CN103454325B - Photocatalysed glucose microelectrode sensor and preparation method thereof - Google Patents
Photocatalysed glucose microelectrode sensor and preparation method thereof Download PDFInfo
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- CN103454325B CN103454325B CN201310398529.9A CN201310398529A CN103454325B CN 103454325 B CN103454325 B CN 103454325B CN 201310398529 A CN201310398529 A CN 201310398529A CN 103454325 B CN103454325 B CN 103454325B
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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 field of electrochemical detection, 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, certain dependence is had to oxygen when glucose microelectrode sensor detects blood sugar, and detect and can must carry out at high potential, thus the electroactive material coexisted may cause a series of spinoff.
In recent years, nano science field has become the science frontier of new century, and it will change production and the life style of the mankind.Meanwhile, nanosecond science and technology propose many challenges newly to people in 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, semiconductor-quantum-point oneself become people research focus.The effort that people prepare quantum dot and its character of research carried out for two more than ten years, achieved huge progress.Quantum dot is a kind of nano particle by II-VI group and III gang element set, and it has electricity and the optical property of Size dependence, and at light emitting diode, non-property optics, solar cell, the fields such as life science are widely used.Semiconductor-quantum-point material obtained at present, mainly contains following several large class: (1) IV race quanta point material, as: Si, Ge; (2) iii-v quanta point material, as: the quantum dots such as InAs, GaSb, GaN; (3) II-VI group quanta point material, as: the quantum dots such as CdSe, ZnSe, CdTe.
Because semiconductor nano quantum dot has unique photoelectric property, wide optical absorption spectra, narrow and adjustable emission spectrum, high Optic-electronic Stabilization are qualitative etc., and the advantage such as high surface, make them be easy to amalyzing substances react and produce corresponding signal, therefore, semiconductor nano quantum dot is increasing in field of biosensors range of application.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of photocatalyst-type glucose microelectrode sensor and preparation method thereof, for solving problem in prior art.
For achieving the above object and other relevant objects, the present invention utilizes semiconductor-quantum-point to have maximum light absorption at a particular wavelength, electronics generation transition produces photocurrent, is fixed on enzyme electrode by quantum dot, thus prepares photocatalyst-type glucose microelectrode sensor as light activated element.
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, micro optical fiber is provided with in described base material, the light that described micro optical fiber transmits passes perpendicularly through working electrode, and described semiconductor-quantum-point is CdSe@CdS semiconductor-quantum-point.
Preferably, described working electrode, electrode and contrast electrode be provided with separately to a stitch corresponding with it, described each stitch is all positioned at the top of microelectrode sensors.
Preferably, described each electrode (working electrode, to electrode, contrast electrode) mutually between insulation, and according to working electrode, be arranged in order to top from the end of microelectrode sensors the order of electrode, contrast electrode.
Preferably, described microelectrode sensors surface is provided with one deck biocompatibility protective seam.Concrete finger whole microelectrode sensors surface (comprising each electrode surface), is equipped with one deck biocompatibility protective seam.
Preferred, the material of described biocompatibility protective seam is organic silicone.
Preferred further, described biocompatibility protective seam is organic silicone, such as dimethyl siloxane and hydrophilic modifying thing thereof.
Biocompatibility protective seam can regulate glucose through; Decorative layer can be protected not come off; This sensor can be made by good biocompatibility, reduce the immunological rejection of human body.
Preferably, described working electrode is indium tin oxide (ITO, Indium tin oxide) conductive glass electrode.
To SnO in indium tin oxide in the present invention
2: In
2o
3ratio there is no particular/special requirement.
Preferably, SnO in indium tin oxide
2: In
2o
3ratio is usual 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 Ag/AgCl electrode.
Preferably, the wavelength coverage of light 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, be also provided with carbon nano tube modified layer.
Preferred, on the perform region of described working electrode, the order of each decorative layer is, first modifies one deck carbon nano-tube, then modifies layer of semiconductor quantum dot, then modify one deck glucose oxidase.
