CN103454325A - Photocatalysed glucose microelectrode sensor and preparation method thereof - Google Patents
Photocatalysed glucose microelectrode sensor and preparation method thereof Download PDFInfo
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- CN103454325A CN103454325A CN2013103985299A CN201310398529A CN103454325A CN 103454325 A CN103454325 A CN 103454325A CN 2013103985299 A CN2013103985299 A CN 2013103985299A CN 201310398529 A CN201310398529 A CN 201310398529A CN 103454325 A CN103454325 A CN 103454325A
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Abstract
The invention relates to the field of electrochemical detection and particularly relates to a photocatalysed glucose microelectrode sensor and a preparation method thereof. The photocatalysed glucose microelectrode sensor comprises a base material, wherein a working electrode, a counter electrode and a reference electrode are arranged on the base material, a semiconductor quantum dot modified layer and a glucose oxidase modified layer are arranged on a working region of the working electrode, a micro optical fiber is arranged in the base material, light transmitted by the micro optical fiber vertically penetrates through the working electrode, and a semiconductor quantum dot is a CdSe@CdS semiconductor quantum dot. The photocatalysed glucose microelectrode sensor provided by the invention can be used for detecting the blood glucose under a lower potential in the absence of oxygen.
Description
Technical field
The present invention relates to the Electrochemical Detection field, particularly relate to a kind of photocatalyst-type glucose microelectrode sensor and preparation method thereof.
Background technology
Traditional glucose microelectrode sensor is modified electrode by glucose oxidase, when glucose microelectrode sensor detects blood sugar, oxygen is had to certain dependence, and detect and must can carry out at high potential, thereby the electroactive material coexisted may cause a series of spinoff.
In recent years, the nano science field has become the science frontier of new century, and it will change the mankind's production and life style.Simultaneously, nanosecond science and technology propose many new challenges to people aspect basic science, promote the development of basic science.Semiconductor-quantum-point is the typical structure of semiconductor nano material, and it plays a significant role in areas of information technology.Due to quantum size effect and surface effect, oneself becomes the focus of people's research semiconductor-quantum-point.People prepare the effort of quantum dot and its character of research and carried out for two more than ten years, have obtained huge progress.Quantum dot is a kind of nano particle by II-VI family and III gang element set, and it has electricity and the optical property of Size dependence, at light emitting diode, and non-property optics, solar cell, the fields such as life science are widely used.The semiconductor-quantum-point material made at present mainly contains following several large class: (1) IV family quanta point material, as: Si, Ge; (2) III-V family quanta point material, as: the quantum dots such as InAs, GaSb, GaN; (3) II-VI family quanta point material, as: the quantum dots such as CdSe, ZnSe, CdTe.
Because the semiconductor nano quantum dot has unique photoelectric property, wide optical absorption spectra, narrow and can to regulate emission spectrum, high Optic-electronic Stabilization qualitative etc., and the advantage such as high surface, making them be easy to amalyzing substances reacts and produces corresponding signal, therefore, the semiconductor nano quantum dot is increasing in the field of biosensors range of application.
Summary of the invention
The shortcoming of prior art, the object of the present invention is to provide a kind of photocatalyst-type glucose microelectrode sensor and preparation method thereof, for solving the prior art problem in view of the above.
Reach for achieving the above object other relevant purposes, the present invention utilizes semiconductor-quantum-point to have maximum light absorption under specific wavelength, electronics generation transition produces photocurrent, quantum dot is fixed on enzyme electrode as light activated element, thereby prepares photocatalyst-type glucose microelectrode sensor.
First aspect present invention provides a kind of photocatalyst-type glucose microelectrode sensor, comprise base material, described base material is provided with working electrode, to electrode and contrast electrode, the perform region of described working electrode is provided with semiconductor-quantum-point decorative layer and glucose oxidase decorative layer, be provided with micro optical fiber in described base material, the light that described micro optical fiber transmits is vertically through working electrode, and described semiconductor-quantum-point is CdSe@CdS semiconductor-quantum-point.
Preferably, described working electrode, electrode and contrast electrode are provided with to a stitch corresponding with it separately, described each stitch all is positioned at the top of microelectrode sensor.
Preferably, described each electrode (working electrode, to electrode, contrast electrode) mutually between insulation, and according to working electrode, the order of electrode, contrast electrode is arranged in order from end to the top of microelectrode sensor.
Preferably, described microelectrode sensor surface is provided with one deck biocompatibility protective seam.Specifically refer to whole microelectrode sensor surface (comprising each electrode surface), be equipped with one deck biocompatibility protective seam.
Preferred, the material of described biocompatibility protective seam is organic silicone.
Further preferred, described biocompatibility protective seam is organic silicone, for example dimethyl siloxane and hydrophilic modifying thing thereof.
