CN107576704A - Microcysin LR molecular engram optical electro-chemistry sensor and its preparation and application - Google Patents
Microcysin LR molecular engram optical electro-chemistry sensor and its preparation and application Download PDFInfo
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Abstract
The present invention relates to one kind to be based on visible optical drive Cu2The microcysin LR molecular engram optical electro-chemistry sensor of O/PPy composites and its preparation and application.Using ITO electro-conductive glass as matrix, upper molecular engram film, the Cu that the molecular engram film is absorbed by visible-range are deposited by electrochemical techniques2O semiconductors are combined as photoelectric material and the polypyrrole containing microcysin LR room, using visible ray as excitation source, carry out the detection of microcysin LR concentration using i t technologies on CHI660e work stations.Compared with prior art, the application of microcysin LR molecular engram optical electro-chemistry sensor of the invention has the following advantages that：Optical electro-chemistry response is sensitive, and detection range is wide, can be in 1.0ngL‑1~10.0ugL‑1Concentration range in detected, strong antijamming capability；And the preparation method of the present invention is simple and quick, cost is low, is applicable to the quick online detection of water body.
Description
Technical field
The invention belongs to water pollution to analyze detection field, and visible optical drive Cu is based on more particularly, to one kind2O/PPy is compound
The microcapsule algae toxin molecular engram optical electro-chemistry sensor of material and its preparation and application.
Background technology
Microcystin (Microcystins) is a kind of monocyclic polypeptide compound discharged after algae death, and its structure is steady
Fixed, difficult degradation, easily it is enriched with vivo, is a kind of hepatotoxin of strong tumor promotion, to protein phosphatase 1 A, protein phosphatase
Enzyme 2A and stomach have strong inhibitory action.The current separated Microcystin structure identified there are about kind more than 90, wherein
Microcapsule algae toxin is that toxicity is most strong, a kind of most hypotype of content.Also it has been specified that drinking in the World Health Organization (WHO)
The maximum level of Microcystin must not exceed 1ugL in water-1.In consideration of it, development is rapidly and efficiently, cost is low, high sensitivity,
The wide microcapsule algae toxin sensor of detection range just seems and is extremely necessary.
The method of detection microcapsule algae toxin is many at present, such as high performance liquid chromatography (HPLC), Chromatography/Mass Spectrometry connection
With, Raman detection etc., these methods are although sensitive credible, but cost is high, it is necessary to technical professional is operated, and easily
Introduce toxic reagent as acetonitrile.And the sensitivity of protease inhibition analysis method or physiological-toxicity experiment is low, and can not
Accomplish timely on-line checking.
Molecular engram optical electro-chemistry sensor is the high selectivity and the height of optical electro-chemistry detection of binding molecule engram technology
Sensitivity, there is the advantages that cost is low, simple to operate, detection range is wide, and detection speed is fast.In the last few years, visible ray model is utilized
The semi-conducting material of absorption is enclosed as photoelectric material, it is seen that optical drive excites electronics to obtain photoelectricity of the photoelectric current as detection signal
Chemical detection analysis method gradually grows up, it is possible to achieve the quick online detection of microcapsule algae toxin, high sensitivity, inspection
It is wide to survey scope.
The content of the invention
It is an object of the invention to provide one kind to be based on visible optical drive Cu2The microcapsule algae toxin of O/PPy composites
Molecular engram optical electro-chemistry sensor and preparation method and application.Inventive sensor preparation cost is low, can be with simple and quick
The microcapsule algae toxin for realizing wide scope accurate Sensitive Detection.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of microcapsule algae toxin molecular engram optical electro-chemistry sensor, it is based on visible optical drive Cu2O/PPy is answered
The microcapsule algae toxin molecular engram optical electro-chemistry sensor of condensation material, the sensor lead to using ITO electro-conductive glass as matrix
The upper molecular engram film of electrochemical deposition technique deposition is crossed, the molecular engram film is by Cu2O photoelectric materials with containing Microcystin-
The polypyrrole (PPy) in LR rooms is combined.
