CN109187506A - Based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor preparation method and application - Google Patents
Based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor preparation method and application Download PDFInfo
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Abstract
The invention discloses based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor preparation method and application, feature be include Fe3O4The preparation step of nanocrystal；Hexamethylene, TritonX-100, Fe are sequentially added in the twoport flask fixed3O4- NCs solution, TEOS, ammonium hydroxide after being stirred to react 2h, add BPA template molecule acetonitrile solution and 3- aminopropyl triethoxysilane, after reacting 12h, the step of washing away the sediment i.e. Fe3O4-NCs-MIPs that just template molecule falls off；By Fe3O4- NCs-MIPs solution, perfluorinated sulfonic acid ethanol solution, which are successively dripped, obtains working electrode Nafion/Fe in glassy carbon electrode surface3O4The step of-NCs-MIPs/GCE；Advantage be have good selectivity, stability and high sensitivity.
Description
Technical field
The present invention relates to a kind of Electrochemiluminescsensor sensors, are based on molecularly imprinted polymer-four more particularly, to one kind
The preparation method and application of Fe 3 O Electrochemiluminescsensor sensor.
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.
Molecular imprinting technology (Molecularly imprinted technology, MIT) is that analogue antigen-antibody is special
Property recognition mechanism, by the molecularly imprinted polymer (molecularly imprinted polymers, MIPs) of preparation to mould
The bionics techniques of plate molecule realization specific recognition and selective absorption.It is compared with antibody, MIPs has high temperature resistant, high pressure, acid
Alkali, is not easy the advantages that being biodegradable at organic solvent, has preferable stability, mechanical strength, easy to maintain, and have repetition
The potentiality used.But it is open based on molecularly imprinted polymer-ferroso-ferric oxide electrogenerated chemiluminescence not yet both at home and abroad at present
The correlative study of the preparation method and application of sensor is reported.
Summary of the invention
Technical problem to be solved by the invention is to provide one kind to have good selectivity, stability and high sensitivity
Based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor preparation method and application.
The technical scheme of the invention to solve the technical problem is: a kind of be based on-four oxygen of molecularly imprinted polymer
Change the preparation method of three-iron Electrochemiluminescsensor sensor, the specific steps are as follows:
(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) Fe3O4The preparation of-NCs-MIPs
37.5mL hexamethylene, 9.0mL TritonX-100 are sequentially added in the twoport flask fixed, are stirred under 300r/min
After mixing 15min, 100.0 μ L are sequentially added in synthetic system, concentration is the Fe of 20mg/mL3O4- NCs solution, 250.0 μ
LTEOS, the ammonium hydroxide that 500.0 μ L mass concentrations are 25%, after being stirred to react 2h, add the BPA mould of 550.0 μ L 25.0mg/mL
The 3- aminopropyl triethoxysilane of plate molecule acetonitrile solution and 114.0 μ L, after reacting 12h；By hybrid reaction in twoport flask
Liquid takes out and is added 50mL acetone stopped reaction, and after standing 40min, in 9000r/min high speed centrifugation 10min, centrifugation terminates to go
Except supernatant, take precipitating that 30.0mL ultrapure water is added, ultrasonic disperse is uniform, in 9000r/min high speed centrifugation 20min, centrifugation knot
Supernatant is removed after beam；Take precipitating that 30.0mL is added by ethyl alcohol and the acetonitrile mixed solution that 8:2 is formed by volume, ultrasonic disperse
Uniformly, 40min is stood so that template molecule falls off, and later in 9000r/min high speed centrifugation 15min, after removing supernatant, it is heavy to take
Form sediment be added 30.0mL by ethyl alcohol and the acetonitrile mixed solution that 8:2 is formed by volume, ultrasonic disperse is uniform, stand 40min so as to
Template molecule falls off, and later in 9000r/min high speed centrifugation 15min, removes supernatant, is by finally obtained sediment
Fe3O4-NCs-MIPs, the drying of room temperature nitrogen is dry, weighs and be dissolved in ethyl alcohol constant volume, spare；
(3) preparation of working electrode is modified
The Al for being 0.05 ~ 0.07 μm by glass-carbon electrode partial size2O3Sanding and polishing is carried out, removes surface contaminants with ultrapure water
Ultrasound 10min cleaning electrode surface afterwards is taken out electrode, is dried at room temperature spare；The Fe that will be prepared3O4- NCs-MIPs solution is super
After sound 2min, vortex 5min, the 5.0 finely dispersed Fe of μ L are drawn3O4- NCs-MIPs drips on glassy carbon electrode surface, and room temperature is dried in the air
The 1% perfluorinated sulfonic acid solution that 5.0 μ L volumetric concentrations are is dripped after dry again, room temperature naturally dry forms molecular engram in electrode surface
Film layer obtains Nafion/Fe3O4- NCs-MIPs/GCE is based on the electroluminescent chemistry of molecularly imprinted polymer-ferroso-ferric oxide
Luminescence sensor.
