-consuming on the one hand and reduce the reproducibility of the experiment on the other hand.
The enzyme-free detection is that the electron transfer directly occurs between the glucose and the catalytic electrode in the detection process, so that the enzyme-free detection is free from the dependence on the enzyme, and has higher sensitivity and long-term stability compared with the enzyme detection. However, the enzyme-free electrode in the prior art can obtain high sensitivity only under the strong alkaline condition, and under the neutral and acidic conditions, the electrode is easy to adsorb oxidation products and environmental ions to cause poisoning, thereby greatly limiting the practical application of the electrode.
The applicant discloses a patent with publication number CN108802141A, and proposes a method for detecting glucose under neutral and acidic conditions, in which a high negative potential is applied during electrochemical pretreatment of a working electrode, so that a hydrogen evolution reaction occurs at the working electrode, and the hydrogen evolution reaction continuously consumes hydrogen ions near the electrode to raise the pH near the electrode, and finally, the alkalinity required for sensitive detection of glucose is achieved. However, the applicant has further found that as hydrogen gas is evolved, a large number of bubbles are generated near the working electrode, affecting the accuracy and sensitivity of the detection.
Disclosure of Invention
The purpose of the invention is as follows: one of the objects of the present invention is to provide an enzyme-free glucose electrochemical sensor that eliminates a large number of air bubbles generated near the working electrode, and improves the accuracy and sensitivity of detection.
Another object of the present invention is to provide a method for detecting an enzyme-free glucose electrochemical sensor.
The technical scheme is as follows: the enzyme-free glucose electrochemical sensor comprises a three-electrode system consisting of a reference electrode, a counter electrode and a working electrode, wherein the working electrode comprises a metal organic framework with electrochemical catalytic activity and a metal nanoparticle composite material wrapped by the metal organic framework; the metal nano-particles and the metal organic framework can cooperate to generate a hydrogen overflow effect.
Preferably, the metal organic framework comprises at least one of the ZIF series, MIL series, MOF series.
Preferably, the metal organic framework comprises at least one of ZIF-8, ZIF-67, MIL-100, MIL-101, MOF-4, MOF-74.
Preferably, the metal nanoparticles comprise at least one of palladium, platinum, ruthenium, rhodium, nickel.
Preferably, the surface of the working electrode is coated with a permselective membrane.
The invention provides a method for detecting glucose by the enzyme-free glucose electrochemical sensor, which comprises the following steps:
(1) electrochemical pretreatment of working electrode: applying a high negative potential;
(2) electrochemical oxidation of glucose: applying a potential required for glucose oxidation;
(3) electrochemical cleaning of the working electrode: a positive potential is applied.
The electrochemical pretreatment electrode is activated by applying a high negative potential for a period of time to enable the working electrode to generate hydrogen evolution reaction, and the hydrogen evolution reaction continuously consumes hydrogen ions near the electrode to enable the pH near the electrode to rise and finally reach the alkalinity required by sensitive detection of glucose; the electrochemical oxidation of glucose is to oxidize glucose to obtain an electrochemical signal by applying a conventional potential for a period of time, wherein the conventional potential is the potential required by glucose oxidation on the surface of the working electrode, and the magnitude of the conventional potential is related to the material of the working electrode; the electrochemical cleaning of the electrode is to clean the electrode by applying a positive potential for a period of time after the detection is finished so as to remove oxidation products on the surface of the electrode and not influence the next detection.
Preferably, when the working electrode is a gold electrode, a high negative potential of-1.6 to-3.0V is applied for 10 to 30s, a potential required for glucose oxidation of 0.05 to 0.4V is applied for 3 to 10s, a positive potential of 0.7 to 1.0V is applied for 1 to 10 s.
Preferably, the working electrode is a platinum electrode, when the metal nanoparticles are platinum, the high negative potential of-1.4V to-3V is applied for 8-30 s, the potential required by glucose oxidation is applied for 0.05V to 0.4V for 3-10 s, and the positive potential is applied for 0.7-1.0V for 1-10 s.
