CN109115851A - A kind of preparation method and purposes of the optical electro-chemistry aptamer sensor detecting bisphenol-A - Google Patents
A kind of preparation method and purposes of the optical electro-chemistry aptamer sensor detecting bisphenol-A Download PDFInfo
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- CN109115851A CN109115851A CN201810938876.9A CN201810938876A CN109115851A CN 109115851 A CN109115851 A CN 109115851A CN 201810938876 A CN201810938876 A CN 201810938876A CN 109115851 A CN109115851 A CN 109115851A
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Abstract
The invention belongs to photoelectric material and optical electro-chemistry detection fields, a kind of preparation method of optical electro-chemistry aptamer sensor detecting bisphenol-A is provided, include the following steps: first, chloro imidazole ion liquid, ethanol solution, g-CN and the sodium hydroxide solution of a certain amount of copper are placed in polytetrafluoroethyllining lining autoclave, autoclave is put into baking oven and is reacted, after reaction cooled to room temperature.Finally, products therefrom is centrifuged, wash, it is dry, obtain CuO/g-CN composite photoelectric material.By the modification of the CuO/g-CN composite photoelectric material of preparation on ITO electro-conductive glass, and bisphenol-A aptamers are assembled, constructs optical electro-chemistry aptamer sensor.Electrode material used in the present invention is to explore its superior photoelectric properties in the CuO/g-CN photoelectricity composite material of visible region response, widened g-CN sill in the application of photoelectric field, also had found a kind of new material for Photoelectric Detection.The optical electro-chemistry aptamer sensor detection sensitivity with higher of building, and strong antijamming capability.
Description
Technical field
The invention belongs to photoelectric material and optical electro-chemistry detection fields, and it is suitable to be related to a kind of optical electro-chemistry for detecting bisphenol-A
Preparation method and purposes with body sensor.
Background technique
Optical electro-chemistry (PEC) detection causes the concern in the whole world as a kind of portable determination method.With biography
The advantages of electrochemical method of system is compared with optical method, and PEC technology summarizes above two method, thus improve sensitivity and
Signal-to-noise ratio.In essence, the principle of PEC analysis method is semiconductor as active specy, under the irradiation of exciting light, photoproduction
Electronics is separated with hole, and then active specy captures electronics or hole, and it is anti-that redox occurs with target detection thing
It answers, to form photovoltage or photoelectric current.In addition, separation of the PEC analysis method due to excitation light source and detection signal, and it is big
It is big to reduce ambient noise, there is higher sensitivity than Conventional electrochemical analysis method.Compared with traditional optical means, PEC
Analysis method have many advantages, such as instrument cost inexpensively, miniaturization.
Organic pollutant refers to the organic compound for causing environmental pollution and generating adverse effect to the ecosystem.China
Organic contamination status is more severe, carries out very urgent to the effectively detection of organic pollutant in environment.Aptamers are energy and egg
The ligands such as white matter or metabolin specifically and the RNA or DNA fragmentation that efficiently combine, are combined using aptamers as amplifier with PEC,
The optical electro-chemistry aptamer sensor constructed can be realized to the high sensitivity of organic matter and highly selective detection.
Summary of the invention
The present invention is directed to propose a kind of CuO/g-CN photoelectricity composite material, and photoelectricity aptamer sensor is constructed to examine with it
Survey organic pollutant.Compared to g-CN monomer, the introducing of CuO accelerates the electric charge transfer of photoelectricity composite material, promotes photoproduction
Electron-hole pair efficiently separates, and obtains superior photoelectric properties.
