CN104062331A - Imprinted sensor based on gold nanoparticles, preparation method and application thereof - Google Patents
Imprinted sensor based on gold nanoparticles, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an imprinted sensor based on gold nanoparticles, a preparation method and an application thereof. The method comprises the following steps: 1)placing a target electrode in a first mixing solution containing Na2SO4 and HAuCl4 and performing electrochemical deposition to prepare the gold nanoparticles for modifying the electrode; 2)under existence of a buffer solution, placing the electrode modified by the gold nanoparticles in a second mixing solution containing o-phenylenediamine and 2,4-dichlorphenoxyacetic acid, employing a cyclic voltammetry method for scanning to prepare a polymer membrane for modifying the electrode; and 3)placing the electrode modified by the polymer membrane in ethanol or an ethanol solution for eluting to prepare the imprinted sensor based on gold nanoparticles; wherein the target electrode is glassy carbon electrode or ITO electrode. The imprinted sensor can detect the 2,4-dichlorophenoxyacetic acid in a sensitive mode.
Description
Technical field
The present invention relates to trace sensor field, particularly, relate to a kind of trace sensor based on golden nanometer particle and its preparation method and application.
Background technology
2,4-dichlorphenoxyacetic acid is a kind of conventional herbicide, be similar to auxin or other plant growth regulator, can stimulating growth, promote plant metabolism, but there is certain toxicity, easily remain in plant surface, people's food-safety problem has been caused to serious impact, therefore, the analyzing and testing of 2,4-dichlorphenoxyacetic acid is just seemed to particularly important.Along with people are more and more higher to the attention degree of food-safety problem, people are also more and more many to the detection method of 2,4-dichlorphenoxyacetic acid, as high performance liquid chromatography, chemoluminescence method etc.Although these method energy Gu Shixian detects 2,4-dichlorphenoxyacetic acid, the defect such as these methods exist as complicated operation, reaction time long, and poor stability and detection sensitivity are low.
Summary of the invention
The object of this invention is to provide a kind of trace sensor based on golden nanometer particle and its preparation method and application, this sensor is to 2,4-dichlorphenoxyacetic acid has excellent selectivity recognition capability and has excellent reproducibility and stability, and the step of simultaneously preparing this sensor is simple.
To achieve these goals, the invention provides a kind of preparation method of the trace sensor based on golden nanometer particle, described method comprises following operation:
1) target electrode is placed in and comprises Na
2sO
4and HAuCl
4the first mixed solution in carry out the operation of electrochemical deposition with preparation gold nano modified electrode;
2), under the existence of buffer solution, described gold nano modified electrode is placed in the second mixed solution that comprises o-phenylenediamine and 2,4-dichlorphenoxyacetic acid and adopts cyclic voltammetry to scan to prepare the operation of polymer film modified electrode;
3) described polymer film modified electrode is placed in to ethanol or ethanolic solution and carries out wash-out to prepare the operation of the trace sensor based on golden nanometer particle,
Wherein, described target electrode is glass-carbon electrode or ITO electrode.
The present invention also provides a kind of trace sensor based on golden nanometer particle, and described trace sensor obtains by above-mentioned method preparation.
The present invention also provides the trace sensor based on golden nanometer particle of preparing according to above-mentioned method in the application detecting in 2,4-dichlorphenoxyacetic acid.
By technique scheme, the present invention has utilized molecular imprinting, and what manual method was synthetic has the technology of specific binding polymkeric substance to template molecule.First its principle for will forming compound by acting forces such as covalent bond, hydrogen bond, Van der Waals forces between template molecule and function monomer, then add crosslinking chemical and initiating agent, form and there is certain 3 D stereo functional material by initiations such as optical, electrical, hot, chemical reaction energy, finally, by chemistry or physical method, template molecule is removed, in the template of imprinted polymer, just left identical with template molecule structure, sizeable " trace hole ".This " trace hole " has specific recognition capability to template molecule.