Preferably, the thickness of described microelectrode sensors is 0.05-1mm, and the work area of working electrode is 2-10mm
2, be 2-15mm to the work area of electrode
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 sensors.Connect wire, be the method using ultrasonic spraying to the preparation of electrode and contrast electrode, on electrode base material, direct spraying goes out accordingly to electrode pattern, contrast electrode figure and connection wire, and the material of spraying can use nano platinum or Nano Silver; Also can use the method for the micro-printing of ink-jet, electrode base material directly prints accordingly to electrode pattern, contrast electrode figure and connection wire, the material of printing can use nano platinum or Nano Silver; Can also adopt photoetching technique on base material, prepare corresponding figure and mask, then Precious Metals-Gold is sputtered by sputtering technology, formed and connect wire, then respectively to platinum shape paired electrode in electrode position sputtering, form contrast electrode at contrast electrode position sputtering silver/silver chloride.The preparation of working electrode uses photoetching, electroforming and injection molding technology to make MEMS(MEMS (micro electro mechanical system), Micro-Electro-MechanicSystem) mould, utilize hot compression molding technology to carry out micro-plastic casting micro optical fiber array, then spray indium tin oxide on the working electrode (s.
Second aspect present invention provides the preparation method of the working electrode of described photocatalyst-type glucose microelectrode sensor, adopts the method for LBL self-assembly, comprises the steps:
A) the indium tin oxide conductive glass electrode as working electrode is carried out pre-service, make its surface band negative charge; Gained working electrode is immersed polyallylamine hydrochloride (PAH) and Phen cobalt ([Co (Phen)
3]
2+/3+) mixed aqueous solution, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
B) gained working electrode is immersed in carbon nano-tube aqueous solutions, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
C) gained working electrode is immersed polyallylamine hydrochloride (PAH) and Phen cobalt ([Co (Phen)
3]
2+/3+) mixed aqueous solution, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
D) gained working electrode is immersed in semiconductor-quantum-point aqueous solution, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
E) gained working electrode is immersed polyallylamine hydrochloride (PAH) and Phen cobalt ([Co (Phen)
3]
2+/3+) mixed aqueous solution, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
F) finally gained working electrode is immersed in the glucose oxidase enzyme aqueous solution prepared, after taking-up, clean and dry up with nitrogen with deionized water rinsing.
Preferably, in described step a), indium tin oxide conductive glass electrode as working electrode is carried out pre-service, the concrete steps of its surface band negative charge are made to be: to prepare the concentrated sulphuric acid/hydrogen peroxide treatment liquid, then the concentrated sulphuric acid/hydrogen peroxide treatment liquid is put in the working electrode area of microelectrode, 70-80 DEG C of water bath with thermostatic control process 1-2 hour, takes out and fully cleans with deionized water from treating fluid.Again hydrogen peroxide/WITH AMMONIA TREATMENT liquid is put in the working electrode area of microelectrode, 60-70 DEG C of water bath with thermostatic control process 1-2 hour, finally clean with deionized water rinsing.
Preferred, the described concentrated sulphuric acid/hydrogen peroxide treatment liquid, is formed (volume ratio) by proportioning 7:3 configuration by concentrated sulfuric acid aqueous solution and aqueous hydrogen peroxide solution.
Preferred further, the concentration of described concentrated sulfuric acid aqueous solution is 95 ~ 98wt%.
Preferred further, described aqueous hydrogen peroxide solution is commercially available, and concentration is about 30wt%.
Preferred, described hydrogen peroxide/WITH AMMONIA TREATMENT liquid, is formed (volume ratio) by proportioning 1:1 configuration by aqueous hydrogen peroxide solution and ammoniacal liquor.
Preferred further, the concentration of described ammoniacal liquor is 25 ~ 28wt%.
Preferred further, described aqueous hydrogen peroxide solution is commercially available, and concentration is about 30wt%.
Preferably, described step a), c), e) in, immerse polyallylamine 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, polyallylamine hydrochloride (PAH) and Phen cobalt ([Co (Phen)
3]
2+/3+) mixed aqueous solution in, the concentration of polyallylamine hydrochloride (PAH) is 1-2mg/mL, Phen cobalt ([Co (Phen)
3]
2+/3+) concentration be 1-2mg/mL.