A kind of preparation method for the optical electro-chemistry aptamer sensor detecting bisphenol-A, includes the following steps:
(1) CuO/g-CN photoelectricity composite material is prepared by hydro-thermal method:
It is placed in polytetrafluoroethyllining lining autoclave firstly, weighing a certain amount of copper-based chloro imidazole ion liquid, then moves
Taking a certain amount of ethanol solution to pour into kettle and stirring makes mixing sufficiently, then weighs a certain amount of g-CN in proportion and autoclave is added
In, ultrasound is completely dispersed carbonitride in the above solution, then a certain amount of certain density hydrogen-oxygen is added dropwise in proportion into solution
Change sodium solution, it is lasting to stir；After stirring, autoclave is put into baking oven and carries out hydro-thermal reaction, after reaction, taken out anti-
Answer kettle and cooled to room temperature；Sample is collected by centrifugation, washing and alcohol are washed for several times, and then re-dry, obtains CuO/g-CN；
(2) CuO/g-CN photoelectricity composite material is distributed in deionized water, ultrasonic disperse, obtains stable suspension；
(3) take the suspended drop-coated of step (2) on ITO electro-conductive glass, natural drying at room temperature, deionized water is rinsed, so
Natural drying at room temperature, obtained modified electrode are denoted as CuO/g-CN-ITO again afterwards；
Take certain density bisphenol-A aptamers drop coating on made CuO/g-CN-ITO, natural drying at room temperature, deionization
Water rinses, then natural drying at room temperature again, obtains optical electro-chemistry aptamer sensor CuO/g-CN-aptamer-ITO.
In step (1), the copper-based chloro imidazole ion liquid be bis- (1- alkyl -3- methylimidazole) tetrachloros conjunction copper from
Sub- liquid [Cxmim]2CuCl4, x=2~16.
In step (1), the copper-based chloro imidazole ion liquid, ethyl alcohol, carbonitride and sodium hydroxide usage ratio be
0.15~0.9mmol:19mL:0.28g:0.35~2mmol.
In step (1), the temperature of hydro-thermal reaction is 140~160 DEG C, reaction time 10h；The drying temperature is 50
~70 DEG C, drying time be 12~for 24 hours.
In step (2), the turbid liquid concentration is 1.0mg/mL.
In step (3), the usage ratio of suspension and bisphenol-A aptamers are as follows: 50 μ L:25 μ L；The bisphenol-A aptamers
Concentration is 0.2~1 μm of ol/L, and the sequence of bisphenol-A aptamers is 5 '-CCGGTGGGTGGTCAGGTGGGATAGCGTTCCGCGTA
TGGCCCAGCGCATCACGGGTTCGCACCA-3′。
Optical electro-chemistry aptamer sensor produced by the present invention is used to detect the purposes of bisphenol-A, the specific steps are as follows:
(1) measurement of standard curve: the CuO/g-CN- that a series of bisphenol-A drop coating of known concentrations is made in step (3) is taken
On aptamer-ITO, natural drying at room temperature, deionized water is rinsed, and natural drying at room temperature, obtained modified electrode is denoted as CuO/
g-CN-aptamer-BPA-ITO；
Using the CuO/g-CN-aptamer-BPA-ITO modified electrode of preparation as working electrode, Ag/AgCl is as reference
Electrode, Pt are used as to electrode, and using phosphate buffer solution as electrolyte, its photoelectric current is measured under the test potential of -0.1V
Response obtains a series of concentration-photoelectric current corresponding relationship, and then obtains the standard curve of bisphenol-A；
(2) take a certain amount of drop-coated to be measured on the made CuO/g-CN-aptamer-ITO of step (3), room temperature is naturally dry
Dry, deionized water is rinsed, and natural drying at room temperature, obtained modified electrode is denoted as CuO/g-CN-aptamer-BPA-ITO；
Using the CuO/g-CN-aptamer-BPA-ITO modified electrode of preparation as working electrode, Ag/AgCl is as reference
Electrode, Pt are used as to electrode, and using phosphate buffer solution as electrolyte, its photoelectric current is measured under the test potential of -0.1V
Response, the concentration of bisphenol-A in liquid can must be detected by bringing photocurrent values into standard curve conversion.