In the present invention, as shown in Figure 1, first the method for utilizing electrochemical deposition is plated to layer of gold nanometer layer in target electrode, then adopt the mode of electrochemical polymerization that o-phenylenediamine (function monomer) is carried out to polymerization formation polymeric layer on gold nano layer, then by 2, the function monomer of 4-dichlorphenoxyacetic acid (template molecule) on polymeric layer is combined, finally by wash-out, template molecule is removed, thereby make to have formed and 2 on polymeric layer, 4-dichlorphenoxyacetic acid structure is identical, sizeable " trace hole ", thereby make this trace sensor to 2, 4-dichlorphenoxyacetic acid has excellent selectivity recognition capability.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for instructions, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the schematic diagram that the present invention prepares the trace sensor based on golden nanometer particle;
Fig. 2 is the SEM figure of gold nano modified electrode in embodiment 1;
Fig. 3 is the SEM figure of polymer film modified electrode in embodiment 1;
Fig. 4 is the EDS figure of polymer film modified electrode in embodiment 1;
Fig. 5 is the DPV figure of MIP/Au/GCE to 2,4-D in embodiment 1;
Fig. 6 is the test result statistical graph of MIP/Au/GCE to 2,4-D in embodiment 1;
Fig. 7 is the test result statistical graph of MIP/Au/GCE to 2,4-D in embodiment 2;
Fig. 8 is the test result statistical graph of MIP/Au/GCE to 2,4-D in embodiment 3;
Fig. 9 is the test result statistical graph of MIP/Au/GCE to 2,4-D in embodiment 4;
Figure 10 is the test result statistical graph of MIP/Au/GCE to 2,4-D in embodiment 5;
Figure 11 is the test result statistical graph of MIP/Au/GCE to 2,4-D in embodiment 6;
Figure 12 is the test result statistical graph of MIP/Au/GCE to 2,4-D in embodiment 7;
Figure 13 is MIP/Au/GCE, NIP/Au/GCE, MIP/GCE and the NIP/GCE DPV figure to 2,4-D in test example 1;
Figure 14 is MIP/Au/GCE and the test result statistical graph of NIP/Au/GCE to 2,4-D in embodiment 7;
Figure 15 is MIP/Au/GCE, NIP/Au/GCE, MIP/GCE and the NIP/GCE test result statistical graph to 2,4-D, DL, PA, 4-CPA and 2,4-CA in embodiment 7;
Figure 16 is the EDS figure of gold nano modified electrode in embodiment 1.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The preparation method who the invention provides a kind of trace sensor based on golden nanometer particle, described method comprises following operation:
1) target electrode is placed in and comprises Na
2sO
4and HAuCl
4the first mixed solution in carry out the operation of electrochemical deposition with preparation gold nano modified electrode;
2), under the existence of buffer solution, described gold nano modified electrode is placed in the second mixed solution that comprises o-phenylenediamine and 2,4-dichlorphenoxyacetic acid and adopts cyclic voltammetry to scan to prepare the operation of polymer film modified electrode;
3) described polymer film modified electrode is placed in to ethanol or ethanolic solution and carries out wash-out to prepare the operation of the trace sensor based on golden nanometer particle;
Wherein, described target electrode is glass-carbon electrode or ITO electrode.
As shown in Figure 1, first the present invention is comprising Na in target electrode
2sO
4and HAuCl
4the first mixed solution in carry out electrochemical deposition and make to form gold nano sedimentary deposit obtain gold nano modified electrode on the surface of target electrode.Then gold nano modified electrode is being comprised to o-phenylenediamine and 2, in the second mixed solution of 4-dichlorphenoxyacetic acid, carrying out cyclic voltammetry scanning makes o-phenylenediamine form polymeric layer in the polymerization of gold nano modified electrode, while 2, function monomer (o-phenylenediamine) combination on 4-dichlorphenoxyacetic acid (template molecule) and polymeric layer is to form polymer film modified electrode.Then polymer film modified electrode is soaked in ethanol or ethanolic solution to wash-out 2,4-dichlorphenoxyacetic acid makes the surface of polymer film form " trace hole " to make the trace sensor based on golden nanometer particle." trace hole " and 2 like this, 4-dichlorphenoxyacetic acid structure is identical, size to fit, thereby makes the trace sensor based on golden nanometer particle to have excellent selectivity recognition capability to 2,4-dichlorphenoxyacetic acid.
In the present invention, in order to improve the efficiency that forms gold nano layer on target electrode surface, preferably, in the operation of preparation gold nano modified electrode, with respect to the Na of 100mmol
2sO
4, described HAuCl
4content be 10-30mmol.
In the present invention, in order further to improve the efficiency that forms gold nano layer on target electrode surface, preferably, described the first mixed solution also comprises solvent, with respect to the Na of 100mmol
2sO
4, the volume of described solvent is 0.8-1L.Described solvent has wide range of choice, and taking cost into account, more preferably, the solvent of described the first mixed solution is distilled water; More preferably, the solvent of described the first mixed solution is intermediate water.
