CN102901755A - High-sensitivity glucose electrochemical sensor and preparation method thereof - Google Patents

High-sensitivity glucose electrochemical sensor and preparation method thereof Download PDF

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Publication number
CN102901755A
CN102901755A CN2012103302837A CN201210330283A CN102901755A CN 102901755 A CN102901755 A CN 102901755A CN 2012103302837 A CN2012103302837 A CN 2012103302837A CN 201210330283 A CN201210330283 A CN 201210330283A CN 102901755 A CN102901755 A CN 102901755A
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high sensitivity
preparation
electrochemical sensor
glucose sensor
cnfs
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陈智栋
丁妮妮
张静
王文昌
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CHANGZHOU JIANGGONG KUOZHI ELECTRONIC TECHNOLOGY CO LTD
Changzhou University
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CHANGZHOU JIANGGONG KUOZHI ELECTRONIC TECHNOLOGY CO LTD
Changzhou University
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Abstract

The invention provides a high-sensitivity glucose electrochemical sensor which is obtained by modifying the surface of a conventional electrode with a layer of a palladium-platinum alloy loaded carbon nanofiber composite, i.e., a sensitive film of PdPt-CNFs. A preparation method for the electrochemical sensor comprises the following steps: dispersing palladium-platinum alloy loaded carbon nanofibers in a solvent through ultrasonic dispersion to obtain a uniform dispersion liquid; dropwise coating the dispersion liquid on the surface of a conventional clean electrode; evaporating the solvent; then immobilizing glucose oxidase; and after air-drying at room temperature, carrying out cross-linking above a glutaraldehyde saturated vapor pressure liquid level so as to obtain the high-sensitivity glucose electrochemical sensor. According to the invention, the prepared nanocomposite has good biocompatibility and is beneficial for immobilization of biological enzyme, and the preparation method is simple and fast and has low cost; the electrochemical sensor prepared in the invention has high sensitivity and good stability and reproducibility, so the electrochemical sensor is expected to be widely used in fields like diagnosis of diabetes, clinical medicine and food process checking.

