CN103926295A - Biosensor and manufacturing method for same - Google Patents
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- CN103926295A CN103926295A CN201410174544.XA CN201410174544A CN103926295A CN 103926295 A CN103926295 A CN 103926295A CN 201410174544 A CN201410174544 A CN 201410174544A CN 103926295 A CN103926295 A CN 103926295A
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Abstract
The invention discloses a biosensor and a manufacturing method for the same, and belongs to the technical field of sensor detection. The biosensor comprises an electrode, wherein a composite film is arranged on the surface of the electrode, and comprises a biomolecular probe and conductive metal doped metal oxide nanoparticles; metal oxide has semiconductor properties; the molar ratio of conductive metal to the metal oxide is 0.5 to 10 percent. According to the biosensor and the manufacturing method for the same, the surface of the electrode is wrapped with the composite film comprising the conductive metal doped metal oxide nanoparticles and the biomolecular probe, the nanoparticles are introduced into the construction of a biosensitive interface by utilizing the characteristics of surface effects, quantum size effects, dielectric confinement effects and the like of the nanoparticles, and the conductive metal is doped into the metal oxide nanoparticles, so that the electron transfer efficiency of the composite film is improved, an oxidation-reduction electrochemical signal is enhanced, the sensitivity of the sensor is improved, and the limit of detection is reduced.
Description
Technical field
The present invention relates to sensor detecting field, particularly relate to a kind of biology sensor and preparation method thereof.
Background technology
Biology sensor is to combine the multiple discipline development of life science, analytical chemistry, materialogy, information science technology and emerging nanoscale science and technology and the product of intersection.It can carry out express-analysis and tracking to multiple life and chemical substance, has that selectivity is high, analysis speed is fast, highly sensitive, cost is low, can in complicated system, carry out the even feature such as in-vivo analysis of on-line monitoring.Oneself obtains progressively propagation and employment in fields such as clinical diagnosis, food analysis, environmental protection and biotechnology, biochip, bionics so far.
At present, the preparation great majority of electrochemica biological sensor electrode are all to utilize the bare electrodes such as gold, platinum, silver, carbon, glass carbon, and then electrode face finish enzyme or other groups, realize the detection to micromolecular compound, and in these methods, because many biomolecule have the shortcomings such as poorly conductive as enzyme, protein etc., after film forming, make the transmission of electron pair be hindered, electrochemical signals dies down, and has reduced sensitivity and the detection limit of electrochemica biological sensor.
In routine techniques, the metal oxide materials of doping (as the TiO 2 series of niobium doping etc.) preparation adopts solid phase method, liquid phase method or combustion synthesis conventionally.
Solid phase method is synthetic has advantages of that sintetics amount is large, but there also have into phase temperature to be high, usually above 1000 DEG C, needs repeatedly compressing tablet, grinds in preparation process, and generated time is long, is conventionally greater than 24 hours.And synthetic product particle is large, grain size is difficult to uniformity, and doping efficiency is not ideal enough.
The advantage of liquid phase method is to prepare the controlled nano particle of even particle size, but having difficulties aspect the preparation of dopen Nano level metal oxide, doped chemical usually can not enter in metal oxide lattice, can not realize doping truly, can only be to mix, this class material is actually the mixing of bi-material, can know and see that the two characteristic peak separately, the electrochemical properties that composite material shows are the two coefficient results in XRD analysis.
The titania-doped grain diameter of niobium prepared by combustion method is tiny, belongs to nano-scale particle, becomes phase temperature and liquid phase method to be close.But what the maximum deficiency of this method was use is the explosive inflammable raw material such as ammonium nitrate, monobel, while especially burning, if experiment condition control is bad, easily occurs mishap operating personnel being existed to security threat in operating process, and danger is higher.
Therefore, find one and can under relatively mild condition, synthesize, and the synthetic method that the performance index of product can be suitable with combustion method has great significance.
Summary of the invention
Based on this, the object of the invention is to overcome the defect of prior art, a kind of biology sensor is provided, compared with the conventional sensors of this sensor and the bare electrode finishing enzymes such as gold, platinum, silver, carbon, glass carbon, has advantages of that detection sensitivity is high, detection limit is low.
For achieving the above object, the present invention takes following technical scheme:
A kind of biology sensor, comprises electrode, and described electrode surface is provided with composite membrane, and described composite membrane comprises the metal oxide nanoparticles of probe biomolecule and conducting metal doping;
Described metal oxide is the metal oxide of tool semiconductor property;
Described conducting metal and metal oxide molar percentage are 0.5-10%.