The dosage of the bisphenol-A is 20 μ L；The concentration of bisphenol-A is 0~5*10-5g/L。
The phosphate buffer solution is the sodium dihydrogen phosphate and disodium hydrogen phosphate intermodulation by configuring 0.1mol/L, makes pH
Value is made for 7.0, concentration 0.1mol/L.
The invention has the benefit that
(1) electrode material used in the present invention is the CuO/g-CN photoelectricity composite material in visible region response, is explored
Its superior photoelectric properties, has widened g-CN sill in the application of photoelectricity aptamers detection field, is also photoelectricity aptamers
Detection has found a kind of new material.
(2) present invention can carry out quantitative analysis to organic pollutant, have apparent practicability.The present invention be collection detection and
It administers in the detection means of one, possesses wide practical application space.
(3) detection means used in the present invention detection sensitivity with higher, and strong antijamming capability.
(4) synthetic method used in the present invention is hydro-thermal method, have many advantages, such as it is time saving, it is convenient.
Detailed description of the invention
Fig. 1 be CuO/g-CN material infrared (FT-IR) figure of Fourier, wherein a be g-CN, b 10wt%CuO/g-CN,
C is CuO.
Fig. 2 (A) is outer (UV-Vis) figure of solid violet of CuO/g-CN material, and wherein a is g-CN, b 10wt%CuO/g-
CN；It (B) is transient state fluorescence (PL) figure of CuO/g-CN material, wherein a is g-CN, b 10wt%CuO/g-CN.
Fig. 3 (A) is AC impedance (EIS) figure of CuO/g-CN material, and wherein a is pure ITO, and b g-CN-ITO, c are
10wt%CuO/g-CN-ITO, d 10wt%CuO/g-CN-aptamer-ITO, e 10wt%CuO/g-CN-aptamer-
BPA-ITO；It (B) is photoelectricity flow graph (a g-CN, the b 10wt% of modified electrode 10wt%CuO/g-CN-ITO and g-CN-ITO
CuO/g-CN)。
Fig. 4 is the photosignal response diagram that detecting electrode 10wt%CuO/g-CN-aptamer-BPA-ITO detects bisphenol-A,
Wherein figure A is the detection resulting photoelectricity flow graph of various concentration bisphenol-A, schemes B for bisphenol A concentration-photocurrent values line for being drawn
Sexual intercourse figure.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described, so that those skilled in the art more fully understand
The present invention, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
(1) preparation of 5wt%CuO/g-CN photoelectricity composite material is made by hydro-thermal method:
25mL poly- four is placed in firstly, weighing bis- (1- cetyl -3- methylimidazole) tetrachloros of 0.0895g and closing copper ion liquid
In vinyl fluoride liner autoclave, the ethanol solution for then pipetting 19mL, which pours into kettle and stirs 15min, makes mixing sufficiently, then weighs
The g-CN of 0.2831g is added in autoclave, and ultrasonic 30min is completely dispersed g-CN in the above solution, then into solution by than
The sodium hydroxide solution of 0.25mL (1.5M) is added dropwise in example, persistently stirs 30min.After stirring, autoclave is put into 140 DEG C
After reacting 10h in baking oven, reaction kettle and cooled to room temperature are taken out.Finally, obtained product high speed at 12000rpm
Separation, and the sample being collected by centrifugation washing and alcohol are washed for several times, then dry 12h obtains 5wt% in 60 DEG C of baking oven
CuO/g-CN sample；
(2) preparation of modified electrode:
It is ITO electro-conductive glass preprocessing process first, ITO electro-conductive glass is successively surpassed in deionized water, ethyl alcohol respectively
After sound cleans half an hour, repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1mol/L NaOH aqueous solution, it will
It is boiled, and is kept for 30 minutes, is cleaned and is dried up stand-by with deionized water.Configure the water-soluble of 1mg/mL 5wt%CuO/g-CN
Liquid is carried out ultrasonic disperse, obtains stable suspension.Then, take the 50 suspended drop-coateds of μ L pretreated in step 1
On ITO electro-conductive glass, the 5wt%CuO/g-CN of surface modification not yet in effect is washed off after natural drying at room temperature with deionized water,
Natural drying at room temperature, obtained modified electrode are denoted as 5wt%CuO/g-CN-ITO.
