CN107478707A - A kind of novel electrode and its assay method for blood sugar detection - Google Patents

A kind of novel electrode and its assay method for blood sugar detection Download PDF

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Publication number
CN107478707A
CN107478707A CN201710568928.3A CN201710568928A CN107478707A CN 107478707 A CN107478707 A CN 107478707A CN 201710568928 A CN201710568928 A CN 201710568928A CN 107478707 A CN107478707 A CN 107478707A
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electrode
modified
cnt
glucose
carbon
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申贵隽
蔡正浩
王川
申远
孙晶
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Dalian University
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Dalian University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention relates to electrochemical analysis detection technique field, more particularly to a kind of novel electrode and its assay method available for blood sugar detection, including being working electrode by glass-carbon electrode or modified electrode, saturated calomel electrode is reference electrode, platinum filament for auxiliary electrode group into three-electrode system, modified electrode is the CNT/palladium nanostructure composite material prepared using electrodeposition process, it is an object of the invention to use the nano combined modified electrode of CNT/palladium, establish a kind of new method for determining blood glucose, study electrochemical behavior of the blood glucose on the modified electrode, this method has higher selectivity to glucose, higher sensitivity, and it is easier to operate.

Description

A kind of novel electrode and its assay method for blood sugar detection
Technical field
The present invention relates to electrochemical analysis detection technique field, and in particular to a kind of novel electrode available for blood sugar detection And its assay method.
Background technology
Glucose, it is the important raw material of industry, is mainly used in food industry, such as produces candy, cake, beverage.Curing Treatment field, glucose are widely applied in the transfusion of patient.Its oxidized product is gluconic acid, is to produce medicine of replenishing the calcium The important source material of thing-calcium gluconate.Positive D-mannitol can be generated by being reduced, and can be used to synthesize vitamin C.At present, people couple Substantial amounts of research has been done in the detection of glucose, have also been developed the detection method of a variety of glucose, mainly have chromatography, Spectroscopic methodology, bioanalysis and electrochemical process.Because electrochemical process detects glucose compared to other method stability, sensitivity is all Have greatly improved, so it receives great attention in glucose detection field, achieve quick development.
The content of the invention
It is an object of the invention to use CNT/palladium nanostructure composite material modified glassy carbon electrode, a kind of survey is established Determine the new method of blood glucose, electrochemical behavior of the research blood glucose on the modified electrode, a kind of new point is provided for the measure of blood glucose Analysis method.
To achieve the above object, the technical solution adopted by the present invention is:Including being work by glass-carbon electrode or modified electrode Electrode, saturated calomel electrode are reference electrode, platinum filament for auxiliary electrode group into three-electrode system.Modified electrode is carbon nanometer Pipe/palladium nanostructure composite material.The three-electrode system is placed in the serum handled well, in -0.8~0.4V potential ranges it Between with 100mV/s sweep speed under the conditions of, record peak current is that cyclic voltammetric in the range of 0.06~2.0 mg/mL is bent in concentration Line.Specific operating procedure includes:
1)The preparation of sensor:The pretreatment of glass-carbon electrode, the purifying of CNT and carboxylated, electro-deposition prepare carbon nanometer Pipe/palladium nano structural composite electrode material;
2)The optimization of condition determination:The species of cushioning liquid, PH influence, the influence of sedimentation time, the influence of sweep speed;
3)The measure of actual sample:Working electrode is glass-carbon electrode(GCE), reference electrode is saturated calomel electrode(SCE), to electricity Extremely platinum electrode, form three-electrode system;The three-electrode system is placed in the serum handled well, remembered with optimum experimental condition It is the cyclic voltammetry curve in the range of 0.06~2.0 mg/mL that peak current, which is recorded, in concentration.
The present invention has good electric conductivity using glass-carbon electrode, and combines CNT, the property of palladium bichloride, is made one Kind has highly sensitive electrode to glucose.Then by optimizing sedimentation time, buffer solution species, sweep speed, bottom liquid pH Etc. parameter, obtain that there is higher selectivity, higher sensitivity and the electrochemical analysis side for being easier operation to glucose Method, and this method is determined applied to actual sample.
Brief description of the drawings
The present invention is further detailed explanation with specific embodiment below in conjunction with the accompanying drawings.
Accompanying drawing 1 is the sulfuric acid activated figure of bare electrode.
Accompanying drawing 2 is cyclic voltammogram of the Different electrodes in potassium ferricyanide solution.
Accompanying drawing 3 is cyclic voltammetry curve of the Different electrodes in 0.5mg/mL glucose solution.
Accompanying drawing 4 is PH Optimal Curve.
Accompanying drawing 5 is the Optimal Curve of sedimentation time.
Accompanying drawing 6 is the Optimal Curve of sweep speed.
Accompanying drawing 7 is schemed for the CV of different glucose solution.
Accompanying drawing 8 is the glucose solution I-V Characteristic Analysis figure with CNT/palladium bichloride modified electrode various concentrations Reduction peak, the canonical plotting made.
Embodiment
To a kind of novel electrode for blood sugar detection involved in the present invention and utilize the electrode pair referring to the drawings The electrochemical method that blood glucose is measured is described in detail.
To realize the purpose of invention, the technical solution adopted by the present invention is:Including being work by glass-carbon electrode or modified electrode Make electrode, saturated calomel electrode is reference electrode, platinum filament for auxiliary electrode group into three-electrode system.Modified electrode is carbon nanometer Pipe/palladium nanostructure composite material.
