CN104892839A - Surface molecular imprinting polyion liquid of reduced graphene oxide for detecting bisphenol A and preparation method and application of surface molecular imprinting polyion liquid - Google Patents
Surface molecular imprinting polyion liquid of reduced graphene oxide for detecting bisphenol A and preparation method and application of surface molecular imprinting polyion liquid Download PDFInfo
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Abstract
The invention discloses surface molecular imprinting polyion liquid of reduced grapheme oxide for detecting bisphenol A and a preparation method and an application of the surface molecular imprinting polyion liquid. The polyion liquid is a composite material which is formed in a polymerization manner by using the reduced grapheme oxide, functional monomer, cross-linking agents and template molecules under the effect of initiating agents; the template molecules of the composite material are removed; the functional monomer is 1-vinyl-3-ethylimidazole hexafluorophosphate; the cross-linking agents are ethylene glycol dimethyl acrylic ester and 1, 4-butane-3, 3'-bis-1- ethylimidazole hexafluorophosphate; and the template molecules are the bisphenol A. The surface molecular imprinting polyion liquid which is prepared in the polymerization manner by using 1-vinyl-3-ethylimidazole hexafluorophosphate as the functional monomer and using the 1, 4-butane-3, 3'-bis-1- ethylimidazole hexafluorophosphate as the cross-linking agents has high adsorption capacity, the detection range of the bisphenol A is 0.01050.0 micrometer, and a detection limit is 0.005 micrometer (S/N=3).
Description
Technical field
The present invention relates to a kind of surface molecule print poly ion liquid, particularly relating to surface molecule print poly ion liquid of a kind of redox graphene for detecting dihydroxyphenyl propane and its preparation method and application.
Background technology
Along with the development of the mankind, environmental problem is day by day serious, thus causes global concern.Therefore in order to protect human health, it is vital for setting up quick, easy, high-sensitive environment detection method.Dihydroxyphenyl propane (BPA) [2,2-bis-(4-hydroxy phenyl) propane] be one of starting material for the manufacture of resins such as polycarbonate, epoxy resin, resol, be widely used in daily life as in baby bottles, water tumbler, beverage bottle and other packaging materials for food.Simultaneously dihydroxyphenyl propane is also a kind of environmental endocrine disruptors, can imitate the oestrogenic hormon in human body, changes endogenous hormones synthesis, the hormone concentration in hormone metabolism and blood, thus affects the health of human and animal.Therefore set up quick, easy, dihydroxyphenyl propane detection method be significant.The main method of current detection dihydroxyphenyl propane has liquid phase chromatography, fluorescent spectrometry, mass spectrometer, enzyme-linked immunosorbent assay and electrochemical process etc.Due to electrochemical process have sensitive, cost is low, the feature such as simple to operate, and becomes a kind of common method of rapid detection dihydroxyphenyl propane.
Ionic liquid (ILs) refers in room temperature or close to presenting salt that is liquid, that be made up of zwitterion completely under room temperature, also referred to as low temperature molten salt.The broad interest of domestic and international research worker has been caused as a kind of novel green solvent, have outside the advantages such as nontoxic, low volatilization, viscosity is large, also there is adjustable Lewis acidity, electrochemical window wide ranges, insignificant vapour pressure and good thermotolerance.Due to its wide electrochemical window, therefore start by extensive concern in electrochemical field.
The structural similitude of redox graphene (RGO) and graphene oxide (GO), compared with GO, it not only has higher specific surface area, also possesses good thermostability and more excellent electroconductibility, is therefore regarded as new high-performance nano material.In order to further develop RGO matrix material, expand its range of application, many investigators have prepared the matrix material of RGO by the method such as galvanic deposit, chemical polymerization, and these matrix materials have more excellent dispersiveness, better electroconductibility etc. compared with RGO.In addition, in order to again improve the highly selective of matrix material, molecular imprinting can be applied in the preparation of matrix material by we.