Fe described in step (3)3O4- NCs-MIPs solution concentration is 20.0mg/mL.
The above-mentioned method that bisphenol-A is detected based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor, tool
Steps are as follows for body: using based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor, as working electrode, platinum filament is electric
Extremely auxiliary electrode, Ag/AgCl are reference electrode, carry out electrogenerated chemiluminescence point using MPI-E type electrogenerated chemiluminescence system
Analysis；System condition: PBS buffer solution concentration is 60mM, and pH 10.0, luminol concentration is 0.6mM；Instrument condition: photomultiplier transit
Then it is molten that bisphenol-A to be measured is added in pipe negative high voltage 600V, sweep speed 100mV/s, potential range -0.6 ~+1.0V in electrolytic cell
Liquid carries out electrochemical luminescence test to its system, according to the quantitative relationship of electrochemical luminescence intensity and bisphenol A concentration, determine to
The concentration of bisphenol-A in sample.
Compared with the prior art, the advantages of the present invention are as follows: present invention firstly discloses be based on molecularly imprinted polymer-four
Fe 3 O Electrochemiluminescsensor sensor preparation method and its application, the sensor are based on Nafion/Fe3O4-NCs-MIPs/
The Electrochemiluminescsensor sensor of the detection bisphenol-A of GCE composite material, with magnetic Fe3O4Nanocrystal (Fe3O4- NCs) be
Catalyst, perfluorinated sulfonic acid (nafion) are film forming agent, and glassy carbon electrode (GCE, 3mm) is working electrode, prepare Nafion/
Fe3O4- NCs-MIPs/GCE modified electrode.Due to Fe3O4- NCs has good magnetism, and there is MIPs excellent selection to adsorb
Property, the excellent performance of the two is combined into the stability that can effectively improve Electrochemiluminescsensor sensor, sensitivity and spy
Different selectivity.Cyclic voltammetry sweep test is carried out in -0.6 ~ 1.0V potential range, due to Fe3O4Nanocrystal has excellent
Monodispersity and superparamagnetism, the anodic electrochemiluminescence of luminol can be significantly increased, luminol is enable to generate surely
Fixed electrochemiluminescence signal.Further by optimizing detection condition, such as luminol, PBS concentration, polymer volume and pH
Deng based on MIPs-Fe3O4- NCs there is specific adsorption and BPA electrochemical oxidation to send out the electroluminescent chemistry of luminol BPA
Light has quenching effect, obtain can in rapid quantitative detection biological sample and bottled water BPA content electrogenerated chemiluminescence
Detection architecture.The system detection range is 0.002 g/L(r=0.9978 the μ of μ g/L ~ 50.0), detection is limited to 0.2ng/L.In the flesh of fish
And in bottled water sample, the rate of recovery is 93.5% ~ 98.3%, and relative standard deviation (RSD) is less than 6.1%.The result shows that this is electroluminescent
Chemiluminescence sensor is for having good accuracy and confidence level when the detection of BPA in actual sample.
Detailed description of the invention
Fig. 1 is Fe3O4The transmission electron microscope figure (TEM) of-NCs；
Fig. 2 is Fe3O4- NCs fluorescence pattern；
Fig. 3 is Fe3O4- NCs B-H loop, illustration are external magnetic field to Fe3O4The influence of-NCs solution；
Fig. 4 is scanning electron microscope (SEM) photograph and transmission electron microscope picture；Wherein A:Fe3O4The scanning electron microscope (SEM) photograph of-NCs-MIPs；B:Fe3O4-NCs-
The scanning electron microscope (SEM) photograph of NIPs；C:Fe3O4The transmission electron microscope picture of-NCs-MIPs；D:Fe3O4The transmission electron microscope picture of-NCs-NIPs；
Fig. 5 is molecularly imprinted polymer FTIR spectrum, and wherein a is Fe3O4-NCs-MIPs；B is Fe3O4-NCs-NIPs；
Fig. 6 is electrochemistry cyclic voltammetric map, and wherein a is Nafion/Fe3O4- NCs-MIPs/GCE, b are bare glassy carbon electrode, c
For Nafion/Fe3O4-NCs-NIPs/GCE；Test system are as follows: 5.0mM potassium ferricyanide solution (contains 0.1M potassium chloride)；
Fig. 7 is electrochemical impedance map, and wherein a is Nafion/Fe3O4- NCs-MIPs/GCE, b are bare glassy carbon electrode, and c is
Nafion/Fe3O4-NCs-NIPs/GCE；Electrolyte is to contain 5.0mM [Fe (CN)6]3-/4-, 0.1M KCl, 0.06M PBS
Mixed solution；
Fig. 8 is influence of the luminol concentration to electrogenerated chemiluminescence intensity；NIPs represents electrochemical luminescence sensor in figure
Nafion/Fe3O4- NCs-NIPs/GCE's writes a Chinese character in simplified form, and MIPs represents electrochemical luminescence sensor Nafion/Fe3O4-NCs-
MIPs/GCE's writes a Chinese character in simplified form；
Fig. 9 is influence of the polymer concentration to electrogenerated chemiluminescence intensity；NIPs represents electrochemical luminescence sensor in figure
Nafion/Fe3O4- NCs-NIPs/GCE's writes a Chinese character in simplified form, and MIPs represents electrochemical luminescence sensor Nafion/Fe3O4-NCs-
MIPs/GCE's writes a Chinese character in simplified form；
Figure 10 is influence of the PBS buffer solution concentration to electrogenerated chemiluminescence intensity；NIPs represents electrochemical luminescence sensor in figure
Nafion/Fe3O4- NCs-NIPs/GCE's writes a Chinese character in simplified form, and MIPs represents electrochemical luminescence sensor Nafion/Fe3O4-NCs-
