CN102539493A - Preparation method of reduction state graphene and platinum nanometer particle composite material modified molecularly imprinted membrane electrochemical sensor - Google Patents
Preparation method of reduction state graphene and platinum nanometer particle composite material modified molecularly imprinted membrane electrochemical sensor Download PDFInfo
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Abstract
The invention discloses a preparation method of a reduction state graphene and platinum nanometer particle composite material modified molecularly imprinted membrane electrochemical sensor. The method sequentially comprises the steps of electrode pretreatment process, platinum nanometer particle electrochemical deposition on the electrode surface, polyelectrolyte modification on the reduction state graphene, platinum nanometer particle assembly, molecularly imprinted layer self assembly, electro-polymerization reaction and template molecule elution. The molecularly imprinted membrane electrochemical sensor prepared by the preparation method provided by the invention has the advantages that the selectivity is good, the sensitivity and the anti-jamming capability are high, and the fast detection on trace environment estrogen in complex substrates can be carried out.
Description
Technical field
The invention belongs to technical field of analysis and detection, be specifically related to a kind of preparation method who goes back ortho states Graphene and nano platinum particle compound substance decorating molecule marking membrane electrochemical sensor.
Background technology
In recent years, big quantity research shows, has the multiple material that can simulate and disturb animal and human body function in the environment, for example estradiol, ethinyloestradiol and bisphenol-A etc.After these exogenous estrogen get into human bodies, with normocrinic hormone competition, ins conjunction with the hormone receptor in the cell, cause human hormone's surplus, endocrine system disorder influences the operate as normal of human body sex hormone, and obstacle appears in multiple function.These estrogenic residual domestic and international great attentions that caused become the focus that the whole world is paid close attention to day by day for the detection of environmental estrogens such as estradiol.
At present, the detection method for estradiol mainly contains: liquid phase tandem mass spectrometry, ELISA etc.Though can obtain higher sensitivity, these methods all need complicated sample pre-treatment process, and are also harsh to the requirement of experiment condition.And estradiol this is lower in occurring in nature content, difficultly from the matrix of complicacy, detect, thus set up a kind of fast, simple, cost is low, the tool high sensitivity and optionally method be the current problem of paying close attention to.
Electrochemical sensor all has application in every field, for example: DNA and protein electrochemical sensor, organic molecule electrochemical sensor, nonpolar molecule electrochemical sensor etc.Because of its have higher sensitivity, simplicity of design, cheap, have good stable property and reuse, can realize that characteristics such as monitoring in real time are known.But electrochemical sensor often lacks selectivity, this also limited should technology development.
Since the Vlatakis of Sweden Lund university etc. has reported the achievement in research of the molecularly imprinted polymer of relevant theophylline on " Nature ", molecular imprinting just becomes chemistry and one of biological cross discipline, and has obtained flourish in recent years.Molecular imprinting generally is used for the separation and the enrichment of complex matrices predetermined substance with its distinctive precordainment, identity and practicality, so that detect fast.Electrochemical sensor and molecular imprinting are organically combined, just can realize real-time detection, and can obtain higher sensitivity.
At present, the preparation method of molecular imprinting electrochemical sensor is mainly electropolymerization, but the molecular imprinting film that electropolymerization forms is commonly the weak inductive film, has influenced the sensitivity of electrochemical sensor.Therefore, the sensitivity of raising molecular imprinting electrochemical sensor gradually becomes the hot issue of current research.
Summary of the invention
The objective of the invention is above-mentioned shortcoming to electrochemical sensor and electropolymerization molecular imprinting film; To go back ortho states Graphene and platinum nano material, molecular imprinting and electrochemical sensor technology organically combines; A kind of preparation method who goes back ortho states Graphene and nano platinum particle compound substance decorating molecule marking membrane electrochemical sensor is provided; The molecular imprinting membrane electrochemical sensor that obtains can be maximized favourable factors and minimized unfavourable ones, and realizes having the trace micro substance high-sensitivity detection of high selectivity.At present, electropolymerization method preparation is gone back the ortho states Graphene and nano platinum particle compound substance decorating molecule marking membrane electrochemical sensor does not appear in the newspapers.
