CN102645469B - Preparation method of laccase/multihole nanometer titanium dioxide modified electrode - Google Patents
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- CN102645469B CN102645469B CN201110041863.XA CN201110041863A CN102645469B CN 102645469 B CN102645469 B CN 102645469B CN 201110041863 A CN201110041863 A CN 201110041863A CN 102645469 B CN102645469 B CN 102645469B
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Abstract
The invention relates to a preparation method of a laccase/multihole nanometer titanium dioxide modified electrode. The preparation method comprises the steps of material preparation, preparation for combine use of hydrothermal method and calcination method of a multihole nanometer titanium dioxide carrier, adsorption and immobilization of laccase on the carrier and electrode modification. Immobilized laccase is uniformly scattered in Nafion dilute solution so as to modify a glassy carbon electrode which is used as a work electrode, so that a three-electrode system is established, and the three-electrode system is connected with an electrochemistry work station so as to detect the electrochemistry response of the three-electrode system on water pollutant hydroquinone through cyclic voltammetry. Compared with the prior art, the method disclosed by the invention has the advantages that the cost is low, the preparation is simple, the enzyme activity of the immobilized laccase is high, the sensibility is high, and the like.
Description
Technical field
The present invention relates to field of biosensors, especially relate to a kind of preparation method with laccase/porous nano titania modified electrode.
Background technology
Aldehydes matter exists widely in environment, as a kind of noxious material, the mankind's health has been caused to great harm, and therefore the detection of aldehydes matter just becomes problem demanding prompt solution, also environmental monitoring is had great significance simultaneously.P-dihydroxy-benzene is widely used in industrial circle, it is one of phenolic comp ' ds pollution of the very strong and degraded that is difficult to of a kind of toxicity, existing p-dihydroxy-benzene detection method mainly adopts chromatography, has analytical instrument costliness, complicated operation, in time the defect of on-line monitoring.Biology sensor refers to as molecular recognition elements, test analyte to be had to the analytical instrument of high selectivity with immobilized biological component (as: enzyme, antigen, antibody, hormone etc.) or biosome itself (as cell, organelle, tissue etc.).Biology sensor is one and interpenetrates the new subject of growing up by multiple subjects such as biology, chemistry, physics, medical science, electronics, material technologies.Enzyme electrode is first generation biology sensor, it is the electrochemica biological sensor using enzyme as molecular recognition device, by an immobilised enzymes sensitive membrane and married electrode forms with it energy converting system, it combines immobilised enzymes and electrode, thereby have advantages of unique: the advantage of (1) its existing insoluble enzyme system, has again the high sensitivity of electro-chemical systems; (2), due to the exclusive reaction of enzyme, make it have very high selectivity; (3) enzyme electrode is safe and reliable, highly sensitive, analysis speed fast, operate the features such as simple and easy, instrument and equipment simple and be easy to carry.The main absorption method of method, covalent coupling method and the crosslinked combined techniques of immobilised enzymes, wherein absorption method possesses skills simply, process conditions gentleness, the feature that the various and carrier of alternative carrier can activation cycle recycling.At present, enzyme electrode is successfully applied to the fields such as medical science, national defence, environment, food industry and agricultural, becomes a kind of strong analysis tool.
Summary of the invention
Object of the present invention is exactly to provide a kind of technique simple, with low cost, easy to detect, the portable preparation method with laccase/porous nano titania modified electrode in order to overcome the defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
With a preparation method for laccase/porous nano titania modified electrode, it is characterized in that, the method comprises the following steps:
(1) adopt hydro-thermal method to be combined with calcination method and prepare porous nano titanium dioxide microballoon sphere carrier;
(2) after mixing with rare laccase solution, porous nano titanium dioxide microballoon sphere carrier step (1) being prepared in vibration tank adsorption of immobilization, obtains laccase/porous nano titanium dioxide immobilized enzyme;
(3) laccase/porous nano titanium dioxide immobilized enzyme step (2) being prepared, evenly spread to after multipolymer (Nafion) lean solution of tetrafluoroethene and perfluor-2-(sulfonic acid ethoxy) propyl vinyl ether, the mixed solution obtaining is evenly dropped on glass-carbon electrode, then natural drying at normal temperatures.