The biocompatibility protective seam can be regulated seeing through of glucose; Can protect decorative layer not come off; Can be so that this sensor, by good biocompatibility, reduces the immunological rejection of human body.
Preferably, described working electrode is indium tin oxide (ITO, Indium tin oxide) conductive glass electrode.
In the present invention to SnO in indium tin oxide
2: In
2o
3ratio there is no specific (special) requirements.
Preferably, SnO in indium tin oxide
2: In
2o
3ratio is common mass ratio, i.e. SnO
2: In
2o
3mass ratio be 1:9.
Preferably, described is platinum electrode to electrode.
Preferably, described contrast electrode is the Ag/AgCl electrode.
Preferably, the light wavelength scope that described micro optical fiber transmits is 350-1250nm.Be preferably 580nm-680nm.
Preferably, the particle size range of described semiconductor-quantum-point is 4-10nm.
Preferably, on the perform region of described working electrode, also be provided with carbon nano tube modified layer.
Preferred, on the perform region of described working electrode, the order of each decorative layer is first to modify one deck carbon nano-tube, then modify the layer of semiconductor quantum dot, then modify one deck glucose oxidase.
Preferably, the thickness of described microelectrode sensor is 0.05-1mm, and the work area of working electrode is 2-10mm
2, to the work area of electrode, be 2-15mm
2, the work area of contrast electrode is 1-10mm
2.
Photocatalyst-type glucose microelectrode sensor provided by the present invention, its preparation technology is except working electrode, all identical with conventional photocatalyst-type microelectrode sensor.Connect wire, be the method for using ultrasonic spraying to the preparation of electrode and contrast electrode, on electrode base material, direct spraying goes out accordingly electrode pattern, contrast electrode figure and connects wire, and the material of spraying can be used nano platinum or Nano Silver; Also can use the method for the micro-printing of ink-jet, directly print accordingly electrode pattern, contrast electrode figure on electrode base material and connect wire, the material of printing can be used nano platinum or Nano Silver; Can also adopt photoetching technique to prepare corresponding figure and mask on base material, then by sputtering technology sputter Precious Metals-Gold, form to connect wire, then respectively on to the electrode position sputter platinum form electrode, form contrast electrode at contrast electrode position sputtering silver/silver chloride.The preparation of working electrode is to use photoetching, electroforming and injection molding technology to make the MEMS(MEMS (micro electro mechanical system), Micro-Electro-Mechanic System) mould, utilize the hot compression molding technology to carry out micro-plastic casting micro optical fiber array, then on working electrode, spray indium tin oxide.
Second aspect present invention provides the preparation method of the working electrode of described photocatalyst-type glucose microelectrode sensor, adopts the method for self assembly layer by layer, comprises the steps:
A) will carry out pre-service as the indium tin oxide conductive glass electrode of working electrode, make its surface band negative charge; The gained working electrode is immersed to polypropylene amine hydrochloride (PAH) and Phen cobalt ([Co (Phen)
3]
2+/3+) mixed aqueous solution, after taking-up, with deionized water, rinse well and dry up with nitrogen;
B) the gained working electrode is immersed in carbon nano-tube aqueous solutions, after taking-up, with deionized water, rinse well and dry up with nitrogen;
C) the gained working electrode is immersed to polypropylene amine hydrochloride (PAH) and Phen cobalt ([Co (Phen)
3]
2+/3+) mixed aqueous solution, after taking-up, with deionized water, rinse well and dry up with nitrogen;
D) the gained working electrode is immersed in the semiconductor-quantum-point aqueous solution, after taking-up, with deionized water, rinse well and dry up with nitrogen;
E) the gained working electrode is immersed to polypropylene amine hydrochloride (PAH) and Phen cobalt ([Co (Phen)
3]
2+/3+) mixed aqueous solution, after taking-up, with deionized water, rinse well and dry up with nitrogen;
F) finally the gained working electrode is immersed in the glucose oxidase enzyme aqueous solution prepared, after taking-up, with deionized water, rinse well and dry up with nitrogen.
Preferably, in described step a), to carry out pre-service as the indium tin oxide conductive glass electrode of working electrode, make the concrete steps of its surface band negative charge be: to prepare the concentrated sulphuric acid/hydrogen peroxide treatment liquid, then the concentrated sulphuric acid/hydrogen peroxide treatment liquid is put into in the working electrode zone of microelectrode, 1-2 hour is processed in 70-80 ℃ of water bath with thermostatic control, takes out from treating fluid and fully cleans with deionized water.Again hydrogen peroxide/WITH AMMONIA TREATMENT liquid is put into in the working electrode zone of microelectrode, 1-2 hour is processed in 60-70 ℃ of water bath with thermostatic control, finally with deionized water, rinses well.
