CN114660147A - Based on Fe doped NiMoO4Non-enzymatic glucose electrochemical sensor and preparation method and application thereof - Google Patents

Based on Fe doped NiMoO4Non-enzymatic glucose electrochemical sensor and preparation method and application thereof Download PDF

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CN114660147A
CN114660147A CN202210320911.7A CN202210320911A CN114660147A CN 114660147 A CN114660147 A CN 114660147A CN 202210320911 A CN202210320911 A CN 202210320911A CN 114660147 A CN114660147 A CN 114660147A
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glucose
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enzymatic glucose
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母昭德
廖星星
白丽娟
钟沐月
周佳旭
张启帆
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Chongqing Medical University
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Abstract

The invention provides a Fe-based doped NiMoO4Non-enzymatic glucose electrochemical sensor. The invention adopts a simple one-pot heating method and adjusts Fe3+Source and Ni2+Content of source, for NiMoO4The material is functionally treated to improve NiMoO4The obtained catalyst shows excellent glucose oxidation performance due to the self limitation of the nano particles, and the prepared non-enzymatic glucose electrochemical sensor is used for detecting glucose, has the characteristics of simplicity and easiness in operation, high catalyst sensitivity, strong anti-interference capability and the like, provides a new opportunity for the development of the non-enzymatic glucose sensor, and has important significance.

Description

Based on Fe doped NiMoO4Non-enzymatic glucose electrochemical sensor and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochemical detection, in particular to a non-enzymatic glucose catalyst, a non-enzymatic glucose electrochemical sensor, a preparation method and a detection method thereof.
Background
Diabetes (Diabetes) is a metabolic disease characterized by hyperglycemia and insulin resistance, and is mainly of two types: type I is caused by insufficient insulin secretion from the islet cells, while type II is caused by insufficient utilization of the insulin produced by the body's pancreas. Currently, diabetes remains a worldwide health problem, one of the serious diseases that lead to death and disability. The blood sugar level in human blood is an important index for diabetes diagnosis, and the rise of the blood sugar level causes more serious life threat to the diabetic patients, such as heart, nerve, kidney, eye, brain and peripheral vascular diseases. Delaying the onset and progression of diabetes-related complications to minimize the risk of diabetes and thereby reduce diabetes-related mortality. In addition, a significant drop in blood glucose can lead to a fatal disease known as hypoglycemia, where persistent hypoglycemia can cause severe damage to the patient's kidneys and other vital organs. Therefore, timely and efficient monitoring of blood glucose is a primary task in preventing the above-mentioned life-threatening diseases.
At present, in the field of analytical detection, various methods and technologies for detecting glucose have been developed, including colorimetric methods, spectroscopic analyses, fluorescence analyses, electrochemical detection, chemiluminescence and transdermal methods, and among numerous detection methods, electrochemical detection of glucose has received extensive attention and research from domestic and foreign scholars due to its advantages of fast response speed, high sensitivity, low detection limit, low cost, simple operation, and the like.
Glucose electrochemical sensors are classified into enzymatic glucose electrochemical sensors and non-enzymatic glucose electrochemical sensors. The glucose sensor based on the enzyme is widely applied due to high sensitivity and good selectivity, but the glucose sensor also has the problems of high cost, low repeatability, complex and fussy enzyme immobilization process, reduced enzyme activity and the like, and limits the large-scale application of the glucose sensor. Compared with an enzyme sensor, a glucose sensor based on non-enzyme has been widely researched due to the advantages of high sensitivity, low cost, good selectivity, good stability and the like, and the working principle of the sensor is based on direct electrochemical oxidation-reduction of glucose on an electrode, and the surface of a bare electrode is modified by a nano material to provide a larger surface area, enhance sensing reaction and electron transfer, so that the non-enzyme sensing of the glucose is realized.
The concept of non-enzymatic glucose sensors was first proposed by Walther Loeb, and over the past few years, a number of nanomaterials were used to fabricate non-enzymatic glucose sensors, such as noble metals (Pd, Au, Ag, Ru, etc.), metal alloys (Pt-Ru, Pt-Ni, Pd-Mn, etc.), metal oxides (Co-Ru, Pt-Ni, Pd-Mn, etc.)3O4、CuO、Fe3O4Etc.), hydroxides (Cu (OH)2、Co(OH)2、Ni(OH)2Etc.). In addition, bimetallic oxides are a class of oxides with excellent sensor potential due to their electrocatalytic activity, environmental friendliness, biocompatibility and low cost. These oxides have higher catalytic activity than other compounds such as metals and metal oxides alone. However, the intrinsic electronic conductivity of spinel bimetallic oxides is still not optimal for efficient transport of electrons and for carrying out redox reactions, resulting in their low electrochemical sensitivity and stability.