Described Phen cobalt passes through solid state reaction method by hydrated cobalt chloride (CoCl
22H
2o) with phenanthroline (C
12h
8n
2h
2o) preparation is ground according to a certain percentage.
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 carries out acidification is: carbon nano-tube be added in the nitration mixture of the excessive concentrated sulphuric acid and red fuming nitric acid (RFNA), ultrasonic process 4-6h, centrifugal, and gained carbon nano-tube is washed neutrality; Again after centrifugal, drying, in gained carbon nano-tube, add suitable deionized water, the ultrasonic object of ultrasonic 1-2h(, for disperse, scatter in water by carbon nano-tube again).
Carbon nano-tube is carried out acidification, and the carbon nano-tube after process forms electronegative carboxylic group on surface.
Preferably, in described step d), the time that working electrode immerses semiconductor-quantum-point aqueous solution is 5-10min.
Preferably, in described step d), 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 citric acid monohydrate sodium (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 selenourea (C is added
3h
8n
2se), and logical nitrogen carries out deoxygenation, last microwave heating again, and reaction conditions is high fire, and 0.5-2 minute, takes out mixed solution after heating, and room temperature leaves standstill cooling.Thioacetamide (CH is added in above-mentioned mixed liquor
3cSNH
2), rock after mixing, back flow reaction is carried out in reaction system heating, and reaction conditions is 60-70 DEG C, and in course of reaction, a straight-through nitrogen is protected, and can obtain the quantum dot needed for testing.
Those skilled in the art can rule of thumb, by the adjustment reaction time, to obtain the CdSe@CdS semiconductor quantum of different-grain diameter.
The molar feed ratio of six perchloric acid hydrate cadmiums, two citric acid monohydrate sodium, selenourea, thioacetamide is: 8:17-25:2-3:2-3.
Preferably, in described step f), the time that working electrode immerses 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 one deck biocompatibility protective seam is prepared on gained microelectrode surface.
The preparation method of described biocompatibility protective seam is: by the method for dip-coating, spraying or spin coating, organic silicone is modified electrode surface.
Third aspect present invention provides the application of described photocatalyst-type glucose microelectrode sensor in glucose detection field.
As mentioned above, photocatalyst-type glucose microelectrode sensor provided by the present invention does not a kind ofly need oxygen, can detect the photocatalyst-type glucose microelectrode sensor of blood sugar compared with electronegative potential.
This glucose microelectrode sensor is in glucose oxidase layer, have Phen cobalt ([Co (Phen) 3] 2+/3+) and glucose oxidase mutually to mix, Phen cobalt can 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 and is called reduction-state by oxidation state, and the Phen cobalt of oxidation state ([Co (Phen)
3]
3+) glucose oxidase of redox state can 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 by optical excitation, and its valence-band electrons transits to conduction band and then transfers on working electrode surface; Semiconductor-quantum-point valence band produces the hole with oxidisability because losing electronics, hole again can the ([Co (Phen) of redox state
3]
2+), thus form electronic loop endlessly, produce stable photocurrent.(its concrete mechanism as illustrated in figures 4 a and 4b)
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 that LBL self-assembly method modifies working electrode.
Fig. 4 A and Fig. 4 B is the Cleaning Principle figure 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
-1phen cobalt compound (Co (Phen) is determined in scope
3cl
2) infrared spectrum.
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 way of specific instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this instructions can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this instructions also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Notice, in the following example, the concrete process equipment that indicates or device all adopt conventional equipment in this area or device; All force value and scope all refer to absolute pressure.