The preparation method of the microcapsule algae toxin molecular engram optical electro-chemistry sensor, specifically includes following steps：
(1)Cu2The preparation of O photoelectric materials：By Cu2SO4Solution and CH3CH (OH) COOH solution and PVP are uniformly mixed,
Stirred under room temperature condition, and adjust the pH to 8~10 of mixed solution, using ITO electro-conductive glass as working electrode, platinized platinum is to electricity
Pole, Ag/AgCl are reference electrode, under the conditions of 55~65 DEG C, electro-deposition are carried out on CHI660e work stations, obtains electro-deposition
Cu2The ITO electro-conductive glass of O photoelectric materials, it is standby after cleaning；
(2) preparation of molecular engram film：Microcapsule algae toxin is uniformly mixed with pyrroles (Py) monomer, adds high chlorine
Sour lithium is as supporting electrolyte, the Cu with electro-deposition obtained by step (1)2The ITO electro-conductive glass of O photoelectric materials is as work electricity
Pole, platinized platinum is used as carries out electropolymerization, then cleaning is dry as reference electrode to electrode, Ag/AgCl on CHI660e work stations
Dry stand-by, obtaining polymerization has the ito glass of molecular engram film；
(3) removal of template molecule：Certain density dipotassium hydrogen phosphate solution is configured as template liquid is removed, by step (2)
The middle ito glass for having molecular engram film that polymerize is used as working electrode, platinized platinum as to electrode, Ag/AgCl as reference electrode,
Template is carried out on CHI660e work stations to handle, and will finally go template ITO electro-conductive glass to obtain being based on visible ray after being cleaned and dried
Drive Cu2The microcapsule algae toxin molecular engram optical electro-chemistry sensor of O/PPy composites.
In step (1), according to mol ratio, Cu2SO4：CH3CH(OH)COOH：PVP is 1:5:0.1~1:10:30, be preferably
1:5:0.1~1:5:10.
In step (1), the time of stirring is preferably 2 hours, but the time does not limit, it is more it is a little less can.
In step (1), regulation pH can use certain density NaOH solution, can also use other alkali lye.
In step (1), the condition of electro-deposition is：First with -0.3V current potential constant potential 100~200s of electro-deposition, then with -0.2V
600~800s of current potential potentiostatic electrodeposition.
It is in step (1), the step of cleaning：Cu will be deposited2The ITO electro-conductive glass of O photoelectric materials puts acetone, second respectively
Ultrasound 10~20 minutes, are subsequently placed in dried for standby under 40-60 DEG C of environment in alcohol, deionized water.
Wherein, dry environment is preferably air dry oven.
In step (2), microcapsule algae toxin is 1 with pyrroles (Py) monomer mole ratio:10~1:50.
In step (2), the concentration after lithium perchlorate adds is preferably 0.1molL-1。
In step (2), the condition of electropolymerization is：Between 0~0.8V using cyclic voltammetric technology carry out electropolymerization 15~
20 minutes.
Cyclic voltammetric technology described here is this area routine techniques, it is necessary to regular circulation volt-ampere skill when implementing of the invention
The process conditions of art.
In step (2), cleaning refers to clean using deionized water, is subsequently placed in dried for standby under 40-60 DEG C of environment.
In step (3), the condition for going template to handle is：Constant potential+1.5V carries out template 10~30 minutes.
In step (3), cleaning refers to clean using deionized water, is subsequently placed in dried for standby under 40-60 DEG C of environment.
In step (3), the concentration as the dipotassium hydrogen phosphate solution for removing template liquid is preferably 0.2molL-1。
The microcapsule algae toxin molecular engram optical electro-chemistry sensor is used for quick detection microcapsule algae toxin, specifically
Step is as follows：
(1) standard curve is drawn：Using pH a series of the micro- of concentration is configured in 7.2~7.4 PBS phosphate buffer solutions
The standard liquid of capsule microcystins-LR, using the microcapsule algae toxin molecular engram optical electro-chemistry sensor as working electrode,
Using platinized platinum as to electrode, Ag/AgCl is as reference electrode, using visible ray as excitation source, in CHI660e electrochemical operations
I-t technologies are utilized on standing, add -0.2V bias, different light is obtained according to concentration being detected successively in proper order from low to high
Electric current, linear relationship is finally created with the concentration of density of photocurrent and microcapsule algae toxin, draw standard curve；
(2) microcapsule algae toxin of unknown solubility is equally configured to PBS phosphate buffer solutions of the pH 7.2~7.4
In, obtain photoelectric current under the test condition of step (1), using the standard curve of drafting can try to achieve unknown microcystin-
LR concentration.