Although electrochemical glucose detection has shown a number of advantages in recent years, these novel materials also have certain disadvantages in detecting glucose, such as selectivity of oxidation of an enzyme-free glucose sensor is not as good as that of an enzyme electrode sensor, and when a large amount of Ascorbic Acid (AA) and/or Uric Acid (UA) exists in a sample, there is a corresponding response current in detection using an electrode. And the cost of part of enzyme-free glucose sensors is higher, and the sensors are easy to generate chloride ion poisoning and the like, so that the application of the sensors is greatly limited. Therefore, the preparation of the enzyme-free glucose sensor which has low cost and high selectivity and can quickly and reliably detect glucose has important significance.
Disclosure of Invention
In a first aspect, the present invention provides a non-enzymatic glucose catalyst.
Except for special description, the parts are parts by weight, and the percentages are mass percentages.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a non-enzymatic glucose catalyst having the formula:
Ni1-XFeXMoO4wherein X is 0.01-0.05.
The non-enzymatic glucose catalyst is prepared by the following steps:
1) mixing nickel nitrate hexahydrate, ferric nitrate nonahydrate, sodium molybdate dihydrate and ultrapure water according to the molar ratio of 0.99-0.95: 0.01-0.05: 1:1.67, and uniformly stirring by using a magnetic stirrer;
2) integrally transferring the product obtained in the step 1) into a drying oven, and drying to obtain a precipitate;
3) collecting the precipitate obtained in the step 2), placing the precipitate in a crucible, and calcining the precipitate in a muffle furnace to obtain the catalyst.
Research shows that when the temperature of the muffle furnace is increased to 750 ℃, the prepared product is sintered in the crucible, and the prepared catalyst cannot be normally used. Preferably, the muffle furnace calcining temperature is 400-600 ℃; the calcination time is 1-4 h.
According to an embodiment of the invention, the temperature rise rate of the calcination temperature in the muffle calcination process is 5.5-9.0 ℃/min.
According to one embodiment of the invention, the magnetic stirring time in the step 1) is 1 h; in the step 2), the drying temperature is 80 ℃, and the drying time is 11-12 h; in the step 3), the muffle furnace calcining temperature is 450 ℃, the calcining time is 2h, and the heating speed is 7.5 ℃/min.
In a second aspect, the present invention provides a non-enzymatic glucose electrochemical sensor for glucose detection.
A non-enzymatic glucose electrochemical sensor for glucose detection, comprising: mixing the above non-enzyme grapeDispersing sugar catalyst in ultrapure water to obtain catalyst solution, and dropwise adding the catalyst solution into H2SO4And drying the surface of the electrochemically activated glassy carbon electrode at room temperature to obtain the non-enzymatic glucose electrochemical sensor for glucose detection.
The preparation method of the catalyst solution comprises the following steps: adding 1mg of non-enzymatic glucose catalyst powder into 1mL of ultrapure water, and performing ultrasonic treatment for 30min to obtain a uniformly dispersed catalyst solution.
A non-enzymatic glucose electrochemical sensor for glucose detection, comprising the steps of:
1) piranha washing solution (98% H) for glassy carbon electrode2SO4/30％H2O2Soaking for 30min at a ratio of 3:1, v/v), and washing with ultrapure water for later use;
2) respectively using Al of 0.3 mu m and 0.05 mu m for the electrode obtained in the step 1)2O3Polishing the powder to form a mirror surface, then respectively carrying out ultrasonic treatment on the electrodes according to the sequence of ultrapure water, absolute ethyl alcohol and ultrapure water, and drying for later use;
3) subjecting the electrode obtained in step 2) to a temperature of 0.5M H2SO4Performing electrochemical activation, washing with ultrapure water, and drying;
4) and (3) dripping 10 mu L of catalyst solution onto the surface of the glassy carbon electrode cleaned in the step 3), and drying at room temperature to obtain the non-enzymatic glucose electrochemical sensor for glucose detection.
In a third aspect, the present invention provides a method for detecting glucose using a non-enzymatic glucose electrochemical sensor.