Preferred, the described concentrated sulphuric acid/hydrogen peroxide treatment liquid, form (volume ratio) by concentrated sulfuric acid aqueous solution and aqueous hydrogen peroxide solution by proportioning 7:3 configuration.
Further preferred, the concentration of described concentrated sulfuric acid aqueous solution is 95～98wt%.
Further preferred, described aqueous hydrogen peroxide solution is commercially available, and concentration is about 30wt%.
Preferred, described hydrogen peroxide/WITH AMMONIA TREATMENT liquid, form (volume ratio) by aqueous hydrogen peroxide solution and ammoniacal liquor by proportioning 1:1 configuration.
Further preferred, the concentration of described ammoniacal liquor is 25～28wt%.
Further preferred, described aqueous hydrogen peroxide solution is commercially available, and concentration is about 30wt%.
Preferably, described step a), c), e) in, immerse polypropylene amine hydrochloride (PAH) and Phen cobalt ([Co (Phen)
3]
2+/3+) time of mixed aqueous solution be 5-10min.
Preferably, described step a), c), e) in, polypropylene amine hydrochloride (PAH) and Phen cobalt ([Co (Phen)
3]
2+/3+) mixed aqueous solution in, the concentration of polypropylene amine hydrochloride (PAH) is 1-2mg/mL, Phen cobalt ([Co (Phen)
3]
2+/3+) concentration be 1-2mg/mL.
Described Phen cobalt passes through the solid state reaction method by hydrated cobalt chloride (CoCl
22H
2o) with phenanthroline (C
12h
8n
2h
2o) grind according to a certain percentage preparation.
Preferably, in described step b), the time that working electrode immerses carbon nano-tube solution is 5-10min.
Preferably, in described step b), the concentration of carbon nano-tube aqueous solutions is 10-20mg/mL.
The concrete grammar that described carbon nano-tube is carried out acidification is: carbon nano-tube is added in the nitration mixture of the excessive concentrated sulphuric acid and red fuming nitric acid (RFNA), and ultrasonic processing 4-6h, centrifugal, the gained carbon nano-tube is washed to neutrality; After centrifugal, drying, add suitable deionized water in the gained carbon nano-tube again, the ultrasonic purpose of ultrasonic 1-2h(, for disperseing again, is about to carbon nano-tube and scatter in water).
Carbon nano-tube is carried out to acidification, and the carbon nano-tube after processing forms electronegative carboxylic group on surface.
Preferably, in described step d), the time that working electrode immerses the semiconductor-quantum-point aqueous solution is 5-10min.
Preferably, in described step d), the semiconductor-quantum-point aqueous solution is CdSe@CdS semiconductor-quantum-point aqueous solution, and concentration is 1 * 10
-6-5 * 10
-6mol/L.
The preparation method of described semiconductor-quantum-point aqueous solution is: by six perchloric acid hydrate cadmium (Cd (ClO
4)
26H
2o) and two hydration sodium citrate (Na
3c
6h
5o
72H
2o) be dissolved in deionized water, logical nitrogen carries out deoxygenation, with NaOH, the potential of hydrogen of mixed solution is transferred to 9.0.And then add selenourea (C
3h
8n
2se), and logical nitrogen carries out deoxygenation again, last microwave heating, and reaction conditions is high fire, and 0.5-2 minute takes out mixed solution after heating, and room temperature is standing cooling.Add thioacetamide (CH in above-mentioned mixed liquor
3cSNH
2), after rocking and mixing, the reaction system heating being carried out to back flow reaction, reaction conditions is 60-70 ℃, in course of reaction, a straight-through nitrogen is protected, and can obtain testing required quantum dot.
Those skilled in the art can be rule of thumb, by adjusting the reaction time, to obtain the CdSe@CdS semiconductor quantum of different-grain diameter.
The molar feed ratio of six perchloric acid hydrate cadmiums, two hydration sodium citrates, selenourea, thioacetamide is: 8:17-25:2-3:2-3.
Preferably, in described step f), the time that working electrode immerses the glucose oxidase enzyme aqueous solution is 5-10min.
Preferably, in described step f), the concentration of glucose oxidase enzyme aqueous solution is 20-100mg/mL.
Preferably, also on gained microelectrode surface, prepare one deck biocompatibility protective seam.
The preparation method of described biocompatibility protective seam is: the method by dip-coating, spraying or spin coating is modified electrode surface by organic silicone.
Third aspect present invention provides the application of described photocatalyst-type glucose microelectrode sensor in the glucose detection field.
As mentioned above, photocatalyst-type glucose microelectrode sensor provided by the present invention is a kind ofly not need oxygen, can detect the photocatalyst-type glucose microelectrode sensor of blood sugar than electronegative potential.