The objective of the invention is to realize in the following manner:
A kind of preparation method who goes back ortho states Graphene and nano platinum particle compound substance decorating molecule marking membrane electrochemical sensor, this method may further comprise the steps:
A) electrode pre-service: glass-carbon electrode after polishing, is put into Piranha solution and soaked afterwash; Piranha solution of the present invention is 30%H
2O
2: dense H
2SO
4=3: 7, V/V.
B) nano platinum particle electrochemical deposition: the glass-carbon electrode of cleaning is placed the mixed solution of sulfur acid and chloroplatinic acid, in-0.2～0.6V potential range, with 30～100mVs
-1Sweep speed scan round 3～25min; Use absolute ethyl alcohol and deionized water drip washing then successively, nitrogen dries up, and places Piranha solution to soak again, and deionized water drip washing is clean, and nitrogen dries up, and promptly gets the nano platinum particle modified electrode; Soak time is 2～5min;
C) go back the assembling of ortho states Graphene and nano platinum particle: will go back the ortho states Graphene and be assembled to electrode surface, and after drying under the room temperature platinum nanoparticle will be assembled to modified electrode, and dry under the room temperature; Assembling adopt when going back the ortho states Graphene concentration be 0.4～0.6mg/mL go back the ortho states graphene aqueous solution;
D) molecular self-assembled monolayer modified electrode and electric polymerization reaction: the modified electrode that step c) is obtained is immersed in and contains function monomer, 17 beta estradiols and NaClO
4Tetrahydrofuran solution in, seal after filling nitrogen, place 15～24h in the room temperature lucifuge environment; In-0.2～0.6V potential range, with 50mVs
-1Sweep speed cyclic voltammetry scan 5～20 circle, take out, deionized water drip washing, nitrogen dries up; Wherein, 17 beta estradiols, function monomer, NaClO
4The ratio of amount of substance is 6: 6～180: 0.001～0.03;
E) wash-out template molecule: the immersion of electropolymerization rear electrode is contained H
2SO
4Aqueous acetone solution in handle 5～60min.
Step " b) " the middle preferred 70mVs of sweep speed
-1, preferred 20～25min of scan round time.Mixed solution in the step " b) " is preferably and contains 0.5molL
-1Sulfuric acid and 5mmolL
-1The chloroplatinic acid mixed aqueous solution.
What go back in the step " c) " that the ortho states Graphene is assembled to that electrode surface uses is to drip a coating method.Also the ortho states Graphene be assembled to glass-carbon electrode (amount on the surface of Φ=3mm) is S～30 μ L, is preferably 10 μ L, go back the ortho states graphene aqueous solution use before ultrasonic 20～40min.What nano platinum particle was assembled to that electrode surface uses in the step " c) " is to drip a coating method.Nano platinum particle is assembled to glass-carbon electrode, and (Φ=3mm) amount on surface is 5～30 μ L, is preferably 20 μ L, ultrasonic 20～40min before nano platinum particle uses.
The function monomer of selecting for use in the step " d) " is the pyridines material that contains sulfydryl, and the described pyridines material that contains sulfydryl is preferably 6-sulfydryl nicotinic acid or 4-amino-3-mercaptopyridine.17 beta estradiols, function monomer in the step " d) ", NaClO
4The ratio of amount of substance is 6: 6～30: 0.001～0.03.
What use in the step " e) " is acetone water (acetone and water volume ratio are 1: the 1) solution that contains 0.5mol/L sulfuric acid.