In the present invention, in order to make the tightr of gold nano layer and target electrode combination, preferably, in the operation of preparation gold nano modified electrode, the current potential of described electrochemical deposition is-0.5～-0.7V.
In the present invention, for the thickness of controlling gold nano layer has more excellent selectivity recognition capability with the trace sensor that makes preparation to 2,4-dichlorphenoxyacetic acid, preferably, the time of described electrochemical deposition is 400-900s.
In the present invention, for the trace sensor that makes preparation has more excellent selectivity recognition capability to 2,4-dichlorphenoxyacetic acid, preferably, in the operation of preparing polymer film modified electrode, with respect to the o-phenylenediamine of 1mol, described 2, the consumption of 4-dichlorphenoxyacetic acid is 0.2-1mol.
In the present invention, for the trace sensor that makes preparation has more excellent selectivity recognition capability to 2,4-dichlorphenoxyacetic acid, preferably, described buffer solution is NaAc-HAc (sodium acetate-acetic acid) buffer solution, and more preferably, the pH of described buffer solution is 4.5-5.5; In order further to improve trace sensor, 2,4-dichlorphenoxyacetic acid is had to more excellent selectivity recognition capability, more preferably, with respect to the o-phenylenediamine of 1mmol, the volume of described buffer solution is 30-60mL.
In the present invention, for the trace sensor that makes preparation has more excellent selectivity recognition capability to 2,4-dichlorphenoxyacetic acid, preferably, and in the operation of preparing polymer film modified electrode, the current potential-1～1V of described scanning; More preferably, the number of turns of described scanning is 10-50 circle; Further preferably, the speed of described scanning is 30-100mV/s.
In the present invention, in order to accelerate elution efficiency, in order to make the more thorough of wash-out, preferably, the time of described wash-out is 5-30min.
In the present invention, in order to accelerate elution efficiency, in order to make the more thorough of wash-out, preferably, the solvent of described ethanolic solution is water, and massfraction >=99% of ethanol.
In the present invention, in order to make the easier deposited gold nanometer layer in target electrode surface, preferably, before the operation of preparation gold nano modified electrode, the method also comprises carries out pretreated operation by described target electrode: carry out surface finish with target electrode described in alumina powder foot couple, then the described target electrode after polishing is carried out to ultrasonic cleaning with second alcohol and water respectively again, and the described target electrode after cleaning is placed in to K
3[Fe (CN)
6]/K
4[Fe (CN)
6] adopt cyclic voltammetry to carry out electrochemical treatment until the current potential value difference △ Ep≤75mV of oxidation peak and reduction peak in solution; In order to make the surface of target electrode more clean, preferably, the particle diameter of described alumina powder is 0.3-1 μ m; More preferably, described K
3[Fe (CN)
6]/K
4[Fe (CN)
6] concentration of solution is 0.1mmol/L-1mmol/L.In addition described K,
3[Fe (CN)
6]/K
4[Fe (CN)
6] solution can be prepared in accordance with the following methods, by getting K
3[Fe (CN)
6], K
4[Fe (CN)
6] and KCl and mix to be dissolved in deionized water according to the ratio of mol ratio 1:1:1 and make, as the K of 0.1mmol/L
3[Fe (CN)
6]/K
4[Fe (CN)
6] solution is the K by getting 0.1mmol
3[Fe (CN)
6], the K of 0.1mmol
4[Fe (CN)
6] and 0.1molKCl mix to be dissolved in the deionized water of 1L and make.
The invention provides a kind of trace sensor based on golden nanometer particle, described trace sensor obtains by above-mentioned method preparation.
The invention provides the trace sensor based on golden nanometer particle of preparing according to above-mentioned method in the application detecting in 2,4-dichlorphenoxyacetic acid.
Below will describe the present invention by embodiment and test case.In following examples and test case, the test of cyclic voltammetry (CV) parameter is undertaken by the electrochemical workstation CHI660C of Shanghai Chen Hua instrument company, the test of differential pulse voltammetry (DPV) parameter is undertaken by electrochemical workstation CHI660C, the test (SEM) of scanning electron microscope is that scanning electron microscope S-4800 is by carrying out, X-ray energy spectrum is analyzed (EDS) and is undertaken by scanning electron microscope S-4800, in all Electrochemical Detection, comparison electrode is platinum electrode below, and contrast electrode is saturated calomel electrode.