(3) preparation of detecting electrode:
Take the certain density bisphenol-A aptamers drop coating of 25 μ L on made 5wt%CuO/g-CN-ITO, room temperature is naturally dry
The bisphenol-A aptamers of surface absorption not yet in effect, natural drying at room temperature, obtained modification electricity are washed off after dry with deionized water
Pole is denoted as 5wt%CuO/g-CN-aptamer-ITO.20 microlitres of certain density bisphenol-As are taken to be applied to made 5wt%CuO/g-
On CN-aptamer-ITO, the bisphenol-A of surface absorption not yet in effect is washed off after natural drying at room temperature with deionized water, room temperature is certainly
So dry, obtained modified electrode is denoted as 5wt%CuO/g-CN-aptamer-BPA-ITO.
(4) optical electro-chemistry detection method and condition:
Light source is derived from high brightness xenon lamp source of parallel light system instrument, and (CHF-XM35-500W, Beijing are smooth with 500W xenon lamp
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filter.Electrochemistry experiment uses CHI
660E electrochemical workstation (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system: modified electrode is work electricity
Pole, platinum electrode are to electrode, and saturation Ag/AgCl electrode is reference electrode (all current potentials are both with respect to SCE).5wt%CuO/
The photoelectric properties test of g-CN carries out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), and current potential is 0V (vs
SCE), 5wt%CuO/g-CN-aptamer-BPA-ITO photoelectric respone test room temperature, phosphate buffer solution (0.1mol/L,
PH=7.0 it is carried out in), current potential is -0.1V (vs SCE).EIS experiment is containing 5mmol/L Fe (CN)6 3-/4-0.1mol/L
It is carried out in KCl solution, frequency range is 0.01Hz~10kHz, initial potential 0.24V, AC amplitude 5mV.
Embodiment 2:
(1) preparation of 10wt%CuO/g-CN photoelectricity composite material is made by hydro-thermal method:
25mL polytetrafluoroethyl-ne is placed in firstly, weighing bis- (1- octyl -3- methylimidazole) tetrachloros of 0.1888g and closing copper ion liquid
In alkene liner autoclave, the ethanol solution for then pipetting 19mL, which pours into kettle and stirs 15min, makes mixing sufficiently, then weighs
The g-CN of 0.2831g is added in autoclave, and ultrasonic 30min is completely dispersed carbonitride in the above solution, then presses into solution
The sodium hydroxide solution of 0.25mL (3.2M) is added dropwise in ratio, persistently stirs 30min.After stirring, autoclave is put into 140 DEG C
Baking oven in react 10h after, take out reaction kettle and cooled to room temperature.Finally, obtained product is high at 12000rpm
Speed separation, and the sample being collected by centrifugation washing and alcohol are washed for several times, then dry 12h obtains 10wt% in 60 DEG C of baking oven
CuO/g-CN sample；
(2) preparation of modified electrode:
It is ITO electro-conductive glass preprocessing process first, ITO electro-conductive glass is successively surpassed in deionized water, ethyl alcohol respectively
After sound cleans half an hour, repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1mol/L NaOH aqueous solution, it will
It is boiled, and is kept for 30 minutes, is cleaned and is dried up stand-by with deionized water.Configure the water-soluble of 1mg/mL 10wt%CuO/g-CN
Liquid is carried out ultrasonic disperse, obtains stable suspension.Then, take the 50 suspended drop-coateds of μ L pretreated in step 1
On ITO electro-conductive glass, the 10wt%CuO/g-CN of surface modification not yet in effect is washed off after natural drying at room temperature with deionized water,
Natural drying at room temperature, obtained modified electrode are denoted as 10wt%CuO/g-CN-ITO.In order to be prepared into above-mentioned preparation method
To 10wt%CuO/g-CN-ITO compare, by similar approach be made g-CN-ITO modified electrode.