When being detected for pond water or river, after pond water or river are first filtered 3 times with sand core funnel, then with precipitating
The calcium ions and magnesium ions of part in water removal are removed in agent, and a certain amount of phosphate is then added in water sample and is configured to PBSs of the pH 7.2~7.4
After phosphate buffer solution, photoelectric current is obtained under the test condition of step (1), each water sample is tried to achieve using the standard curve of drafting
Middle microcystin-LR concentration.
In the present invention, selectivity test is also carried out, selective test method is：Containing known microcapsule algae toxin
In the PBS phosphate buffer solutions of concentration, the chaff interference that concentration is known 100~200 times of microcapsule algae toxin concentration is added,
Photoelectric current is obtained under the test condition of step (1), compared with the photoelectric current measured during by with being not added with chaff interference, you can obtain
Influence size of the chaff interference to microcapsule algae toxin molecular engram optical electro-chemistry sensor quick detection.
The present invention also simulates the detection method of pure water, pond water or river, and pond water, river are first taken out with sand core funnel
After filter 3 times, then the calcium ions and magnesium ions of part in water removal are removed with precipitating reagent, then pure water adds one without pre-treatment in water sample
Quantification of phosphate is configured to pH after 7.2~7.4 PBS phosphate buffer solutions, then takes two parts of the water sample prepared, is separately added into
Different amounts of microcapsule algae toxin is configured to the entity water sample of the microcapsule algae toxin containing various concentrations, equally in step (1)
Photoelectric current is obtained under test condition, microcystin-LR concentration in each water sample is tried to achieve using the standard curve of drafting.
The Cu that the present invention is absorbed using visible-range2O semiconductors are as photoelectric material, it is seen that light as excitation source,
By the use of microcapsule algae toxin as template, the binding site of microcapsule algae toxin is created in pyrroles's polymerization process, then pass through
Certain electrochemical techniques remove microcapsule algae toxin template in the room for leaving definite shape and binding ability, when addition one
After the microcapsule algae toxin for determining concentration, Microcystin molecule can is specifically bonded on room, passes through i-t technologies
Test shows that the optical electro-chemistry sensor is high to the detection sensitivity of Microcystin, and detection speed is fast, and detection range is wide, resists
Interference performance is strong, and new method is provided for the quick online detection of microcapsule algae toxin.
Compared with traditional detection technique, microcapsule algae toxin molecular engram optical electro-chemistry sensor of the invention is answered
With having the following advantages that：Optical electro-chemistry response is sensitive, and detection range is wide, can be in 1.0ngL-1~10.0ugL-1Concentration model
Enclose it is interior detected, strong antijamming capability；And the preparation method of the present invention is simple and quick, cost is low, is applicable to water body
Quick online detection.
Brief description of the drawings
Fig. 1 is the ac impedance spectroscopy for preparing microcapsule algae toxin molecular engram optical electro-chemistry sensor process.(a)
Cu2The ITO electro-conductive glass of O modifications, the molecular engram optical electro-chemistry sensor of (b) containing microcapsule algae toxin, (c) remove mould
The molecular engram optical electro-chemistry sensor of plate.
Fig. 2 is microcapsule algae toxin solution of the microcapsule algae toxin molecular engram optical electro-chemistry sensor in various concentrations
In photocurrent response figure, the concentration that a~k represents microcapsule algae toxin is respectively 0,1.0ngL-1, 5.0ngL-1,
10.0ng·L-1, 50.0ngL-1, 100.0ngL-1, 300.0ngL-1, 500.0ngL-1,1.0ug·L-1, 3.0ug
L-1, 10.0ugL-1。
Fig. 3 is the Linear Fit Chart of photocurrent response and microcapsule algae toxin solution concentration.