MIPs/GCE's writes a Chinese character in simplified form；
Figure 11 is influence of the pH to electrogenerated chemiluminescence intensity；NIPs represents electrochemical luminescence sensor Nafion/ in figure
Fe3O4- NCs-NIPs/GCE's writes a Chinese character in simplified form, and MIPs represents electrochemical luminescence sensor Nafion/Fe3O4- NCs-MIPs/GCE's
It writes a Chinese character in simplified form；
Figure 12 is Electrochemiluminescsensor sensor electrochemically stable sex expression in detection architecture；Wherein a is that BPA is not added；B is
BPA is added, BPA concentration is 5 μ g/L；
Figure 13 is BPA concentration (μ g/L) shown in inhibition of the different BPA concentration to Electrochemiluminescsensor sensor luminous intensity,
a-f: 0.2ng/L, 50ng/L, 0.4μg/L, 5.0μg/L, 0.5mg/L, 5.0mg/L.Test condition: 60mM, pH are
10.0 PBS buffer solution；0.6mM luminol；Polymer concentration is 20.0mg/mL；Sweep speed is 100mV/s；
Figure 14 is the linear relationship chart of different BPA concentration and Electrochemiluminescsensor sensor luminous intensity；,
Figure 15 is BPA, DES, HES, DI and E2Five kinds of inhibitor to the specific suppression result of Electrochemiluminescsensor sensor,
BPA and its analogue concentration are 5.0ng/mL；NIPs represents electrochemical luminescence sensor Nafion/Fe in figure3O4-NCs-
NIPs/GCE's writes a Chinese character in simplified form, and MIPs represents electrochemical luminescence sensor Nafion/Fe3O4- NCs-MIPs/GCE's writes a Chinese character in simplified form；
Figure 16 is BPA, DES, HES, DI and E2Five kinds of inhibitor to the Reverse transcriptase of Electrochemiluminescsensor sensor as a result,
BPA and its analogue concentration are 5.0ng/mL, and NIPs represents electrochemical luminescence sensor Nafion/Fe in figure3O4-NCs-
NIPs/GCE's writes a Chinese character in simplified form, and MIPs represents electrochemical luminescence sensor Nafion/Fe3O4- NCs-MIPs/GCE's writes a Chinese character in simplified form.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
Specific embodiment one
Based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor preparation method, the specific steps are as follows:
(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. 1
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 as shown in Figure 2, 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 from figure 3, it can be 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) Fe3O4The preparation of-NCs-MIPs
37.5mL hexamethylene, 9.0mL TritonX-100 are sequentially added in the twoport flask fixed, are stirred under 300r/min
After mixing 15min, 100.0 μ L are sequentially added in synthetic system, concentration is the Fe of 20mg/mL3O4- NCs solution, 250.0 μ
LTEOS, the ammonium hydroxide that 500.0 μ L mass concentrations are 25%, after being stirred to react 2h, add the BPA mould of 550.0 μ L 25.0mg/mL
The APTES (3- aminopropyl triethoxysilane) of plate molecule (solvent is acetonitrile) and 114.0 μ L, after reacting 12h；Twoport is burnt
Mixed reaction solution takes out and is added 50mL acetone stopped reaction in bottle, after standing 40min, in 9000r/min high speed centrifugation
10min, centrifugation terminate removal supernatant, take precipitating that 30.0mL ultrapure water is added, and ultrasonic disperse is uniform, in 9000r/min high speed
It is centrifuged 20min, removes supernatant after centrifugation；Taking precipitating that 30.0mL is added, 8:2 is formed by volume by ethyl alcohol and acetonitrile
Mixed solution, ultrasonic disperse is uniform, stands 40min and falls off so as to template molecule, later in 9000r/min high speed centrifugation 15min,
After removing supernatant, take precipitating that 30.0mL is added by ethyl alcohol and the acetonitrile mixed solution that 8:2 is formed by volume, ultrasonic disperse is equal
It is even, 40min is stood so that template molecule falls off, later in 9000r/min high speed centrifugation 15min, removes supernatant, is obtained final
The sediment arrived i.e. Fe3O4-NCs-MIPs, the drying of room temperature nitrogen is dry, weighs and be dissolved in ethyl alcohol constant volume, spare；Fe3O4-NCs-NIPs
Synthesis and elution process other than template molecule is not added, the same Fe of other steps3O4-NCs-MIPs。
As shown in figure 4, by scanning electron microscope and transmission electron microscope to prepared Fe3O4- NCs-MIPs and Fe3O4-NCs-
The size and micromorphology of NIPs is characterized.By Fig. 4 A, B it is found that preparation molecularly imprinted polymer be uniformly dispersed,
Uniform micro-sphere structure, diameter is in 80.0nm or so, and Fe3O4- NCs-NIPs polymer surfaces are relatively rough, this master
If after being washed away due to template molecule, being formd caused by three-dimensional hole on polymer microballoon surface.It can from Fig. 4 C, D
Know, Fe3O4- NCs is in the position of core inside polymer microballoon, illustrates Fe3O4- NCs is wrapped in by layer of silica gel is stable
The inside, so as to play its good magnetic selection index system.Fe3O4- NCs-MIPs and Fe3O4- NCs-NIPs is compared, and size is big
Small and appearance form difference is little, still, Fe3O4- NCs-NIPs microballoon size is more inhomogenous and microballoon between be not easy to scatter
Come, this can reduce Fe3O4The selectivity and ion permeability of-NCs-NIPs.
