CN101320036B - Detection method of non-enzyme glucose - Google Patents

Detection method of non-enzyme glucose Download PDF

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Publication number
CN101320036B
CN101320036B CN 200810124404 CN200810124404A CN101320036B CN 101320036 B CN101320036 B CN 101320036B CN 200810124404 CN200810124404 CN 200810124404 CN 200810124404 A CN200810124404 A CN 200810124404A CN 101320036 B CN101320036 B CN 101320036B
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electrode
glucose
mesoporous
detection
tubulose
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CN101320036A (en
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戴志晖
包建春
白红艳
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Nanjing Normal University
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Nanjing Normal University
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Abstract

The invention relates to a detecting method of glucose without enzyme, which is characterized in that the method comprises the following steps: insoluble microsphere material is added in two mutually overlapped Al2O3 templates for the space occupying; an electrodeposition method is used for electrodepositioning metal onto the Al2O3 templates; the Al2O3 templates and the space occupying material are dissolved to form mesoporous tubular metal nanometer material; mesoporous tubular metal is used for modifying an electrode; the mesoporous tubular metal is used for modifying the electrode to directly detect the glucose. The electrodepositioned metal is selected from Pd, Ag, Au or Cu. Compared with a solid tube, the detection method is provided with wider detection limit, higher sensitivity andbetter stability and reproducibility for the glucose detection. According to the experiment, the linear range of the glucose detection is 0.1-58mM, the detection limit is 0.08mM, and the stability isbetter. The method can be applied to the glucose concentration detection in clinic and environmental chemistry.