A method for detecting glucose using a non-enzymatic glucose electrochemical sensor, comprising the steps of:
1) the electrode of the non-enzymatic glucose sensor is placed in 0.1M NaOH (pH 13.0) solution for characterization, glucose solutions with different concentrations are added into the NaOH solution, and the current change value of the glucose solution is measured;
2) and (3) drawing a working curve according to the linear relation between the current change value obtained in the step 1) and the glucose concentration.
3) And (3) detecting a sample to be detected by using the non-enzymatic glucose sensor, and calculating the obtained current value through the working curve prepared in the step 2) to obtain the glucose concentration of the sample to be detected.
The invention has the beneficial effects that:
the invention adopts a simple one-pot heating method and adjusts Fe3+Source and Ni2+Content of source, for NiMoO4The material is functionally treated to improve NiMoO4The nanoparticles themselves are limited and the resulting catalyst exhibits excellent glucose oxidation properties. The method has the characteristics of simple and easy operation, high catalyst sensitivity, strong anti-interference capability and the like, is a feasible synthetic scheme of the non-enzymatic glucose sensor, provides new opportunities for the development of the non-enzymatic glucose sensor, and has important significance.
Drawings
FIG. 1 is a graph of a sensitivity test of a non-enzymatic glucose sensor constructed using the catalyst prepared in example 1 of the present invention, wherein A is a cyclic voltammogram of a modified electrode at a voltage ranging from-0.2 to 0.6V in 0.1M NaOH (pH 13.0) at a scan rate of 50mV/s versus 0 to 9mM glucose; graph B is a calibration curve of the change in oxidation peak current versus different concentrations of glucose.
FIG. 2 shows the results of measurements of glucose concentrations in non-enzymatic glucose sensors constructed by the catalysts prepared in examples 1, 2, 3 and 6 of the present invention, wherein FIG. A shows the i-t current responses of different modified electrodes to 0.01-9 mM glucose at 0.55V in 0.1M NaOH (pH 13.0); panel B is a linear relationship between sensor i-t current response and different concentrations of glucose.
FIG. 3 is a graph of stability tests for a non-enzymatic glucose sensor constructed using the catalyst prepared in example 1 of the present invention.
FIG. 4 is a reproducibility test result of a non-enzymatic glucose sensor constructed by the catalyst prepared in example 1 of the present invention.
FIG. 5 is a test chart of the specificity of a non-enzymatic glucose sensor constructed by the catalyst prepared in example 1 of the present invention, in which interferents are 0.05mM AA, DA, UA, UR, D-Fru, SU, MA, LA and NaCl.
Detailed Description
The present invention is described in detail below with reference to specific examples, which are given for the purpose of further illustrating the invention and are not to be construed as limiting the scope of the invention, and the invention may be modified and adapted by those skilled in the art in light of the above disclosure. The raw materials and reagents used in the invention are all commercial products.
The main chemical reagents used in the examples of the present invention are as follows:
Na2MoO4·2H2O、Ni(NO3)2·6H2O、Fe(NO3)3·9H2o and sodium hydroxide (NaOH) were purchased from Aladdin Biotechnology Ltd, Shanghai, China.
The equipment and technical parameters used are as follows:
the instrument comprises the following steps: cyclic Voltammetry (CV) and i-t tests were performed using a Metrohm Autolab b.v. electrochemical workstation (switzerland Modular instrument). The electrochemical detection adopts a three-electrode system: the modified glassy carbon electrode (diameter 4mm) is used as a working electrode, a platinum wire is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode. The pH meter monitors the pH value (S210 SevenCompact, mettler-toledo, shanghai, china). A three electrode system was used to generate Cyclic Voltammetry (CV) from-0.2 to 0.6V at a scan rate of 50mV/s in 0.1M NaOH (pH 13.0).
Example 1 preparation of Ni0.99Fe0.01MoO4Catalyst and process for preparing same
The method comprises the following steps:
sequentially adding nickel nitrate hexahydrate, ferric nitrate nonahydrate, sodium molybdate dihydrate and solvent ultrapure water into a 50mL beaker according to the molar ratio of 0.99:0.01:1:1.67, stirring for 1h by a magnetic stirrer, putting the obtained product into an 80 ℃ oven for 12h to obtain dry precipitated powder, putting the powder into a crucible, heating at 450 ℃ in a muffle furnace at the heating rate of 7.5 ℃/min, and calcining for 2h to obtain the catalyst. Adding 1mg of the prepared catalyst powder into 1mL of ultrapure water, and carrying out ultrasonic treatment for 30min to obtain a uniformly dispersed catalyst solution.