Biology sensor of the present invention, the particular feature that utilizes metal oxide nanoparticles to have, as larger in specific surface area, surface reaction activity is high, catalytic efficiency is high, high adsorption capacity, electrochemical activity and good bio-compatibility etc., be conducive to biomacromolecule fixing on sensor electrode, thereby prepare one deck and biomolecule at electrode surface and have the nano level metal oxide materials composite membrane of fine compatibility, this nano level metal oxide materials can be connected between biomolecule and electrode as wire, the medium that can serve as again electronics transmission promotes the electronics transfer rate of activated centre and electrode surface, increase the reversibility of redox materials in electrode surface reaction, can significantly improve the detection performance of biology sensor, and, the present invention is also by doped conducting metal in metal oxide nanoparticles, improve the electronics transmission efficiency of this composite membrane, strengthen redox electrochemical signals, thereby can realize the object that improves transducer sensitivity and reduce detection limit, can guarantee that again this composite membrane and biomolecule have good compatibility.
In an embodiment, described conducting metal is at least one in niobium, vanadium, tungsten, manganese therein.Above-mentioned conducting metal can improve the electronics transmission efficiency of composite membrane preferably.
In an embodiment, described metal oxide is titania, vanadium oxide, nickel oxide or manganese oxide therein.Above-mentioned metal oxide had both had good characteristic of semiconductor, had advantages of that again cost is low, was easy to get.
In an embodiment, described electrode is copper or tungsten electrode therein, or is formed at the ITO electrode (being indium-tin oxide electrode) in substrate of glass.Select above-mentioned electrode, avoided the expensive problem that uses noble metal electrode to cause.
In an embodiment, described conducting metal is at least one in niobium, vanadium therein; Described metal oxide is titania; Described conducting metal and metal oxide molar percentage are 5-10%; The particle diameter of the metal oxide nanoparticles of described conducting metal doping is 10-50nm; Described electrode is the ITO electrode being formed in substrate of glass.At least one in niobium, vanadium is doped in titania with above-mentioned molar percentage, and the particle diameter of nano particle is controlled on the inherent ITO electrode of 10-50nm scope and prepares composite membrane, can reach best cooperation, make the biology sensor obtaining there is very high sensitivity.
In an embodiment, described probe biomolecule is glucose oxidase or DNA probe therein.Can, according to the testing goal of this biology sensor, required probe biomolecule be set flexibly.
The present invention also provides a kind of method for making of above-mentioned biology sensor, comprises the following steps:
The preparation of the metal oxide nanoparticles of conducting metal doping: get conductive metal ion total mole number 1-3 complexing agent doubly, by complexing agent: the mass ratio that water is 1:60-1:30 adds water, stirring and dissolving at 60 DEG C-100 DEG C, form solution, add red fuming nitric acid (RFNA), the volume ratio of described red fuming nitric acid (RFNA) and water is 1:50-1:30, again burning raw material is added in above-mentioned solution, at 80 DEG C-100 DEG C after stirring and dissolving, add ammoniacal liquor regulator solution pH value to 7-8, add subsequently the soluble salt of conducting metal, and continue stirring reaction 1-3 hour be stirred to solution clear at 80 DEG C-100 DEG C after, then at 180 DEG C-220 DEG C, dry, obtain the lax solid expanding, oven dry will be calcined 4-6 hour after this solid abrasive till no longer expanding to this solid at 600 DEG C-700 DEG C, obtains the metal oxide nanoparticles of conducting metal doping,
At electrode face finish composite membrane: the metal oxide nanoparticles of shitosan and conducting metal doping is joined in solvent, make the metal oxide nanoparticles of conducting metal doping dispersed, obtain finely dispersed suspending liquid; This hanging drop is applied to electrode surface, and the solution that contains probe biomolecule is also dripped in electrode surface, naturally dry, form the composite membrane of the metal oxide nanoparticles that contains probe biomolecule and conducting metal doping at electrode surface.
The method for making of biology sensor of the present invention, first adopt sol-gel process synthesis nano blended metal oxide presoma, then prepare conducting metal blended metal oxide nano particle by suitable temperature, the method is not only easy to operate and safe, and greatly shorten preparation time, the one-tenth phase temperature that has reduced material, material particle size and the combustion method of preparation are suitable; Compared with Liquid preparation methods nanosize metal oxide, realize doping truly; And this method, compared with conventional method, has good stability.Subsequently, interaction between recycling shitosan and probe biomolecule, successfully biomolecule (as single stranded DNA etc.) probe is fixed to area load and has on the electrode of metal oxide nanoparticles of conducting metal doping, form the composite membrane of the metal oxide nanoparticles that contains probe biomolecule and conducting metal doping at electrode surface, thereby prepare highly sensitive sensor.