Molecular imprinting refers to a kind of molecular recognition technology by using template or microsphere to mould specific recognition site in polymer synthesis process.In recent years, surface molecule print technology becomes study hotspot just gradually, this technology is by the templated molecularly imprinted surface to nano material, molecular recognition site is increased after wash-out, accelerate to be identified as simultaneously a little with the aggregate speed of template molecule, the adsorptive power of further raising nano print material, and effectively can solve that trace in conventional polymeric embedded deeply, tension and be difficult to the shortcomings such as wash-out; Surface imprinted material is prepared from based on carrier simultaneously, and it has some physicochemical property of carrier equally, as the imprinted polymer material based on quantum dot, Z 250 has fluorescence property and magnetic property.
Summary of the invention
The invention provides a kind of surface molecule print poly ion liquid dihydroxyphenyl propane to the redox graphene of better adsorptive power.
A kind of surface molecule print poly ion liquid of redox graphene, it is polymerized under initiator effect by redox graphene, function monomer, linking agent and template molecule formed and remove the matrix material of template molecule, and described function monomer is 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate; Described linking agent is ethylene glycol dimethacrylate and Isosorbide-5-Nitrae-butane-3,3 '-bis--1-vinyl imidazole hexafluorophosphate; Described template molecule is dihydroxyphenyl propane.
Concrete, described initiator is Diisopropyl azodicarboxylate.
Preferably, the mol ratio of described 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, ethylene glycol dimethacrylate, Isosorbide-5-Nitrae-butane-3,3 '-bis--1-vinyl imidazole hexafluorophosphate is 1 ~ 3: 4 ~ 6: 4 ~ 6; More preferably, mol ratio is 2: 5: 5.
Preferably, described redox graphene is 0.1 ~ 0.2g: 0.1mmol with the molal ratio of template molecule; More preferably, molal ratio is 0.2g: 0.1mmol.
Preferably, the mol ratio of described function monomer and initiator is 1 ~ 3: 1; More preferably, mol ratio is 2: 1.
The present invention also provides the preparation method of the surface molecule print poly ion liquid of described redox graphene, comprise the following steps: template molecule is added in solvent, add function monomer, linking agent, initiator and redox graphene again, mix and carry out polyreaction, react rear collection product, remove the template molecule in product, final drying obtains the surface molecule print poly ion liquid of described redox graphene.
Preferably, the temperature of described polyreaction is 60 ~ 80 DEG C, and the time is 12 ~ 36 hours; More preferably, temperature is 60 DEG C, and the time is 24h.
Present invention also offers-kind of the electrochemical sensor utilizing the surface molecule print poly ion liquid of described redox graphene to make.
Present invention also offers described electrochemical sensor and detect the application in dihydroxyphenyl propane.
The present invention has synthesized five kinds of ionic liquids, and using 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate as function monomer, with EGDMA and 1,4-butane-3,3 '-bis--1-vinyl imidazole hexafluorophosphate is double crosslinker, and with the good redox graphene of electro catalytic activity for carrier, BPA is template molecule, adopt surface molecule print technical process to prepare RGO-MIPs, and construct RGO-MIPs electrochemical sensing; And optimize selection and the proportioning of ionic liquid, experimental result shows, the ionic liquid of phosphofluoric acid salt form has larger response to detection system, and with traditional with compared with imprinted material prepared by function monomer of MAA, AA, 4-VP, this material has good adsorptivity to BPA; Under optimal condition, the sensing range of dihydroxyphenyl propane is 0.01-50.0 μM, detects and is limited to 0.05 μM (S/N=3), also illustrates that RGO-MIPs material has good adsorptive power for dihydroxyphenyl propane; The present invention is that the design and application of ionic liquid is laid a good foundation, simultaneously also for RGO-MIPs provides a new application direction.
Accompanying drawing explanation
Fig. 1 is preparation flow figure and the Electrochemical Detection result of RGO-MIPs imprinted material of the present invention.