Fig. 4 is the selectivity test lab diagram of microcapsule algae toxin molecular engram optical electro-chemistry sensor.S0~S10 points
Do not represent microcapsule algae toxin, L-threonine, methyl amimoacetic acid, ALANINE, L-arginine salt hydrochloride, D-Fructose, glucose,
Bisphenol-A, 2,4-D, p-bromobenzaldehyde, N, N- dimethylbenzaldehydes.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
One kind is based on visible optical drive Cu2The microcapsule algae toxin molecular engram optical electro-chemistry sensing of O/PPy composites
The preparation of device：
(1)Cu2The preparation of O photoelectric materials：By Cu2SO4Solution and CH3CH (OH) COOH solution and a certain amount of PVP are pressed
According to mol ratio Cu2SO4：CH3CH (OH) COOH is 1:5：0.1 uniformly mixing, 2h under the conditions of being stirred at room temperature, is adjusted with NaOH solution
PH to 8~10, using ITO electro-conductive glass as working electrode, platinized platinum is that Ag/AgCl is reference electrode, in 60 DEG C of conditions to electrode
Under, on CHI660e work stations, first with -0.3V current potential constant potential electro-deposition 150s, then with -0.2V current potential potentiostatic electrodepositions
700s, the finally Cu by electro-deposition2The ITO electro-conductive glass of O photoelectric materials is respectively placed in a certain amount of acetone, ethanol, deionization
Ultrasound 10~20 minutes, are subsequently placed in dried for standby in 40 DEG C of air dry oven in water.
(2) preparation of molecular engram film：It is 1 in molar ratio by microcapsule algae toxin and pyrroles (Py) monomer:30 is uniformly mixed
Close, add certain density lithium perchlorate as supporting electrolyte, the Cu with electro-deposition in step (1)2O photoelectric materials
As working electrode, platinized platinum is used as to electrode ITO electro-conductive glass, and Ag/AgCl is as reference electrode, on CHI660e work stations,
Carried out electropolymerization certain time using cyclic voltammetric technology between certain 0~0.8V of potential range, about 15 minutes, finally will
The ito glass of molecular engram film is cleaned with deionized water in polymerization, 60 DEG C of dried for standby.
(3) removal of template molecule：Certain density dipotassium hydrogen phosphate solution is configured as template liquid is removed, by step (2)
The ITO electro-conductive glass of molecular engram film is used as to electrode as working electrode, platinized platinum on middle electropolymerization, and Ag/AgCl is as reference
Electrode, template is carried out 10~30 minutes with certain constant potential+1.5V on CHI660e work stations, will finally remove template ITO
Electro-conductive glass is cleaned with deionized water, 60 DEG C of dried for standby, that is, obtains visible ray driving Cu2The Microcystis aeruginosa of O/PPy composites
Toxin molecular engram optical electro-chemistry sensor.
Fig. 1 is the AC impedance of microcapsule algae toxin molecular engram optical electro-chemistry sensor process prepared by the present embodiment
Collection of illustrative plates.(a)Cu2The ITO electro-conductive glass of O modifications, the molecular engram optical electro-chemistry sensor of (b) containing microcapsule algae toxin,
(c) the molecular engram optical electro-chemistry sensor of removing template is removed, is illustrated in Cu2Modified on O photoelectric semiconductor materials polypyrrole with
Electron transfer speed accelerates afterwards, and after removing microcapsule algae toxin template and leaving hole, is more beneficial for the exchange of electronics
Transmission, resistance greatly reduce.
Embodiment 2
It can be seen that optical drive Cu2The microcapsule algae toxin molecular engram optical electro-chemistry sensor of O/PPy composites is quickly examined
The method for surveying microcapsule algae toxin：
(1) standard curve is drawn：Using pH a series of the micro- of concentration is configured in 7.2~7.4 PBS phosphate buffer solutions
The standard liquid of capsule microcystins-LR, template ITO electro-conductive glass is gone to be used as working electrode by prepared in embodiment 1, with platinum
Piece is used as to electrode, and Ag/AgCl is as reference electrode, using visible ray as excitation source, on CHI660e electrochemical workstations
Using i-t technologies, add -0.2V bias, different photoelectric currents obtained according to concentration being detected successively in proper order from low to high,
Linear relationship is finally created with the concentration of density of photocurrent and microcapsule algae toxin, draws standard curve.