In an embodiment, described complexing agent is citric acid or edetate therein.
In an embodiment, described burning raw material is butyl titanate therein, and the soluble salt of described conducting metal is at least one in niobic acid ammonium oxalates hydrate or ammonium metavanadate.Adopt above-mentioned raw materials, niobium and/or the vanadium that can obtain doping best results are titania-doped.
In an embodiment, the concentration of described shitosan is 0.2g/mL-1g/mL therein; Described solvent is the buffer solution that pH value is 4-5, preferably 0.05M, the acetic acid buffer solution that pH is 4.2.Under this solution environmental, can make suspending liquid disperse more evenly, and be beneficial to the fixing of follow-up probe biomolecule.
Compared with prior art, the present invention has following beneficial effect:
Biology sensor of the present invention, by comprising that the metal oxide nanoparticles of conducting metal doping and the compound of probe biomolecule are coated on electrode surface, the surface effect of utilizing nano particle to have, the feature such as quantum size effect and Dielectric confinement effect, nano particle is incorporated in the structure at bio-sensing interface, and by doped conducting metal in metal oxide nanoparticles, improve the electronics transmission efficiency of this composite membrane, strengthen redox electrochemical signals, thereby can realize the object that improves transducer sensitivity and reduce detection limit, can guarantee that again this composite membrane and biomolecule have good compatibility.
The method for making of biology sensor of the present invention, adopt sol-gel process synthesis nano blended metal oxide presoma, then prepare conducting metal blended metal oxide nano particle by suitable temperature, reduce the one-tenth phase temperature of material, and have advantages of easy to operate and safe, preparation time is short, and the nano particle of preparing has that particle diameter is little, good uniformity, the effective feature of doping.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment.
Embodiment 1
A method for making for biology sensor, comprises the following steps:
1) preparation of the metal oxide nanoparticles of conducting metal doping.
First, take the monohydrate potassium of 6.0g (0.0286mol), add in the beaker that contains 200ml deionized water, at 80 DEG C, add thermal agitation until citric acid fully dissolves.Then (massfraction is about 65% to the red fuming nitric acid (RFNA) of past solution the inside interpolation 5ml, and density is about 1.4g/cm
3), the while accurately measures the butyl titanate (being equivalent to the titania of 0.1mol) of 35ml, is slowly added drop-wise in solution, and the about 2h of constant agitation at 90 DEG C is until dissolve change clarification.Keep temperature and stirring condition constant, in solution, drip a certain amount of ammoniacal liquor, until the pH=7.0 of solution.
Subsequently, accurately take the niobic acid ammonium oxalates hydrate of 1.510g (0.005mol), the ammonium metavanadate of 0.5850g (0.005mol) is added in solution, and stir it is fully dissolved at 90 DEG C of temperature, continue to stir 2h.After completing, this solution is dried to 1～2h at 200 DEG C, till the brown materials that makes to obtain no longer expands.After finally brown dilator being ground, at 650 DEG C, calcine 5h and become phase, thereby obtain needed niobium, vanadium codope titanium dioxide (NVTO) nano particle.
After testing, the particle diameter of niobium obtained above, vanadium codoping titanium dioxide nano particle is 20-50nm, and homogeneity is better, through XRD analysis (X-ray diffraction analysis), fail to observe niobium, vanadium diffraction peak, illustrate that niobium, vanadium are successfully doped in titania lattice, realized doping truly.
2) at electrode face finish composite membrane.
20g shitosan (CHIT) is joined in 20ml acetic acid buffer solution (0.05M, pH4.2) to ultrasonic dissolution.In chitosan solution, add 5mg niobium obtained above, vanadium codoping titanium dioxide nano particle again, ultrasonic processing, the titanium dioxide nano-particle of niobium, vanadium codope is dispersed in solution, thereby obtained disperseing the CHIT-NVTO suspending liquid of niobium, vanadium codoping titanium dioxide nano particle.Then pipette this CHIT – NVTO hanging drop of 10 μ L with pipettor and be added to ITO conductive glass electrode surface (0.25cm
2), naturally dry at ambient temperature, thereby obtain CHIT – NVTO/ITO nano-complex electrode, for subsequent use.