Preferably, the working electrode is a platinum electrode, when the metal organic framework is Co-MOF or Co-ZIF, the time for applying high negative potential of-1.4V to-3V is 8-30 s, the time for applying potential required by glucose oxidation is 0.4V-0.7V and is 3-10 s, and the time for applying positive potential is 0.7-1.0V and is 1-10 s.
Wherein Co-MOF represents MOF series materials in which the metal source is cobalt, and Co-ZIF represents ZIF series materials in which the metal source is cobalt.
The working principle is as follows: firstly, the detection method provided by the invention applies high negative potential pretreatment to generate alkaline conditions, the working electrode is a metal organic framework with electrochemical catalytic activity and wraps a metal nanoparticle composite material, and the metal nanoparticles and a metal organic framework compound can generate a hydrogen overflow effect. On one hand, the composite material has electrocatalytic activity and can sensitively detect glucose as a catalyst, and on the other hand, the composite material has a hydrogen overflow effect, so that bubbles generated in the detection process can be eliminated, and a stable detection signal is provided.
Has the advantages that: compared with the prior art, the invention can obtain the following beneficial effects: 1. the invention utilizes the metal organic framework to wrap the metal nano particle composite material as the electrocatalyst, thereby not only obtaining high sensitivity, but also effectively avoiding the interference of bubbles generated in the pretreatment process to signals. 2. The invention can remove the influence of the pH value of the sample on the detection result, and can carry out the enzyme-free glucose detection in neutral and acidic samples, which is originally required to be carried out under the alkaline condition.
Drawings
FIG. 1 is a schematic diagram of a screen printed electrode structure according to the present invention;
FIG. 2 is a schematic view of a sweat guide belt for detecting sweat according to the present invention;
fig. 3 is a diagram of a smart phone and app detection interface connected to a sweat detection sweatband according to the present invention;
FIG. 4 is a graph of the linear relationship between glucose concentration and detection current of the present invention.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
Example 1
2.912g of Co (NO)3)2·6H2O and 3.284g of 2-methylimidazole were dissolved in 160mL of a methanol solution, respectively, and then the 2-methylimidazole solution was slowly added to the methanol solution of cobalt nitrate and stirred for 24 hours. And (4) centrifuging, washing with methanol, repeating for 3 times, and drying in a constant-temperature drying oven at 70 ℃ to obtain ZIF-67. Dissolving 100mg of palladium acetate in 10mL of acetone, then adding 100mg of ZIF-67 into the palladium acetate solution, stirring for 1 hour under 56 ℃ oil bath condition, then slowly adding 1mL of formic acid and stirring, centrifuging, washing with acetone, repeating for 3 times, and then placing in a 70 ℃ constant temperature drying oven for drying to obtain Pd @ ZIF-67. Ultrasonically dispersing 10mgPd @ ZIF-67 in 200 mu L of ethanol, transferring 3 mu L of dispersion liquid by using a liquid transfer machine, dripping the dispersion liquid on the surface of a glassy carbon electrode with the section diameter of 2mm, naturally drying to obtain a working electrode, and forming a three-electrode system by using silver-silver chloride as a reference electrode and platinum wires as a counter electrode.
The glucose in the buffer was detected in 0.1M phosphate buffer pH 5.0 using an electrochemical workstation. The multi-potential detection is selected in the technical menu bar in the setting, and the potentials which need to be applied in sequence are set in the parameter setting. In this test, the three potential settings are: the negative potential is-2.0V for 20s, the potential required by glucose oxidation is +0.65V for 5s, and the potential required by glucose oxidation is +1.0V for 2s, the detection is a cyclic process, the glucose concentration is changed in the detection process to obtain the relationship between the glucose oxidation current and the glucose concentration, and the detection current and the glucose concentration are in a linear relationship within the range of 5-1200 mu M.