Particle diameter is the Al of 0.3 μ m
2o
3, high auric acid (HAuCl
4), K
3[Fe (CN)
6] and o-phenylenediamine (o-PD) are all products of traditional Chinese medicines chemical reagent company limited, 2,4-dichlorphenoxyacetic acid (2,4-D), 2,4-chlorophenesic acid (2,4-CA), DL-mandelic acid (DL), 4-chlorophenoxyacetic acid (4-CPA) and phenoxy acetic acid (PA) they are all products of Shanghai Aladdin company, water is redistilled water, K
4[Fe (CN)
6] be the product of Chinese Shanghai experiment reagent company limited.
Embodiment 1
1) pre-service of glass-carbon electrode
Carry out surface finish processing with the alumina powder foot couple glass-carbon electrode that particle diameter is 0.3 μ m, and carry out ultrasonic processing in ethanol and intermediate water solution.Subsequently the glass-carbon electrode of processing is inserted to [the Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-in solution, carry out CV and detect that to make the peak difference △ Ep of its oxidation peak and reduction peak be 75mV, then at 25 DEG C, be dried.
2) preparation of gold nano modified electrode
Pretreated glass-carbon electrode is inserted to the Na that comprises 0.1mol/L
2sO
4hAuCl with 30mmol/L
4in the first mixed solution, electro-deposition 600s under the condition of-0.6V, obtains golden nanometer particle modified electrode.
Gold nano modified electrode is carried out to EDS detection, and as shown in figure 16, gold nano modified electrode has Au element to result as shown in Figure 16.Gold nano modified electrode is carried out to SEM detection, result as shown in Figure 2, is analyzed knownly by Fig. 2 and Figure 16, formed the gold nano grain of " needle " shape Nano grade on the surface of glass-carbon electrode simultaneously.
3) preparation of polymer film modified electrode
Gold nano modified electrode is inserted in the second mixed solution, carry out electropolymerization by CV method, current potential is-1.0V～1.0V, and sweeping the rate of hastening is 50mV/s, and the scanning number of turns is 20 circles; Wherein, to comprise pH be 5.2 NaAc-HAc buffer solution, the o-phenylenediamine and 5 × 10 of 0.02mol/L to the second mixed solution
-32 of mol/L, 4-dichlorphenoxyacetic acid.
Polymer film modified electrode is carried out to SEM detection, and result as shown in Figure 3, known by comparison diagram 2 and Fig. 3, and the surface of gold nano modified electrode has formed polymeric layer.Polymer film modified electrode is carried out to EDS detection simultaneously, result as shown in Figure 4, from Fig. 4 and Figure 16, on polymer film modified electrode, have containing Cl, and decorated by nano-gold electrode does not contain Cl, and step 3) in only have 2 containing Cl material, 4-D (2,4-dichlorphenoxyacetic acid), thus indirectly illustrate that 2,4-D is present on the polymeric layer of polymer film modified electrode.
4) preparation of trace sensor (MIP/Au/GCE)
It is to soak wash-out in 99% ethanolic solution that polymer film modified electrode is inserted to massfraction, and elution time is 10min.
MIP/Au/GCE is placed in to [the Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-to variable concentrations in solution 2,4-D solution carries out DPV detection, wherein, detection current potential is-0.2～0.5V, the solvent of 2,4-D solution is that pH is 6.86 PBS buffer solution, as shown in Figure 5 and Figure 6, as seen from the figure, MIP/Au/GCE is to 1 × 10 for testing result
-9mol/L-3 × 10
-42 of mol/L, 4-D has excellent sensitivity, and detects current value I and 2,4-D concentration (C) and have good linear relationship, and linear equation is I/ μ A=4.55227E7C/ μ mol/L-23.23407, detects and is limited to 1.6 × 10
-10mol/L, can utilize this equation to detect the concentration of 2,4-D.
Embodiment 2
Carry out according to the method for embodiment 1, difference is, the electrochemical deposition time is respectively 400s, 500s, 700s, 800s and 900s and makes MIP/Au/GCE, then by the MIP/Au/GCE in embodiment 1 and embodiment 2 in the [Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-in solution to 1.5 × 10
-82 of mol/L, 4-D solution carries out DPV detection, and wherein, detection current potential is-0.2～0.5V, and testing result as shown in Figure 7, known by Fig. 7, and the MIP/Au/GCE making in the time of electrochemical deposition time 600s is the sensitiveest to 2,4-D.