(2) microcapsule algae toxin of unknown solubility is equally configured to PBS phosphate buffer solutions of the pH 7.2~7.4
In, obtain photoelectric current under the test condition of step (1), using the standard curve of drafting can try to achieve unknown microcystin-
LR concentration.
(3) selectivity test：In the PBS phosphate buffer solutions containing known microcapsule algae toxin concentration, add dense
Spend for the chaff interference of known 100~200 times of microcapsule algae toxin concentration, photoelectric current obtained under the test condition of step (1),
Compared with the photoelectric current measured during by with being not added with chaff interference, you can obtain chaff interference to microcapsule algae toxin molecular engram light
The influence size of electrochemical sensor quick detection.
(4) pure water, pond water, the detection of river：Pond water, river first with sand core funnel filter 3 times after, then with precipitate
The calcium ions and magnesium ions of part in water removal are removed in agent, then pure water adds a certain amount of phosphate in water sample and be configured to without pre-treatment
PH is after 7.2~7.4 PBS phosphate buffer solutions, then takes two parts of the water sample prepared, is separately added into different amounts of microcystin
Element-LR is configured to the entity water sample of the microcapsule algae toxin containing various concentrations, equally obtains light under the test condition of step (1)
Electric current, microcystin-LR concentration in each water sample is tried to achieve using the standard curve of drafting.
Fig. 2 is that the optical electro-chemistry sensor prepared in embodiment 1 is molten in the various concentrations microcapsule algae toxin of the present embodiment
Photocurrent response figure in liquid, the concentration that a~k represents microcapsule algae toxin are respectively 0,1.0ngL-1, 5.0ngL-1,
10.0ng·L-1, 50.0ngL-1, 100.0ngL-1, 300.0ngL-1, 500.0ngL-1,1.0ug·L-1, 3.0ug
L-1, 10.0ugL-1From figure 2 it can be seen that being continuously increased with microcapsule algae toxin concentration, photoelectric current gradually subtracts
It is small, it may be possible to because after microcapsule algae toxin occupies the room on pyrroles, to hinder the transmission of electronics, cause photoelectric current
Decline.
Fig. 3 is the photocurrent values and microcapsule algae toxin measured according to Fig. 2 under the microcapsule algae toxin of various concentrations
The Linear Fit Chart of solution concentration, the straight line as can be seen from the figure fitted are divided into two sections, and linear relationship is also fine, can distinguish
Equation Δ I/I can be used0=0.2558+0.1975logC and Δ I/I0=0.5154+0.0597logC expressions, wherein R2Respectively
0.9848 and 0.9891, lowest detection is limited to 0.23ngL-1Wherein C is microcapsule algae toxin concentration, and I is photoelectric current.
Fig. 4 is that the selectivity test of the microcapsule algae toxin molecular engram optical electro-chemistry sensor prepared in embodiment 1 is real
Test figure.S0~S10 represents microcapsule algae toxin respectively, L-threonine, methyl amimoacetic acid, ALANINE, L-arginine salt hydrochloride,
D-Fructose, glucose, bisphenol-A, 2,4-D, p-bromobenzaldehyde, N, N- dimethylbenzaldehydes, it can be seen that different is dry
Photoelectric respone very little of the thing in this optical electro-chemistry sensor is disturbed, most of interference are below 10%, individually 10%~20%
Between, it is believed that test of the presence of these chaff interferences on microcapsule algae toxin influences little, it may be said that micro- prepared by bright
The selectivity of capsule microcystins-LR molecular engram optical electro-chemistry sensor is very high, strong antijamming capability.
According to the microcapsule algae toxin molecular engram optical electro-chemistry sensor application prepared in embodiment 1 in actual water sample
Test result show, in the detection of entity water, the rate of recovery of microcapsule algae toxin between 98%~103%, detection knot
Fruit is accurate, it may be said that bright the method may be advantageously employed in the detection of entity water.