Hydro-thermal method described in step (1) comprises the following steps: in the aqueous solution of cyclopentadienyl titanium dichloride, drip ethylenediamine, control temperature of reaction is 100-150 DEG C, reaction time is 5-8h, and the first sample obtaining is used deionized water, the each centrifuge washing of absolute ethyl alcohol three times successively.
The concentration of the aqueous solution of described cyclopentadienyl titanium dichloride is 1-3mg/mL, and the volume ratio of the ethylenediamine of dropping and the aqueous solution of cyclopentadienyl titanium dichloride is (0.01-0.015): 1.
Calcination method described in step (1) comprises the following steps: adopt to control and heat up, to be placed in tubular furnace through the synthetic product obtaining of hydro-thermal method, controlling heating rate is 3-4 DEG C/s, calcining heat is 400 DEG C, calcination time is 2h, then controlling warm speed is that 3-4 DEG C/s cools the temperature to room temperature, obtains porous nano titanium dioxide microballoon sphere carrier.
The concentration of the rare laccase solution described in step (2) is 0.01g/ml, contains porous nano titanium dioxide microballoon sphere carrier 4mg in rare laccase solution of every milliliter.
The temperature of the adsorption of immobilization described in step (2) is 4 DEG C, and adsorption time is 12h, after immobilization, clean with deionized water is centrifugal, and dry at normal temperatures.
The concentration of multipolymer (Nafion) lean solution of the tetrafluoroethene described in step (3) and perfluor-2-(sulfonic acid ethoxy) propyl vinyl ether is 0.05wt%, the content of controlling laccase/porous nano titanium dioxide immobilized enzyme in every milliliter of Nafion lean solution is 1mg, controlling mixing temperature is 6 DEG C, ultrasonic mixing 6min.
Glass-carbon electrode described in step (3) is respectively the Al of 0.3 μ m and 0.05 μ m with particle diameter on polishing cloth
2o
3powder polishing, drier under infrared lamp after each ultrasonic cleaning 5min in red fuming nitric acid (RFNA), distilled water and absolute ethyl alcohol successively.
Laccase/porous nano titania modified electrode that utilization prepares is set up three electrode system, and adopting sodium hydrogen phosphate-citric acid is that liquid of the blank end detects respectively p-dihydroxy-benzene electrochemical response situation in water body.
Described three-electrode system comprises working electrode laccase/porous nano titania modified electrode, to electrode Pt electrode, contrast electrode Ag/NaCl electrode, sodium hydrogen phosphate-citric acid solution pH of employing is 5.6, concentration is 0.1mol/L, and the concentration of p-dihydroxy-benzene is 0.05mol/L.
Detect p-dihydroxy-benzene electrochemical response situation and measure by the response of cyclic voltammetry, the scope of scanning voltage is-1.4V～1.4V that sweep velocity is 0.05mv/s.
Compared with prior art, the present invention has the following advantages:
(1) the application is a kind of preparation method based on laccase/porous nano titania modified electrode, with low cost, preparation is simple, the specific surface area higher by means of porous nanometer material can provide more attachment site for laccase, carry enzyme amount high, and fix owing to only adopting absorption method, enzyme loss of activity in immobilization process is little, and laccase electrode is active strong;
(2) laccase/porous nano titania modified electrode of the application has stronger electronic conduction ability, has obvious electrochemical response for water pollutant p-dihydroxy-benzene, has great application potential on catechol pollutant monitoring.
Brief description of the drawings
Fig. 1 is the SEM photo of porous nano titanium dioxide microballoon sphere carrier;
Fig. 2 is porous nano titanium dioxide microballoon sphere carrier XRD figure;
Fig. 3 is the fourier infrared figure of pure laccase, porous nano titanium dioxide microballoon sphere carrier and laccase/porous nano titanium dioxide immobilized enzyme;
Fig. 4 is the cyclic voltammetry curve of naked glass-carbon electrode to water body phenolic comp ' ds pollution p-dihydroxy-benzene;
Fig. 5 is the cyclic voltammetry curve of porous nano titanium dioxide microballoon sphere modified electrode to water body phenolic comp ' ds pollution p-dihydroxy-benzene;
Fig. 6 is the cyclic voltammetry curve of laccase/porous nano titania modified electrode to water body phenolic comp ' ds pollution p-dihydroxy-benzene.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
A preparation method for laccase/porous nano titania modified electrode, the method comprises the following steps:
The preparation of porous nano titanium dioxide microballoon sphere carrier
(1) hydrothermal synthesis method preparation, 20mg Ti (CP)
2cl
2be scattered in 10ml deionized water in reactor, and drip 2～3 ethylenediamines.120 DEG C of Water Under thermal response 6h, cooling room temperature, with water, the each centrifuge washing of absolute ethyl alcohol three times;
(2) step (1) gained sample is obtained after tubular furnace is calcined 2h under 400 DEG C of conditions, control heats up, rate of temperature fall is 3～4 DEG C/s, obtains porous nano titanium dioxide microballoon sphere carrier.Prepared porous nano titanium dioxide microballoon sphere carrier S EM figure and XRD figure are respectively as shown in Figure 1 and Figure 2.