Fig. 2 is the infrared spectra of GO (a), RGO (b), RGO-MIPs (c).
Fig. 3 A is the thermal gravimetric analysis curve figure of GO (a), RGO (b) and RGO-MIPs (c); Fig. 3 B is the Raman spectrogram of GO (a), RGO (b) and RGO-MIPs (c).
Fig. 4 is the scanning electron microscope (SEM) photograph of GO (A), RGO (B) and RGO-MIPs (C, D) and the projection Electronic Speculum figure of GO (E), RGO (F) and RGO-MIPs (G, H).
Fig. 5 is the XRD figure of GO (a), RGO (b) and RGO-MIPs (c).
Fig. 6 is that the ratio of ionic liquid function monomer (A), ionic liquid linking agent (B), ionic liquid linking agent (C) and EGDMA is on the impact of MIPs modified electrode DPV current-responsive; And conventional molecular trace electrochemical sensor prepared by difference in functionality monomer (D) is to the typical curve of BPA, wherein, (a) ionic liquid; (b) AA; (c) 4-VP; (d) MAA; Test condition 0.1M PBS, 10 μMs of BPA.
Fig. 7 A is that after RGO-MIPs (a) and RGO-NIPs (b) modified electrode adsorb 30.0 μMs of BPA, CV schemes; Fig. 7 B is that RGO-MIPs (a) and RGO-NIPs (b) modified electrode adsorb DPV response current figure after 30.0 μMs of BPA; Adsorption time: 5min.
Fig. 8 is that RGO (a), RGO-MIPs (b), RGO-NIPs (c), GCE (d) are at 5mM K
3[Fe (CN)
6] with 0.1M KCl in cyclic voltammetric collection of illustrative plates (CV).
Fig. 9 is that RGO (a), RGO-MIPs (b), RGO-NIPs (c), GCE (d) are at 5mM K
3[Fe (CN)
6], 5mM K
4[Fe (CN)
6] with 50mM KCl in electrochemical impedance collection of illustrative plates (EIS).
Figure 10 is the concentration (A) of RGO-MIPs, adsorption time (B), pH (C) affect RGO-MIPs modified electrode DPV current-responsive; Test condition 0.1M PBS, 5 μMs of BPA.
Figure 11 is that sensor RGO-MIPs and RGO-NIPs modified electrode adsorb the DPV current-responsive after 5min to 5.0 μMs of BPA and analogue.
Figure 12 A is the linear DPV response curve of RGO-MIPs sensor to BPA; The concentration (μM) of BPA: 0 (a), 0.01 (b), 0.05 (c), 0.5 (d), 1.0 (e), 3.0 (f), 5.0 (g), 7.0 (h), 10.0 (i), 30.0 (j), 50.0 (k); Figure 12 B is sensor RGO-MIPs (a), and RGO-NIPs (b) measures the typical curve of BPA; Condition determination: adsorption time 5min, 0.1M PBS (pH=8.0).
Embodiment
The raw material that the present invention adopts is as shown in table 1:
The reagent chemicals that table 1 is required for the present invention
Remarks: the purifying of (1) 4-vinylpridine: get 20mL 4-vinylpridine in 50mL round-bottomed flask, at 100 DEG C, cut is collected in underpressure distillation.(2) purifying of methacrylic acid: get 20mL methacrylic acid in 50mL round-bottomed flask, at 50 DEG C, cut is collected in underpressure distillation.
1, the synthesis of ionic liquid
(1) the synthesis ([C of bromination 1-vinyl-3-ethyl imidazol(e)
2min] [Br])
Get after 0.1mol1-vinyl imidazole and 0.1mol monobromethane mix, add 30mL methyl alcohol, 60 DEG C of backflow 15h.Be cooled to room temperature after question response completes, pour in 500mL ether, by lower floor's organic filtration out, room temperature in vacuo dried overnight, products therefrom is bromination 1-vinyl-3-ethyl imidazol(e).
