CN109187507A - A kind of Electrochemiluminescsensor sensor and its preparation method and application for detecting bisphenol-A - Google Patents
A kind of Electrochemiluminescsensor sensor and its preparation method and application for detecting bisphenol-A Download PDFInfo
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- CN109187507A CN109187507A CN201810666793.9A CN201810666793A CN109187507A CN 109187507 A CN109187507 A CN 109187507A CN 201810666793 A CN201810666793 A CN 201810666793A CN 109187507 A CN109187507 A CN 109187507A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G01N21/76—Chemiluminescence; Bioluminescence
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Abstract
The invention discloses a kind of Electrochemiluminescsensor sensors and preparation method thereof for detecting bisphenol-A, including working electrode, working electrode includes substrate, composite layer and decorative layer, and feature is that substrate is vitreous carbon conductive material, and composite layer is evenly dispersed magnetic Fe on the surface of the substrate3O4Nanocrystal, decorative layer are made of the perfluorinated sulfonic acid for modifying in composite layer surface, using alkaline luminol solution as electrolyte, construct the Electrochemiluminescsensor sensor for detecting bisphenol-A, preparation method includes Fe3O4The preparation of nanocrystal；By Fe3O4- NCs solution, perfluorinated sulfonic acid ethanol solution, which are successively dripped, obtains working electrode Nafion/Fe in glassy carbon electrode surface3O4- NCs/GCE, as detecting the Electrochemiluminescsensor sensor of bisphenol-A, advantage be have good selectivity, stability and high sensitivity.
Description
Technical field
The invention belongs to Nano-function thin films and biosensor technology field, and in particular to one kind is double for detecting
The Electrochemiluminescsensor sensor and its preparation method and application of phenol A.
Background technique
Bisphenol-A, i.e. 4,4- dihydroxy-diphenyl propane (abbreviation BPA) are a kind of interior point of environment with estrogen active
Interfering substance (endorsing disrupting chemicals, EDCs) is secreted, serious pollution and danger are caused to ecological environment
Evil.Bisphenol-A is one of most popular industrial compound in the world, mainly for the production of polycarbonate, epoxy resin, rubber
A variety of high molecular materials such as anti-aging agent, coating and fine chemical product.It is colourless that the addition of bisphenol-A can be such that plastic products have
The characteristics such as bright, durable light and handy and good protecting against shock, therefore it is widely used in the packaging of tinned food and beverage, feeding bottle, water
In the common daily necessities manufacture such as sealant, spectacle lens used in cup, tooth filling.Bisphenol-A meeting under the conditions ofs heated, sunshine etc.
It is precipitated and migrates.Zoopery discovery, bisphenol-A have the effect of oestrogen-like hormone, low dosage can also make the female sex premature of animal generation,
The effects of decline of male sperm number, prostate increase.In addition, there is data to show that bisphenol-A has certain embryotoxicity and teratogenesis
Property, the generation of the cancers such as animal ovary cancer, prostate cancer, leukaemia can be obviously increased.Studies have shown that BPA is in rat model reality
In testing, oral half lethal dose (LD50) it is 3250.0mg/kg；In Experimental model of small mice, oral half lethal dose is
2400.0mg/kg.The limitation that human body takes in BPA is 1.0 μ g/kg.day.Based on BPA to the serious damaging effect of human body, development
It is detected, monitoring technology has important practical significance.
Currently, the detection method in relation to bisphenol-A is concentrated mainly on gas-chromatography, gas phase-mass spectrometry, liquid chromatogram, liquid
Phase-mass spectrometry, DNA aptamers method, immunochromatographic method, capillary electrophoresis etc., these methods are although sensitivity is higher, accurate
Property it is good, but need to carry out sample to be tested cumbersome pretreatment, required instrument is mostly expensive and bulky and hulking, needs professional skill
Art personnel carry out daily maintenance, exist time-consuming, it is at high cost, be not suitable for the shortcomings such as on-site test.In view of Effects of Bisphenol A on Human
Serious destructive and current detection technology the limitation of class and ecological environment, the technology of development detection bisphenol-A are very necessary.
Electrochemiluminescprocess process technology is extensive due to the advantages that its background interference is small, high sensitivity, the range of linearity wide, easy to operate
Applied to fields such as clinical diagnosis, Pharmaceutical Analysis, environmental monitorings, but there are strong lights for existing Electrochemiluminescsensor sensor
Degree and the problem that stability is insufficient, sensitivity is low.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of to have good selection in the detection of environmental water sample BPA
Property, stability and high sensitivity for detecting Electrochemiluminescsensor sensor of bisphenol-A and its preparation method and application.
The technical scheme of the invention to solve the technical problem is: a kind of for detecting the electroluminescent chemistry of bisphenol-A
Luminescence sensor, including working electrode, the working electrode include substrate, composite layer and decorative layer, it is characterised in that: institute
The substrate stated is vitreous carbon conductive material, and the composite layer is the magnetic Fe being dispersed on the substrate surface3O4It receives
Meter Jing Ti, the decorative layer are made of the perfluorinated sulfonic acid for modifying in composite layer surface, are electrolysis with alkaline luminol solution
Liquid constructs the Electrochemiluminescsensor sensor for detecting bisphenol-A.