Example 2 preparation of Ni with reference to the procedure of example 10.97Fe0.03MoO4A catalyst; example 3 preparation of Ni with reference to the procedure of example 10.95Fe0.05MoO4A catalyst; example 4 preparation of Ni with reference to the procedure of example 10.9Fe0.1MoO4A catalyst; example 5 preparation of Ni with reference to the procedure of example 10.8Fe0.2MoO4A catalyst; example 6 preparation of NiMoO with reference to the procedure of example 14A catalyst.
In order to evaluate the response of the synthesized catalyst to glucose, a preliminary electrochemical test was conducted on 10mM glucose using the prepared catalyst, and the results are shown in Table 1
TABLE 1 different concentrations of Fe-doped NiMoO4Response of non-enzymatic glucose catalysts to glucose (n ═ 3)
Figure BDA0003571686340000051
As can be seen from Table 1, the catalyst prepared by the present invention has a higher current response to glucose, and example 1 (Ni)0.99Fe0.01MoO4) Example 2 (Ni)0.97Fe0.03MoO4) Example 3 (Ni)0.95Fe0.05MoO4) The prepared catalyst has a much higher or close to example 6 (NiMoO)4) The current response of (c).
Example 7 preparation of non-enzymatic glucose electrochemical sensor for glucose detection
The method comprises the following steps:
1) piranha washing solution (98% H) for glassy carbon electrode2SO4/30％H2O2Soaking for 30min at a ratio of 3:1, v/v), and washing with ultrapure water for later use;
2) respectively using Al of 0.3 mu m and 0.05 mu m for the electrode obtained in the step 1)2O3Polishing the powder to form a mirror surface, then respectively carrying out ultrasonic treatment on the electrode according to the sequence of ultrapure water, absolute ethyl alcohol and ultrapure water, and drying for later use;
3) the electrode obtained in the step 2) is placed in0.5M H2SO4Performing electrochemical activation, washing with ultrapure water, and drying;
4) and (3) dripping 10 mu L of the catalyst solution prepared in the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 6 on the surface of the glassy carbon electrode cleaned in the step 3), and drying at room temperature to obtain the non-enzymatic glucose electrochemical sensor for glucose detection. The preparation method of the catalyst solution comprises the following steps: adding 1mg of non-enzymatic glucose catalyst powder into 1mL of ultrapure water, and performing ultrasonic treatment for 30min to obtain a uniformly dispersed catalyst solution.
Example 8 detection of glucose Using a non-enzymatic glucose electrochemical sensor
Glucose was detected using the non-enzymatic glucose electrochemical sensor constructed in example 7, following the following procedure:
drawing a working curve
1) The non-enzymatic glucose sensor constructed by the catalyst prepared in example 1 is used as a working electrode, 0-9 mM glucose solution is sequentially added into electrolyte NaOH for CV test, and the result is shown in FIG. 1. The measurement result shows that the current response value and the glucose concentration are in a good linear relation within the range of 0-9 mM, and the linear correlation coefficient is 0.9983.
2) Example 7 the modified electrode of step 4) was used as a working electrode, 0.01 to 9mM glucose solution was sequentially added to the electrolyte NaOH, i-t current response was recorded, and the measurement results of the working curve (as shown in FIG. 2) were plotted to show that the current response value and the glucose concentration were in a good linear relationship within the range of 0.01 to 9 mM. Comparative current response results, it can be seen from the graph that the prepared catalyst has good current response and faster response time to glucose, and example 1 (Ni)0.99Fe0.01MoO4) The prepared catalyst has much higher performance than that of example 6 (NiMoO)4) The linear correlation coefficient of (a) was 0.9934, and the detection limit was 0.55 μ M (S/N — 3).
Secondly, testing the stability of the sensor: the non-enzymatic glucose sensor constructed by the catalyst prepared in example 1 is used as a working electrode, and the current is almost kept unchanged within 2500s under the optimal condition (as shown in figure 3), which indicates that the sensor has good stability.
Thirdly, testing the repeatability of the sensor: the catalyst prepared in example 1 was dropped on five different glassy carbon electrodes as working electrodes, and the current responses of the catalyst to glucose on 5 different electrodes were measured (as shown in fig. 4), and the Relative Standard Deviation (RSD) was obtained as 5.5%, indicating that the sensor reproducibility was good.