(3) preparation of detecting electrode:
Take 25 microlitres of certain density bisphenol-A aptamers drop coatings on made 10wt%CuO/g-CN-ITO, room temperature is certainly
The bisphenol-A aptamers of surface absorption not yet in effect are so washed off after drying with deionized water, natural drying at room temperature, obtained repairs
Decorations electrode is denoted as 10wt%CuO/g-CN-aptamer-ITO, takes the certain density bisphenol-A drop coating of 20 μ L in made 10wt%
On CuO/g-CN-aptamer-ITO, the bisphenol-A of surface absorption not yet in effect is washed off after natural drying at room temperature with deionized water,
Natural drying at room temperature, obtained modified electrode are denoted as 10wt%CuO/g-CN-aptamer-BPA-ITO.
(4) optical electro-chemistry detection method and condition:
Light source is derived from high brightness xenon lamp source of parallel light system instrument, and (CHF-XM35-500W, Beijing are smooth with 500W xenon lamp
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filter.Electrochemistry experiment uses CHI
660E electrochemical workstation (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system: modified electrode is work electricity
Pole, platinum electrode are to electrode, and saturation Ag/AgCl electrode is reference electrode (all current potentials are both with respect to SCE).10wt%CuO/
The photoelectric properties test of g-CN carries out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), and current potential is 0V (vs
SCE), the photoelectric respone of 10wt%CuO/g-CN-aptamer-BPA-ITO is tested in room temperature, phosphate buffer solution (0.1mol/
L, pH=7.0) in carry out, current potential be -0.1V (vs SCE).EIS experiment is containing 5mmol/L Fe (CN)6 3-/4-0.1mol/
It is carried out in L KCl solution, frequency range is 0.01Hz~10kHz, initial potential 0.24V, AC amplitude 5mV.
Embodiment 3:
(1) preparation of 20wt%CuO/g-CN photoelectricity composite material is made by hydro-thermal method:
25mL poly- four is placed in firstly, weighing bis- (1- dodecyl -3- methylimidazole) tetrachloros of 0.4244g and closing copper ion liquid
In vinyl fluoride liner autoclave, the ethanol solution for then pipetting 19mL, which pours into kettle and stirs 15min, makes mixing sufficiently, then weighs
The g-CN of 0.2831g is added in autoclave, and ultrasonic 30min is completely dispersed carbonitride in the above solution, then presses into solution
The sodium hydroxide solution of 0.25mL (7.1M) is added dropwise in ratio, persistently stirs 30min.After stirring, autoclave is put into 140 DEG C
Baking oven in react 10h after, take out reaction kettle and cooled to room temperature.Finally, obtained product is high at 12000rpm
Speed separation, and the sample being collected by centrifugation washing and alcohol are washed for several times, then dry 12h obtains 20wt% in 60 DEG C of baking oven
CuO/g-CN sample；
(2) preparation of modified electrode:
It is ITO electro-conductive glass preprocessing process first, ITO electro-conductive glass is successively surpassed in deionized water, ethyl alcohol respectively
After sound cleans half an hour, repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1mol/L NaOH aqueous solution, it will
It is boiled, and is kept for 30 minutes, is cleaned and is dried up stand-by with deionized water.Configure the water-soluble of 1mg/mL 20wt%CuO/g-CN
Liquid is carried out ultrasonic disperse, obtains stable suspension.Then, take the 50 suspended drop-coateds of μ L pretreated in step 1
On ITO electro-conductive glass, the 20wt%CuO/g-CN of surface modification not yet in effect is washed off after natural drying at room temperature with deionized water,
Natural drying at room temperature, obtained modified electrode are denoted as 20wt%CuO/g-CN.In order to what is be prepared with above-mentioned preparation method
20wt%CuO/g-CN-ITO compares, and g-CN-ITO modified electrode is made by similar approach.