Embodiment 3
Carry out according to the method for embodiment 1, difference is, 2, it is 2 that the concentration of 4-D is respectively 0.002mol/L, 0.004mol/L, 0.01mol/L and 0.02mol/L, the mol ratio of 4-D and o-PD is respectively 0.1,0.2,0.5 and 1, make MIP/Au/GCE, then by the MIP/Au/GCE in embodiment 1 and embodiment 3 in the [Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-in solution to 1.5 × 10
-82 of mol/L, 4-D solution carries out DPV detection, and wherein, detection current potential is-0.2～0.5V, and testing result as shown in Figure 8, as shown in Figure 8, is respectively in the mol ratio of 2,4-D and o-PD the MIP/Au/GCE making at 0.25 o'clock the sensitiveest to 2,4-D.
Embodiment 4
Carry out according to the method for embodiment 1, difference is, the pH of NaAc-HAc buffer solution is respectively 4.5,5.0 and 5.5 and makes MIP/Au/GCE, then by the MIP/Au/GCE in embodiment 1 and embodiment 4 in the [Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-in solution to 1.5 × 10
-82 of mol/L, 4-D solution carries out DPV detection, and wherein, detection current potential is-0.2～0.5V, and testing result as shown in Figure 9, as shown in Figure 9, is that the MIP/Au/GCE that makes for 5.2 o'clock is the sensitiveest to 2,4-D at the pH of NaAc-HAc buffer solution.
Embodiment 5
Carry out according to the method for embodiment 1, difference is, the scanning number of turns is respectively 10 circles, 30 circles, 40 circles and 50 circles and makes MIP/Au/GCE, then by the MIP/Au/GCE in embodiment 1 and embodiment 5 in the [Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-in solution to 1.5 × 10
-82 of mol/L, 4-D solution carries out DPV detection, and wherein, detection current potential is-0.2～0.5V, and as shown in figure 10, as shown in Figure 10, the MIP/Au/GCE making in the time that the scanning number of turns is 20 circle is the sensitiveest to 2,4-D for testing result.
Embodiment 6
Carry out according to the method for embodiment 1, difference is, sweep velocity is respectively 30mV/s, 60mV/s and 100mV/s makes MIP/Au/GCE, then by the MIP/Au/GCE in embodiment 1 and embodiment 6 in the [Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-in solution to 1.5 × 10
-82 of mol/L, 4-D solution carries out DPV detection, and wherein, detection current potential is-0.2～0.5V, and testing result as shown in figure 11, as shown in Figure 11, is that the MIP/Au/GCE that makes for 50 o'clock is the sensitiveest to 2,4-D in sweep velocity.
Embodiment 7
Carry out according to the method for embodiment 1, difference is, elution time is respectively 5min, 15min and 30min makes MIP/Au/GCE, then by the MIP/Au/GCE in embodiment 1 and embodiment 7 in the [Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-in solution to 1.5 × 10
-82 of mol/L, 4-D solution carries out DPV detection, and wherein, detection current potential is-0.2～0.5V, and as shown in figure 12, as shown in Figure 12, the MIP/Au/GCE making in the time of elution time 10min is the sensitiveest to 2,4-D for testing result.
Embodiment 8
Carry out according to the method for embodiment 1, difference is that target electrode is ITO electrode, MIP/Au/GCE is placed in to [the Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-to variable concentrations in solution 2,4-D solution carries out DPV detection, wherein, detection current potential is-0.2～0.5V, the volume of 2,4-D solution is that pH is 6.86 PBS buffer solution, testing result is that this MIP/Au/GCE is 18.47 μ A to the induction current of 2,4-D.
Comparative example 1
Carry out according to the method for embodiment 1, difference is, do not contain the preparation section of gold nano modified electrode, obtains trace sensor (MIP/GCE).
Comparative example 2
Carry out according to the method for embodiment 1, difference is in the second mixed solution, not contain 2,4-D solution and make non-trace sensor (NIP/Au/GCE).
Comparative example 3
Carry out according to the method for embodiment 1, difference is, do not contain in the preparation section of gold nano modified electrode and the second mixed solution and do not contain 2,4-D solution, makes non-trace sensor (NIP/GCE).