This glucose microelectrode sensor, in glucose oxidase layer, has Phen cobalt ([Co (Phen) 3] 2+/3+) and glucose oxidase mutually to mix, and the Phen cobalt can be at oxidation state ([Co (Phen) as electron mediator
3]
3+) and reduction-state ([Co (Phen)
3]
2+) between phase co-conversion and conduction electron.When glucose oxidase enzymatic glucose becomes gluconic acid, glucose oxidase obtains electronics to be changed and is called reduction-state by oxidation state, and the Phen cobalt of oxidation state ([Co (Phen)
3]
3+) can redox state glucose oxidase obtain electronics and change Phen the cobalt ([Co (Phen) of reduction-state into
3]
2+), this reaction does not need the participation of oxygen.Simultaneously, under illumination condition, semiconductor-quantum-point is subject to optical excitation, and its valence band electronic transition is to conduction band and then transfer on working electrode surface; The semiconductor-quantum-point valence band produces the hole with oxidisability because losing electronics, the ([Co (Phen) that hole again can redox state
3]
2+), thereby form electronic loop endlessly, produce stable photocurrent.(its concrete mechanism is as shown in Fig. 4 A and 4B)
The accompanying drawing explanation
Fig. 1 is the vertical view of photocatalyst-type glucose microelectrode sensor of the present invention.
Fig. 2 is the longitudinal diagram of photocatalyst-type glucose microelectrode sensor.
Fig. 3 is the process flow diagram of the working electrode of self-assembling method modification layer by layer.
Fig. 4 A and Fig. 4 B are the detection schematic diagrams of photocatalyst-type glucose microelectrode sensor of the present invention.
Fig. 5 is its ultraviolet-visible absorption spectroscopy and fluorescence spectrum after CdSe@CdS quantum dot dilutes 20 times.
Fig. 6 is at 1800～400cm
-1measured Phen cobalt compound (Co (Phen) in scope
3cl
2) infrared spectrum.
The element numbers explanation
1 base material
2 stitch
3 conductors
4 contrast electrodes
5 pairs of electrodes
6 working electrodes
7 micro optical fibers
Embodiment
Below, by specific instantiation explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this instructions.The present invention can also be implemented or be applied by other different embodiment, and the every details in this instructions also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
Notice, process equipment or device concrete not dated in the following example all adopt conventional equipment or the device in this area; All force value and scope all refer to absolute pressure.
Should be understood that in addition that one or more method steps of mentioning in the present invention do not repel between the step that can also have the additive method step or clearly mention at these before and after described combination step can also insert the additive method step, except as otherwise noted; Will also be understood that, the relation that is connected between one or more equipment of mentioning in the present invention/device is not repelled between two equipment/devices that can also have other equipment/devices or clearly mention at these before and after described unit equipment/device can also insert other equipment/devices, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only for differentiating the convenient tool of various method steps, but not ordering or the enforceable scope of restriction the present invention for limiting various method steps, the change of its relativeness or adjustment, in the situation that without essence change technology contents, when also being considered as the enforceable category of the present invention.
A kind of photocatalyst-type glucose microelectrode sensor as depicted in figs. 1 and 2; comprise base material 1; described base material 1 is provided with working electrode 6, to electrode and contrast electrode; be modified with successively from inside to outside carbon nanotube layer, CdSe@CdS semiconductor-quantum-point layer, glucose oxidase layer, biocompatibility protective seam on the perform region of described working electrode 6; be provided with micro optical fiber 7 in described base material 1, the light that described micro optical fiber 7 transmits is vertically through working electrode 6.Described working electrode 6, electrode 5 and contrast electrode 4 are provided with to a stitch corresponding with it 2 separately, described each stitch 2 all is positioned at the top of microelectrode sensor, and is connected by conductor 3 with each self-corresponding electrode.Working electrode 6, to electrode 5, contrast electrode 4 mutually between insulation, and according to working electrode 6, the order of electrode 5, contrast electrode 4 is arranged in order from end to the top of microelectrode sensor.
Embodiment 1
Preparation CdSe@CdS semiconductor-quantum-point
Take 0.0336g six perchloric acid hydrate cadmium (Cd (ClO
4)
26H
2o) and 0.05g bis-hydration sodium citrate (Na
3c
6h
5o
72H
2o) be dissolved into together in the 45ml deionized water, logical nitrogen carries out deoxygenation 10min, with 2 molar sodium hydroxides (NaOH), the pH value of mixed solution is transferred to 9.0.And then add 0.003g selenourea (C
3h
8n
2se), and logical nitrogen carries out deoxygenation 1min again, finally puts into the micro-wave oven microwave and heats 1min, makes the color of mixed solution from the colourless redness that becomes, and takes out mixed solution, and room temperature is standing cooling.