Ortho states preparation method of graphene also: get 3.0g graphite, add the 120ml concentrated sulphuric acid, under condition of ice bath, stir, divides to add total 16.0g potassium permanganate for 3 times.35-40 ℃ of control temperature of reaction stirred 20 hours.Add water 250ml in batches after stirring end, heated water bath stirs, and 80 ℃ of temperature controls reacted 2 hours, and reactant gradually becomes glassy yellow.Add 40ml hydrogen peroxide stirred overnight after cooling, make the Graphene (GO) of oxidation state.Be washed till pH near 6 through acid washing water successively then.Ultrasonic dispersion GO 1-2 hour.Get 60mg GO and add the ultrasonic 30min of 600mg kayexalate (PSS), stir 24h down at 50 ℃.Add each 4ml of ammoniacal liquor and hydrazine hydrate after cooling, keep 95-100 ℃ to stir 24h.Obtain going back ortho states Graphene (PSS-RGO) through washing and ultrasonic dispersion.
The preparation method of nano platinum particle: with 10mg NaBH
4Add the 6mL cetyl trimethyl ammonium bromide WS (0.08mol L
-1) and be defined as solution A.With 1mL H
2PtCl
6The WS (5mmol L
-1) dropwise add the 10mL cetyl trimethyl ammonium bromide WS (0.08molL
-1), add 25mg NH again
4F, 125mg H
3BO
3And mix, be defined as solution B.Under ultrasonic situation, A solution is slowly dropwise added in the B solution, continue ultrasonic 10min, solution promptly gets nano platinum particle by the faint yellow pitchy that gradually becomes.
2. the present invention detects electrochemical sensor of the present invention through following method:
Electrochemical detection method and condition:
Cyclic voltammetry (CV) method: the detection potential range is-0.2～0.6V, and sweep speed is 50mVs
-1Test end liquid is 0.1molL
-1KCl and 1mmolL
-1Potassium ferricyanide solution.
Differential pulse method (DPV) method: test end liquid is for containing 0.1molL
-1PBS solution (the 0.05molL of KCl
-1, pH7.0), the detection potential range is 0.2～1.0V, sweep speed is 50mVs
-1, the current potential increment is 0.005V, and amplitude is 0.05V, and pulse width is 0.05s, and the sampling width is 0.0167s, be 2s rest time.Electrode is at H before the test
2SO
4Clean in the solution to background current and recover.For making absorption fully, can select 17 beta estradiols (E2) enrichment time in the experiment is 5min.
3. adopt and go back the ortho states Graphene and the Static Adsorption of concentration known solution is tested: get concentration range and be respectively 0.004-50 μ molL with nano platinum particle compound substance decorating molecule marking membrane electrochemical sensor
-1Estradiol solution test, measured concentration is respectively at 0.004-0.06 μ molL
-1, 0.06-50 μ molL
-1The scope internal linear is good, and detectability reaches 0.52ng/mL.
With prior art beneficial effect more of the present invention:
1. molecular imprinting is combined with electrochemical sensor, improved the specificity of electrochemical sensor, can realize that the selectivity of trace trace 17-β estradiol in the complex sample detects.
2. will go back the compound substance of ortho states Graphene and nano platinum particle and modify in electrode surface, the characteristics such as good conduction, catalysis and high-specific surface area of having utilized Graphene and platinum nanoparticle to have, thus increased the sensitivity of electrode greatly.
3. platinum nanoparticle and function monomer be through electropolymerization again after the self assembly of Pt-S key, forms fine and close and combine the firm rete that comprises template molecule specificity hole.Can recently regulate and control marking nanostructured through forming between control electropolymerizatioconditions conditions, template molecule and function monomer, crosslinking chemical.
4. the function monomer of selecting for use is the pyridines material that contains sulfydryl, promptly is that function monomer is again the crosslinking chemical in traditional molecular imprinting, forms the polypyridine film with electric conductivity under the electropolymerizatioconditions conditions.
Description of drawings
Fig. 1 is the cyclic voltammogram of different modifying electrode.