As shown in figure 5, carrying out structure elucidation to the binding site of molecularly imprinted polymer using Fourier transform infrared spectrum.
1057cm-1The absorption peak at place is the characteristic peak of Si-O-Si asymmetric stretching vibration, 788 cm-1With 463 cm-1The absorption peak at place
Disclose the stretching motion of Si-O key.In 2936,1550 cm-1The absorption peak at place and the asymmetric stretch campaign of C-H and N-H are
It is corresponding.These characteristic absorption peaks show that being copolymerized layer of silica gel is successfully grafted on Fe3O4Microballoon form is formd around-NCs,
And-the NH of APTES2Group has successfully been grafted to Fe3O4The surface of-NCs.Further, it is also possible to find out that the feature of MIPs and NIPs is inhaled
It is almost the same to receive peak position, illustrates that the two main component is similar.
(3) preparation of working electrode is modified
The Al for being 0.05 ~ 0.07 μm by glass-carbon electrode partial size2O3Sanding and polishing is carried out, removes surface contaminants with ultrapure water
Ultrasound 10min cleaning electrode surface afterwards is taken out electrode, is dried at room temperature spare；
The Fe that will be prepared3O4After-NCs-MIPs solution ultrasound 2min, vortex 5min, it is finely dispersed to draw 5.0 μ L
Fe3O4- NCs-MIPs drips on glassy carbon electrode surface, and room temperature drips 1% perfluorinated sulfonic acid that 5.0 μ L volumetric concentrations are again after drying molten
Liquid (perfluorinated sulfonic acid ethanol solution is perfluorinated sulfonic acid and ethyl alcohol volume ratio is 1:100), room temperature naturally dry is formed in electrode surface
Molecule engram film layer obtains Nafion/Fe3O4- NCs-MIPs/GCE is based on molecularly imprinted polymer-ferroso-ferric oxide
Electrochemiluminescsensor sensor.NIPs is used to replace MIPs as recognition component, other steps are same as above to arrive Nafion/Fe3O4-
NCs-NIPs/GCE.Cyclic voltammetry and electrochemical impedance spectroscopy are the conventional means that electrochemical Characterization is carried out to modified electrode.
It is illustrated in figure 6 in test system are as follows: 5.0mM Fe (CN) 64-/3-, pH7.4,0.1 M KCl, electric potential scanning model
Enclose -0.6 ~ 1.0V(vs. Ag/AgCl), under the conditions of sweep speed 0.1V/s, the cyclic voltammetry curve map of different modifying electrode.
As can be seen that under same current potential, Fe3O4- NCs-MIPs modified electrode (a) electric current is maximum, Fe3O4- NCs-NIPs modified electrode
(c) electric current is minimum, and bare electrode (b) electric current is therebetween.It can illustrate, Fe3O4-NCs-MIPs、Fe3O4- NCs-NIPs success
It modifies in working electrode surface, and due to Fe3O4- NCs-NIPs ion permeability is poor to cause loop current smaller；Due to
Fe3O4- NCs-MIPs uniform particle sizes and ion permeability is preferable, electron-transport is more unobstructed, to keep loop current larger.By
In Fe3O4- NCs has preferable magnetic and electric conductivity, greatly enhances system ionic in the transmission of MIPs modification thin layer surface
Property, increase so as to cause MIPs modified electrode electric current compared with bare electrode electric current.