Embodiment 2
A preparation method for laccase/porous nano titania modified electrode, the method comprises the following steps:
The preparation of laccase/porous nano titanium dioxide immobilized enzyme
(1) take 20mg carrier and mix with rare laccase solution of 5ml, (approximately 6 DEG C) ultrasonic 10min under room temperature, after put into the lower adsorption of immobilization of vibration tank normal temperature (4 DEG C of left and right) 12 hours.
(2) with repeatedly prepared immobilised enzymes 6 times in cleaning step (1) of deionized water, normal temperature is down to dry, and seals together with discolour silica gel and be stored under 4 DEG C of temperature conditions.Pure laccase, porous nano titanium dioxide microballoon sphere carrier and laccase/porous nano titanium dioxide immobilized enzyme fourier infrared figure comparison diagram are as shown in Figure 3, wherein a is porous nano titanium dioxide microballoon sphere carrier, b is laccase/porous nano titanium dioxide immobilized enzyme, and c is pure laccase.
Embodiment 3
A preparation method for laccase/porous nano titania modified electrode, the method comprises the following steps:
The preparation of laccase/porous nano titania modified electrode
(1) laccase/porous nano titanium dioxide immobilized enzyme that takes 1mg is dissolved in the tetrafluoroethene of 5ml 0.05wt% and multipolymer (Nafion) solution of perfluor-2-(sulfonic acid ethoxy) propyl vinyl ether, and under room temperature, (approximately 6 DEG C) ultrasonic 3min mixes it;
(2) on polishing cloth, be 0.3 μ m and 0.05 μ m Al with particle diameter by glass-carbon electrode respectively
2o
3powder polishing, and successively with being dried after ultrasonic cleaning 5min respectively in red fuming nitric acid (RFNA), distilled water and absolute ethyl alcohol, get the homodisperse laccase/porous nano of 10 μ l TiO under infrared lamp
2/ Nafion mixed liquor drops on clean glass-carbon electrode, natural drying under normal temperature, obtains laccase/porous nano TiO
2modified electrode.
Embodiment 4
The electrochemical response of laccase/porous nano titania modified electrode to water body phenolic comp ' ds pollution p-dihydroxy-benzene, comprises the following steps:
(1) mensuration of the cyclic voltammetry electrochemical response of modified electrode to water body phenolic comp ' ds pollution p-dihydroxy-benzene, adopt three-electrode system (modified electrode, Pt electrode, Ag/NaCl electrode) detect, first by modified electrode in liquid of the blank end of 0.1mol/l sodium hydrogen phosphate-citric acid (PH=5.6) scan round to baseline stability state;
(2) in liquid of the blank end, add certain density p-dihydroxy-benzene solution, the whole solubility that makes p-dihydroxy-benzene is 1 × 10
-5, it is 0.05mv/s that sweep velocity is set, scanning voltage scope is-1.4V～1.4V that employing cyclic voltammetry is recorded empirical curve, and background correction.Naked glass-carbon electrode, porous nano titanium dioxide microballoon sphere modified electrode and laccase/porous nano titania modified electrode to the cyclic voltammetry curve of water body phenolic comp ' ds pollution p-dihydroxy-benzene as shown in Fig. 4～6.