Fourthly, testing the specificity of the sensor: the catalyst prepared in example 1 was dropped on five different glassy carbon electrodes as working electrodes, and several interferents present in serum were used: AA, DA, UA, UR, D-Fru, SU, MA, LA and NaCl at a concentration of 0.05mM, the effect of the different interfering substances on the continuous addition of 0.5mM glucose in 0.1M NaOH (pH 13.0) was determined. The results show (as shown in fig. 5), that the constructed glucose electrochemical sensor has good specificity.
Fifth, the analysis and application of practical samples
In order to evaluate the practical applicability and accuracy of the proposed electrochemical sensor for glucose, the prepared electrochemical sensor was used to detect glucose in a sample of human serum of healthy subjects, and the detection results are shown in table 2, with a relative standard deviation range of 1.7% to 2.8% and a recovery rate of 97.2% to 102.3%.
Table 2 non-enzymatic glucose electrochemical sensor determination of glucose for healthy human serum samples (n ═ 3)
Figure BDA0003571686340000071
The results in table 2 show that the non-enzymatic glucose electrochemical sensor prepared by the invention is feasible for detecting glucose and can meet the requirements of practical analysis.
As a design scheme of the transition metal catalyst, compared with the traditional catalyst, the invention has the advantages of low cost of raw materials, easy synthesis process and simple regulation and control method, and is a feasible synthesis scheme of the glucose catalyst. The catalyst obtained by the invention is NiMoO doped with Fe4The material is functionalized, which is helpful for adjusting NiMoO4Electricity of medium Ni centerSubstructure, improvement of NiMoO4The nano particles are self-limited, and the non-enzymatic glucose electrochemical sensor prepared on the basis has quick response to signals of glucose and higher sensitivity. Therefore, the Fe-doped NiMoO with different concentrations prepared by the invention4The non-enzymatic glucose electrochemical sensor enriches the development direction of the electrochemical detection of glucose and provides a new idea for the development of the electrochemical detection of glucose.

Claims (9)

1. A non-enzymatic glucose catalyst having the formula:
Ni1-XFeXMoO4wherein X is 0.01-0.05.
2. The non-enzymatic glucose catalyst of claim 1, prepared by the steps of:
1) mixing nickel nitrate hexahydrate, ferric nitrate nonahydrate, sodium molybdate dihydrate and ultrapure water according to the molar ratio of 0.99-0.95: 0.01-0.05: 1:1.67, and uniformly stirring by using a magnetic stirrer;
2) integrally transferring the product obtained in the step 1) into a drying oven, and drying to obtain a precipitate;
3) collecting the precipitate obtained in the step 2), placing the precipitate in a crucible, and calcining the precipitate in a muffle furnace to obtain the catalyst.
3. The non-enzymatic glucose catalyst of claim 2, wherein: the muffle furnace calcining temperature is 400-600 ℃; the calcination time is 1-4 h.
4. The non-enzymatic glucose catalyst of claim 2, wherein: the temperature rise speed of the calcining temperature in the muffle furnace calcining process is 5.5-9.0 ℃/min.
5. The non-enzymatic glucose catalyst of claim 2, wherein: the magnetic stirring time in the step 1) is 1 h; the drying temperature in the step 2) is 80 ℃, and the drying time is 11-12 h; in the step 3), the muffle furnace calcining temperature is 450 ℃, the calcining time is 2h, and the heating speed is 7.5 ℃/min.
6. A non-enzymatic glucose electrochemical sensor for glucose sensing, comprising: dispersing the non-enzymatic glucose catalyst of any of claims 1-6 in ultrapure water to produce a catalyst solution, and then dropwise adding the catalyst solution to H2SO4And drying the surface of the electrochemically activated glassy carbon electrode at room temperature to obtain the non-enzymatic glucose electrochemical sensor for glucose detection.
7. The electrochemical sensor of claim 6, wherein: the preparation method of the catalyst solution comprises the steps of adding 1mg of non-enzymatic glucose catalyst powder into 1mL of ultrapure water, and carrying out ultrasonic treatment for 30 min.