Test example 1
By the NIP/GCE in the MIP/GCE in the NIP/Au/GCE in the MIP/Au/GCE in embodiment 1, comparative example 2, comparative example 1 and comparative example 3 in the [Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-solution and contain 2, [the Fe (CN) of 4-D
6]
3-/ [Fe (CN)
6]
4-solution carries out DPV detection, and wherein, detection current potential is-0.2～0.5V, and wherein 2, the concentration of 4-D is 1.5 × 10
-8mol/L, as shown in figure 13, in figure, a, c, e, g represent that respectively MIP/Au/GCE, NIP/Au/GCE, MIP/GCE and NIP/GCE are at [Fe (CN) to testing result independently
6]
3-/ [Fe (CN)
6]
4-dPV figure in solution, b, d, f, h represent that respectively MIP/Au/GCE, NIP/Au/GCE, MIP/GCE and NIP/GCE are containing the [Fe (CN) of 2,4-D independently
6]
3-/ [Fe (CN) 6]
4-dPV figure in solution.As shown in Figure 13, by the electric current difference DELTA i of MIP/GCE and NIP/GCE
nIP/Au/GCE, Δ i
nIP/GCEcontrast, the electric current of trace sensor is all much larger than non-trace sensor, may be due to join as 2,4-D contain 2, [the Fe (CN) of 4-D
6]
3-/ [Fe (CN)
6]
4-after in solution, " trace hole " in trace electrode has specific binding to 2,4-D, make 2,4-D molecule enter " trace hole ", cause " trace hole " again to be occupied by template molecule, molecule is difficult to arrive the surface of electrode, reduces thereby show oxidation peak current in DPV curve.But not trace electrode, owing to itself just there is no imprinted sites, does not therefore have specific binding to template molecule, before and after template molecule adds, molecule is all difficult to arrive the surface of electrode, so two not significantly variations of DPV curves.And the current responsing signal of MIP/Au/GCE is obviously greater than the current responsing signal on MIP/GCE, this may be that satisfactory electrical conductivity and the electrocatalysis of golden nanometer particle causes.
Test example 2
By the NIP/Au/GCE in the MIP/Au/GCE in embodiment 1 and comparative example 2 in the [Fe (CN) of 0.6mmol/L
6]
3-/ [Fe (CN)
6]
4-solution and contain 2 of the variable concentrations, [Fe (CN) of 4-D
6]
3-/ [Fe (CN)
6]
4-solution carries out DPV detection, and wherein 2, the concentration of 4-D is 1.5 × 10
-8mol/L, detection current potential is-0.2～0.5V, as shown in figure 14, as shown in Figure 14, MIP/Au/GCE is 1 × 10 in the concentration of 2,4-D to testing result
-9mol/L-3 × 10
-4this concentration range of mol/L is interior to 2,4-D has good specific binding capacity, and non-trace sensor NIP/Au/GCE do not have obvious binding ability to template molecule, illustrate that thus sensor provided by the invention has good specific binding capacity to template molecule.
Test example 3
NIP/GCE in MIP/GCE in NIP/Au/GCE in MIP/Au/GCE in embodiment 1, comparative example 2, comparative example 1 and comparative example 3 is independently placed in respectively to the [Fe (CN) of the 0.6mmol/L that contains thing to be checked
6]
3-/ [Fe (CN)
6]
4-solution carries out DPV detection, and wherein, thing to be checked is selected from 2,4-D, DL (DL-mandelic acid), PA (phenoxy acetic acid), 4-CPA (4-chlorophenoxyacetic acid) and 2, one in 4-CA (2,4-chlorophenesic acid), and the concentration of thing to be checked is 1.5 × 10
-8mol/L, detection current potential is-0.2～0.5V, testing result as shown in figure 15, as shown in Figure 15, at analogue (DL, PA, 4-CPA and 2, in the situation of existence 4-CA), MIP/Au/GCE is to template molecule 2, the current-responsive of 4-dichlorphenoxyacetic acid is apparently higher than other analogues, NIP/Au/GCE to the response current of template molecule will be much larger than common trace sensing (MIP/GCE) response current to template molecule, MIP/Au/GCE is for 2, 4-D has good selectivity recognition capability and golden nanometer particle has increased the response current that trace sensor detects template molecule.
Test example 4
MIP/Au/GCE in embodiment 1 is placed in to [the Fe (CN) of the 0.6mmol/L that contains 2,4-D
6]
3-/ [Fe (CN)
6]
4-in carry out DPV detection, then use ethanol elution, at [the Fe (CN) that is placed in the 0.6mmol/L that contains 2,4-D
6]
3-/ [Fe (CN)
6]
4-in carry out DPV detection, 20 times repeatedly, add up the current value of each MIP/Au/GCE to 2,4-D response, wherein, the concentration of 2,4-D is 1.5 × 10
-8mol/L, detection current potential is-0.2～0.5V.Statistics is that MIP/Au/GCE is to 2, the relative standard deviation of the current value of 4-D response is 1.89%, 1.89% close to 0, illustrates that thus MIP/Au/GCE can not use two to reduce it to 2 because of not frequent, the accuracy that 4-D detects, thus illustrate that MIP/Au/GCE has good reproducibility.