(3) preparation of detecting electrode:
Take 25 microlitres of certain density bisphenol-A aptamers drop coatings on made 20wt%CuO/g-CN-ITO, room temperature is certainly
The bisphenol-A aptamers of surface absorption not yet in effect are so washed off after drying with deionized water, natural drying at room temperature, obtained repairs
Decorations electrode is denoted as 20wt%CuO/g-CN-aptamer-ITO, takes the certain density bisphenol-A drop coating of 20 μ L in made 20wt%
On CuO/g-CN-aptamer-ITO, the bisphenol-A of surface absorption not yet in effect is washed off after natural drying at room temperature with deionized water,
Natural drying at room temperature, obtained modified electrode are denoted as 20wt%CuO/g-CN-aptamer-BPA-ITO.
(4) optical electro-chemistry detection method and condition:
Light source is derived from high brightness xenon lamp source of parallel light system instrument, and (CHF-XM35-500W, Beijing are smooth with 500W xenon lamp
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filter.Electrochemistry experiment uses CHI
660E electrochemical workstation (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system: modified electrode is work electricity
Pole, platinum electrode are to electrode, and saturation Ag/AgCl electrode is reference electrode (all current potentials are both with respect to SCE).20wt%CuO/
The photoelectric properties test of g-CN carries out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), and current potential is 0V (vs
SCE), the photoelectric respone of 20wt%CuO/g-CN-aptamer-BPA-ITO is tested in room temperature, phosphate buffer solution (0.1mol/
L, pH=7.0) in carry out, current potential be -0.1V (vs SCE).EIS experiment is containing 5mmol/L Fe (CN)6 3-/4-0.1mol/
It is carried out in L KCl solution, frequency range is 0.01Hz~10kHz, initial potential 0.24V, AC amplitude 5mV.
Detailed description of the invention
Fig. 1 be CuO/g-CN material infrared (FT-IR) figure of Fourier, wherein a be g-CN, b 10wt%CuO/g-CN,
C is CuO.It can be found that the characteristic peak of g-CN from a.10wt%CuO/g-CN feature similar with monomer g-CN can be found in b
Peak, this shows that the introducing of CuO does not change the structure of g-CN material of main part.The characteristic peak of CuO is not seen in compound, it may
It is since the content of CuO is low and the infrared signature peak of metal oxide is not strong.
Fig. 2 (A) is outer (UV-Vis) figure of solid violet of CuO/g-CN material, and wherein a is g-CN, b 10wt%CuO/g-
CN.From Fig. 2 (A) it can be seen that compared to monomer g-CN, the 10wt%CuO/g-CN composite material ABSORPTION EDGE after introducing CuO is red
It moves, and has stronger absorption than visible light, illustrate the absorption that the introducing of CuO enhances g-CN to visible light.Fig. 2 (B) is CuO/
Transient state fluorescence (PL) figure of g-CN material, wherein a is g-CN, b 10wt%CuO/g-CN.As can be seen from the figure 10wt%
The emission peak intensity ratio g-CN of CuO/g-CN composite material is low, illustrates that 10wt%CuO/g-CN has lower photo-generate electron-hole
Reassociation rate.