In addition should be understood that the one or more method steps mentioned in the present invention do not repel and can also to there is additive method step or can also insert additive method step before and after described combination step between these steps clearly mentioned, except as otherwise noted; Will also be understood that, the relation that is connected between the one or more equipment/devices mentioned in the present invention is not repelled and can also to be there are other equipment/devices or can also insert other equipment/devices before and after described unit equipment/device between these two equipment/devices clearly mentioned, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also 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; the perform region of described working electrode 6 is modified with from inside to outside successively carbon nanotube layer, CdSe@CdS semiconductor-quantum-point layer, glucose oxidase layer, biocompatibility protective seam; be provided with micro optical fiber 7 in described base material 1, the light that described micro optical fiber 7 transmits passes perpendicularly through working electrode 6.Described working electrode 6, electrode 5 and contrast electrode 4 be provided with separately to a stitch 2 corresponding with it, described each stitch 2 is all positioned at the top of microelectrode sensors, 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, be arranged in order to top from the end of microelectrode sensors the order of electrode 5, contrast electrode 4.
Embodiment 1
Preparation CdSe@CdS semiconductor-quantum-point
Take 0.0336g six perchloric acid hydrate cadmium (Cd (ClO
4)
26H
2and 0.05g bis-citric acid monohydrate sodium (Na O)
3c
6h
5o
72H
2o) be dissolved into together in 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 0.003g selenourea (C is added
3h
8n
2se), and logical nitrogen carries out deoxygenation 1min again, finally puts into micro-wave oven microwave and heats 1min, and make the color of mixed solution become red from colourless, take out mixed solution, room temperature leaves standstill cooling.
Finally, in above-mentioned mixed liquor, 0.0015g thioacetamide (CH is added
3cSNH
2), rock and mix, be injected into by this mixed liquor in clean three-necked bottle, reaction system carries out back flow reaction by oil bath heating, and oil bath temperature is 70 DEG C, and the reaction time is 24h, and in reaction, a straight-through nitrogen is protected.The CdSe@CdS quantum dot needed for testing can be obtained.
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, and fluorescence spectra emission peak position is set to 586nm.As calculated, CdSe quantum dot particle diameter is the concentration of 3.3nm, CdSe@CdS quantum dot solution is 1.59 × 10
-6molL
-1.
Embodiment 2
Solid state reaction legal system is for Phen cobalt ([Co (Phen)
3]
2+/3+)
The ratio of 1:3 in molar ratio, takes hydrated cobalt chloride (CoCl
22H
2o) with Phen (Phen, C
12h
8n
2h
2o) be put in grinding, at room temperature carry out mixing, grinding, first the color of potpourri becomes rose pink, continues grinding, and the color of potpourri gradually becomes green, and grinding is until the color of potpourri becomes crocus gradually from green.
CoCl
26H
2the solid phase reaction of O and Phen is through the course of reaction equation that a green intermediate carries out in two steps and is expressed as:
To the Phen cobalt compound (Co (Phen) of synthesis
3cl
2), characterized by FFIR.At 1800 ~ 400cm
-1co (Phen) is determined in scope
3cl
2infrared spectrum, shown in Fig. 6, its dominant 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, absorption peak position is: 507cm
-1, 472cm
-1, 441cm
-1, 420cm
-1.Phen cobalt (Co (Phen) prepared by solid reaction process
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), photoetching, electroforming and injection molding technology is used to make MEMS(MEMS (micro electro mechanical system), Micro-Electro-MechanicSystem) mould, utilize 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 to electrode pattern, contrast electrode figure, working electrode figure and connection wire, and the material of spraying can use 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 LBL self-assembly, comprises the steps:
A) the indium tin oxide conductive glass electrode as working electrode is carried out pre-service, make its surface band negative charge; Gained working electrode is immersed polyallylamine hydrochloride (1.5mg/mL, PAH) and Phen cobalt (1.5mg/mL, [Co (Phen)
3]
2+/3+) mixed aqueous solution 8min, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
B) gained working electrode is immersed 8min in carbon nano-tube aqueous solutions (15mg/mL), after taking-up, clean and dry up with nitrogen with deionized water rinsing;
C) gained working electrode is immersed the mixed aqueous solution 8min of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
D) gained working electrode is immersed semiconductor-quantum-point aqueous solution (1.59 × 10
-6mol/L, particle diameter 7nm, corresponding optical wavelength 641nm) in 8min, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
E) gained working electrode is immersed the mixed aqueous solution 8min of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
F) finally gained working electrode is immersed 8min in the glucose oxidase enzyme aqueous solution (60mg/mL) for preparing, after taking-up, clean and dry up with nitrogen with deionized water rinsing.