What 10 μ L were prepared contains colorectal cancer DNA probe (1 × 10
-6mol/L) solution is added drop-wise to CHIT – NVTO/ITO nano-complex electrode surface, then electrode is placed in and under room temperature, places nature and dry, finally the bioelectrode after drying is rinsed with 50mM phosphate buffer (pH=7.0), remove surperficial loose DNA, thereby obtain DNA/CHIT – NVTO/ITO bioelectrode, and make biology sensor.
Adopt three-electrode system to measure the biology sensor of the present embodiment, in this three-electrode system, taking the above-mentioned DNA/CHIT – NVTO/ITO bioelectrode preparing as working electrode, taking Ag/AgCl electrode as contrast electrode, taking Pt electrode as electrode is measured, measurement result show, the biology sensor current-responsive of the present embodiment to colorectal cancer DNA 1.0 × 10
-15mol/L-1.0 × 10
-6within the scope of mol/L, have good linear relationship, it detects and is limited to 1.09 × 10
-16mol/L (S/N=3).And in routine techniques, taking silver as electrode, and detect and be limited to 1.0 × 10 at the sensor of electrode face finish colorectal cancer DNA probe
-15mol/L.
Embodiment 2
A method for making for biology sensor, comprises the following steps:
1) preparation of the metal oxide nanoparticles of conducting metal doping.
First, take the monohydrate potassium of 2.10g (0.01mol), add in the beaker that contains 100ml deionized water, at 60 DEG C, add thermal agitation until citric acid fully dissolves.Then (massfraction is about 65% to the red fuming nitric acid (RFNA) of past solution the inside interpolation 3.3ml, and density is about 1.4g/cm
3), the while accurately measures the butyl titanate (being equivalent to the titania of 0.1mol) of 35ml, is slowly added drop-wise in solution, and the about 2h of constant agitation at 80 DEG C is until dissolve change clarification.Keep temperature and stirring condition constant, in solution, drip a certain amount of ammoniacal liquor, until the pH=7.5 of solution.
Subsequently, the niobic acid ammonium oxalates hydrate that accurately takes 1.510g (0.005mol) is added in solution, and stirs it is fully dissolved at 80 DEG C of temperature, continues to stir 3h.After completing, this solution is dried to 1～2h at 180 DEG C, till the brown materials that makes to obtain no longer expands.After finally brown dilator being ground, at 600 DEG C, calcine 6h and become phase, thereby obtain needed niobium titania-doped (NTO) nano particle.
After testing, the particle diameter of niobium doping titanium dioxide nano particle obtained above is 20-50nm, and homogeneity is better, through XRD analysis (X-ray diffraction analysis), fail to observe niobium diffraction peak, illustrate that niobium is successfully doped in titania lattice, realized doping truly.
2) at electrode face finish composite membrane.
10g shitosan (CHIT) is joined in 20ml acetic acid buffer solution (0.05M, pH4.2) to ultrasonic dissolution.In chitosan solution, add 5mg niobium doping titanium dioxide nano obtained above particle again, ultrasonic processing, the titanium dioxide nano-particle of niobium doping is dispersed in solution, thereby has obtained disperseing the CHIT-NTO suspending liquid of niobium doping titanium dioxide nano particle.Then pipette with pipettor glucose oxidase (GOx) that this CHIT – NTO suspending liquid of 10 μ L and 10 μ L prepare and (1mg/dL) be added drop-wise to ITO conductive glass electrode surface (0.25cm
2), naturally dry at ambient temperature, thereby obtain GOx/CHIT – NTO/ITO bioelectrode, and make biology sensor.The not used time of this bioelectrode, need be placed in the refrigerator of 4 DEG C to preserve its activity.
Adopt three-electrode system to measure the biology sensor of the present embodiment, in this three-electrode system, taking the above-mentioned GOx/CHIT – NTO/ITO bioelectrode preparing as working electrode, taking Ag/AgCl electrode as contrast electrode, taking Pt electrode as electrode is measured, measurement result demonstration, the sensor current response of the present embodiment has good linear relationship within the scope of 0.5-150ng/mL to glucose, and it detects and is limited to 0.00895ng/mL (S/N=3).And in routine techniques, taking platinum as electrode, and detect and be limited to 0.05ng/mL at the sensor of electrode face finish glucose oxidase.
Embodiment 3
A method for making for biology sensor, comprises the following steps:
1) preparation of the metal oxide nanoparticles of conducting metal doping.