As Fig. 7 as nyquist diagram it is found that when value indicated by curve semicircle is exactly working electrode surface electron-transport
Resistance value.It can be seen that bare electrode (b), Fe3O4- NCs-MIPs modified electrode (a) and Fe3O4- NCs-NIPs modified electrode (c)
Resistance be respectively 145.0 Ω, 147.0 Ω and 170.0 Ω, illustrate that the molecularly imprinted polymer of preparation is successfully modified in glass carbon electricity
Pole surface.Due to Fe3O4The good ion permeability of-NCs-MIPs and huge specific surface area and Nafion/Fe3O4-NCs-
NIPs/GCE is compared, Nafion/Fe3O4- NCs-MIPs/GCE resistance value is smaller, is more advantageous to electroluminescentization for generating continuous-stable
It learns and shines.Electrochemical impedance spectroscopy combination cyclic voltammetric map can be very good to illustrate that the stability of modified electrode is preferable, functional
Identify that original part-molecularly imprinted polymer can be stabilized and generate effect in electrode surface, this sends out next electroluminescent chemistry
The condition optimizing of optical sensor Response System is of great significance.Wherein the use of perfluorinated sulfonic acid (Nafion) can not only be played
The effect of film forming agent, and Fe can also be promoted3O4The electron transmission of-NCs modified electrode.
Specific embodiment two
Molecular engram-electrochemiluminescdetection detection system condition optimizing, wherein luminol concentration, polymer concentration, PBS are buffered
Liquid concentration and system pH have important shadow to electrochemiluminescence signal intensity and system sensitivity, selectivity and stability
It rings.
1, influence of the luminol concentration to electrogenerated chemiluminescence intensity
As luminous precursor substance, it is most important that can luminol concentration generate continuous, stable optical signal to system.Therefore,
Experiment primarily looks at the influence under 0.2-1.0mM luminol concentration conditions to system electrogenerated chemiluminescence intensity.It can from Fig. 8
Out, with the raising of luminol concentration, electrochemiluminescence signal value constantly enhances.When luminol concentration is increased to 0.6mM,
The relative luminous intensity of system is maximum, and when luminol concentration continues to increase, luminol oxidizing reaction rate is limited, the 3- of excitation state
Aminophthalic acid radical ion (AP2-•) generating rate no longer changes, electrogenerated chemiluminescence intensity is constant.But due to instrument
Baseline value increases, and the relative luminous intensity of system reduces instead.In addition, and Fe3O4- NCs-NIPs is compared, Fe3O4-NCs-MIPs
Stronger, more stable optical signal can be generated, this is primarily due to Fe3O4Caused by the ion permeability of-NCs-MIPs is stronger.?
When using reverse micro emulsion synthetic polymer, NIPs inevitably forms certain void structure, with Fe3O4- NCs-MIPs phase
Than layer of silica gel is comparatively dense, hinders electron transmission and the ion transmission of working electrode, affects excitation state AP2-•Shape
At lower so as to cause electrogenerated chemiluminescence intensity.So luminol concentration selects 0.6mM.
2、Fe3O4Influence of-NCs-MIPs the concentration to system electrogenerated chemiluminescence intensity
As recognition component, the amount of polymer generates weight to stability, selectivity and the durability of working electrode modification thin layer
It acts on.Electrode surface is modified using the polymer of various concentration, investigates influence of the amount to system of different polymer
It is of great significance.It can be seen in figure 9 that system electrogenerated chemiluminescence is strong as polymer concentration increases to 20.0mg/mL
Degree is continuously increased, this is because polymer core-Fe3O4- NCs has good magnetic and electric conductivity, greatly enhances system
Ion is in Fe3O4The mobility on-NCs-MIPs modified electrode surface is continuously increased so as to cause system electrogenerated chemiluminescence intensity；
As polymer concentration is more than 20.0mg/mL, the electrogenerated chemiluminescence intensity of system is gradually reduced, this is because with polymer
The increase of amount, layer of silica gel constantly accumulate in working electrode surface and modified electrode impedance are caused to increase, and hinder electrode surface electricity
Son transmitting, to affect excitation state AP2-•Formation, lead to electrogenerated chemiluminescence strength reduction.Compare Nafion/Fe3O4-
NCs-NIPs/GCE、Nafion/Fe3O4- NCs-MIPs/GCE is results, it can be seen that Fe3O4The electricity of-NCs-NIPs modified electrode
Chemiluminescence signal value is caused to be lower than Fe3O4- NCs-MIPs modified electrode, this also shows again Fe3O4- NCs-NIPs with
Fe3O4- NCs-MIPs structure is slightly different, Fe3O4The ion permeability of-NCs-MIPs is more preferable.In conclusion using dense
The polymer that degree is 20.0mg/mL carries out electrode modification.