Gained microelectrode s1-s5 is carried out accuracy and reperformance test (be platinum electrode to electrode, contrast electrode is Ag/AgCl electrode), 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), photoetching, electroforming and injection molding technology is used to make MEMS(MEMS (micro electro mechanical system), Micro-Electro-MechanicSystem) mould, utilize 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 to electrode pattern, contrast electrode figure, working electrode figure and connection wire, and the material of spraying can use 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 LBL self-assembly, comprises the steps:
A) the indium tin oxide conductive glass electrode as working electrode is carried out pre-service, make its surface band negative charge; Gained working electrode is immersed polyallylamine hydrochloride (1.5mg/mL, PAH) and Phen cobalt (1.5mg/mL, [Co (Phen)
3]
2+/3+) mixed aqueous solution 8min, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
B) gained working electrode is immersed 8min in carbon nano-tube aqueous solutions (15mg/mL), after taking-up, clean and dry up with nitrogen with deionized water rinsing;
C) gained working electrode is immersed the mixed aqueous solution 8min of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
D) gained working electrode is immersed semiconductor-quantum-point aqueous solution (1 × 10
-6mol/L, particle diameter 10nm, corresponding optical wavelength 673nm) in 8min, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
E) gained working electrode is immersed the mixed aqueous solution 8min of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
F) finally gained working electrode is immersed 8min in the glucose oxidase enzyme aqueous solution (60mg/mL) for preparing, after taking-up, clean and dry up with nitrogen with deionized water rinsing.
Gained microelectrode test blood-sugar content (about 10mM), has very high accuracy and repeatability, close with embodiment 3 (be platinum electrode to electrode, contrast electrode is 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), photoetching, electroforming and injection molding technology is used to make MEMS(MEMS (micro electro mechanical system), Micro-Electro-Mechanic System) mould, utilize 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 to electrode pattern, contrast electrode figure, working electrode figure and connection wire, and the material of spraying can use 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 LBL self-assembly, comprises the steps:
A) the indium tin oxide conductive glass electrode as working electrode is carried out pre-service, make its surface band negative charge; Gained working electrode is immersed polyallylamine hydrochloride (1mg/mL, PAH) and Phen cobalt (1mg/mL, [Co (Phen)
3]
2+/3+) mixed aqueous solution 10min, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
B) gained working electrode is immersed 10min in carbon nano-tube aqueous solutions (10mg/mL), after taking-up, clean and dry up with nitrogen with deionized water rinsing;
C) gained working electrode is immersed the mixed aqueous solution 10min of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
D) gained working electrode is immersed semiconductor-quantum-point aqueous solution (5 × 10
-6mol/L, particle diameter 7nm, corresponding optical wavelength 641nm) in 10min, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
E) gained working electrode is immersed the mixed aqueous solution 10min of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
F) finally gained working electrode is immersed 10min in the glucose oxidase enzyme aqueous solution (20mg/mL) for preparing, after taking-up, clean and dry up with nitrogen with deionized water rinsing.
Gained microelectrode test blood-sugar content (about 10mM), has very high accuracy and repeatability, close with embodiment 3 (be platinum electrode to electrode, contrast electrode is 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), photoetching, electroforming and injection molding technology is used to make MEMS(MEMS (micro electro mechanical system), Micro-Electro-MechanicSystem) mould, utilize 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 to electrode pattern, contrast electrode figure, working electrode figure and connection wire, and the material of spraying can use 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 LBL self-assembly, comprises the steps:
A) the indium tin oxide conductive glass electrode as working electrode is carried out pre-service, make its surface band negative charge; Gained working electrode is immersed polyallylamine hydrochloride (2mg/mL, PAH) and Phen cobalt (2mg/mL, [Co (Phen)
3]
2+/3+) mixed aqueous solution 5min, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
B) gained working electrode is immersed 5min in carbon nano-tube aqueous solutions (20mg/mL), after taking-up, clean and dry up with nitrogen with deionized water rinsing;
C) gained working electrode is immersed the mixed aqueous solution 5min of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
D) gained working electrode is immersed semiconductor-quantum-point aqueous solution (5 × 10
-6mol/L, particle diameter 4nm, corresponding optical wavelength 586nm) in 5min, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
E) gained working electrode is immersed the mixed aqueous solution 5min of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
F) finally gained working electrode is immersed 5min in the glucose oxidase enzyme aqueous solution (100mg/mL) for preparing, after taking-up, clean and dry up with nitrogen with deionized water rinsing.