Test example 5
MIP/Au/GCE in embodiment 1 is placed in to [the Fe (CN) of the 0.6mmol/L that contains 2,4-D
6]
3-/ [Fe (CN)
6]
4-in carry out DPV detection, then use ethanol elution, at [the Fe (CN) that is placed in the 0.6mmol/L that contains 2,4-D
6]
3-/ [Fe (CN)
6]
4-in after 1 day, 5 days, 10 days and 30 days, carry out DPV detection, add up the current value of each MIP/Au/GCE to 2,4-D response, wherein, the concentration of 2,4-D is 1.5 × 10
-8mol/L, detection current potential is-0.2～0.5V.Statistics is that MIP/Au/GCE is to 2, the relative standard deviation of the current value of 4-D response is 0.9%, 1.89% close to 0, existed 30 days MIP/Au/GCE with existed the MIP/Au/GCE of 1 day to 2, the current value of 4-D response is about the same, illustrate that thus MIP/Au/GCE can not reduce along with the growth of life period the sensitivity that it detects 2,4-D, MIP/Au/GCE has good stability.
Test example 6
Get three kinds of different soil is configured to it solution and numbers No. 1, No. 2, No. 3 after dissolving, filtration, centrifugal processing; Then, under the existence of the MIP/Au/GCE in embodiment 1, at [Fe (CN)
6]
3-/ [Fe (CN)
6]
4-in solution, adopt standard application of sample method to carry out the detection of the recovery to No. 1, No. 2, No. 3 three kinds of samples.Testing result sees the following form 1, as seen from table, MIP/Au/GCE provided by the invention to the detection recovery of three kinds of actual samples between 89.5% to 95.4%, the higher recovery illustrates that MIP/Au/GCE provided by the invention can be because of the complicated composition of actual water sample to 2, the detection of 4-D brings interference, such MIP/Au/GCE can be competent at completely to manifest real in any water sample 2,4-D detects, MIP/Au/GCE has excellent practicality.
Table 1
| Specimen coding | 2,4-D(mol/L) | The recovery (%) |
| No. 1 | 1.41×10 -8 | 94.2 |
| No. 2 | 1.34×10 -8 | 89.5 |
| No. 3 | 1.431×10 -8 | 95.4 |
| Standard specimen | 1.50×10 -8 | 0 |
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out combination in any between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a preparation method for the trace sensor based on golden nanometer particle, is characterized in that, described method comprises following operation:
1) target electrode is placed in and comprises Na
2sO
4and HAuCl
4the first mixed solution in carry out the operation of electrochemical deposition with preparation gold nano modified electrode;
2), under the existence of buffer solution, described gold nano modified electrode is placed in the second mixed solution that comprises o-phenylenediamine and 2,4-dichlorphenoxyacetic acid and adopts cyclic voltammetry to scan to prepare the operation of polymer film modified electrode;
3) described polymer film modified electrode is placed in to ethanol or ethanolic solution and carries out wash-out to prepare the operation of the trace sensor based on golden nanometer particle;
Wherein, described target electrode is glass-carbon electrode or ITO electrode.
2. preparation method according to claim 1, wherein, in the operation of preparation gold nano modified electrode, with respect to the Na of 100mmol
2sO
4, described HAuCl
4content be 10-30mmol.
Preferably, described the first mixed solution also comprises solvent, with respect to the Na of 100mmol
2sO
4, the volume of described solvent is 0.8-1L;
More preferably, the solvent of described the first mixed solution is distilled water.
3. preparation method according to claim 1, wherein, in the operation of preparation gold nano modified electrode, the current potential of described electrochemical deposition is-0.5～-0.7V;
Preferably, the time of described electrochemical deposition is 400-900s.
4. preparation method according to claim 1, wherein, in the operation of preparing polymer film modified electrode, with respect to the o-phenylenediamine of 1mol, described 2, the consumption of 4-dichlorphenoxyacetic acid is 0.2-1mol.