The preparation method of the above-mentioned Electrochemiluminescsensor sensor for being used to detect bisphenol-A, comprising the following steps:
(1) Fe3O4Nanocrystal (Fe3O4- NCs) preparation
A. it prepares iron oleate precursor liquid: weighing the FeCl of 2.53g3·6H2O is dissolved in the secondary water of 25mL；Take the oil of 8.86mL
Acid is dissolved in the ethyl alcohol of 32mL；Above-mentioned two solution is mixed to join in three-necked flask, is stirred 4 hours at 70 DEG C, solution point
It is two layers, the upper layer deionized water comprising oleic acid iron complexes is washed 3 times in separatory funnel, is then taken off under vacuum condition
Except n-hexane, obtaining waxy solid is oleic acid iron complexes；
B. by the oleic acid iron complexes of 1mL, the Trioctylamine (TOA) of 3mL is dissolved in the octadecylene (ODE) of 8mL, by mixed liquor
It is placed in three-necked flask, is vacuumized at 100 DEG C 1 hour, then under the conditions of nitrogen protection, by reaction temperature with per minute
10 DEG C of rate rises to 320 DEG C, reacts 0.5h, obtains Fe3O4- NCs original solution；
C. in Fe3O4It is separately added into the chloroform of 20mL and the ethyl alcohol of 20mL in-NCs original solution, is centrifuged 10 min in 3000 g, goes
After supernatant, precipitating is dispersed in chloroform again, obtains Fe3O4- NCs solution；
(2) preparation of Electrochemiluminescsensor sensor
A. glass-carbon electrode is subjected to sanding and polishing with the oxidation aluminium paste that partial size is 0.05 ~ 0.07 μm, then uses ethyl alcohol respectively and surpassed
Electrode surface dirt is rinsed in pure water, is dried spare；Wherein oxidation aluminium paste is that alumina powder and ultrapure water 1:1 in mass ratio are mixed
It closes and is made；
B. the finely dispersed Fe that 5.0 μ L concentration are 4-12 mg/mL is drawn3O4- NCs solution drop in glassy carbon electrode surface, to
At room temperature after natural drying, the 1% perfluorinated sulfonic acid ethanol solution drop coating for being by 5 ~ 10 μ L volumetric concentrations in glassy carbon electrode surface,
After natural drying, the clean unadsorbed reagent material of electrode surface is eluted using 0.1M PBS buffer solution, work electricity is obtained after drying
Pole Nafion/Fe3O4It is spare to be stored in 4 DEG C of refrigerators as detecting the Electrochemiluminescsensor sensor of bisphenol-A by-NCs/GCE.
Oxidation aluminium paste described in step (2) is that alumina powder is mixed to prepare with ultrapure water 1:1 in mass ratio.
Fe described in step (2)3O4- NCs solution concentration is 8 mg/mL.
Utilize the method for the above-mentioned Electrochemiluminescsensor sensor detection bisphenol A concentration for detecting bisphenol-A, specific steps
As follows: using Electrochemiluminescsensor sensor as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl is reference electrode insertion
Into the corresponding hole slot of electrolytic cell, electrolytic cell is placed in electrogenerated chemiluminescence detection instrument camera bellows right above photomultiplier tube；It is real
It tests using cyclic voltammetry, photomultiplier tube negative high voltage is set as 500V, and test voltage range is 0 ~+1.8V, and sweep speed is
100mV/s；Test carries out at room temperature, before test, takes 2mL ultrapure water in electrolytic cell, adjusts electrogenerated chemiluminescence body
It is pH is 11.0, it is 5 × 10 that 160 microlitres of concentration are added in the electrogenerated chemiluminescence system-5The luminol aqueous solution of M, so
Bisphenol-A solution to be measured is added in electrolytic cell afterwards, to its system carry out electrochemical luminescence test, according to electrochemical luminescence intensity with
The quantitative relationship of bisphenol A concentration determines the concentration of bisphenol-A in sample to be tested.
Compared with the prior art, the advantages of the present invention are as follows: the present invention is a kind of for detecting the electrogenerated chemiluminescence of bisphenol-A
Sensor and its preparation method and application, the sensor are based on magnetic ferroferric oxide nanocrystal/perfluorinated sulfonic resin film
(Fe3O4- NCs/nafion) composite material detection bisphenol-A Electrochemiluminescsensor sensor, with magnetic Fe3O4It is nanocrystalline
Body (Fe3O4- NCs) it is catalyst, perfluorinated sulfonic acid (nafion) is film forming agent, and glassy carbon electrode (GCE, 3mm) is working electrode,
It is prepared for nafion/Fe3O4- NCs/GCE modified electrode, using alkaline luminol solution as electrolyte, due to Fe3O4Nanocrystal
With excellent monodispersity and superparamagnetism, the anodic electrochemiluminescence of luminol can be significantly increased, and in+1.6V
Place obtains strongest chemiluminescence intensity value, and advantage is as follows:
(1) present invention prepares nafion/Fe using drop-coating3O4- NCs/GCE composite material modified glassy carbon electrode, electrode fabrication
Simply, material price is cheap, environmentally protective, stability is good.