The pretreatment of glass electrode:Glass-carbon electrode is taken in abrasive paper for metallograph(3000#)Upper polishing, then respectively in dry, wet muntjac Successively with 1.0,0.3 and 0.05 μm of Al on leather packing2O3Powder polishes, successively with deionized-distilled water, absolute ethyl alcohol, deionization Distilled water is fully cleaned by ultrasonic, then electrode is placed in 0.5mol/L H2SO4In solution, with 50mV/s sweep speeds, -0.5 ~+1.4V potential regions, use cyclic voltammetry(CV)Scanning 20 circle, will be sulfuric acid activated after electrode take out after use distilled water flushing Totally, it is placed in 0.01g/mL K3[Fe(CN)6In solution, with 50mV/s sweep speeds, in -0.5~+1.2V potential regions, Use cyclic voltammetry(CV)Scanning is until stable.
The purifying of CNT and carboxylated:In the preparation process of CNT, simultaneous amorphous carbon, carbon are received The generation of the amorphous carbon such as rice grain and carbon fiber, to eliminate as much as the influence of impurity band, before CNT carboxylated Purification processes need to be carried out to it.CNT heats 2h before use in 400 DEG C, to remove amorphous carbon thereon, CNT Carboxylated uses nitration mixture reflux oxidation method, i.e., by CNT in V (HNO3):V(H2SO4)=1:It is heated to reflux in 3 mixed liquor 6h, cooled and filtered, with ultra-pure water eccentric cleaning to neutrality, it is put into baking oven and dries.It is configured to 0.5mg/mL CNTs point Dispersion liquid is stand-by.
Electro-deposition prepares CNT/palladium nano structural composite electrode material:Electro-deposition is prepared by CHI660 electrochemistry Work station is carried out, using three-electrode system:Glass-carbon electrode(GCE)For working electrode, platinum filament is to electrode, saturated calomel electrode (SCE)For reference electrode.Take appropriate CNT disperse drop dried under the surface of glass-carbon electrode, infrared lamp i.e. be made carbon receive Mitron modified electrode.This step is due to the reason that CNT has very strong electric conductivity so that the response signal of modified electrode Become apparent from.Carbon nano tube modified modified electrode is placed in 0.5mmol/L palladium chloride solution, in -0.2V potentiostatic electrodepositions 180s, Technique of Nano Pd/carbon nano tube modified electrode is made.
Accompanying drawing 1 is the sulfuric acid activated figure of bare electrode.Glass-carbon electrode is taken in abrasive paper for metallograph(3000#)Upper polishing, then exists respectively Successively with 1.0,0.3 and 0.05 μm of Al in dry, wet chamois leather pad2O3Powder polish, successively with deionized-distilled water, absolute ethyl alcohol, Deionized-distilled water is fully cleaned by ultrasonic, then electrode is placed in 0.5mol/L H2SO4In solution, with 50mV/s sweep speeds, In -0.5~+1.4V potential regions, cyclic voltammetry is used(CV)The circle of scanning 20.Electrode after will be sulfuric acid activated uses distillation after taking out Water is rinsed well, is placed in 0.01g/mL K3[Fe(CN)6] in solution, with 50mV/s sweep speeds, in -0.5~+1.2V electricity Position section, uses cyclic voltammetry(CV)Scanning is until stable.
Accompanying drawing 2 is cyclic voltammogram of the Different electrodes in potassium ferricyanide solution.Successively with glass-carbon electrode, CNT K of modified electrode, CNT/the palladium bichloride modified electrode in 5mmol/L3[Fe(CN)6] scanned using cyclic voltammetry in solution (Potential range -0.4~0.8V, sweep speed 50mV/s).In figure, carbon nano tube modified electrode(Curve c)Compared with glass-carbon electrode(It is bent Line b)Oxidation peak current increase, reduction peak current reduce, show that CNT has been aggregated to GCE surfaces, promote probe ion In the redox reaction of electrode surface.And when modifying palladium bichloride in carbon nano tube surface(Curve a), CNT/chlorination Redox peaks on palladium modified electrode more highlight, and peak current also further enhances, and illustrate that palladium bichloride clearly enhances electrode Electric conductivity so that electron surface electronics circulating rate significantly increases, so as to promote probe molecule K3[Fe(CN)6In electrode table The reversible reaction in face.
Accompanying drawing 3 is cyclic voltammetry curve of the Different electrodes in 0.5mg/mL glucose solution.Delayed with the PBS of pH=6.8 The concentration for rushing solution preparation is 0.5mg/mL glucose solution, and glass-carbon electrode, carbon nano tube modified electrode, palladium bichloride is modified electric Pole, CNT/palladium bichloride modified electrode between -0.8~0.4V potential ranges with 100mV/s sweep speed under the conditions of, it is different The cyclic voltammetry scan of electrode scanning, occurs on CNT/palladium bichloride modified electrode and carbon nano tube modified electrode reversible Oxidation peak and reduction peak, the electrode process for showing glucose is reversible.Simultaneously it is also seen that CNT/chlorination Palladium modified electrode is remarkably reinforced to the electrocatalytic effect of glucose, shows that response of this modified electrode to glucose is maximum.
Accompanying drawing 4 is PH optimal conditions.The PBS that this experiment employs pH=6.7 contains as bottom liquid progress glucose The measure of amount.
Accompanying drawing 5 is the Optimal Curve of sedimentation time.When being 3min between when deposited, catalytic current will appear from maximum.
Accompanying drawing 6 is the Optimal Curve of sweep speed.When surface sweeping speed is 100mV/s, peak current is maximum.
Accompanying drawing 7 is schemed for the CV of different glucose solution.Preparing solution concentration respectively with the PBS cushioning liquid of pH=7 is 0.06mg/mL, 0.5mg/mL, 1.0mg/mL, 1.5mg/mL, 2.0mg/mL glucose solution, under optimum experimental condition, use Cyclic voltammetry carries out modified electrode measure to the glucose solution of various concentrations.
Accompanying drawing 8 is standard curve.With the glucose solution C-V characteristic of CNT/palladium bichloride modified electrode various concentrations The reduction peak of analysis chart, and using Excel softwares, make standard curve.
The present invention has good electric conductivity using glass-carbon electrode, and combines CNT, the property of palladium bichloride, is made one Kind has highly sensitive electrode to glucose.Then by optimizing sedimentation time, buffer solution species, sweep speed, bottom liquid pH Etc. parameter, obtain that there is higher selectivity, higher sensitivity and the electrochemical analysis side for being easier operation to glucose Method.