8. The electrochemical sensor of claim 7, comprising the steps of:
1) piranha washing solution (98% H) for glassy carbon electrode2SO4/30％H2O2Soaking for 30min at a ratio of 3:1, v/v), and washing with ultrapure water for later use;
2) respectively using Al of 0.3 mu m and 0.05 mu m for the electrode obtained in the step 1)2O3Polishing the powder to form a mirror surface, then respectively carrying out ultrasonic treatment on the electrodes according to the sequence of ultrapure water, absolute ethyl alcohol and ultrapure water, and drying for later use;
3) subjecting the electrode obtained in step 2) to a temperature of 0.5M H2SO4Performing electrochemical activation, washing with ultrapure water, and drying;
4) and (3) dripping 10 mu L of catalyst solution onto the surface of the glassy carbon electrode cleaned in the step 3), and drying at room temperature to obtain the non-enzymatic glucose electrochemical sensor for glucose detection.
9. A method for detecting glucose using a non-enzymatic glucose electrochemical sensor, comprising the steps of:
1) characterizing the electrode of the non-enzymatic glucose sensor according to any of the claims 6-8 by placing it in a 0.1M NaOH (pH 13.0) solution, and measuring the change in current by adding glucose solutions of different concentrations to the NaOH solution;
2) and (3) drawing a working curve according to the linear relation between the current change value obtained in the step 1) and the glucose concentration.
3) And (3) detecting the sample to be detected by using the non-enzymatic glucose sensor, and calculating the obtained current value through the working curve prepared in the step 2) to obtain the glucose concentration of the sample to be detected.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101825609A (en) * 2010-04-14 2010-09-08 重庆医科大学 Determination method of serum total bile acid
WO2012134133A2 (en) * 2011-03-31 2012-10-04 고려대학교 산학협력단 Nanowire having diamond deposited thereon, manufacturing method thereof, and biosensor including same
CN104777207A (en) * 2015-04-10 2015-07-15 武汉大学 Three-dimensional nitrogen-doped graphene composite material as well as preparation method and application thereof
WO2017087657A1 (en) * 2015-11-17 2017-05-26 University Of Kansas Methods of forming and using metal alloy oxidative catalysts
CN107991371A (en) * 2017-11-10 2018-05-04 东北电力大学 Cupric oxide non-enzymatic glucose electrochemical sensor
CN108956735A (en) * 2018-05-07 2018-12-07 西北工业大学 A kind of cobalt black of core-shell structure-copper nano-wire combination electrode material and preparation method
CN113244922A (en) * 2021-04-01 2021-08-13 西安理工大学 Non-enzymatic glucose sensor catalyst and preparation method thereof
CN114235907A (en) * 2021-12-13 2022-03-25 重庆医科大学 Electrochemical luminescence immunosensor for non-small cell lung cancer CYFRA21-1 detection and detection method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101825609A (en) * 2010-04-14 2010-09-08 重庆医科大学 Determination method of serum total bile acid
WO2012134133A2 (en) * 2011-03-31 2012-10-04 고려대학교 산학협력단 Nanowire having diamond deposited thereon, manufacturing method thereof, and biosensor including same
CN104777207A (en) * 2015-04-10 2015-07-15 武汉大学 Three-dimensional nitrogen-doped graphene composite material as well as preparation method and application thereof
WO2017087657A1 (en) * 2015-11-17 2017-05-26 University Of Kansas Methods of forming and using metal alloy oxidative catalysts
CN107991371A (en) * 2017-11-10 2018-05-04 东北电力大学 Cupric oxide non-enzymatic glucose electrochemical sensor
CN108956735A (en) * 2018-05-07 2018-12-07 西北工业大学 A kind of cobalt black of core-shell structure-copper nano-wire combination electrode material and preparation method
CN113244922A (en) * 2021-04-01 2021-08-13 西安理工大学 Non-enzymatic glucose sensor catalyst and preparation method thereof
CN114235907A (en) * 2021-12-13 2022-03-25 重庆医科大学 Electrochemical luminescence immunosensor for non-small cell lung cancer CYFRA21-1 detection and detection method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MOHAMMAD NIKPASSAND: "NiFe2O4@SiO2 n Pr@glucose catalyzed sythesis of novel 5-pyrazolin-1,2,4-triazazolidine-3-ones(thiones)", 《CURRENT ORGANIC SYNTHESIS》, pages 91 - 99 *
YUAN YL等: "Dendrimer functionalized reduced graphene oxide as nanocarrier for sensitive pseudobienzyme electrochemical aptasensor", 《BIOSENSORS & BIOELECTRONICS》, pages 474 - 480 *
张姝等: "铁掺杂钼酸镍纳米管的电催化析氧性能研究", 化工新型材料, pages 152 - 160 *

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