Gained microelectrode test blood-sugar content (about 10mM), has very high accuracy and repeatability, close with embodiment 3 (be platinum electrode to electrode, contrast electrode is 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), photoetching, electroforming and injection molding technology is used to make MEMS(MEMS (micro electro mechanical system), Micro-Electro-MechanicSystem) mould, utilize 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 to electrode pattern, contrast electrode figure, working electrode figure and connection wire, and the material of spraying can use 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 LBL self-assembly, comprises the steps:
A) the indium tin oxide conductive glass electrode as working electrode is carried out pre-service, make its surface band negative charge; Gained working electrode is immersed polyallylamine hydrochloride (1.5mg/mL, PAH) and Phen cobalt (1.5mg/mL, [Co (Phen)
3]
2+/3+) mixed aqueous solution 8min, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
B) gained working electrode is immersed 8min in carbon nano-tube aqueous solutions (15mg/mL), after taking-up, clean and dry up with nitrogen with deionized water rinsing;
C) gained working electrode is immersed the mixed aqueous solution 8min of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
D) gained working electrode is immersed semiconductor-quantum-point aqueous solution (3 × 10
-6the corresponding optical wavelength 641nm of mol/L, particle diameter 7nm) in 8min, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
E) gained working electrode is immersed the mixed aqueous solution 8min of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
F) finally gained working electrode is immersed 8min in the glucose oxidase enzyme aqueous solution (60mg/mL) for preparing, after taking-up, clean and dry up with nitrogen with deionized water rinsing.
Gained microelectrode test blood-sugar content (about 10mM), has very high accuracy and repeatability, close with embodiment 3 (be platinum electrode to electrode, contrast electrode is Ag/AgCl electrode).
Embodiment 8
The microelectrode prepared by embodiment 3 is adopted to carry out glucose test;
Get 5 microelectrodes (s1-s5) and test blood-sugar content in a certain blood sample (about 10mM), correct according to measured current value; Wherein, the blood-sugar content in blood sample, through YSI test, is 9.83mM; Therefore, the sensitivity of these 5 microelectrodes is:
Test three variable concentrations blood sugar blood samples with these 5 microelectrodes respectively, the blood-sugar content wherein in blood sample is measured by YSI:
| 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, has very high accuracy and repeatability.
In sum, the present invention effectively overcomes various shortcoming of the prior art and 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 without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (12)
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, micro optical fiber is provided with in described base material, the light that described micro optical fiber transmits passes perpendicularly through described working electrode, and described semiconductor-quantum-point is CdSe@CdS semiconductor-quantum-point; The preparation method of the working electrode of described photocatalyst-type glucose microelectrode sensor, adopts the method for LBL self-assembly, comprises the steps:
A) the indium tin oxide conductive glass electrode as working electrode is carried out pre-service, make its surface band negative charge; Gained working electrode is immersed the mixed aqueous solution of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing; Described step a) in, indium tin oxide conductive glass electrode as working electrode is carried out pre-service, the concrete steps of its surface band negative charge are made to be: to prepare the concentrated sulphuric acid/hydrogen peroxide treatment liquid, then the concentrated sulphuric acid/hydrogen peroxide treatment liquid is put in the working electrode area of microelectrode, 70-80 DEG C of water bath with thermostatic control process 1-2 hour, takes out and fully cleans with deionized water from treating fluid; Again hydrogen peroxide/WITH AMMONIA TREATMENT liquid is put in the working electrode area of microelectrode, 60-70 DEG C of water bath with thermostatic control process 1-2 hour, finally clean with deionized water rinsing;
B) gained working electrode is immersed in carbon nano-tube aqueous solutions, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
C) gained working electrode is immersed the mixed aqueous solution of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
D) gained working electrode is immersed in semiconductor-quantum-point aqueous solution, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
E) gained working electrode is immersed the mixed aqueous solution of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
F) finally gained working electrode is immersed in the glucose oxidase enzyme aqueous solution prepared, after taking-up, clean and dry up with nitrogen with deionized water rinsing.