First, take the disodium ethylene diamine tetraacetate (EDTA) of 0.186g (0.0005mol), add in the beaker that contains 11ml deionized water, at 100 DEG C, add thermal agitation until disodium ethylene diamine tetraacetate fully dissolves.Then add the red fuming nitric acid (RFNA) of 0.22ml toward solution the inside, accurately measure the butyl titanate (being equivalent to the titania of 0.1mol) of 35ml simultaneously, be slowly added drop-wise in solution, the about 1h of constant agitation at 100 DEG C is until dissolving becomes clarification.Keep temperature and stirring condition constant, in solution, drip a certain amount of ammoniacal liquor, until the pH=8.0 of solution.
Subsequently, the ammonium metavanadate that accurately takes 0.06g (0.0005mol) is added in solution, and stirs it is fully dissolved at 100 DEG C of temperature, continues to stir 1h.After completing, this solution is dried to 1～2h at 220 DEG C, till the brown materials that makes to obtain no longer expands.After finally brown dilator being ground, at 700 DEG C, calcine 4h and become phase, thereby obtain needed vanadium titania-doped (VTO) nano particle.
After testing, the particle diameter of vanadium doping titanium dioxide nano particle obtained above is 10-80nm, through XRD analysis (X-ray diffraction analysis), fails to observe vanadium diffraction peak, illustrate that vanadium is successfully doped in titania lattice, realized doping truly.
2) at electrode face finish composite membrane.
4g shitosan (CHIT) is joined in 20ml acetic acid buffer solution (0.05M, pH4.2) to ultrasonic dissolution.In chitosan solution, add 5mg vanadium doping titanium dioxide nano obtained above particle again, ultrasonic processing, the titanium dioxide nano-particle of vanadium doping is dispersed in solution, thereby has obtained disperseing the CHIT-VTO suspending liquid of niobium doping titanium dioxide nano particle.Then pipette with pipettor the solution that contains breast cancer ssDNA probe that this CHIT – VTO suspending liquid of 10 μ L and 10 μ L prepare and be added drop-wise to ITO conductive glass electrode surface (0.25cm
2), naturally dry at ambient temperature, thereby obtain ssDNA/CHIT – VTO/ITO bioelectrode, and make biology sensor.
Adopt three-electrode system to measure the biology sensor of the present embodiment, in this three-electrode system, taking the above-mentioned ssDNA/CHIT – VTO/ITO bioelectrode preparing as working electrode, taking Ag/AgCl electrode as contrast electrode, taking Pt electrode as electrode is measured, measurement result demonstration, the sensor current of the present embodiment responds breast cancer ssDNA 1.0 × 10
-16mol/L-1.0 × 10
-6within the scope of mol/L, have good linear relationship, it detects and is limited to 1.38 × 10
-17mol/L (S/N=3).And in routine techniques, taking gold as electrode, and detect and be limited to 1.5 × 10 at the sensor of electrode face finish breast cancer ssDNA
-15mol/L.
Comparative example 1
The method for making of the method for making of the biology sensor of this comparative example 1 and embodiment 3 is basic identical, and difference is:
Step 1) in the preparation of metal oxide nanoparticles of conducting metal doping, the ammonium metavanadate adding is 0.012g (0.0001mol).
After testing, step 1) particle diameter of the vanadium doping titanium dioxide nano particle that makes is 10-80nm, and through XRD analysis (X-ray diffraction analysis), fails to observe vanadium diffraction peak, illustrate that vanadium is successfully doped in titania lattice, realized doping truly.
But after the biology sensor that this comparative example 1 is made is measured with three-electrode system, obtain detecting of this sensor and be limited to 6.32 × 10
-16mol/L (S/N=3).The detection limit of the sensor making lower than embodiment 3, after analyzing after deliberation, think because the doping of conducting metal vanadium in electrode surface composite membrane is less, less on the electronics transmission efficiency impact of this composite membrane, do not play the effect of obvious enhancing redox electrochemical signals.
Comparative example 2
The preparation method of the metal oxide nanoparticles of conducting metal doping:
First, take the monohydrate potassium of 6.30g (0.03mol), add in the beaker that contains 200ml deionized water, at 60 DEG C, add thermal agitation until citric acid fully dissolves.Then add the red fuming nitric acid (RFNA) of 5ml toward solution the inside, accurately measure the butyl titanate (being equivalent to the titania of 0.1mol) of 35ml simultaneously, be slowly added drop-wise in solution, the about 2h of constant agitation at 80 DEG C is until dissolving becomes clarification.Keep temperature and stirring condition constant, in solution, drip a certain amount of ammoniacal liquor, until the pH=7.5 of solution.