Description

The detection method of enzyme-free glucose
Technical field
The present invention relates to a kind of novelty, easy, quick, sensitive, stable glucose detection method.
Background technology
Glucose is one of chemical component material the most basic in the human body, is the main source that energy is provided for organism.The detection glucose of high sensitivity, high selectivity, high stability has important academic significance and using value.The method of measuring at present glucose is to be based upon on the basis of immobilised enzymes, has high selectivity and sensitivity although utilize immobilised enzymes to detect, and some shortcomings of enzyme will show.Activity such as enzyme reduces in time, and changeableness in immobilization process is subjected to the impact of temperature, humidity, pH value, noxious material.The proposition of enzyme-free glucose detection method can overcome enzyme itself unstable, easily the shortcoming of inactivation, be subjected to the impact of temperature less, oxygen in the sample because it is different from the mechanism of interfering material to measure test substance, can strengthen jamproof ability on measuring not impact greatly.
Summary of the invention
In order to solve the problems referred to above of prior art existence, the purpose of this invention is to provide a kind of detection method of enzyme-free glucose.New method can be easy, quick, sensitive, stable detection glucose.
The scheme of finishing the foregoing invention task is, a kind of detection method of enzyme-free glucose is characterized in that, step is as follows:
At two overlapped Al 2O 3Add insoluble microballoon material in the template and be used for occupy-place;
Method with electro-deposition makes metal electrodeposition arrive this Al 2O 3On the template;
Dissolving Al 2O 3Template and occupy-place material form mesoporous tubular metal nano material;
Then use mesoporous tubular metal modified electrode;
Utilize this mesoporous tubular metal modified electrode that glucose is carried out direct-detection.
The metal of described electro-deposition can be: Pd, Ag, Au, the metals such as Cu.
More detailed and more optimally say, the step of technique scheme is as follows:
(1), preparation one-dimensional mesoporous tubular metal nano particle (for example metal Pd)
A) at two Al of overlapped different size 2O 3Add respectively Cd (NO in the matrix 3) 2Na with same molar weight 2S.Then will contain Cd (NO 3) 2And Na 2The Al of S 2O 3Matrix takes out, and drying is put into PdCl 2And H 3BO 3Mixed solution in carry out constant-current electrolysis, utilize at last the dissolubility of material to dissolve Al 2O 3Template and occupy-place substance C d (NO3) 2And Na 2S namely gets mesoporous tubulose Pd nano particle.
Similar method can also be used to prepare Ag, Au, the one-dimensional mesoporous tubular metal nano particle of the metals such as Cu.PdCl wherein 2Change Ag into, Au, the salt of the metals such as Cu.
(2), detect preparation
On the good glass-carbon electrode of pre-service, drip successively suspension and the polymer film that is coated with mesoporous tubulose Pd nano particle, dry, aging;
Described polymer film can be: polyvinyl alcohol film, naphthols film, chitosan film etc.;
(3), the detection of glucose
Put into electrolytic cell with dripping the glass-carbon electrode that scribbles mesoporous tubulose Pd nano particle and polymer film;
In electrolytic cell, add continuously glucose, carry out Electrochemical Detection, record its ampere response, can obtain testing result.
The scheme of further optimizing is: the detection method of enzyme-free glucose, and concrete operation step is as follows:
(1), the one-dimensional mesoporous tubulose Pd of preparation
A) (seeing Fig. 1) adds Cd (NO in the device 3) 2, slowly suck with rubber pipette bulb, then add the Na of same amount 2S slowly sucks with rubber pipette bulb, and then sample introduction repetitive operation 4～5 times takes out matrix, is placed in the measuring cup dry.
B) electrolytic experiment:
Electrolytic solution: a certain amount of PdCl 2Added among the HCl ultrasonic 3 minutes, to wherein adding H 3BO 3, then regulate pH value to 6.5～7.0 with NaOH solution.
Electrolytic condition: utilize three-electrode system, contrast electrode is saturated calomel electrode (SCE), and auxiliary electrode is platinized platinum, and working electrode is for being equipped with Al 2O 3The electrolytic tank of template.Constant-current electrolysis, electrolysis time are 10 hours and get final product.
C) sample detection: be mesoporous tubular material (seeing accompanying drawing 2) with the transmission electron microscope observing sample.
(2), detect preparation
Mesoporous tubulose Pd suspension and 3% polyvinyl alcohol (PVA) (volume ratio of second alcohol and water is 1: 1) of preparation 3mg/mL in deionized water, on the good glass-carbon electrode of pre-service, drip successively the polyvinyl alcohol (PVA) that is coated with 2 μ L mesoporous tubulose Pd suspensions and 2 μ L 3%, dry, aging;
(3), the detection of glucose
Measure at the CHI660B electrochemical workstation, saturated calomel electrode, platinum electrode and nanoscale iron protosulfide modified glassy carbon electrode are respectively as contrast electrode, to electrode and working electrode, be to add continuously glucose under the 0.6V in operating voltage, record its ampere response (seeing accompanying drawing 3).
Glucose detection method provided by the invention, come direct-detection glucose with mesoporous tubulose Pd, owing to being based upon without on the enzyme basis, can overcome enzyme itself unstable, the shortcoming of easy inactivation, and owing to having large specific surface area, so improved the sensitivity that detects, reached simultaneously easy, quick, sensitive, stable purpose.
More particularly, effect of the present invention has:
1. the work that to prepare the insoluble nano material occupy-place of one-dimensional mesoporous materials'use be a novelty.Directly during electro-deposition, can only obtain the one dimension solid tubes when not using this material, the mensuration that mesoporous pipe and solid tubes compare glucose has wider detectability, higher sensitivity, better stability and reappearance.
2. testing the range of linearity that records glucose detection is 0.1～58mM, detection is limited to 0.08mM, with come catalytic substrate to respond to detect the result that glucose obtains at electrode reaction generation current by glucose oxidase suitable, but stability is better, can be used for the detection of concentration of glucose in clinical and the environmental chemistry.
Description of drawings
Fig. 1 is Experimental equipment;
Fig. 2 is transmission electron microscope (TEM) figure of the used one-dimensional mesoporous tubulose Pd of the present invention;
Fig. 3 is the detection method of a kind of glucose provided by the present invention
Embodiment
Embodiment 1, the detection method of glucose,
(1), the one-dimensional mesoporous tubulose Pd of preparation
A) (seeing accompanying drawing 1) adds Cd (NO in the device 3) 2, slowly suck with rubber pipette bulb, then add the Na of same amount 2S slowly sucks with rubber pipette bulb, and then sample introduction repetitive operation 4～5 times takes out matrix, is placed in the measuring cup dry.
B) electrolytic experiment:
Electrolytic solution: a certain amount of PdCl 2Add simultaneously stirring in ultrasonic 3 minutes among the HCl, to wherein adding H 3BO 3, regulate pH value to 6.5～7.0 with NaOH solution.
Electrolytic condition: utilize three-electrode system, contrast electrode is saturated calomel electrode (SCE), and auxiliary electrode is platinized platinum, and working electrode is for being equipped with Al 2O 3The electrolytic tank of template.Constant-current electrolysis, electrolysis time are 10 hours and get final product.
C) sample detection: be mesoporous tubular material with the transmission electron microscope observing sample.
(2), detect preparation
Mesoporous tubulose Pd suspension and 3% polyvinyl alcohol (PVA) (volume ratio of second alcohol and water is 1: 1) of preparation 3mg/mL in deionized water, on the good glass-carbon electrode of pre-service, drip successively the polyvinyl alcohol (PVA) that is coated with 2 μ L mesoporous tubulose Pd suspensions and 2 μ L 3%, dry, aging;
(3), the detection of glucose
Measure at the CHI660 electrochemical workstation, saturated calomel electrode, platinum electrode and nanoscale iron protosulfide modified glassy carbon electrode are respectively as contrast electrode, to electrode and working electrode, be to add continuously glucose under the 0.6V in operating voltage, record its ampere response.
Embodiment 2, and is substantially the same manner as Example 1, but following change is arranged: one-dimensional mesoporous tubulose Pd changes one-dimensional mesoporous tubulose Au into.
Embodiment 3, and is substantially the same manner as Example 1, but following change is arranged: one-dimensional mesoporous tubulose Pd changes one-dimensional mesoporous tubulose Ag into.
Embodiment 4, and is substantially the same manner as Example 1, but following change is arranged: one-dimensional mesoporous tubulose Pd changes one-dimensional mesoporous tubulose Cu into.