Claims (3)

  1. A kind of 1. novel electrode for blood sugar detection, it is characterised in that including:Glass-carbon electrode or modified electrode are work electricity Pole, saturated calomel electrode are reference electrode, platinum filament for auxiliary electrode group into three-electrode system.
  2. 2. a kind of novel electrode for blood sugar detection as claimed in claim 1, it is characterised in that modified electrode is carbon nanometer Pipe/palladium nanostructure composite material.
  3. 3. a kind of a kind of novel electrode for blood sugar detection using described in claim 1 determines the method for blood glucose, its feature It is, the three-electrode system is placed in the serum handled well, speed is swept with 100mV/s between -0.8~0.4V potential ranges Under the conditions of, record peak current is in the cyclic voltammetry curve that concentration is in the range of 0.06~2.0 mg/mL.
CN201710568928.3A 2017-07-13 2017-07-13 A kind of novel electrode and its assay method for blood sugar detection Pending CN107478707A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102507693A (en) * 2011-11-03 2012-06-20 桂林医学院 Functional-material-based glucose biosensor and manufacturing method thereof
CN102520035A (en) * 2011-11-04 2012-06-27 上海大学 Preparation method for copper oxide-graphene nano-complex modification electrode, and application of modification electrode in glucose detection
CN104918925A (en) * 2012-12-21 2015-09-16 美艾利尔瑞士公司 Test device for electrochemical analysis

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102507693A (en) * 2011-11-03 2012-06-20 桂林医学院 Functional-material-based glucose biosensor and manufacturing method thereof
CN102520035A (en) * 2011-11-04 2012-06-27 上海大学 Preparation method for copper oxide-graphene nano-complex modification electrode, and application of modification electrode in glucose detection
CN104918925A (en) * 2012-12-21 2015-09-16 美艾利尔瑞士公司 Test device for electrochemical analysis

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LING MENG 等: "Nonenzymatic Electrochemical Detection of Glucose Based on Palladium-Single-Walled Carbon Nanotube Hybrid Nanostructures", 《ANALYTICAL CHEMISTRY》 *
SAN HUA LIM 等: "A glucose biosensor based on electrodeposition of palladium nanoparticles and glucose oxidase onto Nafion-solubilized carbon nanotube electrode", 《BIOSENSORS AND BIOELECTRONICS》 *
王荣海 等: "钯复合材料电极催化甲醇氧化机理", 《工业催化》 *

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Application publication date: 20171215