Finally, add 0.0015g thioacetamide (CH in above-mentioned mixed liquor
3cSNH
2), rock and mix, this mixed liquor is injected in clean three-necked bottle, reaction system heats and carries out back flow reaction by oil bath, and oil bath temperature is 70 ℃, and the reaction time is 24h, and in reaction, a straight-through nitrogen is protected.Can obtain testing required CdSe@CdS quantum dot.
Fig. 5 is after CdSe@CdS quantum dot dilutes 20 times, its ultraviolet-visible absorption spectroscopy and fluorescence spectrum, and the first absorption peak position of its ultra-violet absorption spectrum is 560nm, the fluorescence spectrum emission peak positions is 586nm.As calculated, the CdSe quantum point grain diameter is 3.3nm, and the concentration of CdSe@CdS quantum dot solution is 1.59 * 10
-6molL
-1.
Embodiment 2
Standby Phen the cobalt ([Co (Phen) of solid state reaction legal system
3]
2+/3+)
The ratio of 1:3, take hydrated cobalt chloride (CoCl in molar ratio
22H
2o) with Phen (Phen, C
12h
8n
2h
2o) be put in grinding, at room temperature mixed, grind, at first the color of potpourri becomes rose pink, continues to grind, and it is green that the color of potpourri gradually becomes, and grinds until the color of potpourri becomes crocus gradually from green.
CoCl
26H
2the solid phase reaction of O and Phen is that the course of reaction of carrying out in two steps through a green intermediate is expressed as with equation:
To synthetic Phen cobalt compound (Co (Phen)
3cl
2), by FFIR, characterized.At 1800～400cm
-1measured Co (Phen) in scope
3cl
2infrared spectrum, shown in Fig. 6, its main absorption peak position is: 1623cm
-1, 1516cm
-1, 1421cm
-1, 1103cm
-1, 852cm
-1, 773cm
-1, 723cm
-1.Embedded figure is at 600～400cm
-1the infrared spectrogram of amplifying in scope, the absorption peak position is: 507cm
-1, 472cm
-1, 441cm
-1, 420cm
-1.Phen cobalt prepared by solid reaction process (Co (Phen)
3cl
2) infrared spectrum consistent with the result of bibliographical information.
Embodiment 3
The preparation (s1-s5) of glucose microelectrode sensor:
Glucose microelectrode sensor (thickness 0.1mm, working electrode area 6mm
2, to electrode area 9mm
2, contrast electrode area 6mm
2), use photoetching, electroforming and injection molding technology to make the MEMS(MEMS (micro electro mechanical system), Micro-Electro-Mechanic System) mould, utilize the hot compression molding technology to carry out micro-plastic casting micro optical fiber array and form working electrode, on electrode base material, direct spraying goes out accordingly electrode pattern, contrast electrode figure, working electrode figure and connects wire, and the material of spraying can be used nano platinum, Nano Silver or indium tin oxide.
The preparation flow of the functional layer of sensor as shown in Figure 3, adopts the method for self assembly layer by layer, comprises the steps:
A) will carry out pre-service as the indium tin oxide conductive glass electrode of working electrode, make its surface band negative charge; The gained working electrode is immersed to polypropylene amine hydrochloride (1.5mg/mL, PAH) and Phen cobalt (1.5mg/mL, [Co (Phen)
3]
2+/3+) mixed aqueous solution 8min, after taking-up, with deionized water, rinse well and dry up with nitrogen;
B) the gained working electrode is immersed to 8min in carbon nano-tube aqueous solutions (15mg/mL), after taking-up, with deionized water, rinse well and dry up with nitrogen;
C) the gained working electrode is immersed to the mixed aqueous solution 8min of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
D) the gained working electrode is immersed to semiconductor-quantum-point aqueous solution (1.59 * 10
-6mol/L, particle diameter 7nm, corresponding optical wavelength 641nm) middle 8min, after taking-up, rinse well and dry up with nitrogen with deionized water;
E) the gained working electrode is immersed to the mixed aqueous solution 8min of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
F) finally the gained working electrode is immersed to 8min in the glucose oxidase enzyme aqueous solution (60mg/mL) prepared, after taking-up, with deionized water, rinse well and dry up with nitrogen.
Gained microelectrode s1-s5 is carried out to accuracy and reperformance test (be platinum electrode to electrode, contrast electrode is the Ag/AgCl electrode), and result as described in Example 8.