Embodiment 3
One kind is based on visible optical drive Cu2The microcapsule algae toxin molecular engram optical electro-chemistry sensing of O/PPy composites
The preparation of device：
(1)Cu2The preparation of O photoelectric materials：By Cu2SO4Solution and CH3CH (OH) COOH solution and a certain amount of PVP are pressed
According to mol ratio Cu2SO4：CH3CH (OH) COOH is 1:5：5 uniformly mixing, 2h under the conditions of being stirred at room temperature, with certain density NaOH
Solution adjusts pH to 8~10, and using ITO electro-conductive glass as working electrode, platinized platinum is that Ag/AgCl is reference electrode, 55 to electrode
Under the conditions of~65 DEG C, on CHI660e work stations, first with -0.3V current potential constant potential 100~200s of electro-deposition, then with -0.2V electricity
Position 600~800s of potentiostatic electrodeposition, the finally Cu by electro-deposition2The ITO electro-conductive glass of O photoelectric materials is respectively placed in a certain amount of
Ultrasound 10~20 minutes, are subsequently placed in dried for standby in 40 DEG C of air dry oven in acetone, ethanol, deionized water.
(2) preparation of molecular engram film：It is 1 in molar ratio by microcapsule algae toxin and pyrroles (Py) monomer:10~1:50
Uniformly mixing, certain density lithium perchlorate is added as supporting electrolyte, the Cu with electro-deposition in step (1)2O photoelectricity materials
As working electrode, platinized platinum is used as to work electrode, Ag/AgCl the ITO electro-conductive glass of material as reference electrode in CHI660e
On standing, carried out electropolymerization certain time using cyclic voltammetric technology between certain 0~0.8V of potential range, about 15~20 points
Clock, finally the ito glass for polymerizeing upper molecular engram film is cleaned with deionized water, 60 DEG C of dried for standby.
(3) removal of template molecule：Certain density dipotassium hydrogen phosphate solution is configured as template liquid is removed, by step (2)
The ITO electro-conductive glass of molecular engram film is used as to electrode as working electrode, platinized platinum on middle electropolymerization, and Ag/AgCl is as reference
Electrode, template is carried out 10~30 minutes with certain constant potential+1.5V on CHI660e work stations, will finally remove template ITO
Electro-conductive glass is cleaned with deionized water, 60 DEG C of dried for standby.
Embodiment 4
One kind is based on visible optical drive Cu2The microcapsule algae toxin molecular engram optical electro-chemistry sensing of O/PPy composites
The preparation of device：
(1)Cu2The preparation of O photoelectric materials：By Cu2SO4Solution and CH3CH (OH) COOH solution and a certain amount of PVP are pressed
According to mol ratio Cu2SO4：CH3CH (OH) COOH is 1:5:10 uniformly mixing, 2h under the conditions of being stirred at room temperature, with certain density NaOH
Solution adjusts pH to 8~10, and using ITO electro-conductive glass as working electrode, platinized platinum is that Ag/AgCl is reference electrode, 55 to electrode
Under the conditions of~65 DEG C, on CHI660e work stations, first with -0.3V current potential constant potential 100~200s of electro-deposition, then with -0.2V electricity
Position 600~800s of potentiostatic electrodeposition, the finally Cu by electro-deposition2The ITO electro-conductive glass of O photoelectric materials is respectively placed in a certain amount of
Ultrasound 10~20 minutes, are subsequently placed in dried for standby in 40 DEG C of air dry oven in acetone, ethanol, deionized water.
(2) preparation of molecular engram film：It is 1 in molar ratio by microcapsule algae toxin and pyrroles (Py) monomer:10~1:50
Uniformly mixing, certain density lithium perchlorate is added as supporting electrolyte, the Cu with electro-deposition in step (1)2O photoelectricity materials
As working electrode, platinized platinum is used as to work electrode, Ag/AgCl the ITO electro-conductive glass of material as reference electrode in CHI660e
On standing, carried out electropolymerization certain time using cyclic voltammetric technology between certain 0~0.8V of potential range, about 20~30 points
Clock, finally the ito glass for polymerizeing upper molecular engram film is cleaned with deionized water, 60 DEG C of dried for standby.