(A) a bare electrode, the electrode of b platinum electrodeposition particle, c is ortho states Graphene modified electrode also, and d modifies the electrode of going back ortho states Graphene and platinum particles successively according to the embodiment method.Explanation is compared with bare electrode, and the electrode current response of platinum electrodeposition particle obviously increases, and goes back after ortho states Graphene and the platinum particles and modify successively, and the response of electrode current further increases, and explains that modifying rear electrode sensitivity improves greatly.
(B) e molecular imprinting sensor (before wash-out template molecule 17 beta estradiols), f molecular imprinting sensor (behind wash-out template molecule 17 beta estradiols), the non-marking sensor of g.After the wash-out template molecule before the wash-out current-responsive increase, explain that the molecular imprinting hole that forms makes potassium ferricyanide probe be able to entering, and then has increased current-responsive.But not marking sensor does not have the molecular imprinting hole, and the fine and close weak inductive polymer film of formation has hindered the response of the potassium ferricyanide, so that a little less than the response.
Fig. 2 is electron microscope scanning figure: amplify 10000 times and scan.
Among the figure, (A) electro-deposition makes the sem photograph that nano platinum particle (B) is modified at nano platinum particle (C) the molecular imprinting film on Graphene surface.
Fig. 3 is the Static Adsorption process of electrochemical sensor in 17 beta estradiol solution of variable concentrations of embodiment 1 method preparation.
Interior illustration is respectively 0.004,0.006,0.008,0.02,0.04,0.06 μ molL by adding 17 beta estradiol concentration
-1Differential pulse voltammetry test result.As shown in the figure, be 0.004-0.06 μ molL in 17 beta estradiol concentration
-1With 0.06-50 μ molL
-1In the scope, there are linear relationship in current-responsive and 17 beta estradiol concentration.Regression equation is respectively: I
p(μ A)=57.872C (μ M)+1.6678, R=0.9977 and I
p(μ A)=0.7915C (μ M)+6.6906, R=0.9957.Detection is limited to 0.52ng/mL, and maximum adsorption concentration is 150 μ molL
-1
Embodiment
Below through embodiment the present invention is done further and to explain:
Medicine and reagent: Al
2O
3(0.05 μ m, Shanghai occasion China Instr Ltd.), 17 beta estradiols (Zhejiang Province XianJu Pharmacy stock Co., Ltd), potassium chloride (KCl), the potassium ferricyanide (K
3Fe (CN)
6) (analyze pure, the new precious Fine Chemical Works in Shanghai), absolute ethyl alcohol, acetonitrile (analyze pure, chemical reagent company limited of group of nations), chloroplatinic acid (H
2PtCl
6, Chemical Reagent Co., Ltd., Sinopharm Group), tetrahydrofuran (analyze pure, Shishewei Chemical Co., Ltd., Shanghai), phenol (phenol), potassium dihydrogen phosphate (KH
2PO
4), dipotassium hydrogen phosphate (K
2HPO
4) (analyze pure, Shanghai Ling Feng chemistry company limited), 6-sulfydryl nicotinic acid (Sigma-Aldrich company), tetrahydrofuran (Shishewei Chemical Co., Ltd., Shanghai), sulfuric acid (H
2SO
4, Shanghai chemical reagent company limited), experimental water is a redistilled water.0.05molL
-1KH
2PO
4And 0.05molL
-1K
2HPO
4The PBS of WS preparation pH 7.0 (phosphate buffered solution, PBS).
Ortho states preparation method of graphene also: get 3.0g graphite, add the 120ml concentrated sulphuric acid, under condition of ice bath, stir, divides to add total 16.0g potassium permanganate for 3 times.35-40 ℃ of control temperature of reaction stirred 20 hours.Add water 250ml in batches after stirring end, heated water bath stirs, and 80 ℃ of temperature controls reacted 2 hours, and reactant gradually becomes glassy yellow.Add 40ml hydrogen peroxide stirred overnight after cooling, make the Graphene (GO) of oxidation state.Be washed till pH near 6 through acid washing water successively then.Ultrasonic dispersion GO 1-2 hour.Get 60mg GO and add the ultrasonic 30min of 600mg kayexalate (PSS), stir 24h down at 50 ℃.Add each 4ml of ammoniacal liquor and hydrazine hydrate after cooling, keep 95-100 ℃ to stir 24h.Obtain going back ortho states Graphene (PSS-RGO) through washing and ultrasonic dispersion.