Example 2
2.007g of Cr (NO)3)3 9H2O, 5mM 48 wt% HF, 5mM p-98% phthalic acid were mixed with 24mL deionized water and heated at 220 ℃ for 8 hours. Cooling to room temperature, filtering, washing with deionized water and ethanol, soaking the obtained solid in 80 deg.C ethanol for 24 hr, and vacuum drying at 150 deg.C to obtain MIL-101. Mixing 200mg/L H2PtCl6With PVA at a 10: mixing at a molar ratio of 1, stirring in an ice-water bath for 1 hour, and adding 0.01M NaHB4，NaHBH4The molar ratio to metal is 5: 1, stirring, namely adding MIL-101 quickly, stirring for 4 hours at 0 ℃, washing with deionized water, and performing vacuum drying at 100 ℃ to obtain Pt @ MIL-101, ultrasonically dispersing 2mg of MIL-101@ Pt in 200 mu L of ethanol, transferring 3 mu L of dispersed liquid drop by using a liquid transfer machine, coating the dispersed liquid drop on the surface of a glassy carbon electrode with the cross section diameter of 2mm, and performing natural drying to obtain a working electrode, wherein silver-silver chloride is used as a reference electrode, and a platinum wire is used as a counter electrode to form a three-electrode system.
The glucose in the buffer was detected in 0.1M phosphate buffer pH 5.0 using an electrochemical workstation. The multi-potential detection is selected in the technical menu bar in the setting, and the potentials which need to be applied in sequence are set in the parameter setting. In this test, the three potential settings are: applying-2.0V potential for 20s, +0.2V potential for 5s, +1.0V potential for 2s, and detecting as a cyclic process, wherein the glucose concentration is changed in the detection process to obtain the relationship between the glucose oxidation current and the glucose concentration, and the detection current and the glucose concentration are in a linear relationship within the range of 30-900 mu M.
Example 3
0.0608g Zn (NO)3)2、0.0255g H2BDC and 16mL DMF were mixed in a 20mL Teflon container with stirring until clear, N after heating at 100 ℃ for 5 hours2Cooling under the conditions to obtain square crystals, and adding 15mL of DMF and 15mL of H at the temperature of 15 DEG C2Cl2The crystals were washed and dried at 100 ℃ for 12 hours to give MOF-5. In N2Condition 100mg MOF-5 was added to 1mL H2PtCl6Wherein Pt is 1wt% and ultrasonic dispersing at room temperature for 5min, and drying at 60 deg.C for 3 hr. Placing the obtained solid in a stainless steel reactor, and placing the solid in a stainless steel reactor at 220 ℃ and 50mL/min of H2And reacting for 2 hours in a flowing environment to obtain Pt @ MOF-5. Ultrasonically dispersing 2mgPt @ MOF-5 in 200 muL DMF, transferring 3 muL of the dispersion liquid by using a liquid transfer machine, dripping the dispersion liquid on the surface of a glassy carbon electrode with the section diameter of 2mm, naturally drying to obtain a working electrode, and forming a three-electrode system by using silver/silver chloride as a reference electrode and a platinum wire as a counter electrode.
The glucose in the buffer was detected in 0.1M phosphate buffer pH 5.0 using an electrochemical workstation. The multi-potential detection is selected in the technical menu bar in the setting, and the potentials which need to be applied in sequence are set in the parameter setting. In this test, the three potential settings are: applying-2.0V potential for 20s, +0.2V potential for 5s, +1.0V potential for 2s, and detecting in a cyclic process, wherein the glucose concentration is changed in the detection process to obtain the relation between the glucose oxidation current and the glucose concentration, and the detection current and the glucose concentration are in a linear relation in the range of 30-800 mu M.
Example 4
4.94mM of Zn (NO)3)2·6H2O was added to 100mL of methanol to give solution I, 39.62mM of 2-methylimidazole was added to 100mL of methanol to give solution II, and the solution I was poured into the solution II quickly and stirred at room temperature for 1 hour. The precipitate was centrifuged and washed 3 times with methanol, and then dried at 60C for 12h to give ZIF-8 as a white powder. Take 49.53mg of H2PtCl6·6H2O was dissolved in 20mL of deionized water, followed by addition of 22.58mg of polyvinyl alcohol and stirring at room temperature for 1 h. Activated 200mg ZIF-8 was added to the above solution and stirred for 2 h. Under the condition of ice-water bath, 4.8mL of 30mg of sodium borohydride is added dropwise, and stirring is continued for 5 hours. The precipitate was centrifuged and washed 3 times with 20mL deionized water, followed by drying at 60C for 12h to give Pt @ ZIF-8. The Pt @ ZIF-8 prepared according to the above reagent proportion has a Pt content of 4.57%. Ultrasonically dispersing 10mg of Pt @ ZIF-8 in 200 mu L of ethanol, transferring 3 mu L of the dispersion liquid by using a liquid transfer machine, dripping the dispersion liquid on the surface of a glassy carbon electrode with the section diameter of 2mm, naturally drying to obtain a working electrode, and forming a three-electrode system by using silver-silver chloride as a reference electrode and a platinum wire as a counter electrode.