Embodiment 4
The preparation of glucose microelectrode sensor:
Glucose microelectrode sensor (thickness 0.1mm, working electrode area 6mm
2, to electrode area 9mm
2, contrast electrode area 6mm
2), use photoetching, electroforming and injection molding technology to make the MEMS(MEMS (micro electro mechanical system), Micro-Electro-Mechanic System) mould, utilize the hot compression molding technology to carry out micro-plastic casting micro optical fiber array and form working electrode, on electrode base material, direct spraying goes out accordingly electrode pattern, contrast electrode figure, working electrode figure and connects wire, and the material of spraying can be used nano platinum, Nano Silver or indium tin oxide.
The preparation flow of the functional layer of sensor as shown in Figure 3, adopts the method for self assembly layer by layer, comprises the steps:
A) will carry out pre-service as the indium tin oxide conductive glass electrode of working electrode, make its surface band negative charge; The gained working electrode is immersed to polypropylene amine hydrochloride (1.5mg/mL, PAH) and Phen cobalt (1.5mg/mL, [Co (Phen)
3]
2+/3+) mixed aqueous solution 8min, after taking-up, with deionized water, rinse well and dry up with nitrogen;
B) the gained working electrode is immersed to 8min in carbon nano-tube aqueous solutions (15mg/mL), after taking-up, with deionized water, rinse well and dry up with nitrogen;
C) the gained working electrode is immersed to the mixed aqueous solution 8min of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
D) the gained working electrode is immersed to semiconductor-quantum-point aqueous solution (1 * 10
-6mol/L, particle diameter 10nm, corresponding optical wavelength 673nm) middle 8min, after taking-up, rinse well and dry up with nitrogen with deionized water;
E) the gained working electrode is immersed to the mixed aqueous solution 8min of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
F) finally the gained working electrode is immersed to 8min in the glucose oxidase enzyme aqueous solution (60mg/mL) prepared, after taking-up, with deionized water, rinse well and dry up with nitrogen.
Gained microelectrode test blood-sugar content (about 10mM), have very high accuracy and repeatability, close with embodiment 3 (be platinum electrode to electrode, contrast electrode is the Ag/AgCl electrode).
Embodiment 5
The preparation of glucose microelectrode sensor:
Glucose microelectrode sensor (thickness 0.05mm, working electrode area 10mm
2, to electrode area 15mm
2, contrast electrode area 10mm
2), use photoetching, electroforming and injection molding technology to make the MEMS(MEMS (micro electro mechanical system), Micro-Electro-Mechanic System) mould, utilize the hot compression molding technology to carry out micro-plastic casting micro optical fiber array and form working electrode, on electrode base material, direct spraying goes out accordingly electrode pattern, contrast electrode figure, working electrode figure and connects wire, and the material of spraying can be used nano platinum, Nano Silver or indium tin oxide.
The preparation flow of the functional layer of sensor as shown in Figure 3, adopts the method for self assembly layer by layer, comprises the steps:
A) will carry out pre-service as the indium tin oxide conductive glass electrode of working electrode, make its surface band negative charge; The gained working electrode is immersed to polypropylene amine hydrochloride (1mg/mL, PAH) and Phen cobalt (1mg/mL, [Co (Phen)
3]
2+/3+) mixed aqueous solution 10min, after taking-up, with deionized water, rinse well and dry up with nitrogen;
B) the gained working electrode is immersed to 10min in carbon nano-tube aqueous solutions (10mg/mL), after taking-up, with deionized water, rinse well and dry up with nitrogen;
C) the gained working electrode is immersed to the mixed aqueous solution 10min of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
D) the gained working electrode is immersed to semiconductor-quantum-point aqueous solution (5 * 10
-6mol/L, particle diameter 7nm, corresponding optical wavelength 641nm) middle 10min, after taking-up, rinse well and dry up with nitrogen with deionized water;
E) the gained working electrode is immersed to the mixed aqueous solution 10min of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
F) finally the gained working electrode is immersed to 10min in the glucose oxidase enzyme aqueous solution (20mg/mL) prepared, after taking-up, with deionized water, rinse well and dry up with nitrogen.
Gained microelectrode test blood-sugar content (about 10mM), have very high accuracy and repeatability, close with embodiment 3 (be platinum electrode to electrode, contrast electrode is the Ag/AgCl electrode).
Embodiment 6
The preparation of glucose microelectrode sensor:
Glucose microelectrode sensor (thickness 1mm, working electrode area 2mm
2, to electrode area 2mm
2, contrast electrode area 1mm
2), use photoetching, electroforming and injection molding technology to make the MEMS(MEMS (micro electro mechanical system), Micro-Electro-Mechanic System) mould, utilize the hot compression molding technology to carry out micro-plastic casting micro optical fiber array and form working electrode, on electrode base material, direct spraying goes out accordingly electrode pattern, contrast electrode figure, working electrode figure and connects wire, and the material of spraying can be used nano platinum, Nano Silver or indium tin oxide.