The preparation method of nano platinum particle: with 10mg NaBH
4Add the 6mL cetyl trimethyl ammonium bromide WS (0.08mol L
-1) and be defined as solution A.With 1mL H
2PtCl
6The WS (5mmol L
-1) dropwise add the 10mL cetyl trimethyl ammonium bromide WS (0.08molL
-1), add 25mg NH again
4F, 125mg H
3BO
3And mix, be defined as solution B.Under ultrasonic situation, A solution is slowly dropwise added in the B solution, continue ultrasonic 10min, solution promptly gets nano platinum particle by the faint yellow pitchy that gradually becomes.
Embodiment 1
A) electrode pre-service: (Φ=3mm) is through the Al of 0.05 μ m for glass-carbon electrode
2O
3After the suspension polishing, put into Piranha solution (30%H
2O
2: dense H
2SO
4=3: 7, V/V) the middle 2min that soaks uses absolute ethyl alcohol, deionized water ultrasonic cleaning 2min then respectively;
B) nano platinum particle electrochemical deposition: the glass-carbon electrode of cleaning placed contain 0.5molL
-1Sulfuric acid and 5mmolL
-1In the mixed aqueous solution of chloroplatinic acid, in-0.2～0.6V potential range, with 30mVs
-1Sweep speed scan round 3min; Use absolute ethyl alcohol and deionized water drip washing then successively, nitrogen dries up, place Piranha solution to soak 2min again after, deionized water drip washing is clean, nitrogen dries up, and promptly gets the nano platinum particle modified electrode;
C) go back the assembling of ortho states Graphene and nano platinum particle: with the 5 μ L 0.5mg/mL ultrasonic 30min of ortho states graphene aqueous solution also; Drip and be applied to nano platinum particle modified electrode surface; Dry under the room temperature; With the ultrasonic 30min of the nano platinum particle of 5 μ L, drip and to be applied to the electrode surface that dries, dry under the room temperature;
D) molecular self-assembled monolayer modified electrode and electric polymerization reaction: the modified electrode that step c) is obtained is immersed in and contains 6mmolL-16-sulfydryl nicotinic acid, 6mmol L
-117 beta estradiols and 0.01mmol L
-1NaClO
4Tetrahydrofuran solution in, seal after filling nitrogen, place 15h in the room temperature lucifuge environment; In-0.2～0.6V potential range, with 50mVs
-1Sweep speed cyclic voltammetry scan 5 circle, take out, deionized water drip washing, nitrogen dries up; Wherein, 17 beta estradiols, function monomer and NaClO
4The ratio of amount of substance is 6: 6: 0.01;
E) wash-out template molecule: the immersion of electropolymerization rear electrode is contained 0.5molL
-1H
2SO
4Aqueous acetone solution in (wherein the volume ratio of acetone and water is 1: 1) 5min, take out, deionized water drip washing is clean, nitrogen dries up.