Embodiment 5
With a preparation method for laccase/porous nano titania modified electrode, comprise the following steps:
(1) adopt hydro-thermal method to be combined with calcination method and prepare porous nano titanium dioxide microballoon sphere carrier, hydro-thermal method comprises the following steps: in the aqueous solution of the cyclopentadienyl titanium dichloride that is 1mg/mL to concentration, drip ethylenediamine, the volume ratio of the ethylenediamine dripping and the aqueous solution of cyclopentadienyl titanium dichloride is 0.01: 1, controlling temperature of reaction is 100 DEG C, reaction time is 8h, and the first sample obtaining is used deionized water, the each centrifuge washing of absolute ethyl alcohol three times successively; Calcination method comprises the following steps: adopt to control and heat up, to be placed in tubular furnace through the synthetic product obtaining of hydro-thermal method, controlling heating rate is 3 DEG C/s, calcining heat is 400 DEG C, calcination time is 2h, then controlling warm speed is that 3 DEG C/s cools the temperature to room temperature, obtains porous nano titanium dioxide microballoon sphere carrier;
(2) after rare laccase solution that porous nano titanium dioxide microballoon sphere carrier step (1) being prepared is 0.01g/mL with concentration mixes in vibration tank adsorption of immobilization, in rare laccase solution of every milliliter, contain porous nano titanium dioxide microballoon sphere carrier 4mg, controlling temperature is 4 DEG C, adsorption time is 12h, after immobilization, clean with deionized water is centrifugal, and be dried and obtain laccase/porous nano titanium dioxide immobilized enzyme at normal temperatures;
(3) laccase/porous nano titanium dioxide immobilized enzyme step (2) being prepared, evenly spreading to concentration is the Nafion lean solution of 0.05wt%, the content of controlling laccase/porous nano titanium dioxide immobilized enzyme in every milliliter of Nafion lean solution is 1mg, controlling mixing temperature is 6 DEG C, ultrasonic mixing 6min, the mixed solution obtaining is evenly dropped on glass-carbon electrode, and this glass-carbon electrode is respectively the Al of 0.3 μ m and 0.05 μ m with particle diameter on polishing cloth
2o
3powder polishing, drier, then natural drying at normal temperatures under infrared lamp after each ultrasonic cleaning 5min in red fuming nitric acid (RFNA), distilled water and absolute ethyl alcohol successively.
Laccase/porous nano titania modified electrode that utilization prepares is set up three electrode system, comprise working electrode laccase/porous nano titania modified electrode, to electrode Pt electrode, contrast electrode Ag/NaCl electrode, adopting sodium hydrogen phosphate-citric acid is that liquid of the blank end detects respectively p-dihydroxy-benzene electrochemical response situation in water body, sodium hydrogen phosphate-citric acid solution the pH adopting is 5.6, concentration is 0.1mol/L, the concentration of p-dihydroxy-benzene is 0.05mol/L, detecting p-dihydroxy-benzene electrochemical response situation measures by the response of cyclic voltammetry, the scope of scanning voltage is-1.4V～1.4V, sweep velocity is 0.05mv/s.
Embodiment 6
With a preparation method for laccase/porous nano titania modified electrode, comprise the following steps:
(1) adopt hydro-thermal method to be combined with calcination method and prepare porous nano titanium dioxide microballoon sphere carrier, hydro-thermal method comprises the following steps: in the aqueous solution of the cyclopentadienyl titanium dichloride that is 3mg/mL to concentration, drip ethylenediamine, the volume ratio of the ethylenediamine dripping and the aqueous solution of cyclopentadienyl titanium dichloride is 0.015: 1, controlling temperature of reaction is 150 DEG C, reaction time is 5h, and the first sample obtaining is used deionized water, the each centrifuge washing of absolute ethyl alcohol three times successively; Calcination method comprises the following steps: adopt to control and heat up, to be placed in tubular furnace through the synthetic product obtaining of hydro-thermal method, controlling heating rate is 4 DEG C/s, calcining heat is 400 DEG C, calcination time is 2h, then controlling warm speed is that 4 DEG C/s cools the temperature to room temperature, obtains porous nano titanium dioxide microballoon sphere carrier;
(2) after rare laccase solution that porous nano titanium dioxide microballoon sphere carrier step (1) being prepared is 0.01g/mL with concentration mixes in vibration tank adsorption of immobilization, in rare laccase solution of every milliliter, contain porous nano titanium dioxide microballoon sphere carrier 4mg, controlling temperature is 4 DEG C, adsorption time is 12h, after immobilization, clean with deionized water is centrifugal, and be dried and obtain laccase/porous nano titanium dioxide immobilized enzyme at normal temperatures;
(3) laccase/porous nano titanium dioxide immobilized enzyme step (2) being prepared, evenly spreading to concentration is the Nafion lean solution of 0.05wt%, the content of controlling laccase/porous nano titanium dioxide immobilized enzyme in every milliliter of Nafion lean solution is 1mg, controlling mixing temperature is 6 DEG C, ultrasonic mixing 6min, the mixed solution obtaining is evenly dropped on glass-carbon electrode, and this glass-carbon electrode is respectively the A1 of 0.3 μ m and 0.05 μ m with particle diameter on polishing cloth
2o
3powder polishing, drier, then natural drying at normal temperatures under infrared lamp after each ultrasonic cleaning 5min in red fuming nitric acid (RFNA), distilled water and absolute ethyl alcohol successively.