The glucose in the buffer was detected in 0.1M phosphate buffer pH 5.0 using an electrochemical workstation. The multi-potential detection is selected in the technical menu bar in the setting, and the potentials which need to be applied in sequence are set in the parameter setting. In this test, the three potential settings are: applying-2.0V potential 20s, +0.2V potential 5s, +1.0V potential 2s, detecting is a cyclic process, changing the glucose concentration in the detecting process to obtain the relation between the glucose oxidation current and the glucose concentration, and the detecting current and the glucose concentration are in a linear relation in the range of 20 mu M-1400 mu M.
Example 5
12mM Fe (NO)3)·9H2O and 1mM1,3, 5-benzenetricarboxylic acid are added into 5mL of water, the mixture is placed in a stainless steel autoclave and is subjected to heat treatment for 12h at 180C, then the mixture is filtered, washed by water and methanol and dried for 12h at 60C, and MIL-100 is obtained. Adding 100mg MIL-100 into 2.1mg H2PtCl6Stirring the mixture in 5mL of methanol under a nitrogen condition for 30min, irradiating the mixture for 5h by a 300W xenon lamp, centrifuging the mixture, washing the mixture for 3 times by using methanol, and drying the mixture for 12h at 60 ℃ to obtain Pt @ MIL-100, wherein the Pt content is 1%. Ultrasonically dispersing 10mg of Pt @ MIL-100 in 200 mu L of ethanol, transferring 3 mu L of dispersed liquid by using a liquid transfer machine, dripping the dispersed liquid on the surface of a glassy carbon electrode with the section diameter of 2mm, naturally drying to obtain a working electrode, and forming a three-electrode system by using silver-silver chloride as a reference electrode and a platinum wire as a counter electrode.
The glucose in the buffer was detected in 0.1M phosphate buffer pH 5.0 using an electrochemical workstation. The multi-potential detection is selected in the technical menu bar in the setting, and the potentials which need to be applied in sequence are set in the parameter setting. In this test, the three potential settings are: applying-2.0V potential for 20s, +0.2V potential for 5s, +1.0V potential for 2s, and detecting in a cyclic process, wherein the glucose concentration is changed in the detection process to obtain the relation between the glucose oxidation current and the glucose concentration, and the detection current and the glucose concentration are in a linear relation in the range of 80-750 mu M.
Example 6
0.04mM of 2, 5-dihydroxybenzene-1, 4-dicarboxylic acid was reacted with 0.08mM of Zn (NO)3)2·6H2O in 2mL of N, N-dimethylformamide, followed by the addition of 0.4g PVP and 2.5mL of ethanolDispersing for 5 min. Sealing the solution in a 25mL polytetrafluoroethylene autoclave, heating at 120 ℃ for 24 hours, cooling, centrifuging, washing with DMF and ethanol, and drying at 60 ℃ to obtain the MOF-74. 20mg of PVP was dissolved in 45mL of ethanol, 6mM chloroplatinic acid was added dropwise, and after stirring at room temperature for 2min, the mixture was refluxed in a 100mL flask for 3 hours to obtain 0.6mM Pt nanoparticles. Dispersing 30mg of MOF-74 by using 10mL of ethanol, dropwise adding 24mL of the Pt nano particle solution, vigorously stirring for 12h, centrifuging, and washing by using ethanol to obtain Pt @ MOF-74. The Pt @ MOF-74 obtained had a Pt content of 8.5%. Ultrasonically dispersing 10mg of Pt @ MOF-74 into 200 mu L of ethanol, transferring 3 mu L of dispersed liquid by using a liquid transfer machine, dripping the dispersed liquid on the surface of a glassy carbon electrode with the section diameter of 2mm, naturally drying to obtain a working electrode, and forming a three-electrode system by using silver-silver chloride as a reference electrode and a platinum wire as a counter electrode.