A) electrode pre-service: (Φ=3mm) is through the Al of 0.05 μ m for glass-carbon electrode
2O
3After the suspension polishing, put into Piranha solution (30%H
2O
2: dense H
2SO
4=3: 7, V/V) the middle 2min that soaks uses absolute ethyl alcohol, deionized water ultrasonic cleaning 2min then respectively;
B) nano platinum particle electrochemical deposition: the glass-carbon electrode of cleaning placed contain 0.5molL
-1Sulfuric acid and 5mmolL
-1In the chloroplatinic acid mixed aqueous solution, in-0.2～0.6V potential range, with 50mVs
-1Sweep speed scan round 10min; Use absolute ethyl alcohol and deionized water drip washing then successively, nitrogen dries up, place Piranha solution to soak 2min again after, deionized water drip washing is clean, nitrogen dries up, and promptly gets the nano platinum particle modified electrode;
C) go back the assembling of ortho states Graphene and nano platinum particle: with the 0.5mg/mL of the 10 μ L ultrasonic 30min of ortho states graphene aqueous solution also, drip and be applied to electrode surface, dry under the room temperature; With the ultrasonic 30min of the nano platinum particle of 10 μ L, drip and to be applied to the modified electrode that dries, dry under the room temperature;
D) molecular self-assembled monolayer modified electrode and electric polymerization reaction: the modified electrode that step c) is obtained is immersed in and contains 6mmol L
-1Function monomer 6-sulfydryl nicotinic acid, 6mmol L
-117 beta estradiols and contain 0.001mmol L
-1NaClO
4Tetrahydrofuran solution in, seal after filling nitrogen, place 15h in the room temperature lucifuge environment; In-0.2～0.6V potential range, with 50mVs
-1Sweep speed cyclic voltammetry scan 10 circle, take out, deionized water drip washing, nitrogen dries up; Wherein, 17 beta estradiols, function monomer and NaClO
4The ratio of amount of substance is 6: 6: 0.001;
E) wash-out template molecule: the immersion of electropolymerization rear electrode is contained 0.5molL
-1H
2SO
4Aqueous acetone solution in (wherein the volume ratio of acetone and water is 1: 1) 10min, take out, deionized water drip washing is clean, nitrogen dries up.
Embodiment 3
A) electrode pre-service: (Φ=3mm) is through the Al of 0.05 μ m for glass-carbon electrode
2O
3After the suspension polishing, put into Piranha solution (30%H
2O
2: dense H
2SO
4=3: 7, V/V) the middle 2min that soaks uses absolute ethyl alcohol, deionized water ultrasonic cleaning 2min then respectively;
B) nano platinum particle electrochemical deposition: the glass-carbon electrode of cleaning placed contain 0.5molL
-1Sulfuric acid and 5mmolL
-1In the mixed solution of chloroplatinic acid, in-0.2～0.6V potential range, with 70mVs
-1Sweep speed scan round 15min; Use absolute ethyl alcohol and deionized water drip washing then successively, nitrogen dries up, place Piranha solution to soak 2min again after, deionized water drip washing is clean, nitrogen dries up, and promptly gets the nano platinum particle modified electrode;
C) go back the assembling of ortho states Graphene and nano platinum particle: with the 0.5mg/mL of the 15 μ L ultrasonic 30min of ortho states graphene aqueous solution also, drip and be applied to electrode surface, dry under the room temperature; With the ultrasonic 30min of the nano platinum particle of 15 μ L, drip and to be applied to the modified electrode that dries, dry under the room temperature;
D) molecular self-assembled monolayer modified electrode and electric polymerization reaction: with rapid c) modified electrode that obtains is immersed in and contains 6mmol L
-1Function monomer 4-amino-3-mercaptopyridine, 100mmol L
-117 beta estradiols and contain 0.01mmol L
-1NaClO
4Tetrahydrofuran solution in, seal after filling nitrogen, place 15h in the room temperature lucifuge environment; In-0.2～0.6V potential range, with 50mVs
-1Sweep speed cyclic voltammetry scan 15 circle, take out, deionized water drip washing, nitrogen dries up; Wherein, 17 beta estradiols, function monomer and NaClO
4The ratio of amount of substance is 6: 100: 0.01;
E) wash-out template molecule: the immersion of electropolymerization rear electrode is contained 0.5molL
-1H
2SO
4Aqueous acetone solution in (wherein the volume ratio of acetone and water is 1: 1) 30min, take out, deionized water drip washing is clean, nitrogen dries up.