Laccase/porous nano titania modified electrode that utilization prepares is set up three electrode system, comprise working electrode laccase/porous nano titania modified electrode, to electrode Pt electrode, contrast electrode Ag/NaCl electrode, adopting sodium hydrogen phosphate-citric acid is that liquid of the blank end detects respectively p-dihydroxy-benzene electrochemical response situation in water body, sodium hydrogen phosphate-citric acid solution the pH adopting is 5.6, concentration is 0.1mol/L, the concentration of p-dihydroxy-benzene is 0.05mol/L, detecting p-dihydroxy-benzene electrochemical response situation measures by the response of cyclic voltammetry, the scope of scanning voltage is-1.4V～1.4V, sweep velocity is 0.05mv/s.
Claims (2)
1. with a preparation method for laccase/porous nano titania modified electrode, it is characterized in that, the method comprises the following steps:
(1) adopt hydro-thermal method to be combined with calcination method and prepare porous nano titanium dioxide microballoon sphere carrier;
(2) after mixing with rare laccase solution, porous nano titanium dioxide microballoon sphere carrier step (1) being prepared in vibration tank adsorption of immobilization, obtains laccase/porous nano titanium dioxide immobilized enzyme;
(3) laccase/porous nano titanium dioxide immobilized enzyme step (2) being prepared, evenly spread to tetrafluoroethene and perfluor-2-(sulfonic acid ethoxy) after the lean solution of the multipolymer of propyl vinyl ether, the mixed solution obtaining is evenly dropped on glass-carbon electrode, then natural drying at normal temperatures;
Hydro-thermal method described in step (1) comprises the following steps: in the aqueous solution of cyclopentadienyl titanium dichloride, drip ethylenediamine, control temperature of reaction is 100-150 DEG C, reaction time is 5-8h, the first sample obtaining is used deionized water, the each centrifuge washing of absolute ethyl alcohol three times successively, the concentration of the aqueous solution of described cyclopentadienyl titanium dichloride is 1-3mg/mL, and the volume ratio of the ethylenediamine of dropping and the aqueous solution of cyclopentadienyl titanium dichloride is (0.01-0.015) ︰ 1;
Calcination method described in step (1) comprises the following steps: adopt to control and heat up, to be placed in tubular furnace through the synthetic product obtaining of hydro-thermal method, controlling heating rate is 3-4 DEG C/s, calcining heat is 400 DEG C, calcination time is 2h, then controlling rate of temperature fall is that 3-4 DEG C/s cools the temperature to room temperature, obtains porous nano titanium dioxide microballoon sphere carrier;
The concentration of the rare laccase solution described in step (2) is 0.01g/mL, contains porous nano titanium dioxide microballoon sphere carrier 4mg in rare laccase solution of every milliliter;
The temperature of the adsorption of immobilization described in step (2) is 4 DEG C, and adsorption time is 12h, after immobilization, clean with deionized water is centrifugal, and dry at normal temperatures;
Tetrafluoroethene described in step (3) and perfluor-2-(sulfonic acid ethoxy) concentration of multipolymer lean solution of propyl vinyl ether is 0.05wt%, control every milliliter of tetrafluoroethene and perfluor-2-(sulfonic acid ethoxy) content of laccase/porous nano titanium dioxide immobilized enzyme is 1mg in the multipolymer lean solution of propyl vinyl ether, controlling mixing temperature is 6 DEG C, ultrasonic mixing 6min.
2. a kind of preparation method with laccase/porous nano titania modified electrode according to claim 1, is characterized in that, the glass-carbon electrode described in step (3) is respectively the Al of 0.3 μ m and 0.05 μ m with particle diameter on polishing cloth
2o
3powder polishing, drier under infrared lamp after each ultrasonic cleaning 5min in red fuming nitric acid (RFNA), distilled water and absolute ethyl alcohol successively.
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