Subsequently, the niobic acid ammonium oxalates hydrate that accurately takes 4.530g (0.015mol) is added in solution, and stirs it is fully dissolved at 80 DEG C of temperature, continues to stir 3h.After completing, this solution is dried to 1～2h at 180 DEG C, till the brown materials that makes to obtain no longer expands.After finally brown dilator being ground, at 600 DEG C, calcine 6h and become phase, thereby obtain needed niobium titania-doped (NTO) nano particle.
After testing, the particle diameter of niobium doping titanium dioxide nano particle obtained above is 20-50nm, and homogeneity is better, but through XRD analysis (X-ray diffraction analysis), can obviously observe niobium diffraction peak, illustrate that the niobium of part is not successfully doped in titania lattice.Analyze after deliberation, think because the addition of conducting metal niobium is more, cause the lattice of the titania state that reached capacity, cannot again niobium be really doped in lattice.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a biology sensor, is characterized in that, comprises electrode, and described electrode surface is provided with composite membrane, and described composite membrane comprises the metal oxide nanoparticles of probe biomolecule and conducting metal doping;
Described metal oxide is the metal oxide of tool semiconductor property;
Described conducting metal and metal oxide molar percentage are 0.5-10%.
2. biology sensor according to claim 1, is characterized in that, described conducting metal is at least one in niobium, vanadium, tungsten, manganese.
3. biology sensor according to claim 1, is characterized in that, described metal oxide is titania, vanadium oxide, nickel oxide or manganese oxide.
4. biology sensor according to claim 1, is characterized in that, described electrode is copper or tungsten electrode, or is formed at the ITO electrode in substrate of glass.
5. biology sensor according to claim 1, is characterized in that, described probe biomolecule is glucose oxidase or DNA probe.
6. according to the biology sensor described in claim 1-5 any one, it is characterized in that, described conducting metal is at least one in niobium, vanadium; Described metal oxide is titania; Described conducting metal and metal oxide molar percentage are 5-10%; The particle diameter of the metal oxide nanoparticles of described conducting metal doping is 10-50nm; Described electrode is the ITO electrode being formed in substrate of glass.
7. a method for making for the biology sensor described in claim 1-6 any one, is characterized in that, comprises the following steps:
The preparation of the metal oxide nanoparticles of conducting metal doping: get conductive metal ion total mole number 1-3 complexing agent doubly, by complexing agent: the mass ratio that water is 1:60-1:30 adds water, stirring and dissolving at 60 DEG C-100 DEG C, form solution, add red fuming nitric acid (RFNA), the volume ratio of described red fuming nitric acid (RFNA) and water is 1:50-1:30, again burning raw material is added in above-mentioned solution, at 80 DEG C-100 DEG C after stirring and dissolving, add ammoniacal liquor regulator solution pH value to 7-8, add subsequently the soluble salt of conducting metal, and continue stirring reaction 1-3 hour be stirred to solution clear at 80 DEG C-100 DEG C after, then at 180 DEG C-220 DEG C, dry, obtain the lax solid expanding, oven dry will be calcined 4-6 hour after this solid abrasive till no longer expanding to this solid at 600 DEG C-700 DEG C, obtains the metal oxide nanoparticles of conducting metal doping,
At electrode face finish composite membrane: the metal oxide nanoparticles of shitosan and conducting metal doping is joined in solvent, make the metal oxide nanoparticles of conducting metal doping dispersed, obtain finely dispersed suspending liquid; This hanging drop is applied to electrode surface, and the solution that contains probe biomolecule is also dripped in electrode surface, naturally dry, form the composite membrane of the metal oxide nanoparticles that contains probe biomolecule and conducting metal doping at electrode surface.
8. the method for making of biology sensor according to claim 7, is characterized in that, described complexing agent is citric acid or edetate.
9. the method for making of biology sensor according to claim 7, is characterized in that, described burning raw material is butyl titanate, and the soluble salt of described conducting metal is at least one in niobic acid ammonium oxalates hydrate or ammonium metavanadate.
10. the method for making of biology sensor according to claim 7, is characterized in that, the concentration of described shitosan is 0.2g/mL-1g/mL; Described solvent is the buffer solution that pH value is 4-5.
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Application publication date: 20140716 |