A) electrode pre-service: (Φ=3mm) is through the Al of 0.05 μ m for glass-carbon electrode
2O
3After the suspension polishing, put into Piranha solution (30%H
2O
2: dense H
2SO
4=3: 7, V/V) the middle 2min that soaks uses absolute ethyl alcohol, deionized water ultrasonic cleaning 2min then respectively;
B) nano platinum particle electrochemical deposition: the glass-carbon electrode of cleaning placed contain 0.5molL
-1Sulfuric acid and 5mmolL
-1In the mixed solution of chloroplatinic acid, in-0.2～0.6V potential range, with 100mVs
-1Sweep speed scan round 25min; Use absolute ethyl alcohol and deionized water drip washing then successively, nitrogen dries up, place Piranha solution to soak 2min again after, deionized water drip washing is clean, nitrogen dries up, and promptly gets the nano platinum particle modified electrode;
C) go back the assembling of ortho states Graphene and nano platinum particle: with the 0.5mg/mL of the 30 μ L ultrasonic 30min of ortho states graphene aqueous solution also, drip and be applied to electrode surface, dry under the room temperature; With the ultrasonic 30min of the nano platinum particle of 30 μ L, drip and to be applied to the modified electrode that dries, dry under the room temperature;
D) molecular self-assembled monolayer modified electrode and electric polymerization reaction: with rapid c) modified electrode that obtains is immersed in and contains 6mmol L
-1Function monomer sulfydryl nicotinic acid, 6mmol L
-117 beta estradiols and contain 0.001mmol L
-1NaClO
4Tetrahydrofuran solution in, seal after filling nitrogen, place 15h in the room temperature lucifuge environment; In-0.2～0.6V potential range, with 50mVs
-1Sweep speed cyclic voltammetry scan 20 circle, take out, deionized water drip washing, nitrogen dries up; Wherein, 17 beta estradiols, function monomer and NaClO
4The ratio of amount of substance is 6: 6: 0.001;
E) wash-out template molecule: the immersion of electropolymerization rear electrode is contained 0.5molL
-1H
2SO
4Aqueous acetone solution in (wherein the volume ratio of acetone and water is 1: 1) 60min, take out, deionized water drip washing is clean, nitrogen dries up.
Claims (9)
1. preparation method who goes back ortho states Graphene and nano platinum particle compound substance decorating molecule marking membrane electrochemical sensor is characterized in that this method may further comprise the steps:
A) electrode pre-service: after the glass-carbon electrode polishing, put into Piranha solution and soak afterwash;
B) nano platinum particle electrochemical deposition: the glass-carbon electrode of cleaning is placed the mixed solution of sulfur acid and chloroplatinic acid, in-0.2～0.6V potential range, with 30～100mVs
-1Sweep speed scan round 3～25min; Use absolute ethyl alcohol and deionized water drip washing then successively, nitrogen dries up, place Piranha solution to soak again after, deionized water drip washing is clean, nitrogen dries up, and promptly gets the nano platinum particle modified electrode;
C) go back the assembling of ortho states Graphene and nano platinum particle: will go back the ortho states Graphene and be assembled to electrode surface, and after drying under the room temperature platinum nanoparticle will be assembled to modified electrode, and dry under the room temperature; Assembling adopt when going back the ortho states Graphene concentration be 0.4～0.6mg/mL go back ortho states Graphene solution;
D) molecular self-assembled monolayer modified electrode and electric polymerization reaction: the modified electrode that step c) is obtained is immersed in and contains function monomer, 17 beta estradiols and NaClO
4Tetrahydrofuran solution in, seal after filling nitrogen, place 15～24h in the room temperature lucifuge environment; In-0.2～0.6V potential range, with 50mVs
-1Sweep speed cyclic voltammetry scan 5～20 circle, take out, deionized water drip washing, nitrogen dries up; Wherein, 17 beta estradiols, function monomer, NaClO
4The ratio of amount of substance is 6: 6～180: 0.001～0.03;
E) wash-out template molecule: the immersion of electropolymerization rear electrode is contained H
2SO
4Aqueous acetone solution in handle 5～60min.
2. the preparation method of molecular imprinting membrane electrochemical sensor according to claim 1 is characterized in that in the step " b) " with 70mVs
-1Sweep speed scan round.