(3) removal of template molecule：Certain density dipotassium hydrogen phosphate solution is configured as template liquid is removed, by step (2)
The ITO electro-conductive glass of molecular engram film is used as to electrode as working electrode, platinized platinum on middle electropolymerization, and Ag/AgCl is as reference
Electrode, template is carried out 10~30 minutes with certain constant potential+1.5V on CHI660e work stations, will finally remove template ITO
Electro-conductive glass is cleaned with deionized water, 60 DEG C of dried for standby.
Embodiment 5
One kind is based on visible optical drive Cu2The microcapsule algae toxin molecular engram optical electro-chemistry sensing of O/PPy composites
The preparation of device：
(1)Cu2The preparation of O photoelectric materials：By Cu2SO4Solution and CH3CH (OH) COOH solution and a certain amount of PVP are pressed
According to mol ratio Cu2SO4：CH3CH (OH) COOH is 1:5:10 uniformly mixing, 2h under the conditions of being stirred at room temperature, with certain density NaOH
Solution adjusts pH to 8~10, and using ITO electro-conductive glass as working electrode, platinized platinum is that Ag/AgCl is reference electrode, 55 to electrode
Under the conditions of~65 DEG C, on CHI660e work stations, first with -0.3V current potential constant potential 100~200s of electro-deposition, then with -0.2V electricity
Position 600~800s of potentiostatic electrodeposition, the finally Cu by electro-deposition2The ITO electro-conductive glass of O photoelectric materials is respectively placed in a certain amount of
Ultrasound 10~20 minutes, are subsequently placed in dried for standby in 40 DEG C of air dry oven in acetone, ethanol, deionized water.
(2) preparation of molecular engram film：It is 1 in molar ratio by microcapsule algae toxin and pyrroles (Py) monomer:10~1:50
Uniformly mixing, certain density lithium perchlorate is added as supporting electrolyte, the Cu with electro-deposition in step (1)2O photoelectricity materials
As working electrode, platinized platinum is used as to work electrode, Ag/AgCl the ITO electro-conductive glass of material as reference electrode in CHI660e
On standing, carried out electropolymerization certain time using cyclic voltammetric technology between certain 0~0.8V of potential range, about 15~20 points
Clock, finally the ito glass for polymerizeing upper molecular engram film is cleaned with deionized water, 60 DEG C of dried for standby.
(3) removal of template molecule：Certain density dipotassium hydrogen phosphate solution is configured as template liquid is removed, by step (2)
The ITO electro-conductive glass of molecular engram film is used as to electrode as working electrode, platinized platinum on middle electropolymerization, and Ag/AgCl is as reference
Electrode, template is carried out 30~40 minutes with certain constant potential+1.5V on CHI660e work stations, will finally remove template ITO
Electro-conductive glass is cleaned with deionized water, 60 DEG C of dried for standby.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel do not depart from improvement that scope made and modification all should be the present invention's according to the announcement of the present invention
Within protection domain.
Claims (10)
1. a kind of microcapsule algae toxin molecular engram optical electro-chemistry sensor, it is characterised in that the sensor is conductive with ITO
Glass is matrix, deposits upper molecular engram film by electrochemical deposition technique, the molecular engram film is by Cu2O photoelectric materials are with containing
The polypyrrole for having microcapsule algae toxin room is combined.
2. a kind of preparation method of microcapsule algae toxin molecular engram optical electro-chemistry sensor as claimed in claim 1, its feature
It is, preparation method specifically includes following steps：
(1)Cu2The preparation of O photoelectric materials：By Cu2SO4Solution and CH3CH (OH) COOH solution and PVP are uniformly mixed, room temperature bar
Stirred under part, and adjust the pH to 8~10 of mixed solution, using ITO electro-conductive glass as working electrode, platinized platinum is to electrode, Ag/
AgCl is reference electrode, and under the conditions of 55~65 DEG C, electro-deposition is carried out on CHI660e work stations, obtains electro-deposition Cu2O
The ITO electro-conductive glass of photoelectric material, it is standby after cleaning；
(2) preparation of molecular engram film：Microcapsule algae toxin is uniformly mixed with pyrrole monomer, add lithium perchlorate as
Supporting electrolyte, the Cu with electro-deposition obtained by step (1)2The ITO electro-conductive glass of O photoelectric materials is made as working electrode, platinized platinum
For to electrode, Ag/AgCl carries out electropolymerization as reference electrode on CHI660e work stations, is then cleaned and dried stand-by, obtains
There is the ito glass of molecular engram film to polymerization；
(3) removal of template molecule：Dipotassium hydrogen phosphate solution has molecular engram film as template liquid is removed, by polymerization in step (2)
Ito glass as working electrode, platinized platinum is as enterprising in CHI660e work stations as reference electrode to electrode, Ag/AgCl
Row goes template to handle, and will finally go template ITO electro-conductive glass to obtain being based on visible optical drive Cu after being cleaned and dried2O/PPy is compound
The microcapsule algae toxin molecular engram optical electro-chemistry sensor of material.