3, influence of the PBS buffer solution concentration to system electrogenerated chemiluminescence intensity
As electrolyte, the influence that the concentration of PBS reacts electrogenerated chemiluminescence is very important.It can be seen from fig. 10 that
Within the scope of 15.0-60.0mM, with the raising of PBS concentration, electrogenerated chemiluminescence intensity also constantly enhances；When concentration is more than
60.0mM, system electrogenerated chemiluminescence intensity constantly reduce.This is primarily due to the ion concentration of PBS solution in 15.0-
Within the scope of 60.0mM, electroluminescent chemical reaction rate can be enhanced, more effectively generate excitation state AP2-•, to make system electrochemistry
Luminous intensity becomes larger；When PBS buffer solution concentration further increases, ion is more assembled in polymer hole to be hindered instead
Effective transmitting of luminous precursor substance-luminol, therefore make the reduction of system luminous intensity.Therefore, PBS buffer solution concentration selects
60.0mM。
4, influence of the pH to system electrogenerated chemiluminescence intensity
In general, the polymer foil that strong acid, highly basic easily lead to modified electrode surface falls off, and luminol electrogenerated chemiluminescence system
It is very sensitive to acid, alkalinity, therefore, it is particularly significant to inquire into influence of the system pH to electrogenerated chemiluminescence intensity and stability.
It can be seen from figure 11 that system electrochemiluminescence signal value is fainter when pH is 6.0,7.0；When pH is in 8.0-10.0
When range, with the enhancing of alkalinity, system electrogenerated chemiluminescence intensity constantly increases, and when pH is equal to 10.0, luminous intensity is most
Greatly, stability is best；When system solution pH is further increased, system electrogenerated chemiluminescence value reduces instead.This be mainly because
For, as pH is incrementally increased in system, OH-Concentration also constantly increases, and luminol ionization constantly enhancing leads to excitation state AP2-•It is raw
Increase at amount, to improve system optical signal yield；When pH is further increased, modified electrode surface polymer layer is not only resulted in
It falls off, and BPA is promoted to decompose in detection architecture, therefore selective system pH is 10.0.
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:
Electrogenerated chemiluminescence test is carried out in the electrolytic cell of a homemade Teflon material, pedestal is transparent quartzy material
Material, volume 10.0mL.Using based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor as working electrode,
Platinum electrode is auxiliary electrode (to electrode), and Ag/AgCl (the KCl saturated solution that AgCl was saturated) is reference electrode, is used
MPI-E type electrogenerated chemiluminescence system carries out Electrochemiluminescprocess process；System condition: PBS buffer solution concentration is 60mM, pH
It is 10.0, luminol concentration is 0.6mM；Instrument condition: photomultiplier tube negative high voltage 600V, sweep speed 100mV/s, current potential model
Enclose -0.6 ~+1.0V.Bisphenol-A is added in electrolytic cell makes 20.0,30.0,40.0,50.0,60.0,70.0 μ g/L of its concentration,
Electrochemical luminescence test is carried out to the above system, using electrogenerated chemiluminescence intensity (ECL intensity) as quantitative analysis pair
As.
The stability and repeatability of Electrochemiluminescsensor sensor are of great significance to its practical application.In optimum optimization
Under the conditions of, continuous 10 scanning is carried out to the Electrochemiluminescsensor sensor using cyclic voltammetry.
As shown in figure 12, under -0.6 ~+1.0V potential, exist in BPA and in the absence of BPA, scan electroluminescentization 10 times
Luminous signal intensity value is highly stable, shows that the Electrochemiluminescsensor sensor of preparation has good stability.The result shows that establishing
Electroluminescent chemical detection method have preferable stability, repeatability, can be applied to the actually detected of BPA.
As shown in figure 13, when BPA additive amount be a-f:0.2ng/L, 50ng/L, 0.4 μ g/L, 5.0 μ g/L, 0.5mg/L,
When 5.0mg/L, the electrogenerated chemiluminescence intensity value of detection architecture constantly declines.Electrochemiluminescsensor sensor is sent out based on BPA
Effective inhibition of optical signal value, experiment have further been investigated between BPA addition concentration and electrochemiluminescence signal inhibiting value
Linear relationship.
As shown in figure 14, with the logarithm Log(C of BPA concentration valueBPA) be abscissa, with luminous intensity inhibiting value be vertical seat
Mark carries out linear fit analysis.As can be seen that when BPA concentration is 2.0ng/L ~ 5.0mg/L, log concentration value Log(CBPA) with
Good linear relationship is presented in electrogenerated chemiluminescence intensity, and linearly dependent coefficient 0.9978 further dilutes BPA concentration, with
Signal-to-noise ratio is 3(S/N=3) it is used as standard, the detection limit for measuring this method can achieve 0.2 ng/L, have higher sensitivity.