1H NMR(400MHz，DMSO，ppm)：9.74(s，1H)，8.27(s，1H)，8.00(s，1H)，6.00(dd，1H)，5.37(dd，1H)，5.32(dd，1H)，4.25(q，2H)，1.41(t，3H)；
13C NMR(400MHz，DMSO，ppm)：135.04，128.85，123.09，119.31，108.87，44.83，15.06。
Concrete reaction formula is:
(2) the synthesis ([C of 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate
2min] [PF
6])
With PF
6 -, BF
4 -for the ionic liquid of anionic functional group can pass through above-mentioned obtained ionic liquid and corresponding inorganic salt, i.e. NH
4pF
6, NaBF
4between anion metathesis be obtained by reacting.The above-mentioned ionic liquid of 0.05mol and 0.055mol NH
4pF
6after mixing in 50mL water, stirred at ambient temperature 12h.Wherein in order to react relatively more complete, NH
4pF
6it is more excessive a little to need.After reacting completely, suction filtration, and wash for several times with intermediate water, after room temperature in vacuo dried overnight, products therefrom is 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate.
1H NMR(400MHz，DMSO，ppm)：9.78(s，1H)，8.38(s，1H)，7.93(s，1H)，7.28(dd，1H)，5.94(dd，1H)，5.42(dd，1H)，4.32(q，2H)，1.45(t，3H)；
13C NMR(400MHz，DMSO，ppm)：135.24，129.04，123.29，119.32，108.88，44.80，16.56。
Concrete reaction formula is as follows:
(3) the synthesis ([C of 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate
2min] [BF
4])
By 0.05mol bromination 1-vinyl-3-ethyl imidazol(e) and 0.07mol NaBF
4after mixing in 75mL dehydrated alcohol, stirred at ambient temperature 48h.After reacting completely, suction filtration, and with washed with diethylether for several times, after room temperature in vacuo dried overnight, products therefrom is 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate.
1H NMR(400MHz，DMSO，ppm)：9.34(s，1H)，8.13(s，1H)，7.90(s，1H)，7.25(dd，1H)，5.93(dd，1H)，5.42(dd，1H)，4.32(q，2H)，1.41(t，3H)；
13C NMR(400MHz，DMSO，ppm)：135.23，128.76，123.29，119.20，108.77，44.63，15.54。
Concrete reaction formula is as follows:
2, the synthesis of ionic liquid linking agent
(1) the synthesis ([C of bromination Isosorbide-5-Nitrae-butane-3,3 '-bis--1-vinyl imidazole
4min
2] [Br])
Get after 0.1mol 1-vinyl imidazole and 0.05mol Isosorbide-5-Nitrae-dibromobutane mix, add 30mL methyl alcohol, 60 DEG C are stirred 15h.Be cooled to room temperature after question response completes, pour in 500mL ether, by lower floor's organic filtration out, room temperature in vacuo dried overnight, products therefrom is bromination Isosorbide-5-Nitrae-butane-3,3 '-bis--1-vinyl imidazole.
1H NMR(400MHz，DMSO，ppm)：9.74(s，1H)，8.28(s，1H)，8.02(s，1H)，7.34(dd，1H)，6.00(d，1H)，5.42(d，1H)，4.30(s，2H)，1.87(s，2H)；
13C NMR(400MHz，DMSO，ppm)：135.48，128.93，123.28，119.19，108.72，48.39，25.75.
Concrete reaction formula is as follows:
(2) the synthesis ([C of Isosorbide-5-Nitrae-butane-3,3 '-bis--1-vinyl imidazole hexafluorophosphate
4min
2] [PF
6])
By above-mentioned for 0.05mol bromination linking agent and 0.05mol NH
4pF
6after mixing in 50mL water, stirred at ambient temperature 12h.After reacting completely, suction filtration, and wash with water for several times, after room temperature in vacuo dried overnight, products therefrom is Isosorbide-5-Nitrae-butane-3,3 '-bis--1-vinyl imidazole hexafluorophosphate.