Claims (1)

1. the detection method of an enzyme-free glucose is characterized in that, step is as follows:
At two overlapped Al 2O 3Add insoluble microballoon material in the template and be used for occupy-place;
Method with electro-deposition makes metal electrodeposition arrive this Al 2O 3On the template;
Dissolving Al 2O 3Template and occupy-place material form mesoporous tubular metal nano material;
Then use mesoporous tubular metal modified electrode;
Utilize this mesoporous tubular metal modified electrode that glucose is carried out direct-detection;
The metal of described electro-deposition is selected from: Pd, Ag, Au or Cu;
The concrete operation step of above method is as follows:
(1), the one-dimensional mesoporous tubulose Pd of preparation
A) in device, add Cd (NO 3) 2, slowly suck with rubber pipette bulb, then add the Na of same amount 2S slowly sucks with rubber pipette bulb, and then sample introduction repetitive operation 4～5 times takes out matrix, is placed in the measuring cup dry;
B) electrolytic experiment:
Electrolytic solution: a certain amount of PdCl 2Added among the HCl ultrasonic 3 minutes, to wherein adding H 3BO 3, then regulate pH value to 6.5～7.0 with NaOH solution;
Electrolytic condition: utilize three-electrode system, contrast electrode is saturated calomel electrode, and auxiliary electrode is platinized platinum, and working electrode is for being equipped with Al 2O 3The electrolytic tank of template; Constant-current electrolysis, electrolysis time are 10 hours and get final product;
C) sample detection: be mesoporous tubular material with the transmission electron microscope observing sample;
(2), detect preparation:
Mesoporous tubulose Pd suspension and 3% polyvinyl alcohol (PVA) of preparation 3mg/mL in deionized water, the volume ratio of second alcohol and water is 1: 1, on the good glass-carbon electrode of pre-service, drip successively the polyvinyl alcohol (PVA) that is coated with 2 μ L mesoporous tubulose Pd suspensions and 2 μ L3%, dry, aging;
(3), the detection of glucose:
Measure at CHI 660B electrochemical workstation, saturated calomel electrode, platinum electrode and nanoscale iron protosulfide modified glassy carbon electrode are respectively as contrast electrode, to electrode and working electrode, be to add continuously glucose under the 0.6V in operating voltage, record its ampere response.
CN 200810124404 2008-07-01 2008-07-01 Detection method of non-enzyme glucose Expired - Fee Related CN101320036B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103103572A (en) * 2012-11-29 2013-05-15 扬州大学 Preparation method and application of palladium nanomaterial used as non-enzymatic glucose sensor
CN103399059A (en) * 2013-07-11 2013-11-20 上海师范大学 Au(111)-like nano-particle non-enzyme glucose sensor electrode, and preparation method and application of same
CN108796463A (en) * 2018-06-29 2018-11-13 吉林大学 A kind of compound film electrode for examination of glucose concentration, preparation method and applications

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Courjault F.，et al..Effect of glucose and insulin deprivation on differentiation and carbohydrate metabolism of rabbit proximal tubular cells in primary culture.《Biochimica et Biophysica Acta》.1993,147-159. *
丁海云.纳米铜修饰玻碳电极的制备及其对葡萄糖的催化氧化.《分析化学》.2008,第36卷(第6期),839-842.
李祥子.氧化铝模板电沉积功能纳米材料研究进展.《化学研究》.2006,第17卷(第2期),97-101.
氧化铝模板电沉积功能纳米材料研究进展;李祥子;《化学研究》;20060630;第17卷(第2期);97-101 *
纳米铜修饰玻碳电极的制备及其对葡萄糖的催化氧化;丁海云;《分析化学》;20080630;第36卷(第6期);839-842 *

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