(2) Electrochemiluminescsensor sensor prepared by the present invention is used for the detection of bisphenol-A, and easy to operate, the range of linearity is wide,
Detection limit is low, and simple, quick, the highly sensitive detection to bisphenol-A may be implemented.BPA concentration is electroluminescent in 0.01 ~ 50.0mg/L
There is preferable linear dependence (r=0.9972) between chemiluminescence signal inhibition response and BPA concentration, detection is limited to 0.66
μg/L。
(3) in actual water sample detection, actual sample recovery of standard addition is 96.0% ~ 105.0%, and relative standard deviation is less than
4.8%.The result shows that Electrochemiluminescsensor sensor preparation process is relatively simple, testing result is stablized, have preferable quasi-
Exactness and precision.
In conclusion a kind of Electrochemiluminescsensor sensor for detecting bisphenol-A of the present invention and preparation method thereof and answering
With, based on ferroferric oxide nano crystal enhanced sensitivity luminol Electrochemiluminescsensor sensor detection BPA, preparation and detection method
Simply, high sensitivity is not influenced by analogue etc. in bisphenol-A detection process, and anti-interference is good, the electrogenerated chemiluminescence
Sensor has good selectivity in the detection of environmental water sample BPA, stability and the advantages that high sensitivity.
Detailed description of the invention
Fig. 1 is the present invention for detecting the Electrochemiluminescsensor sensor building schematic diagram of bisphenol-A；
Fig. 2 is Fe3O4The transmission electron microscope figure (TEM) of-NCs；
Fig. 3 is Fe3O4- NCs fluorescence pattern；
Fig. 4 is Fe3O4- NCs B-H loop, illustration are external magnetic field to Fe3O4The influence of-NCs solution；
Fig. 5 is influence of the different nanocrystals to electrogenerated chemiluminescence system；
Fig. 6 is the electrochemical impedance spectroscopy of modified electrode: perfluorinated sulfonic acid/Fe3O4- NCs modified electrode (a), perfluorinated sulfonic acid modification electricity
Pole (b), Fe3O4- NCs modified electrode (c) and bare electrode (d)；
Fig. 7 is the electrochemical impedance spectroscopy of modified electrode；Perfluorinated sulfonic acid/cadmium antimonide nanocrystal modified electrode (a), perfluorinated sulfonic acid/
Fe3O4- NCs modified electrode (b), perfluorinated sulfonic acid/zinc sulfide nano crystal modified electrode (c), perfluorinated sulfonic acid/selenizing zinc nanocrystalline
Body modified electrode (d) and bare electrode (e)；
Fig. 8 is influence of the luminol additive amount to electrogenerated chemiluminescence intensity；
Fig. 9 is Fe3O4Influence of-NCs the concentration to electrogenerated chemiluminescence intensity；
Figure 10 is influence of the pH value size to electrogenerated chemiluminescence intensity；
Figure 11 is the electrochemically stable sex expression in detection architecture of Electrochemiluminescsensor sensor；
Figure 12 be inhibition of the different BPA concentration to Electrochemiluminescsensor sensor shown in, when BPA additive amount be 0.02,0.05,
0.1, when 0.2,0.5,1.0,2.0,5.0mg/L, the electrogenerated chemiluminescence intensity value of detection architecture constantly declines；
Figure 13 is the linear relationship chart of different BPA concentration and Electrochemiluminescsensor sensor luminous intensity；
Figure 14 is CYP, DES, E2, four kinds of inhibitor such as INN and BPA be to the selection inhibition pair of the Electrochemiluminescsensor sensor
Than figure.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
Specific embodiment one
It is a kind of for detecting the Electrochemiluminescsensor sensor of bisphenol-A, including working electrode, the working electrode includes base
Bottom, composite layer and decorative layer, substrate are vitreous carbon conductive material, and composite layer is to be dispersed on the substrate surface
Magnetic Fe3O4Nanocrystal, decorative layer is made of the perfluorinated sulfonic acid for modifying in composite layer surface, with alkaline luminol solution
For electrolyte, the Electrochemiluminescsensor sensor for detecting bisphenol-A is constructed, preparation method is as shown in Figure 1, include following
Step:
(1) Fe3O4Nanocrystal (Fe3O4- NCs) preparation
A. it prepares iron oleate precursor liquid: weighing the FeCl of 2.53g3·6H2O is dissolved in the secondary water of 25mL；Take the oil of 8.86mL
Acid is dissolved in the ethyl alcohol of 32mL；Above-mentioned two solution is mixed to join in three-necked flask, is stirred 4 hours at 70 DEG C, solution point
It is two layers, the upper layer deionized water comprising oleic acid iron complexes is washed 3 times in separatory funnel, is then taken off under vacuum condition
Except n-hexane, obtaining waxy solid is oleic acid iron complexes；