The glucose in the buffer was detected in 0.1M phosphate buffer pH 5.0 using an electrochemical workstation. The multi-potential detection is selected in the technical menu bar in the setting, and the potentials which need to be applied in sequence are set in the parameter setting. In this test, the three potential settings are: applying-2.0V potential 20s, +0.2V potential 5s, +1.0V potential 2s, detecting is a cyclic process, changing the glucose concentration in the detecting process to obtain the relation between the glucose oxidation current and the concentration, and the detecting current and the glucose concentration are in a linear relation in the range of 50 mu M-2000 mu M.
Example 7
In contrast to example 1, the three potential settings were: the-1.6V potential was applied for 30s, the glucose oxidation potential was applied for 0.4V 10s, and the glucose oxidation potential was applied for 0.7V 10 s. The detection current and the glucose concentration are in a linear relation within the range of 80-800 mu M.
Example 8
In contrast to example 1, the three potential settings were: the-2.5V potential was applied for 8s, the glucose oxidation potential was applied for 0.7V 3s, and the glucose oxidation potential was applied for 1.0V 1 s. The detection current and the glucose concentration are in a linear relation within the range of 60-800 mu M.
Example 9
In contrast to example 2, the three potential settings were: the-3.0V potential was applied for 10s, the glucose oxidation potential was applied for 0.05V 10s, and 1V 1 s. The detection current and the glucose concentration are in a linear relationship within the range of 50-700 mu M.
Example 10
In contrast to example 2, the three potential settings were: the-1.6V potential was applied for 30s, the glucose oxidation potential was applied for 0.3V 3s, and the glucose oxidation potential was applied for 0.7V 10 s. The detection current and the glucose concentration are in a linear relation within the range of 200-800 mu M.
Example 11
In contrast to example 3, the three potential settings were: the-1.6V potential was applied for 30s, the glucose oxidation potential was applied for 0.3V 10s, and the glucose oxidation potential was applied for 0.7V 10 s. The detection current and the glucose concentration are in a linear relationship within the range of 200-1100 mu M.
Example 12
In contrast to example 3, the three potential settings were: the-3.0V potential was applied for 10s, the glucose oxidation potential was applied for 0.1V 2s, and the glucose oxidation potential was applied for 1.0V 2 s. The detection current and the glucose concentration are in a linear relationship within the range of 30-700 mu M.
Example 13
And (3) manufacturing an enzyme-free glucose electrochemical detection test strip, wherein fig. 1 is a screen printing electrode structure diagram of the enzyme-free glucose electrochemical detection. The conductive carbon paste was printed on the PET film 1 by a screen printing method as a counter electrode 5 and a conductive coating 2, the mixed conductive carbon paste containing Pd @ ZIF-67 prepared in example 1 was screen printed on the PET film as a working electrode 3, and the Ag/AgCl paste was coated on the PET film as a reference electrode 4. And (3) sticking a patterned double-sided adhesive layer 6 on the surface of the sample container 1 for limiting an electrochemical detection area, and covering a hydrophilic PET membrane 7 treated by Tween 20 on the double-sided adhesive layer for absorbing analysis liquid. In order to improve the detection selectivity, a liquid transfer machine is used for sucking 1 mu L of 0.5% perfluorosulfonic acid solution to be dripped on the surface of the gold electrode, after natural drying, a liquid transfer machine is used for sucking 2.5 mu L of 8% polychlorotrifluoroethylene oil to be dripped on the surface of the gold electrode, and natural drying is carried out.
The glucose electrochemical detection test strip without enzyme is used for manufacturing the sweat guide belt for sweat detection, and fig. 2 is a real object diagram of the sweat guide belt for sweat detection. The flexible circuit board 9 with the Bluetooth device and the test paper connector 10 are fixed inside the sweat guide belt 8, one end of the prepared enzyme-free glucose electrochemical detection test paper strip is inserted into the test paper connector 10, and the other end of the prepared enzyme-free glucose electrochemical detection test paper strip extends into the sweat guide belt groove to facilitate absorption of an analysis solution. The detected flexible circuit board performs digital-to-analog conversion through a DA chip, and applies voltage to an electrode system; the operational amplifier is used for signal conversion and amplification, the nrf 51822 Bluetooth chip is used as a core, the AD function is carried out for digital signal acquisition, and signal transmission is carried out between the Bluetooth antenna and an upper computer.