1H NMR(400MHz，DMSO，ppm)：9.76(s，1H)，8.38(s，1H)，8.22(s，1H)，7.35(dd，1H)，6.05(d，1H)，5.43(d，1H)，4.32(s，2H)，1.82(s，2H)；
13C NMR(400MHz，DMSO，ppm)：135.38，128.92，123.48，119.59，108.82，48.49，25.85。
Concrete reaction formula is as follows:
3, the synthesis of traditional imprinted polymer
0.1mmol dihydroxyphenyl propane is added successively in the round-bottomed flask of 50mL, 0.4mmol function monomer (acrylamide, methacrylic acid, 4-vinylpridine), 2.0mmol EGDMA, 0.2mmol AIBN, flask mouth is sealed with sealed membrane, 60 DEG C of oil bath reaction 24h after inflated with nitrogen deoxygenation inflated with nitrogen deoxygenation 30min.Products therefrom solvent (methyl alcohol: acetic acid=1: 1) surname extraction removing template molecule, 60 DEG C of vacuum-dryings can obtain imprinted polymer.
4, the synthesis of RGO-MIPs
The preparation of redox graphene (RGO): 0.1g GO joins in the water of 200mL, ultrasonic 2h, then 100 μ L hydrazine hydrates (80%) and 1.4mL strong aqua (28%) is added, by this solution heated and stirred 1 hour at 95 DEG C, then water washing, suction filtration, finally at 60 DEG C, vacuum-drying obtains RGO.
The preparation of RGO-MIPs: add 0.1mmol dihydroxyphenyl propane and mixed solvent 30mL solvent (acetonitrile: toluene=1: 1) in 50mL round-bottomed flask successively, add 0.02g RGO and 0.4mmol 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate again, magnetic agitation 2h carries out prepolymerization, then 1.0mmol EGDMA and 1.0mmol 1 is added, 4-butane-3,3 '-bis--1-vinyl imidazole hexafluorophosphate and 0.2mmol AIBN.Flask mouth is sealed with sealed membrane, 60 DEG C of oil bath reaction 24h after inflated with nitrogen deoxygenation 30min.Products therefrom solvent (methyl alcohol: acetic acid=1: 1) surname extraction removing template molecule, 60 DEG C of vacuum-dryings can obtain RGO-MIPs.
Adopt same procedure, do not add template molecule and prepare blank polymer (non-imprinted polymer, RGO-NIPs).
5, the preparation of electrochemical sensor
Naked glass-carbon electrode uses the Al of 0.3 μm and 0.05 μm successively
2o
3powder polished finish becomes minute surface, and then uses dehydrated alcohol and the ultrasonic 5min of intermediate water successively, drying at room temperature.The RGO-MIPs (or RGO-NIPs) of 2.5mg is added in the chitosan solution of 1mL 0.5%, ultrasonicly to mix, finally get this mixing solutions 5 μ L and drip the naked glassy carbon electrode surface being applied to and just having dried, be drying to obtain RGO-MIPs/GCE (RGO-NIPs/GCE).
6, the preparation of RGO-MIPs and Electrochemical Detection thereof
Preparation and the electrochemical detection thereof of RGO-MIPs ask for an interview Fig. 1.First graphene oxide is reduced in water and hydrazine, prepare RGO; Then be carrier with RGO, dihydroxyphenyl propane (BPA) is template molecule, 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate is function monomer, first RGO acts on preadsorption BPA and function monomer by π-π, makes to carry out prepolymerization on RGO surface both it, then with EGDMA and 1,4-butane-3,3 '-bis--1-vinyl imidazole hexafluorophosphate is double crosslinker, and AIBN is initiator, thus has prepared RGO-MIPs.