The preparation flow of the functional layer of sensor as shown in Figure 3, adopts the method for self assembly layer by layer, comprises the steps:
A) will carry out pre-service as the indium tin oxide conductive glass electrode of working electrode, make its surface band negative charge; The gained working electrode is immersed to polypropylene amine hydrochloride (2mg/mL, PAH) and Phen cobalt (2mg/mL, [Co (Phen)
3]
2+/3+) mixed aqueous solution 5min, after taking-up, with deionized water, rinse well and dry up with nitrogen;
B) the gained working electrode is immersed to 5min in carbon nano-tube aqueous solutions (20mg/mL), after taking-up, with deionized water, rinse well and dry up with nitrogen;
C) the gained working electrode is immersed to the mixed aqueous solution 5min of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
D) the gained working electrode is immersed to semiconductor-quantum-point aqueous solution (5 * 10
-6mol/L, particle diameter 4nm, corresponding optical wavelength 586nm) middle 5min, after taking-up, rinse well and dry up with nitrogen with deionized water;
E) the gained working electrode is immersed to the mixed aqueous solution 5min of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
F) finally the gained working electrode is immersed to 5min in the glucose oxidase enzyme aqueous solution (100mg/mL) prepared, after taking-up, with deionized water, rinse well and dry up with nitrogen.
Gained microelectrode test blood-sugar content (about 10mM), have very high accuracy and repeatability, close with embodiment 3 (be platinum electrode to electrode, contrast electrode is the Ag/AgCl electrode).
Embodiment 7
The preparation of glucose microelectrode sensor:
Glucose microelectrode sensor (thickness 0.15mm, working electrode area 4mm
2, to electrode area 7mm
2, contrast electrode area 4mm
2), use photoetching, electroforming and injection molding technology to make the MEMS(MEMS (micro electro mechanical system), Micro-Electro-Mechanic System) mould, utilize the hot compression molding technology to carry out micro-plastic casting micro optical fiber array and form working electrode, on electrode base material, direct spraying goes out accordingly electrode pattern, contrast electrode figure, working electrode figure and connects wire, and the material of spraying can be used nano platinum, Nano Silver or indium tin oxide.
The preparation flow of the functional layer of sensor as shown in Figure 3, adopts the method for self assembly layer by layer, comprises the steps:
A) will carry out pre-service as the indium tin oxide conductive glass electrode of working electrode, make its surface band negative charge; The gained working electrode is immersed to polypropylene amine hydrochloride (1.5mg/mL, PAH) and Phen cobalt (1.5mg/mL, [Co (Phen)
3]
2+/3+) mixed aqueous solution 8min, after taking-up, with deionized water, rinse well and dry up with nitrogen;
B) the gained working electrode is immersed to 8min in carbon nano-tube aqueous solutions (15mg/mL), after taking-up, with deionized water, rinse well and dry up with nitrogen;
C) the gained working electrode is immersed to the mixed aqueous solution 8min of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
D) the gained working electrode is immersed to semiconductor-quantum-point aqueous solution (3 * 10
-6mol/L, the corresponding optical wavelength 641nm of particle diameter 7nm) middle 8min, after taking-up, rinse well and dry up with nitrogen with deionized water;
E) the gained working electrode is immersed to the mixed aqueous solution 8min of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
F) finally the gained working electrode is immersed to 8min in the glucose oxidase enzyme aqueous solution (60mg/mL) prepared, after taking-up, with deionized water, rinse well and dry up with nitrogen.
Gained microelectrode test blood-sugar content (about 10mM), have very high accuracy and repeatability, close with embodiment 3 (be platinum electrode to electrode, contrast electrode is the Ag/AgCl electrode).
Embodiment 8
Adopt the prepared microelectrode of embodiment 3 to carry out the glucose test;
Get 5 microelectrodes (s1-s5) and test blood-sugar content in a certain blood sample (about 10mM), proofreaied and correct according to measured current value; Wherein, the blood-sugar content in blood sample, through the YSI test, be 9.83mM; Therefore, the sensitivity of these 5 microelectrodes is:
With three variable concentrations blood sugar blood samples of this 5 microelectrode tests, wherein the blood-sugar content in blood sample is measured by YSI respectively:
| ? | s1 | s2 | s3 | s4 | s5 | aver(s1-s5) | YSI |
| Blood sample 1 | 3.92 | 3.83 | 3.54 | 3.56 | 3.44 | 3.66 | 3.59 |
| Blood sample 2 | 13.8 | 14.6 | 14.3 | 14.5 | 13.7 | 14.18 | 14.2 |
| Blood sample 3 | 33.9 | 35.2 | 32.9 | 34.2 | 35.3 | 34.30 | 34.6 |
Known, microelectrode test blood-sugar content of the present invention, have very high accuracy and repeatability.