Description

A kind of high sensitivity electrochemical glucose sensor and preparation method thereof
Technical field
The invention belongs to the electrochemical sensor field, be specifically related to electrochemical sensor of a kind of high sensitivity glucose and preparation method thereof.
Background technology
Along with the fast development of society and the raising of people's living standard, diabetes prevalence also increases thereupon, according to the World Health Organization (WHO) in 2011, there have been at present 3.46 hundred million populations to suffer from diabetes, can be in real time, the concentration of reliable detection blood sugar is the effective ways of diagnosis and control diabetes.
Electrochemical sensor is owing to Electrochemical Detection highly sensitive, that selectivity good, the experiment advantages such as easy quick, required instrument and equipment is cheap are widely used in living matter.Exploitation for detection of the subtle change of concentration of glucose in the body, highly sensitive glucose sensor has important scientific meaning and practical value.
In recent years, nano material and structure are with its excellent surface effect, the characteristic such as catalytic efficiency is high, bio-compatibility is good and be widely used in the fields such as sensing, catalysis; Carbon nano-fiber is a kind of novel material with carbon element that has potential using value aspect galvanochemistry, has specific surface area large, accelerates the characteristics such as electronics transmission.According to both advantages, in more existing documents nano particle is combined with carbon nano-tube now and prepares glucose sensor, such as " glucose biological sensor of Based on Pt Nanoparticles Modified Aligned Carbon Nanotubes Electrode ", " modifying the electrochemical glucose biology sensor of Aligned carbon nanotubes electrode based on palladium nano-particles " and " new PdPt bimetal nano particles modifying multiwall carbon nano-tube catalyzer on the basis of preparation and application ampere glucose biological sensor " (" Fabrication and application of amperometric glucose biosensor based on a novel PtPd bimetallic nanoparticle decorated multi-walled carbon nanotube catalyst "), although these methods have obtained certain effect, existing electrochemical sensor also exists sensitivity lower, the problem that detection limit is too high.
Summary of the invention
Problem to be solved by this invention is: in the prior art, there is the defective that sensitivity is lower, detection limit is too high in electrochemical sensor.
For addressing the above problem, the technical solution used in the present invention is:
The invention provides a kind of high sensitivity electrochemical glucose sensor, this electrochemical sensor is the carbon nano-fiber composite material in the load of electrode face finish one deck pallas;
As preferably, the content of platinum and palladium is respectively 15 ~ 16% and 4 ~ 6% of compound substance gross mass, and carbon nano-fiber content is 79 ~ 80% of gross mass;
As preferably, carbon nano-fiber is the solid carbon nanofiber material, and with carbon nano-tube, namely the hollow Nano carbon fibrous material is compared, solid carbon nanofiber has intrinsic many advantages, such as lower production cost, better stability, more marginal position and easier to be surface-functionalized;
Further, the diameter of solid carbon nanofiber is 50 ~ 150nm, and length is 2 ~ 10 μ m.
The invention provides in a kind of high sensitivity electrochemical glucose sensor, the preparation method of PdPt-CNFs, step is:
A, take by weighing carbon nano-fiber, join and contain H 2PtCl 63H 2O and K 2PdCl 4Solution in, mix ultrasonic agitation even;
The pH of B, adjusting mentioned solution stirs between 9.5 to 10;
C, when stirring, draw NaBH with glue head dropper 4Solution slowly is added drop-wise in the resulting mixed solution of step B, and then stirring reaction filters afterwards, and with the deionized water washing, drying obtains PdPt-CNFs.
As preferably, novel PdPt-CNFs has good biocompatibility as the electrode sensitive material.
The present invention also provides a kind of manufacture method of high sensitivity electrochemical glucose sensor, concrete operations are: PdPt-CNFs is distributed to ultrasonic dispersion obtains uniform dispersion liquid in the solvent, then dispersant liquid drop is applied to behind the electrode surface of conventional cleaning and the evaporating solvent again fixing glucose oxidase, room temperature is carried out the crosslinked high sensitivity electrochemical glucose sensor that obtains after placing and drying again above containing glutaraldehyde saturated vapor pressure liquid level;
As preferably, solvent is nitrogen, and nitrogen-dimethyl formamide as spreading agent, is compared with ethanol with deionized water commonly used, and it can disperse PdPt-CNFs better;
As preferably, the concentration of glutaraldehyde saturated vapor pressure is 25%, and electrode is 10min in the vapour pressure overhung time.
The invention has the beneficial effects as follows: utilize have the excellent surface effect, catalytic efficiency is high, bio-compatibility is good nanoscale pallas and specific surface area is large, excellent adsorption, the advantage of the solid carbon nanofiber that electronics transmits can accelerated, and the crosslinked action of glutaraldehyde, realized that the high activity of enzyme fixes, increase and effectively transmit electronics between enzyme and the electrode, thereby improve the activity of enzyme, greatly improved the sensitivity to glucose detection, this high sensitivity electrochemical glucose sensor is 2.5 μ mol L to the range of linearity of glucose detection -1~ 8.4mmol L -1, sensitivity is up to 12.3 μ Ammol -1(174 μ Ammol -1Cm -2), so far, containing enzymatic glucose sensor with other and compare, sensitivity is the highest, detects to be limited to 0.7 μ mol L -1, and preparation electrochemical glucose sensor operation is simple, favorable reproducibility.