RGO-MIPs is dissolved in chitosan, and drip be applied to glassy carbon electrode surface, preparation RGO-MIPs/GCE; Then the PBS that this modified electrode is placed in containing BPA is adsorbed, and carry out Electrochemical Detection in this adsorption liquid.After RGO-MIPs removing template, can produce the hole of mating with BPA size, have specific adsorption to BPA, therefore, RGO-MIPs/GCE can realize the specific detection of BPA.
7, the infrared spectrum characterization of RGO-MIPs
Fig. 2 is the infrared spectrogram of GO (a), RGO (b) and RGO-MIPs (c).As can be seen from the GO (a) of Fig. 2,3433cm
-1locate the stretching vibration that strong absorption peak belongs to O-H on GO, 1725cm
-1and 1396cm
-1it is the formation vibration peak of the stretching vibration peak of C=O and the O-H of C-OH on GO.And when GO is after hydrazine hydrate reduction, as shown in the RGO (b) of Fig. 2,3433cm
-1the absorption peak at place obviously dies down, and 1725cm
-1the peak at place disappears, 1634cm
-1the peak at place still exists, and this is because reduction can not destroy C=C.The infrared spectrogram that the RGO-MIPs (c) of Fig. 2 is RGO-MIPs, as can be seen from the figure, at 1557cm
-1, 1162cm
-1and 841cm
-1occurred new absorption peak, and these peaks belong to stretching vibration and the PF of C=N, C-N on imidazole ring respectively
6 -characteristic peak, illustrate that MIPs has been polymerized on RGO surface, prove that RGO-MIPs is successfully prepared.
8, the thermogravimetric analysis of RGO-MIPs and Raman Characterization
Fig. 3 A is thermogravimetric analysis (TGA) graphic representation of GO (a), RGO (b) and RGO-MIPs (c).GO has larger mass loss between 50 DEG C ~ 200 DEG C, and (curve a), this is mainly because the decomposition of a large amount of oxy radical in GO, and is the decomposition due to carbon skeleton the mass loss of 200 DEG C ~ 700 DEG C less.Loss reaches 80%.Compare GO, RGO has good thermostability, and loss is about 28% (curve b).But RGO-MIPs has larger mass loss at 250 DEG C ~ 400 DEG C, loss about reaches 50% (curve c), and this mainly derives from the decomposition of the carbon skeleton of MIPs.TGA result describes RGO-MIPs and successfully prepares.
Fig. 3 B is the Raman spectrogram of GO (a), RGO (b) and RGO-MIPs (c).As can be seen from the figure, occurred two strong peaks herein, belong to D peak and G peak respectively, D peak belongs to sp
3caused by the carbon atom vibration of hydridization, G peak then belongs to sp
2the carbon atom of hydridization is caused by the vibration of lattice inner plane.And the strength ratio (I at D peak and G peak
d/ I
g) be used to represent a kind of method orderly, unordered in carbon structure, therefore, to the I of these three kinds of materials
d/ I
gratio contrast, the I of GO, RGO and RGO-MIPs
d/ I
gbe respectively: 0.95,1.02,1.05.In general, I
d/ I
gratio larger, its material internal randomness is larger.By the I of the visible RGO-MIPs of data
d/ I
gmaximum, this is because the surface of RGO has been arrived in MIPs grafting.Can find out that the peak intensity of RGO-MIPs is obviously weak than RGO, this is because RGO only has sub-fraction in RGO-MIPs simultaneously.Raman spectrum result further demonstrates RGO-MIPs and successfully prepares, and also illustrate that RGO-MIPs is the matrix material of Graphene simultaneously.