B. by the oleic acid iron complexes of 1mL, the Trioctylamine (TOA) of 3mL is dissolved in the octadecylene (ODE) of 8mL, by mixed liquor
It is placed in three-necked flask, is vacuumized at 100 DEG C 1 hour, then under the conditions of nitrogen protection, by reaction temperature with per minute
10 DEG C of rate rises to 320 DEG C, reacts 0.5h, obtains Fe3O4- NCs original solution；
C. in Fe3O4It is separately added into the chloroform of 20mL and the ethyl alcohol of 20mL in-NCs original solution, is centrifuged 10 min in 3000 g, goes
After supernatant, precipitating is dispersed in chloroform again, obtains Fe3O4- NCs solution；
First by Lorentz transmission electron microscope, to the Fe of preparation3O4The form pattern of-NCs carries out microscopic sdIBM-2+2q.p.approach.Such as Fig. 2
Fe3O4Shown in the transmission electron microscope figure (TEM) of-NCs, four Fe of synthesis3O4- NCs is well dispersed, size is uniform, size
About 22.0nm, good dispersibility are conducive to the stabilization of electrochemical properties, make the Electrochemiluminescsensor sensor tool of building
There are preferable stability and repeatability.Meanwhile from the figure 3, it may be seen that Fe3O4The fluorescence exciting wavelength of-NCs, launch wavelength are respectively
300 nm and 590nm, it is possible thereby to release the Fe of preparation3O4- NCs is the nano particle with certain fluorescent characteristic, and there are items
Under part, there is certain sensitization to luminol electrogenerated chemiluminescence reaction system.Further figure 4, it is seen that
Fe3O4The superparamagnetism of-NCs determines that specific direction is presented without assembling nodule in it, this is conducive to it in electrode surface
It is uniformly dispersed, to keep the Electrochemiluminescsensor sensor property of preparation relatively stable；
(2) preparation of Electrochemiluminescsensor sensor
A. glass-carbon electrode is subjected to sanding and polishing with the oxidation aluminium paste that partial size is 0.05 ~ 0.07 μm, then uses ethyl alcohol respectively and surpassed
Electrode surface dirt is rinsed in pure water, is dried spare；Wherein oxidation aluminium paste is that alumina powder and ultrapure water 1:1 in mass ratio are mixed
It closes and is made；
B. the finely dispersed Fe that 5.0 μ L concentration are 4-12 mg/mL is drawn3O4- NCs solution drop in glassy carbon electrode surface, to
At room temperature after natural drying, by 1% perfluorinated sulfonic acid ethanol solution that 5 ~ 10 μ L volumetric concentrations are, (perfluorinated sulfonic acid ethanol solution is
Perfluorinated sulfonic acid and ethyl alcohol volume ratio are 1:100) drop coating is in glassy carbon electrode surface, after natural drying, using 0.1M PBS buffer solution
The unadsorbed reagent material of clean electrode surface is eluted, working electrode Nafion/Fe is obtained after drying3O4- NCs/GCE is as used for
The Electrochemiluminescsensor sensor for detecting bisphenol-A, it is spare to be stored in 4 DEG C of refrigerators.By Nafion/GCE, Nafion/ZnS/GCE,
Nafion/ZnSe/GCE, Nafion/CdS/GCE and Nafion/CdTe/GCE are prepared using same method for use as comparison
Experimental analysis.
The electrochemical Characterization of Electrochemiluminescsensor sensor: electrochemical impedance test is carried out to modification using CHI660E
Electrode surface carries out electrochemical Characterization.Studies have shown that metal nanocrystal is to the chemiluminescence of luminol cathodic electrochromic or anode electricity
Cause chemiluminescence that there is preferable enhancing performance；Therefore, this experiment is first using cyclic voltammetry and corresponding electroluminescent chemistry hair
Optical analysis is used for different metal nanocrystal and Fe3O4Comparative analysis, characterization between-NCs modified electrode.Work as cyclic voltammetric
When method scanning potential range is -1.8 ~+1.8V, luminol cathodoluminescence is not found, it was found that the faint anode hair of luminol
Light.As shown in figure 5, the anodic electrochemiluminescence value of bare glassy carbon electrode reaches maximum when potential is 1.58V；When potential is
When 1.4V, Fe3O4The anodic electrochemiluminescence value of nanocrystal, ZnS nanocrystalline body and ZnSe nanocrystal modified electrode reaches
It is maximum.Comparison discovery, CdS nanocrystal and CdTe nanometer crystalline body hardly have sensitization to luminol cathodoluminescence.From
In Fig. 5 as can be seen that at 1.4V potential, Fe3O4Electrogenerated chemiluminescence maximum intensity caused by nanocrystal modified electrode,
Its signal value is 4 times of the electrochemiluminescence signal value that ZnS nanocrystalline body modified electrode generates.This is because Fe3O4It is nanocrystalline
The good electrocatalytic effect of body produces sensitization to luminol electrogenerated chemiluminescence.