1 present invention of table is compared with other BPA detection methods
| Method | Sample | The range of linearity (mg/kg, L) | Detection limit (μ g/kg, L) | The rate of recovery (%, n=3) |
| HPLC | Soft drink | 1.0×10-4-8.6×10-4 | 0.02 | 90.0-94.0 |
| Tyr-diazonium-MWCNTs/ BDD[110] | Water | 2.33×10-6-2.28 | 0.23 | 95.0-103.0 |
| SBSE -derivatization -GC–MS | River water | 0.002-0.1 | 0.5 | 97.6-104.6 |
| Spectrophotometric - HPLC | Bottled water | 0.24-8.4 | 150.0 | 93.6-99.3 |
| HPLC-FLD | Fish | 0.1-18 | 10.0 | 95.0-99.0 |
Inquire into BPA oxidation electrogenerated chemiluminescence inhibit between relationship, when BPA concentration be 20.0,30.0,40.0,
50.0, when 60.0,70.0 μ g/L, electrogenerated chemiluminescence system electric current is constantly reduced with the increase of BPA concentration, dense with BPA
The logarithm Log(C of angle valueBPA) it is abscissa, linear fit is carried out as ordinate using system current value and shows linear pass
System, linearly dependent coefficient 0.9970.This illustrate BPA electrogenerated chemiluminescence inhibit to there are related between its electrochemical oxidation
Property.
Specific embodiment four
The test of molecular engram-Electrochemiluminescsensor sensor selective depression
To be based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor as working electrode, supplemented by platinum electrode
It helps electrode (to electrode), Ag/AgCl (the KCl saturated solution that AgCl was saturated) is reference electrode, uses the electroluminescent chemistry of MPI-E type
Luminescent system carries out Electrochemiluminescprocess process；System condition: PBS buffer solution concentration is 60mM, and pH 10.0, luminol is dense
Degree is 0.6mM；Instrument condition: photomultiplier tube negative high voltage 600V, sweep speed 100mV/s, potential range -0.6 ~+1.0V.Mirror
Double phenyl, double hydroxyl structure characteristics in BPA, this experimental selection diethylstilbestrol (DES), hexestrol (HES), dienestrol
(DI) and β estradiol (E2) as analogue be used to detect preparation Electrochemiluminescsensor sensor selectivity.Electricity
CL enhancement efficiency is caused, (I is defined as0-I)/I0, wherein I0For initial electrogenerated chemiluminescence intensity value (unit: a.u.), I
For the electrogenerated chemiluminescence intensity value (unit: a.u.) after BPA is added.
It can be seen from Figure 15 when the analyte of same amount is added, BPA, DES, HES, DI and E2To Nafion/
Fe3O4It is respectively 75.0%, 36.0%, 35.0%, 27.0% and that the electrogenerated chemiluminescence intensity of-NCs-MIPs/GCE, which inhibits efficiency,
23.0%.In the detection range of linearity, which has good effect to the specific detection of BPA.When
When the analyte of same amount is added, BPA, DES, HES, DI and E2To the inhibition efficiency of the electrogenerated chemiluminescence intensity of NIPs/GCE
20.0% or so.As shown in figure 16, in Reverse transcriptase experiment, Nafion/Fe3O4The inhibition efficiency of-NCs-MIPs/GCE
About 75.0%, Nafion/Fe3O4The inhibition efficiency of-NCs-NIPs/GCE has aobvious 55.0% or so compared with selective depression
It writes and is promoted.This has absolutely proved Nafion/Fe3O4- NCs-MIPs/GCE and Nafion/Fe3O4- NCs-NIPs/GCE is special
Property identification on significant difference, also further illustrate Fe3O4- NCs-MIPs is as recognition component for electrogenerated chemiluminescence point
Analysis field can be effectively improved the selectivity and sensitivity of senser element.
Specific embodiment five
In order to measure foundation based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor in actual sample
Detection application effect, carried out matrix mark-on experiment.
Fish sample (Tilapia mossambica, Tilapia) is bought from Ningbo City road woods market, and the 2.00 g ± 0.01g flesh of fish is accurately weighed
Sample is in 15.0mL polypropylene centrifuge tube, 8000r/min homogeneous 5min, addition 5.0mL methanol/ethanol/isopropanol (7:2:1,
V/v/v) mixed solution shakes 2min, and 4000r is centrifuged 5min, shifts supernatant in another clean centrifuge tube.According to above
Process extracts once again, merge gained supernatant, 2h is stood in -18 °C of refrigerators, after taking-up it is rapid cross absorbent cotton, by filtrate in
Nitrogen is blown to close to drying at room temperature, and 1mL acetonitrile is added and redissolves, to which sample introduction is analyzed.
Bottled water (pure water, 500.0mL) is purchased from Ningbo Jiangbei District supermarket, takes appropriate amount of sample that certain density BPA is added
Standard items, it is excessively spare after film.