In sum, the present invention has effectively overcome various shortcoming of the prior art and the tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, be modified or be changed above-described embodiment.Therefore, such as in affiliated technical field, have and usually know that the knowledgeable, not breaking away from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (13)
1. a photocatalyst-type glucose microelectrode sensor, comprise base material, described base material is provided with working electrode, to electrode and contrast electrode, the perform region of described working electrode is provided with semiconductor-quantum-point decorative layer and glucose oxidase decorative layer, be provided with micro optical fiber in described base material, the light that described micro optical fiber transmits is vertically through described working electrode, and described semiconductor-quantum-point is CdSe@CdS semiconductor-quantum-point.
2. a kind of photocatalyst-type glucose microelectrode sensor as claimed in claim 1, is characterized in that, described microelectrode sensor surface also is provided with one deck biocompatibility protective seam.
3. a kind of photocatalyst-type glucose microelectrode sensor as claimed in claim 1, is characterized in that, described working electrode is the indium tin oxide conductive glass electrode.
4. a kind of photocatalyst-type glucose microelectrode sensor as claimed in claim 1, is characterized in that, described is platinum electrode to electrode.
5. a kind of photocatalyst-type glucose microelectrode sensor as claimed in claim 1, is characterized in that, described contrast electrode is the Ag/AgCl electrode.
6. the preparation method of the working electrode of the described photocatalyst-type glucose of claim as arbitrary as claim 1-5 microelectrode sensor, adopt the method for self assembly layer by layer, comprises the steps:
A) will carry out pre-service as the indium tin oxide conductive glass electrode of working electrode, make its surface band negative charge; The gained working electrode is immersed to the mixed aqueous solution of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
B) the gained working electrode is immersed in carbon nano-tube aqueous solutions, after taking-up, with deionized water, rinse well and dry up with nitrogen;
C) the gained working electrode is immersed to the mixed aqueous solution of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
D) the gained working electrode is immersed in the semiconductor-quantum-point aqueous solution, after taking-up, with deionized water, rinse well and dry up with nitrogen;
E) the gained working electrode is immersed to the mixed aqueous solution of polypropylene amine hydrochloride and Phen cobalt, after taking-up, with deionized water, rinse well and dry up with nitrogen;
F) finally the gained working electrode is immersed in the glucose oxidase enzyme aqueous solution prepared, after taking-up, with deionized water, rinse well and dry up with nitrogen.
7. the preparation method of the working electrode of photocatalyst-type glucose microelectrode sensor as claimed in claim 6, it is characterized in that, in described step a), to carry out pre-service as the indium tin oxide conductive glass electrode of working electrode, make the concrete steps of its surface band negative charge be: to prepare the concentrated sulphuric acid/hydrogen peroxide treatment liquid, then the concentrated sulphuric acid/hydrogen peroxide treatment liquid is put into in the working electrode zone of microelectrode, 1-2 hour is processed in 70-80 ℃ of water bath with thermostatic control, takes out from treating fluid and fully cleans with deionized water; Again hydrogen peroxide/WITH AMMONIA TREATMENT liquid is put into in the working electrode zone of microelectrode, 1-2 hour is processed in 60-70 ℃ of water bath with thermostatic control, finally with deionized water, rinses well.
8. the preparation method of the working electrode of photocatalyst-type glucose microelectrode sensor as claimed in claim 6, it is characterized in that, described step a), c), e) in, in the mixed aqueous solution of polypropylene amine hydrochloride and Phen cobalt, the concentration of polypropylene amine hydrochloride is 1-2mg/mL, and the concentration of Phen cobalt is 1-2mg/mL.
9. the preparation method of the working electrode of photocatalyst-type glucose microelectrode sensor as claimed in claim 6, is characterized in that, in described step b), the concentration of carbon nano-tube aqueous solutions is 10-20mg/mL.
10. the preparation method of the working electrode of photocatalyst-type glucose microelectrode sensor as claimed in claim 6, is characterized in that, in described step d), the concentration of semiconductor-quantum-point aqueous solution is 1 * 10
-6-5 * 10
-6mol/L.
11. the preparation method of the working electrode of photocatalyst-type glucose microelectrode sensor as claimed in claim 6, is characterized in that, in described step f), the concentration of glucose oxidase enzyme aqueous solution is 10-20mg/mL.
12. the preparation method of the working electrode of photocatalyst-type glucose microelectrode sensor as claimed in claim 6, is characterized in that, after described step f), also at the gained working electrode surface, prepares one deck biocompatibility protective seam.
13. the described photocatalyst-type glucose of claim as arbitrary as claim 1-5 microelectrode sensor is in the application in glucose detection field.
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