Working electrode modification and electrogenerated chemiluminescence mechanism can be tested by electrochemical impedance to be illustrated.Such as figure
6 how shown in this Tequ line, and semicircle camber line, cross corresponding to the vertical tangent line of semicircle camber line occur in all modified electrodes
Coordinate value is the resistance value of modified electrode.As shown in fig. 6, bare electrode, perfluorinated sulfonic acid modified electrode, Fe3O4- NCs modification electricity
Pole, perfluorinated sulfonic acid/Fe3O4Resistance value corresponding to-NCs modified electrode is respectively 150.0 Ω, 130.0 Ω, 1400 Ω and 123.0
Ω.The result shows that perfluorinated sulfonic acid and Fe3O4- NCs arrives working electrode surface, and perfluorinated sulfonic acid/Fe by successfully modification3O4-
NCs modified electrode has preferable electrical conductance.Respectively perfluorinated sulfonic acid/Fe3O4- NCs, perfluorinated sulfonic acid and Fe3O4- NCs modification
Resistance value to bare electrode surface, gained modified electrode is below bare electrode.Should the result shows that, perfluorinated sulfonic acid and Fe3O4- NCs is equal
It can effectively promote the conductivity of working electrode, Fe3O4- NCs is capable of the electron transport rate of promotion system.May be used also from Fig. 6
With discovery, perfluorinated sulfonic acid/Fe3O4The resistance ratio Fe of-NCs modified electrode3O4- NCs(ferroferric oxide nano crystal) modified electrode
Resistance value it is lower, illustrate perfluorinated sulfonic acid combination Fe3O4- NCs modified electrode is than simple Fe3O4- NCs modified electrode has more
High charge transfer effciency, this also illustrates that the use of perfluorinated sulfonic acid can not only play the role of film forming agent, and can also promote
Fe3O4The electron transmission of-NCs modified electrode.In addition, as shown in Figure 7, perfluorinated sulfonic acid/selenizing zinc nanocrystals modified electrode and complete
Fluosulfonic acid/zinc sulfide nano crystal modified electrode resistance value is all than perfluorinated sulfonic acid/Fe3O4The resistance value of-NCs modified electrode is big.
This explanation, perfluorinated sulfonic acid/ferroferric oxide nano crystal modified electrode have higher conductivity, this is consistent with Fig. 6 result.It is comprehensive
Upper described, perfluorinated sulfonic acid/ferroferric oxide nano crystal modified electrode benefits to the sensitization of luminol electrogenerated chemiluminescence
In its good conductivity and electrochemical catalysis activity.Therefore, perfluorinated sulfonic acid/Fe is selected3O4- NCs modified electrode carries out following
Optimization experiment.
Specific embodiment two
The optimization of electrogenerated chemiluminescence system
1, influence of the luminol additive amount to electrogenerated chemiluminescence intensity
As electrogenerated chemiluminescence precursor substance, influence of the luminol concentration to detection architecture electrogenerated chemiluminescence intensity to close weight
It wants.Luminol concentration is too low, will affect the generation of excitation state luminol, to influence electrogenerated chemiluminescence efficiency；Luminol is dense
Height is spent, will affect Electrochemiluminescsensor sensor stability and sensitivity, and is unfavorable for luminol electrogenerated chemiluminescence letter
Number value amplification.It can see in influence from Fig. 8 luminol concentration to electrogenerated chemiluminescence intensity, when luminol solution is (dense
Degree be 5.0 × 10-5 M, be dissolved in 0.01 M sodium hydroxide) additive amount from 0.0 increase to 160.0 μ L when, electroluminescentization of system
It learns luminous signal value to increase sharply, and reaches maximum value (1560a.u.) at 160.0 μ L；When luminol concentration continues to increase
When, the constantly decline again of the electrochemiluminescence signal value of detection architecture, and detecting instrument noise figure rises.Therefore, concentration is
The additive amount of the luminol solution of 5.0 × 10-5 M selects 160.0 μ L.
2、Fe3O4Influence of-NCs the concentration to electrogenerated chemiluminescence intensity
As luminol electrogenerated chemiluminescence sensitizer, Fe3O4The concentration of-NCs has important shadow to the sensitivity of detection architecture
It rings.Fe3O4- NCs concentration is too low, will lead to the decline of modified electrode conductivity, is unfavorable for the generation of excitation state luminol, thus shadow
Ring the amplification of the optical signal value of detection architecture；Fe3O4- NCs concentration is too high, and the decorative layer thickness on modified electrode surface can become larger, no
Resistance value is only increased, and is easy to fall off, to influence the stability of detection architecture.Therefore, we are to Fe3O4- NCs's is dense
Degree is optimized.As a result, as shown in figure 9, working as Fe3O4When-NCs concentration increases to 8.0 mg/mL from 1.0 mg/mL, detection architecture
Electrogenerated chemiluminescence intensity constantly increase, and reach maximum value in 8.0 mg/mL；Work as Fe3O4- NCs concentration continues to increase
When, the electrogenerated chemiluminescence intensity of detection architecture reduces rapidly.Therefore, Fe3O4The concentration of-NCs selects 8.0 mg/mL.