Recovery testu result in 2 actual sample of table
For the flesh of fish and bottled water actual sample, recovery testu (n=3) is carried out to verify the Electrochemiluminescsensor sensor
Performance in practical applications.Relative standard between the accuracy and precision recovery of standard addition and parallel sample of method
Deviation is evaluated.As shown in table 2, in flesh of fish sample, when adding concentration is 10.0,20.0,50.0 μ g/L, the rate of recovery
Between 93.5%~95.0%, it is parallel between relative standard deviation be lower than 6.1%；In bottled water, when addition concentration is
0.1, when 0.2,0.5 μ g/L, between 96.3%~98.3%, the relative standard deviation between parallel sample is lower than the rate of recovery
4.5%.The MIPs/GCE of preparation is placed in refrigerator and is saved, under the conditions of the mark-on of 20.0 μ g/L, test is primary daily, surveys
The relative standard deviation of three days acquired results is tried less than 0.6%.Repetition prepares the Electrochemiluminescsensor sensor, in 20.0 μ g/
Under the conditions of the mark-on of L, the relative standard deviation value of acquired results is less than 5.5% three times.The result shows that poly- based on molecular engram
The Electrochemiluminescsensor sensor for closing the preparation of object modified glassy carbon electrode has preferably the BPA detection in the flesh of fish and bottled water
Accuracy and precision.
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 (3)
1. a kind of based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor preparation method, feature exists
In specific step is as follows:
(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) Fe3O4The preparation of-NCs-MIPs
37.5mL hexamethylene, 9.0mL TritonX-100 are sequentially added in the twoport flask fixed, are stirred under 300r/min
After mixing 15min, 100.0 μ L are sequentially added in synthetic system, concentration is the Fe of 20mg/mL3O4- NCs solution, 250.0 μ
LTEOS, the ammonium hydroxide that 500.0 μ L mass concentrations are 25%, after being stirred to react 2h, add the BPA mould of 550.0 μ L 25.0mg/mL
The 3- aminopropyl triethoxysilane of plate molecule acetonitrile solution and 114.0 μ L, after reacting 12h；By hybrid reaction in twoport flask
Liquid takes out and is added 50mL acetone stopped reaction, and after standing 40min, in 9000r/min high speed centrifugation 10min, centrifugation terminates to go
Except supernatant, take precipitating that 30.0mL ultrapure water is added, ultrasonic disperse is uniform, in 9000r/min high speed centrifugation 20min, centrifugation knot
Supernatant is removed after beam；Take precipitating that 30.0mL is added by ethyl alcohol and the acetonitrile mixed solution that 8:2 is formed by volume, ultrasonic disperse
Uniformly, 40min is stood so that template molecule falls off, and later in 9000r/min high speed centrifugation 15min, after removing supernatant, it is heavy to take
Form sediment be added 30.0mL by ethyl alcohol and the acetonitrile mixed solution that 8:2 is formed by volume, ultrasonic disperse is uniform, stand 40min so as to
Template molecule falls off, and later in 9000r/min high speed centrifugation 15min, removes supernatant, is by finally obtained sediment
Fe3O4-NCs-MIPs, the drying of room temperature nitrogen is dry, weighs and be dissolved in ethyl alcohol constant volume, spare；
(3) preparation of working electrode is modified
The Al for being 0.05 ~ 0.07 μm by glass-carbon electrode partial size2O3Sanding and polishing is carried out, removes surface contaminants with ultrapure water
Ultrasound 10min cleaning electrode surface afterwards is taken out electrode, is dried at room temperature spare；The Fe that will be prepared3O4- NCs-MIPs solution is super
After sound 2min, vortex 5min, the 5.0 finely dispersed Fe of μ L are drawn3O4- NCs-MIPs drips on glassy carbon electrode surface, and room temperature is dried in the air
The 1% perfluorinated sulfonic acid solution that 5.0 μ L volumetric concentrations are is dripped after dry again, room temperature naturally dry forms molecular engram in electrode surface
Film layer obtains Nafion/Fe3O4- NCs-MIPs/GCE is based on the electroluminescent chemistry of molecularly imprinted polymer-ferroso-ferric oxide
Luminescence sensor.
2. according to claim 1 based on molecularly imprinted polymer-ferroso-ferric oxide Electrochemiluminescsensor sensor system
Preparation Method, it is characterised in that: Fe described in step (3)3O4- NCs-MIPs solution concentration is 20.0mg/mL.
3. a kind of of any of claims 1-2 based on molecularly imprinted polymer-ferroso-ferric oxide electrogenerated chemiluminescence
The method of sensor detection bisphenol-A, it is characterised in that specific step is as follows: to be based on molecularly imprinted polymer-ferroso-ferric oxide
Electrochemiluminescsensor sensor is working electrode, and platinum electrode is auxiliary electrode, and Ag/AgCl is reference electrode, uses MPI-E type
Electrogenerated chemiluminescence system carries out Electrochemiluminescprocess process；System condition: PBS buffer solution concentration be 60mM, pH 10.0,
Luminol concentration is 0.6mM；Instrument condition: photomultiplier tube negative high voltage 600V, sweep speed 100mV/s, potential range -0.6 ~
Then bisphenol-A solution to be measured is added in+1.0V in electrolytic cell, carry out electrochemical luminescence test to its system, sent out according to electrochemistry
The quantitative relationship of luminous intensity and bisphenol A concentration determines the concentration of bisphenol-A in sample to be tested.
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