Description of drawings
The XRD figure of Fig. 1 CNFs and PdPt-CNFs, the collection of illustrative plates that wherein is positioned at the top are the XRD figure of PdPt-CNFs; The collection of illustrative plates that is positioned at the below is the XRD figure of CNFs
Fig. 2 electrochemical sensor of the present invention is at 0.1mol L -1, in the phosphate buffered solution of pH=7.0, add the current-time curvel of different glucose; Built-in figure is the current-time curvel figure of front 450s
The canonical plotting of Fig. 3 concentration of glucose of the present invention and response current
Embodiment
The present invention is further detailed explanation with following examples by reference to the accompanying drawings now, but will be appreciated that, these embodiment are the usefulness for illustrating only, and should not be interpreted as restriction of the invention process.
The water that uses in the experimentation is deionized water, tests used reagent and is and analyzes purely, and experiment is all at room temperature carried out.
The preparation of embodiment 1PdPt-CNFs
A takes by weighing solid carbon nanofiber (diameter is 50 ~ 150nm, and length is 2 ~ 10 μ m) 0.01g, adds to contain 3.0ml 3.5mmol L -1H 2PtCl 63H 2O and 3.0ml 3.0mmol L -1K 2PdCl 4Mixed solution in, mix ultrasonic agitation 30min.
B 0.05mol L -1NaOH regulate mentioned solution pH between 9.5 to 10, stir 10min.
C takes by weighing the NaBH of 0.01g 4Be dissolved in the deionized water of 25ml, when stirring, slowly be added drop-wise in the mixed solution of the pH that has mixed up with the speed of glue head dropper absorption NaBH4 solution with 2 to 3 seconds/, stirred afterwards 2 hours, then filter, with the deionized water washing, drying obtains PdPt-CNFs in 60 degree baking ovens.
Fig. 1 is the XRD figure of CNFs and PdPt-CNFs, and the collection of illustrative plates that wherein is positioned at the top is the XRD figure of PdPt-CNFs; The collection of illustrative plates that is positioned at the below is the XRD figure of CNFs, as seen from the figure 26.1 ° of diffraction peaks that appearance is very strong, is (002) face of hexagonal system structure CNFs.According to Pd (JCPDS-ICDD, Card No.46-1043) and Pt (JCPDS-ICDD, Card No.04-0802) standard spectrogram and document " Fabrication and application of amperometric glucose biosensor based on a novel PtPd bimetallic nanoparticle decorated multi-walled carbon nanotube catalyst " show and have synthesized the PdPt-CNFs compound substance.
The preparation of embodiment 2 high sensitivity glucose sensors
Glass-carbon electrode take diameter as 3mm is basal electrode, respectively at the Al of 0.3 and 0.5 μ m 2O 3After being polished into minute surface on the burnishing powder, use successively the nitric acid of 1:1, ethanol and deionized water supersound washing 3min.
The PdPt-CNFs for preparing is dispersed in the DMF solvent, and concentration is 4mg ml -1, ultrasonic 30min gets 2 μ l with microsyringe and drips and be coated in the above-mentioned glass-carbon electrode surface of having handled well, drips after drying under the room temperature to be coated with 2 μ l 6mg ml again -1Glucose oxidase, dry under the room temperature, electrode is suspended on contains glutaraldehyde saturated vapor pressure top 10min, thereby make the high sensitivity electrochemical glucose sensor.
Embodiment 3 test experience
Test experience is to carry out at CHI660D electrochemical workstation and three-electrode system, contrast electrode is saturated calomel electrode, is platinum electrode to electrode, and working electrode adopts the electrochemical sensor of the embodiment of the invention 2 preparations, under the condition of optimizing, with the 0.1mol L of pH=7.0 -1Phosphate buffered solution be end liquid, under 0.6V, add time current curve that different glucose obtains as shown in Figure 1, the range of linearity (as shown in Figure 2) that can draw this electrochemical glucose sensor is 2.5 μ mol L -1~ 8.4mmol L -1, sensitivity is up to 12.3 μ Ammol -1(174 μ Ammol -1Cm -2), the linear dependence degree is fine, and R=0.997, detection limit are low to moderate 0.7 μ mol.
In the present invention's prior art relatively as: the range of linearity of Fabrication and application of amperometric glucose biosensor based on a novel PtPd bimetallic nanoparticle decorated multi-walled carbon nanotube catalyst is 62 μ mol L -1~ 14.07mmol L -1Sensitivity is 112 μ Ammol -1Cm -2R=0.998; Detection is limited to 31 μ mol L -1
In " glucose biological sensor of Based on Pt Nanoparticles Modified Aligned Carbon Nanotubes Electrode ", the range of linearity of product is 10 μ mol L -1~ 7mmol L -1Sensitivity is 10.417 μ A mmol -1Detection is limited to 8.89 μ mol.
In " modifying the electrochemical glucose biology sensor of Aligned carbon nanotubes electrode based on palladium nano-particles ", the range of linearity of product is 30 μ mol L -1~ 0.6mmol L -1Detection is limited to 7.26 μ mol.
Electrochemical glucose sensor of the present invention has the enzymatic glucose electrochemical sensor to compare with other, and sensitivity is the highest, and detection limit is minimum, and therefore, sensor performance of the present invention is excellent.