3, influence of the pH to electrogenerated chemiluminescence intensity
Since luminol electrogenerated chemiluminescence is a pH dependent form reaction, when pH value is too low, it is unfavorable for the hydrolysis of luminol
Ionization, to influence the progress of electrogenerated chemiluminescence reaction；When pH value is excessively high, not only BPA structure can be destroyed, but also be detected
The background luminous value of system can rise, and reduce the sensitivity of sensor, thus experiment discussion pH when being 7.0 ~ 12.0 to detection
The influence of system electrogenerated chemiluminescence intensity.As shown in Figure 10, when detection architecture pH is 7.0 ~ 11.0, electrogenerated chemiluminescence is strong
Degree becomes larger with the increase of system pH, and maximum value is obtained at 11.0；When detection architecture pH continues to increase, electroluminescentization
It learns luminous intensity to decline rapidly, and the background luminous value rapid increase of detection architecture.Therefore, pH value selection 11.0.
Specific embodiment three
Utilize the electricity for being used to detect bisphenol-A being prepared under two optimal conditions of above-mentioned specific embodiment one and specific embodiment
The method for causing chemiluminescence sensor detection bisphenol A concentration, the specific steps are as follows: using Electrochemiluminescsensor sensor as work electricity
Pole, platinum electrode are auxiliary electrode (to electrode), and Ag/AgCl (the KCl saturated solution that AgCl was saturated) is reference electrode insertion
Into the corresponding hole slot of electrolytic cell, electrolytic cell is placed in electrogenerated chemiluminescence detection instrument camera bellows right above photomultiplier tube.It is real
It tests using cyclic voltammetry (CV), photomultiplier tube negative high voltage is set as 500V, and test voltage range is 0 ~+1.8V(vs. Ag/
AgCl), sweep speed 100mV/s.Test carries out at room temperature, before test, takes 2mL ultrapure water in electrolytic cell, adjusts
It is 11.0 that economize on electricity, which causes chemical luminous system pH, and it is 5 × 10 that 160 microlitres of concentration are added in electrogenerated chemiluminescence system-5The Rumi of M
Promise aqueous solution.Bisphenol-A is added in electrolytic cell makes its concentration 0,0.02,0.05,0.1,0.4,0.5,1.0,2.0,5.0mg/
L carries out electrochemical luminescence test to the above system, using electrogenerated chemiluminescence intensity (ECL intensity) as quantitative analysis
Object.
The stability and repeatability of Electrochemiluminescsensor sensor are of great significance to its practical application.In optimum optimization
Under the conditions of, continuous 15 scanning is carried out to the Electrochemiluminescsensor sensor using cyclic voltammetry.
As shown in figure 11, under 0.0-1.8 V potential, 15 times scanning electrochemiluminescence signal intensity value is highly stable
(RSD < 0.42%) shows that the Electrochemiluminescsensor sensor of preparation has good stability.In addition, being prepared for using identical method
Five electrodes are used to test the repeatability of the detection method, the results showed that, in the presence of BPA, using electroluminescentization of five electrodes
It is relatively stable (RSD=3.6%) to learn luminous signal value；After three weeks, the luminous signal response of the Electrochemiluminescsensor sensor is still
The 96.2% of original value can be reached.The result shows that the electroluminescent chemical detection method of foundation has preferable stability, repeatability, energy
Enough applied to the actually detected of BPA.
As shown in figure 12, when BPA additive amount is 0.02,0.05,0.1,0.2,0.5,1.0,2.0,5.0mg/L, detection
The electrogenerated chemiluminescence intensity value of system constantly declines.
As shown in figure 13, with the logarithm Log(C of BPA concentration valueBPA) be abscissa, by ordinate of luminous intensity values into
Line Fitting Analysis.As can be seen that when BPA concentration is within the scope of 0.02 ~ 5.0mg/L, the logarithm and inspection of BPA concentration value
Good linear relationship, linearly dependent coefficient 0.9972 are presented between the luminous intensity values of survey system.0.02mg/L ~
In the range of linearity of 5.0mg/L, BPA concentration is further diluted, is 3(S/N=3 using signal-to-noise ratio) as standard, measure this method
Detection limit can achieve 0.66 μ g/L.