The glucose detection adopts a multi-step potential method, firstly, a potential of +1.0V is applied for 2s to remove adsorbates on the surface of an electrode, then a potential of-2.0V is applied for 20s to form an auxiliary electro-catalytic layer on the surface of a working electrode, and finally, the potential of +0.65V is used for oxidizing glucose to obtain an electrochemical signal. The control of the multi-step potential is realized by a circuit board fixed inside the bracelet.
As shown in fig. 3, the smart phone and app detection interface connected to the sweat detection sweat guiding band is operated according to the following steps:
(1) the sweat guide belt is worn on the wrist, the switch is turned on, and the indicator light is on at the moment to show that the bracelet works normally;
(2) opening a mobile phone app detection interface, clicking connection after logging in to perform Bluetooth connection with the bracelet;
(3) exercise or waiting for sweating;
(4) clicking a 'detection' key to measure;
(5) when the countdown is finished, reading app display data, namely the number of the perspiration sugar;
(6) clicking "detect again" can make a re-measurement;
(7) after using the completion, disconnection bluetooth closes the bracelet.
FIG. 4 shows the relationship between sweat glucose and current detected by the sweat conduction band for detecting sweat in this embodiment, and the current magnitude and glucose concentration are in a linear relationship in the range of 10 μ M-1000 μ M.
The enzyme-free glucose electrochemical sensor can detect glucose in sweat, and other solutions containing glucose, such as glucose concentration in blood, urine or saliva, and can be realized by Bluetooth, computer data transmission and other modes.
Claims (8)
1. The non-enzyme glucose electrochemical sensor comprises a three-electrode system consisting of a reference electrode, a counter electrode and a working electrode, and is characterized in that the working electrode comprises a metal organic framework with electrochemical catalytic activity and a metal nanoparticle composite material wrapped by the metal organic framework; the metal nano-particles and the metal organic framework can cooperate to generate a hydrogen overflow effect.
2. The enzyme-free glucose electrochemical sensor of claim 1, wherein the metal-organic framework comprises at least one of a ZIF series, an MIL series, and an MOF series.
3. The enzyme-free glucose electrochemical sensor of claim 2, wherein the metal-organic framework comprises at least one of ZIF-8, ZIF-67, MIL-100, MIL-101, MOF-4, MOF-74.
4. The enzyme-free glucose electrochemical sensor of claim 1, wherein the metal nanoparticles comprise at least one of palladium, platinum, ruthenium, rhodium, and nickel.
5. The enzyme-free glucose electrochemical sensor of claim 1 wherein the surface of the working electrode is coated with a selectively permeable membrane.
6. A method for the detection using the enzyme-free glucose electrochemical sensor of claim 1, comprising the steps of:
(1) electrochemical pretreatment of working electrode: applying a high negative potential;
(2) electrochemical oxidation of glucose: applying a potential required for glucose oxidation;
(3) electrochemical cleaning of the working electrode: a positive potential is applied.
7. The method for detecting glucose with an electrochemical sensor based on enzyme-free glucose as claimed in claim 6, wherein the working electrode is a platinum electrode, and when the metal nanoparticles are platinum, the high negative potential of-1.4V to-3V is applied for 8-30 s, the potential required for glucose oxidation is applied for 0.05V to 0.4V for 3-10 s, and the positive potential is applied for 0.7-1.0V for 1-10 s.