Claims (7)

1. high sensitivity electrochemical glucose sensor, it is characterized in that: described electrochemical sensor is the carbon nano-fiber composite material in the load of electrode face finish one deck pallas, wherein in the pallas, the content of platinum and palladium is respectively 15 ~ 16% and 4 ~ 6% of compound substance gross mass, and carbon nano-fiber content is 79 ~ 80% of gross mass.
2. high sensitivity electrochemical glucose sensor as claimed in claim 1, it is characterized in that: described carbon nano-fiber is solid carbon nanofiber.
3. solid carbon nanofiber as claimed in claim 2, it is characterized in that: the diameter of described solid carbon nanofiber is 50 ~ 150nm, length is 2 ~ 10 μ m.
4. as in each described high sensitivity electrochemical glucose sensor of claims 1 to 3, the preparation process of PdPt-CNFs is:
A, take by weighing carbon nano-fiber, join and contain H 2PtCl 63H 2O and K 2PdCl 4Solution in, mix ultrasonic agitation even;
The pH of B, adjusting mentioned solution stirs between 9.5 to 10;
C, when stirring, draw NaBH with glue head dropper 4Solution slowly is added drop-wise in the resulting mixed solution of step B, and then stirring reaction filters afterwards, and with the deionized water washing, drying obtains PdPt-CNFs.
5. such as the preparation method of each described high sensitivity electrochemical glucose sensor of claim 1 to 4, it is characterized in that: PdPt-CNFs is distributed to ultrasonic dispersion obtains uniform dispersion liquid in the solvent, then dispersant liquid drop is applied to behind the electrode surface of conventional cleaning and the evaporating solvent again fixing glucose oxidase, room temperature is carried out the crosslinked high sensitivity electrochemical glucose sensor that obtains after placing and drying again above containing glutaraldehyde saturated vapor pressure liquid level.
6. the preparation method of high sensitivity electrochemical glucose sensor as claimed in claim 5, it is characterized in that: described solvent is nitrogen, nitrogen-dimethyl formamide.
7. the preparation method of high sensitivity electrochemical glucose sensor as claimed in claim 5, it is characterized in that: the concentration of described glutaraldehyde saturated vapor pressure is 25%, electrode is 10min in the vapour pressure overhung time.
CN2012103302837A 2012-09-07 2012-09-07 High-sensitivity glucose electrochemical sensor and preparation method thereof Pending CN102901755A (en)

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Cited By (4)

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CN103424446A (en) * 2013-08-13 2013-12-04 常州大学 High-sensitivity non-enzymatic glucose electrochemical sensor and production method thereof
CN104651877A (en) * 2015-01-15 2015-05-27 常州大学 Preparation method of two metal composite materials and application
CN111239220A (en) * 2020-01-17 2020-06-05 广西师范大学 Preparation method of enzyme-free glucose sensor based on protein as carrier
CN112485317A (en) * 2020-11-11 2021-03-12 苏州健雄职业技术学院 Electrochemical method and device for detecting bisphenol A

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103424446A (en) * 2013-08-13 2013-12-04 常州大学 High-sensitivity non-enzymatic glucose electrochemical sensor and production method thereof
CN103424446B (en) * 2013-08-13 2015-09-16 常州大学 A kind of highly sensitive enzyme-free glucose electrochemical sensor and preparation method thereof
CN104651877A (en) * 2015-01-15 2015-05-27 常州大学 Preparation method of two metal composite materials and application
CN111239220A (en) * 2020-01-17 2020-06-05 广西师范大学 Preparation method of enzyme-free glucose sensor based on protein as carrier
CN111239220B (en) * 2020-01-17 2021-03-26 广西师范大学 Preparation method of enzyme-free glucose sensor based on protein as carrier
CN112485317A (en) * 2020-11-11 2021-03-12 苏州健雄职业技术学院 Electrochemical method and device for detecting bisphenol A

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Application publication date: 20130130