Specific embodiment four
Selectivity test of the Electrochemiluminescsensor sensor to structure of bisphenol A analog
Using Electrochemiluminescsensor sensor as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl is inserted into for reference electrode
In the corresponding hole slot of electrolytic cell, electrolytic cell is placed in electrogenerated chemiluminescence detection instrument camera bellows right above photomultiplier tube.Experiment
Using cyclic voltammetry (CV), photomultiplier tube negative high voltage is set as 500V, and test voltage range is 0 ~+1.8V(vs. Ag/
AgCl), sweep speed 100mV/s.Test carries out at room temperature, before test, takes 2mL ultrapure water in electrolytic cell, adjusts
It is 11.0 that economize on electricity, which causes chemical luminous system pH, and it is 5 × 10 that 160 microlitres of concentration are added in the electrogenerated chemiluminescence system-5M's
Luminol aqueous solution.Bisphenol-A (BPA) is added in electrolytic cell, hexestrol (INN), β estradiol (E2), diethylstilbestrol
(DES), cypermethrin (CYP) makes its concentration be 2.0 mg/L, carries out electrochemical luminescence test to the above system.With (I0-
I)/I0It is defined as inhibiting rate, wherein I0In the absence of indicating inhibitor, the electrogenerated chemiluminescence intensity value of detection architecture；I is indicated
In the presence of inhibitor, the electrogenerated chemiluminescence intensity value of detection architecture.Under optimal testing conditions, Experimental comparison is tested
CYP、DES、E2, four kinds of inhibitor such as INN and BPA be to the selection inhibition of the Electrochemiluminescsensor sensor.
As shown in figure 14, BPA is 97.4% to the inhibiting rate of the Electrochemiluminescsensor sensor luminous intensity, inhibitory effect
It is the most significant；INN is 1.9% to the inhibiting rate of the Electrochemiluminescsensor sensor luminous intensity, and inhibitory effect is not significant；CYP,
DES and E2The luminous intensity of the Electrochemiluminescsensor sensor is not inhibited not only, produces gain effect instead.As a result table
Bright, by controlling oxidation potential range, which has preferable selection inhibition to BPA, in chaff interferent
Under existence condition, remain to play preferable application effect.
Specific embodiment five
In order to measure detection application effect of the Electrochemiluminescsensor sensor of foundation in actual sample, matrix mark-on has been carried out
Experiment.
Tap water is derived from University Of Ningbo, and river is derived from Ningbo river in Zhejiang Province river.The water sample adopted uses 0.45 μm of membrane filtration first
After removal of impurities, pH value is adjusted to 11.0 spare using the NaOH solution that concentration is 1.0 M.It is dense used by the experiment of matrix mark-on
Degree is respectively 0.01,0.1,0.2 mg/L.
Recovery testu in 1 actual sample of table
For two kinds of actual samples of tap water and river, recovery testu (n=3) has been carried out to verify the electrogenerated chemiluminescence
The performance of sensor in practical applications.The accuracy of method and precision can be between recovery of standard addition and parallel samples
Relative standard deviation is evaluated.If table 1 shows, in river sample, when adding concentration is 0.01,0.1,0.2mg/L, recycling
Rate between 96.0% ~ 101.2%, it is parallel between relative standard deviation be lower than 4.6%；In tap water, when addition concentration is
0.1, when 1.0,5.0 μ g/L, between 99.0% ~ 105.0%, the relative standard deviation between parallel sample is lower than the rate of recovery
4.6%.The result shows that the Electrochemiluminescsensor sensor of preparation has preferably accurately the BPA detection in river and tap water
Degree and precision.
In conclusion the present invention is with magnetic Fe3O4Nanocrystal (Fe3O4- NCs) it is catalyst, perfluorinated sulfonic acid (Nafion)
For film forming agent, glassy carbon electrode (Glassy carbon electrode, GCE, 3.0mm) is working electrode, is prepared for
Nafion/Fe3O4- NCs/GCE modified electrode；Using alkaline luminol solution as electrolyte, a kind of novel electroluminescent chemistry hair is constructed
Optical sensor and the specific detection for being successfully applied to BPA in environmental water sample.The result shows that with zinc sulphide, zinc selenide, cadmium sulfide
Compared with cadmium antimonide nano particle, the ferroferric oxide nano crystal well dispersed, with excellent superparamagnetism of synthesis+
Under 1.6V potential, the anodic electrochemiluminescence of Luminol in Alkaline can be significantly increased.By controlling potential, most
Under the conditions of good detection architecture, which has preferable selection inhibition to BPA, and the detection range of linearity is
0.01 ~ 50.0 mg/L (r=0.9972), detection are limited to 0.66 μ g/L.Actual sample recovery of standard addition is 96.0% ~ 105.0%,
Relative standard deviation is less than 4.8%.The result shows that Electrochemiluminescsensor sensor preparation process is relatively simple, testing result is steady
It is fixed, there is preferable accuracy and precision, can satisfy the detection demand of BPA in water sample, sense skill for electrogenerated chemiluminescence
Art provides new approaches in the application of ambient water and drinking water quality monitoring field.
Certainly, above description is not limitation of the present invention, and the present invention is also not limited to the example above.The art
Within the essential scope of the present invention, the variations, modifications, additions or substitutions made also should belong to of the invention those of ordinary skill
Protection scope.