3. the preparation method of microcapsule algae toxin molecular engram optical electro-chemistry sensor according to claim 2, its feature
It is, in step (1), according to mol ratio, Cu2SO4：CH3CH(OH)COOH：PVP is 1:5:0.1~1:10:30.
4. the preparation method of microcapsule algae toxin molecular engram optical electro-chemistry sensor according to claim 2, its feature
It is, in step (1), the condition of electro-deposition is：First with -0.3V current potential constant potential 100~200s of electro-deposition, then with -0.2V electricity
Position 600~800s of potentiostatic electrodeposition.
5. the preparation method of microcapsule algae toxin molecular engram optical electro-chemistry sensor according to claim 2, its feature
It is, in step (2), microcapsule algae toxin is 1 with pyrrole monomer mol ratio:10~1:50.
6. the preparation method of microcapsule algae toxin molecular engram optical electro-chemistry sensor according to claim 2, its feature
It is, in step (2), the concentration after lithium perchlorate adds is 0.1molL-1。
7. the preparation method of microcapsule algae toxin molecular engram optical electro-chemistry sensor according to claim 2, its feature
It is, in step (2), the condition of electropolymerization is：Between 0~0.8V 15~20 points of electropolymerization is carried out using cyclic voltammetric technology
Clock.
8. the preparation method of microcapsule algae toxin molecular engram optical electro-chemistry sensor according to claim 2, its feature
It is, in step (3), the condition for going template to handle is：Constant potential+1.5V carries out template 10~30 minutes.
9. a kind of application of microcapsule algae toxin molecular engram optical electro-chemistry sensor as claimed in claim 1, its feature exist
In the microcapsule algae toxin molecular engram optical electro-chemistry sensor is used for quick detection microcapsule algae toxin, specific steps
It is as follows：
(1) standard curve is drawn：Using pH the Microcystis aeruginosas of concentration a series of is configured in 7.2~7.4 PBS phosphate buffer solutions
The standard liquid of toxin, using the microcapsule algae toxin molecular engram optical electro-chemistry sensor as working electrode, with platinum
Piece is used as to electrode, and Ag/AgCl is as reference electrode, using visible ray as excitation source, on CHI660e electrochemical workstations
Using i-t technologies, add -0.2V bias, different photoelectric currents obtained according to concentration being detected successively in proper order from low to high,
Linear relationship is finally created with the concentration of density of photocurrent and microcapsule algae toxin, draws standard curve；
(2) microcapsule algae toxin of unknown solubility is equally configured to pH in 7.2~7.4 PBS phosphate buffer solutions,
Photoelectric current is obtained under the test condition of step (1), it is dense to try to achieve unknown microcystin-LR using the standard curve of drafting
Degree.
10. the application of microcapsule algae toxin molecular engram optical electro-chemistry sensor according to claim 9, it is characterised in that
When detecting for pond water or river, after pond water or river are first filtered 3 times with sand core funnel, then with precipitating reagent go to remove water
The calcium ions and magnesium ions of middle part, a certain amount of phosphate is then added in water sample it is configured to pH and delay in 7.2~7.4 PBS phosphate
After rushing solution, photoelectric current is obtained under the test condition of step (1), Microcystis aeruginosa in each water sample is tried to achieve using the standard curve of drafting
Poison-LR concentration.
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