Fig. 3 (A) is AC impedance (EIS) figure of CuO/g-CN material, and wherein a is pure ITO, and b g-CN-ITO, c are
10wt%CuO/g-CN-ITO, d 10wt%CuO/g-CN-aptamer-ITO, e 10wt%CuO/g-CN-aptamer-
BPA-ITO.The resistance value of material prepared by the present invention is detected by carrying out AC impedance to working electrode, is further studied
CuO/g-CN material shifts the modification of the ability and BPA aptamers and BPA of electronics on detecting electrode and shifts electricity to detecting electrode
The ability of son.It can be found that the resistance value of CuO/g-CN material ratio g-CN material is low, illustrate the ability ratio of CuO/g-CN transfer electronics
G-CN material is strong, can be more effectively by photo-generate electron-hole to separation.This illustrates that the introducing of CuO makes g-CN have stronger electricity
Sub- transmission capacity accelerates the transfer of charge, promotes the separation in light induced electron and hole, and compound is made to have better photoelectricity
Performance.C is compared, d, e can be found that the transfer of charge has been contained in modification of the BPA aptamers on detecting electrode, contained photoproduction
The separation of electronics and hole makes the reduction of photocurrent response value.On 10wt%CuO/g-CN-aptamer-ITO electrode further
BPA is modified, has further contained the transfer of charge, so that photocurrent response value further decreases, charge has been contained in BPA absorption
Transfer is so that it is also the principle for detecting BPA that photocurrent response value, which reduces this,.Fig. 3 (B) is modified electrode 10wt%CuO/g-CN-
The photoelectricity flow graph (a g-CN, b 10wt%CuO/g-CN) of ITO and g-CN-ITO.Under light irradiation, the electricity of different materials preparation
Extremely different to the response of light, the photo-current intensity of generation is also different.Therefore varying strength can be generated according to different operating electrode
Photoelectric current come illustrate different materials to light difference respond, photoelectric current illustrate more by force working electrode under light illumination light induced electron with
The separative efficiency in hole is higher.As can be seen that compound prepared by the present invention has higher photocurrent values than monomer, this is said
The introducing of bright CuO makes g-CN have stronger electron transmission ability, accelerates the transfer of charge, promotes light induced electron and hole
Separation, make compound have better photoelectric properties.This result and AC impedance (EIS) figure result are coincide.
Fig. 4 is the photosignal response diagram that detecting electrode 10wt%CuO/g-CN-aptamer-BPA-ITO detects bisphenol-A,
Wherein figure A is the detection resulting photoelectricity flow graph of various concentration bisphenol-A, schemes B for bisphenol A concentration-photocurrent values line for being drawn
Sexual intercourse figure.It can be seen from the figure that with the increase of bisphenol A concentration, 10wt%CuO/g-CN-aptamer-BPA-ITO's
Photo-signal is gradually reduced.The detector linear range is 5*10-11-5*10-5G/L, corresponding linear equation are i=-
2.5125logC+2.6505 R2=0.992, detection limit is 4.48*10-11g/L。
Claims (9)
1. a kind of preparation method for the optical electro-chemistry aptamer sensor for detecting bisphenol-A, which comprises the steps of:
(1) CuO/g-CN photoelectricity composite material is prepared by hydro-thermal method:
It is placed in polytetrafluoroethyllining lining autoclave firstly, weighing a certain amount of copper-based chloro imidazole ion liquid, then pipettes one
Quantitative ethanol solution, which is poured into kettle and stirred, makes mixing sufficiently, then weighs a certain amount of g-CN in proportion and be added in autoclave,
Ultrasound is completely dispersed carbonitride in the above solution, then a certain amount of certain density sodium hydroxide is added dropwise in proportion into solution
Solution, it is lasting to stir；After stirring, autoclave is put into baking oven and carries out hydro-thermal reaction, after reaction, takes out reaction kettle
And cooled to room temperature；Sample is collected by centrifugation, washing and alcohol are washed for several times, and then re-dry, obtains CuO/g-CN；
(2) CuO/g-CN photoelectricity composite material is distributed in deionized water, ultrasonic disperse, obtains stable suspension；
(3) take the suspended drop-coated of step (2) on ITO electro-conductive glass, natural drying at room temperature, deionized water is rinsed, then again
Natural drying at room temperature, obtained modified electrode are denoted as CuO/g-CN-ITO；
Take certain density bisphenol-A aptamers drop coating on made CuO/g-CN-ITO, natural drying at room temperature, deionized water is rushed
It washes, then natural drying at room temperature again, obtains optical electro-chemistry aptamer sensor CuO/g-CN-aptamer-ITO.