8. The method for detecting glucose by using an electrochemical sensor without enzyme according to claim 6, wherein the working electrode is a platinum electrode, and when the metal organic framework is Co-MOF or Co-ZIF, the high negative potential of-1.4V to-3V is applied for 8-30 s, the potential required for glucose oxidation is 0.4V to 0.7V for 3-10 s, and the positive potential is 0.7V to 1.0V for 1-10 s.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111122533A (en) * | 2020-04-01 | 2020-05-08 | 烟台职业学院 | ZIF nano enzyme and preparation method and application thereof |
| CN111537589A (en) * | 2020-05-13 | 2020-08-14 | 山东大学 | Method for detecting glucose based on cobalt-based metal organic framework enzyme-free glucose sensor |
| CN112903783A (en) * | 2021-01-25 | 2021-06-04 | 南京美德生物技术有限公司 | Sensor based on bipolar electrode structure and method for glucose enzyme-free detection |
| CN113899798A (en) * | 2021-09-29 | 2022-01-07 | 江苏集奥医工交叉科技有限公司 | Preparation method of enzyme-free glucose sensor with double metal organic framework |
| CN114652306A (en) * | 2022-03-17 | 2022-06-24 | 电子科技大学 | MOFs-based fingertip contact type noninvasive sweat glucose sensor and method |
| CN118641603A (en) * | 2024-08-09 | 2024-09-13 | 浪潮软件科技有限公司 | Human glucose sensor chip and preparation method and medium thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525125A (en) * | 2014-12-17 | 2015-04-22 | 江苏科技大学 | Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof |
| CN108802141A (en) * | 2018-05-07 | 2018-11-13 | 东南大学 | Electrochemical glucose sensor without enzyme and its detection method |
| CN109490385A (en) * | 2018-08-08 | 2019-03-19 | 上海市浦东医院 | Biosensor and preparation method thereof based on Au-ZIF-8/OMC mesoporous carbon |
| CN109507272A (en) * | 2018-11-16 | 2019-03-22 | 天津工业大学 | A kind of NiCoLDH@Au composite material based on ZIF-67 synthesis and its application in glucose sensor |
-
2019
- 2019-09-24 CN CN201910903398.2A patent/CN110632146A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525125A (en) * | 2014-12-17 | 2015-04-22 | 江苏科技大学 | Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof |
| CN108802141A (en) * | 2018-05-07 | 2018-11-13 | 东南大学 | Electrochemical glucose sensor without enzyme and its detection method |
| CN109490385A (en) * | 2018-08-08 | 2019-03-19 | 上海市浦东医院 | Biosensor and preparation method thereof based on Au-ZIF-8/OMC mesoporous carbon |
| CN109507272A (en) * | 2018-11-16 | 2019-03-22 | 天津工业大学 | A kind of NiCoLDH@Au composite material based on ZIF-67 synthesis and its application in glucose sensor |
Non-Patent Citations (2)
| Title |
|---|
| XIAOFEI ZHU 等: "Water Splitting-Assisted Electrocatalytic Oxidation of Glucose with a Metal−Organic Framework for Wearable Nonenzymatic Perspiration Sensing", 《ANALYTICAL CHEMISTRY》 * |
| 郑丽君等: "金属有机骨架用于气体存储、吸附分离的研究进展", 《化工进展》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111122533A (en) * | 2020-04-01 | 2020-05-08 | 烟台职业学院 | ZIF nano enzyme and preparation method and application thereof |
| CN111537589A (en) * | 2020-05-13 | 2020-08-14 | 山东大学 | Method for detecting glucose based on cobalt-based metal organic framework enzyme-free glucose sensor |
| CN111537589B (en) * | 2020-05-13 | 2021-09-21 | 山东大学 | Method for detecting glucose based on cobalt-based metal organic framework enzyme-free glucose sensor |
| CN112903783A (en) * | 2021-01-25 | 2021-06-04 | 南京美德生物技术有限公司 | Sensor based on bipolar electrode structure and method for glucose enzyme-free detection |
| CN113899798A (en) * | 2021-09-29 | 2022-01-07 | 江苏集奥医工交叉科技有限公司 | Preparation method of enzyme-free glucose sensor with double metal organic framework |
| CN113899798B (en) * | 2021-09-29 | 2024-04-05 | 江苏集奥医工交叉科技有限公司 | Preparation method of enzyme-free glucose sensor with bimetal organic framework |
| CN114652306A (en) * | 2022-03-17 | 2022-06-24 | 电子科技大学 | MOFs-based fingertip contact type noninvasive sweat glucose sensor and method |
| CN118641603A (en) * | 2024-08-09 | 2024-09-13 | 浪潮软件科技有限公司 | Human glucose sensor chip and preparation method and medium thereof |
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