5. preparation method according to claim 1, wherein, in the operation of preparing polymer film modified electrode, described buffer solution is NaAc-HAc buffer solution;
Preferably, with respect to the o-phenylenediamine of 1mmol, the volume of described NaAc-HAc buffer solution is 30-60mL,
More preferably, the pH of described NaAc-HAc buffer solution is 4.5-5.5.
6. preparation method according to claim 1, wherein, in the operation of preparing polymer film modified electrode, the current potential-1～1V of described scanning;
Preferably, the number of turns of described scanning is 10-50 circle;
More preferably, the speed of described scanning is 30-100mV/s.
7. preparation method according to claim 1, wherein, in the operation of the trace sensor in preparation based on golden nanometer particle, the time of described wash-out is 5-30min;
More preferably, the solvent of described ethanolic solution is water, and the massfraction of ethanol is >=99%.
8. preparation method according to claim 1, wherein, before the operation of preparation gold nano modified electrode, the method also comprises carries out pretreated operation by described target electrode: carry out surface finish with target electrode described in alumina powder foot couple, then the described target electrode after polishing is carried out to ultrasonic cleaning with second alcohol and water respectively again, and by clean after described target electrode at K
3[Fe (CN)
6]/K
4[Fe (CN)
6] adopt in solution cyclic voltammetry to carry out oxidation peak that electrochemical treatment obtains and the current potential value difference △ Ep≤75mV of reduction peak;
Preferably, the particle diameter of described alumina powder is 0.3-1 μ m;
More preferably, described K
3[Fe (CN)
6]/K
4[Fe (CN)
6] concentration of solution is 0.1mmol/L-1mmol/L.
9. the trace sensor based on golden nanometer particle, is characterized in that, described trace sensor obtains by the method preparation described in any one in claim 1-8.
10. the trace sensor based on golden nanometer particle of preparing according to the method described in any one in claim 1-8 is in the application detecting in 2,4-dichlorphenoxyacetic acid.
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| CN106525948A (en) * | 2016-10-31 | 2017-03-22 | 扬州大学 | Preparation method and application of sensor for molecular imprinting detection of 2,4-d |
| WO2018162611A1 (en) | 2017-03-09 | 2018-09-13 | Universita' Ca' Foscari Venezia | New molecularly-imprinted electrochemical sensors for perfluorooctansulfonate and analytical methods based thereon |
| CN110596226A (en) * | 2019-11-18 | 2019-12-20 | 西北师范大学 | Construction method of molecularly imprinted Au nanoparticle chiral interface |
| CN111909308A (en) * | 2019-05-10 | 2020-11-10 | 湘潭大学 | Method for preparing 2,4-D imprinted microspheres by photoactivation room-temperature RAFT suspension polymerization |
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| CN101787123A (en) * | 2010-03-05 | 2010-07-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Molecular engram polymer and preparation and application thereof |
| CN103149268A (en) * | 2013-03-18 | 2013-06-12 | 桂林理工大学 | Method for utilizing molecularly imprinted electrochemical sensor to detect trace gibberellin A3 |
| CN103575783A (en) * | 2013-11-01 | 2014-02-12 | 济南大学 | Preparation method of molecularly-imprinted electrochemical transducer for detecting propylgallate as well as application thereof |
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| CN101787123A (en) * | 2010-03-05 | 2010-07-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Molecular engram polymer and preparation and application thereof |
| CN103149268A (en) * | 2013-03-18 | 2013-06-12 | 桂林理工大学 | Method for utilizing molecularly imprinted electrochemical sensor to detect trace gibberellin A3 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106525948A (en) * | 2016-10-31 | 2017-03-22 | 扬州大学 | Preparation method and application of sensor for molecular imprinting detection of 2,4-d |
| CN106525948B (en) * | 2016-10-31 | 2019-04-19 | 扬州大学 | A kind of preparation method and application of molecular engram detection 2,4-d sensor |
| WO2018162611A1 (en) | 2017-03-09 | 2018-09-13 | Universita' Ca' Foscari Venezia | New molecularly-imprinted electrochemical sensors for perfluorooctansulfonate and analytical methods based thereon |
| CN111909308A (en) * | 2019-05-10 | 2020-11-10 | 湘潭大学 | Method for preparing 2,4-D imprinted microspheres by photoactivation room-temperature RAFT suspension polymerization |
| CN110596226A (en) * | 2019-11-18 | 2019-12-20 | 西北师范大学 | Construction method of molecularly imprinted Au nanoparticle chiral interface |
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