2. a kind of preparation method of optical electro-chemistry aptamer sensor for detecting bisphenol-A as described in claim 1, feature exist
In in step (1), the copper-based chloro imidazole ion liquid is that bis- (1- alkyl -3- methylimidazole) tetrachloros close copper ion liquid
Body [Cxmim]2CuCl4, x=2~16.
3. a kind of preparation method of optical electro-chemistry aptamer sensor for detecting bisphenol-A as described in claim 1, feature exist
In, in step (1), the copper-based chloro imidazole ion liquid, ethyl alcohol, carbonitride and sodium hydroxide usage ratio be 0.15~
0.9mmol:19mL:0.28g:0.35~2mmol.
4. a kind of preparation method of optical electro-chemistry aptamer sensor for detecting bisphenol-A as described in claim 1, feature exist
In in step (1), the temperature of hydro-thermal reaction is 140~160 DEG C, reaction time 10h；The drying temperature is 50~70
DEG C, drying time be 12~for 24 hours.
5. a kind of preparation method of optical electro-chemistry aptamer sensor for detecting bisphenol-A as described in claim 1, feature exist
In in step (2), the turbid liquid concentration is 1.0mg/mL.
6. a kind of preparation method of optical electro-chemistry aptamer sensor for detecting bisphenol-A as described in claim 1, feature exist
In, in step (3), the usage ratio of suspension and bisphenol-A aptamers are as follows: 50 μ L:25 μ L；The concentration of the bisphenol-A aptamers
For 0.2~1 μm of ol/L, the sequence of bisphenol-A aptamers is 5 '-CCGGTGGGTGGTCAGGTGGGATAGCGTTCCGCGTATGGC
CCAGCGCATCACGGGTTCGCACCA-3′。
7. optical electro-chemistry aptamer sensor made from preparation method described in claim 1~6 any one is used to detect double
The purposes of phenol A.
8. purposes as claimed in claim 7, which is characterized in that steps are as follows:
(1) measurement of standard curve: the CuO/g-CN- that a series of bisphenol-A drop coating of known concentrations is made in step (3) is taken
On aptamer-ITO, natural drying at room temperature, deionized water is rinsed, and natural drying at room temperature, obtained modified electrode is denoted as CuO/
g-CN-aptamer-BPA-ITO；
Using the CuO/g-CN-aptamer-BPA-ITO modified electrode of preparation as working electrode, Ag/AgCl as reference electrode,
Pt is used as to electrode, and using phosphate buffer solution as electrolyte, its photocurrent response is measured under the test potential of -0.1V
Value, obtains a series of concentration-photoelectric current corresponding relationship, and then obtain the standard curve of bisphenol-A；
(2) take a certain amount of drop-coated to be measured on the made CuO/g-CN-aptamer-ITO of step (3), natural drying at room temperature,
Deionized water is rinsed, and natural drying at room temperature, obtained modified electrode is denoted as CuO/g-CN-aptamer-BPA-ITO；
Using the CuO/g-CN-aptamer-BPA-ITO modified electrode of preparation as working electrode, Ag/AgCl as reference electrode,
Pt is used as to electrode, and using phosphate buffer solution as electrolyte, its photocurrent response is measured under the test potential of -0.1V
Value, the concentration of bisphenol-A in liquid can must be detected by bringing photocurrent values into standard curve conversion.
9. purposes as claimed in claim 8, which is characterized in that in step (1), the dosage of bisphenol-A is 20 μ L；Bisphenol-A it is dense
Degree is 0~5*10-5g/L。
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