2. a kind of photocatalyst-type glucose microelectrode sensor as claimed in claim 1, is characterized in that, described microelectrode sensors surface is also 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 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 Ag/AgCl electrode.
6. the preparation method of the working electrode of the photocatalyst-type glucose microelectrode sensor as described in claim as arbitrary in claim 1-5, adopts the method for LBL self-assembly, comprises the steps:
A) the indium tin oxide conductive glass electrode as working electrode is carried out pre-service, make its surface band negative charge; Gained working electrode is immersed the mixed aqueous solution of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing; Described step a) in, indium tin oxide conductive glass electrode as working electrode is carried out pre-service, the concrete steps of its surface band negative charge are made to be: to prepare the concentrated sulphuric acid/hydrogen peroxide treatment liquid, then the concentrated sulphuric acid/hydrogen peroxide treatment liquid is put in the working electrode area of microelectrode, 70-80 DEG C of water bath with thermostatic control process 1-2 hour, takes out and fully cleans with deionized water from treating fluid; Again hydrogen peroxide/WITH AMMONIA TREATMENT liquid is put in the working electrode area of microelectrode, 60-70 DEG C of water bath with thermostatic control process 1-2 hour, finally clean with deionized water rinsing;
B) gained working electrode is immersed in carbon nano-tube aqueous solutions, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
C) gained working electrode is immersed the mixed aqueous solution of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
D) gained working electrode is immersed in semiconductor-quantum-point aqueous solution, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
E) gained working electrode is immersed the mixed aqueous solution of polyallylamine hydrochloride and Phen cobalt, after taking-up, clean and dry up with nitrogen with deionized water rinsing;
F) finally gained working electrode is immersed in the glucose oxidase enzyme aqueous solution prepared, after taking-up, clean and dry up with nitrogen with deionized water rinsing.
7. 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 polyallylamine hydrochloride and Phen cobalt, the concentration of polyallylamine hydrochloride is 1-2mg/mL, and the concentration of Phen cobalt is 1-2mg/mL.
8. the preparation method of the working electrode of photocatalyst-type glucose microelectrode sensor as claimed in claim 6, is characterized in that, described step b) in, the concentration of carbon nano-tube aqueous solutions is 10-20mg/mL.
9. the preparation method of the working electrode of photocatalyst-type glucose microelectrode sensor as claimed in claim 6, is characterized in that, described steps d) in, the concentration of semiconductor-quantum-point aqueous solution is 1 × 10
-6-5 × 10
-6mol/L.
10. the preparation method of the working electrode of photocatalyst-type glucose microelectrode sensor as claimed in claim 6, is characterized in that, described step f) in, the concentration of glucose oxidase enzyme aqueous solution is 10-20mg/mL.
The preparation method of the working electrode of 11. photocatalyst-type glucose microelectrode sensor as claimed in claim 6, is characterized in that, at described step f) after, also prepare one deck biocompatibility protective seam at gained working electrode surface.
The application of photocatalyst-type glucose microelectrode sensor in glucose detection field as described in 12. claims as arbitrary in claim 1-5.
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| CN104965014B (en) * | 2015-07-06 | 2017-06-23 | 济南大学 | The preparation method of the compound carbon paste electrode of quantum dot/enzyme for detecting SAM |
| CN105319260B (en) * | 2015-11-05 | 2017-10-31 | 北京农业信息技术研究中心 | The online glucose sensing approach of plant and device based on microelectrode biosensing technology |
| CN105319257A (en) * | 2015-11-05 | 2016-02-10 | 北京农业信息技术研究中心 | ABA (abscisic acid) concentration detection method based on biosensing technology |
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