3. the preparation method of molecular imprinting membrane electrochemical sensor according to claim 1 is characterized in that the time of scan round in the step " b) " is 20～25min.
4. the preparation method of molecular imprinting membrane electrochemical sensor according to claim 1; It is characterized in that going back in the step " c) " that the ortho states Graphene is assembled to that electrode surface uses is to drip a coating method; Also to be assembled to the amount of electrode surface be 5～30 μ L to ortho states Graphene solution, ultrasonic 20～40min before the use.
5. the preparation method of molecular imprinting membrane electrochemical sensor according to claim 1; What it is characterized in that nano platinum particle in the step " c) " is assembled to that electrode surface uses is to drip a coating method; The amount that nano platinum particle is assembled to electrode surface is 5～30 μ L, ultrasonic 20～40min before the use.
6. the preparation method of molecular imprinting membrane electrochemical sensor according to claim 1 is characterized in that the function monomer of selecting for use in the step " d) " is the pyridines material that contains sulfydryl.
7. the preparation method of molecular imprinting membrane electrochemical sensor according to claim 6 is characterized in that the described pyridines material that contains sulfydryl is a 6-sulfydryl nicotinic acid, 4-amino-3-mercaptopyridine.
8. the preparation method of molecular imprinting membrane electrochemical sensor according to claim 1 is characterized in that 17 beta estradiols, function monomer and NaClO in the step " d) "
4The ratio of amount of substance is 6: 6～30: 0.001～0.03.
9. the preparation method of molecular imprinting membrane electrochemical sensor according to claim 1, what it is characterized in that using in the step " e) " is that the volume ratio that contains 0.5mol/L sulfuric acid is 1: 1 a aqueous acetone solution.
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| CN102879447A (en) * | 2012-08-29 | 2013-01-16 | 闽江学院 | Preparation method for thermal control sulfhydryl ionic liquid modified electrode |
| CN102879588A (en) * | 2012-09-11 | 2013-01-16 | 宁波大学 | Method for detecting estrogens through graphene-nanogold biomimetic immunosensor |
| CN103033549A (en) * | 2012-12-17 | 2013-04-10 | 同济大学 | Preparation method of double-enzyme glucose sensor based on graphene |
| CN103217468A (en) * | 2013-04-17 | 2013-07-24 | 济南大学 | Preparation method and application of current type electrochemical sensor for detecting bisphenol A |
| CN103235144A (en) * | 2013-04-19 | 2013-08-07 | 济南大学 | Preparation method and application of sensor for simultaneously detecting two environmental estrogens |
| CN103675062A (en) * | 2013-12-18 | 2014-03-26 | 济南大学 | Preparation method and application of electrochemical immunosensor for detecting 17 beta-estradiol |
| CN104133070A (en) * | 2014-07-17 | 2014-11-05 | 济南大学 | Preparation method and use of environmental estrogen label-free immunosensor |
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| CN108837849A (en) * | 2018-07-03 | 2018-11-20 | 山东交通学院 | A kind of complex stablizes the preparation method and application of SiC point composite material |
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| CN104165912A (en) * | 2013-06-26 | 2014-11-26 | 江南大学 | Preparation method and use of graphene oxide surface molecularly imprinted sol-gel polymer |
| CN103675062A (en) * | 2013-12-18 | 2014-03-26 | 济南大学 | Preparation method and application of electrochemical immunosensor for detecting 17 beta-estradiol |
| CN104133070A (en) * | 2014-07-17 | 2014-11-05 | 济南大学 | Preparation method and use of environmental estrogen label-free immunosensor |
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| CN108837849A (en) * | 2018-07-03 | 2018-11-20 | 山东交通学院 | A kind of complex stablizes the preparation method and application of SiC point composite material |
| CN108837849B (en) * | 2018-07-03 | 2020-11-03 | 山东交通学院 | Preparation method and application of complex-stabilized SiC dot composite material |
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