Claims (5)
1. a kind of for detecting the Electrochemiluminescsensor sensor of bisphenol-A, including working electrode, the working electrode includes base
Bottom, composite layer and decorative layer, it is characterised in that: the substrate is vitreous carbon conductive material, and the composite layer is uniform
The magnetic Fe being dispersed on the substrate surface3O4Nanocrystal, the decorative layer is by modifying in the complete of composite layer surface
Fluosulfonic acid is constituted, and using alkaline luminol solution as electrolyte, constructs the Electrochemiluminescsensor sensor for detecting bisphenol-A.
2. a kind of described in claim 1 for detecting the preparation method of the Electrochemiluminescsensor sensor of bisphenol-A, feature exists
In the following steps are included:
(1) Fe3O4The preparation of nanocrystal
A. it prepares iron oleate precursor liquid: weighing the FeCl of 2.53g3·6H2O is dissolved in the secondary water of 25mL；Take the oleic acid of 8.86mL
It is dissolved in the ethyl alcohol of 32mL；Above-mentioned two solution is mixed to join in three-necked flask, is stirred 4 hours at 70 DEG C, solution is divided into
Two layers, the upper layer deionized water comprising oleic acid iron complexes is washed 3 times in separatory funnel, is then removed under vacuum condition
N-hexane, obtaining waxy solid is oleic acid iron complexes；
B. by the oleic acid iron complexes of 1mL, the Trioctylamine of 3mL is dissolved in the octadecylene of 8mL, and mixed liquor is placed in three mouthfuls
It in flask, is vacuumized at 100 DEG C 1 hour, then under the conditions of nitrogen protection, by reaction temperature with 10 DEG C of rate per minute
320 DEG C are risen to, 0.5h is reacted, obtains Fe3O4- NCs original solution；
C. in Fe3O4It is separately added into the chloroform of 20mL and the ethyl alcohol of 20mL in-NCs original solution, is centrifuged 10 min in 3000 g, goes
After supernatant, precipitating is dispersed in chloroform again, obtains Fe3O4- NCs solution；
(2) preparation of Electrochemiluminescsensor sensor
A. glass-carbon electrode is subjected to sanding and polishing with the oxidation aluminium paste that partial size is 0.05 ~ 0.07 μm, then uses ethyl alcohol respectively and surpassed
Electrode surface dirt is rinsed in pure water, is dried spare；Wherein oxidation aluminium paste is that alumina powder and ultrapure water 1:1 in mass ratio are mixed
It closes and is made；
B. the finely dispersed Fe that 5.0 μ L concentration are 4-12 mg/mL is drawn3O4- NCs solution is dripped in glassy carbon electrode surface, to room
Under temperature after natural drying, the 1% perfluorinated sulfonic acid ethanol solution drop coating for being by 5 ~ 10 μ L volumetric concentrations is in glassy carbon electrode surface, certainly
After so drying, the clean unadsorbed reagent material of electrode surface is eluted using 0.1M PBS buffer solution, obtains working electrode after drying
Nafion/Fe3O4It is spare to be stored in 4 DEG C of refrigerators as detecting the Electrochemiluminescsensor sensor of bisphenol-A by-NCs/GCE.
3. it is according to claim 2 a kind of for detecting the preparation method of the Electrochemiluminescsensor sensor of bisphenol-A, it is special
Sign is: oxidation aluminium paste described in step (2) is that alumina powder is mixed to prepare with ultrapure water 1:1 in mass ratio.
4. it is according to claim 2 a kind of for detecting the preparation method of the Electrochemiluminescsensor sensor of bisphenol-A, it is special
Sign is: Fe described in step (2)3O4- NCs solution concentration is 8 mg/mL.
5. a kind of Electrochemiluminescsensor sensor using of any of claims 1-4 for detecting bisphenol-A detects
The method of bisphenol-A, it is characterised in that specific step is as follows: using Electrochemiluminescsensor sensor as working electrode, platinum electrode is
Auxiliary electrode, Ag/AgCl are that reference electrode is inserted into the corresponding hole slot of electrolytic cell, and electrolytic cell is placed in electrogenerated chemiluminescence inspection
It surveys in instrument camera bellows right above photomultiplier tube；Experiment uses cyclic voltammetry, and photomultiplier tube negative high voltage is set as 500V, tests
Voltage range is 0 ~+1.8V, sweep speed 100mV/s；Test carry out at room temperature, before test, take 2mL ultrapure water in
In electrolytic cell, electrogenerated chemiluminescence system is adjusted, it is 5 × 10 that 160 microlitres of concentration are added in the electrogenerated chemiluminescence system- 5Then bisphenol-A solution to be measured is added in the luminol aqueous solution of M in electrolytic cell, carry out electrochemical luminescence test to its system,
According to the quantitative relationship of electrochemical luminescence intensity and bisphenol A concentration, the concentration of bisphenol-A in sample to be tested is determined.
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