9, the SEM of RGO-MIPs characterizes and TEM sign
Fig. 4 A is the SEM collection of illustrative plates of GO, can find out GO surface presentation accordion in figure.Fig. 4 B is the SEM collection of illustrative plates of RGO, compares GO, and the plicated layer on RGO surface becomes many, this is because hydrazine reduction causes plicated layer to become many.Fig. 4 C, D are the SEM collection of illustrative plates of RGO-MIPs, find that RGO surface elevation is cross-linked, and plicated layer are obviously thickening, shows the surface of MIPs grafting to RGO.In order to more can the surface topography of clear view material, we additionally use TEM and come to characterize it.Fig. 4 E, F are the TEM figure of GO and RGO, and can find out that GO with RGO surface is similar, be all the accordion of thin layer, and just the fold of RGO is more, and obviously thickening compared to the plicated layer on RGO, RGO-MIPs surface, as shown in Fig. 4 G, H.Can illustrate that RGO-MIPs is successfully prepared by SEM and TEM figure.
10, the XRD of RGO-MIPs characterizes
By XRD, crystal structure analysis is carried out to GO, RGO, RGO-MIPs, as shown in Figure 5, GO has occurred that in 2 θ=10.5 ° a diffraction peak (curve a), its interlamellar spacing is 0.843nm, and after GO is reduced into RGO, its diffraction peak broadens and died down, and move to right to 2 θ=24.5 ° (curve b), after reduction is described, internal crystal structure is destroyed, and its interlamellar spacing becomes 0.363nm, and the interlamellar spacing of minimizing is because RGO surface oxygen functional group disappears.Compared with RGO, the diffraction peak of RGO-MIPs moves to left ° place (curve c) to 2 θ=17.6, and interlamellar spacing is 0.507nm, and interlamellar spacing is compared RGO and become large, this is because connected MIPs on RGO surface, this has also further demonstrated RGO-MIPs and has successfully prepared.
11, the optimization of material of RGO-MIPs
In order to obtain optimum experiment condition, we are optimized material.This is tested us and has synthesized three kinds of ionic liquid function monomers and three kinds of ionic liquid linking agents, adopts DPV method to investigate function monomer, linking agent and crosslinker ratio to the impact of RGO-MIPs modified electrode for the current-responsive of 10 μMs of BPA.As shown in Figure 6A, for traditional imprinted material, adopt bromo ionic liquid linking agent and be 1: 1 with the ratio of EGDMA, the type changing function monomer prepares imprinted material, discovery PF
6type and BF
4the material of type prepared by function monomer is similar for the current-responsive of BPA, but due to PF
6the preparation of type function monomer is easier to, and therefore we select PF
6type ionic liquid is best-of-breed functionality monomer.Fig. 6 B is different linking agent type to be affected for the current-responsive of BPA, and wherein ionic liquid linking agent is all 1: 1 with the ratio of EGDMA, and by (a) figure acquired results, we adopt PF
6type ionic liquid is function monomer, and change type of crosslinking agent and be also 1: 1 with EGDMA ratio, we find PF
6type ionic liquid linking agent is best.Therefore we select PF
6type ionic liquid is linking agent.Traditional imprinted material preparation method linking agent used is EGDMA, this experiment then adopts ionic liquid and EGDMA double crosslinker, therefore the ratio for both is optimized, experimental result as shown in Figure 6 C, although current-responsive is maximum when ionic liquid is 1: 0.5 with EGDMA ratio, but sensor non-selectivity, trace and non-trace current-responsive difference not obvious, therefore we select 1: 1 for both optimum proportions.
The function monomer that traditional immunoblot method is used is generally AA, 4-VP or MAA, linking agent is EGDMA, it is function monomer that this experiment then have employed novel ion liquid, in order to compare its superiority, traditional imprinted material that we have synthesized with ionic liquid, AA, 4-VP, MAA is function monomer, and done Linear Comparison as shown in Figure 6 C.Linear equation is respectively I (μ A)=0.0764C (μM)+0.235889 (a), I (μ A)=0.06929C (μM)+0.07697 (b), I (μ A)=0.06147C (μM)+0.07523 (c), I (μ A)=0.05462C (μM)+0.00949 (d), and we are by K equally
ionic liquid, K
aA, K
4-VPwith K
mAArepresent the slope of these four kinds of conventional molecular trace sensors respectively, then K
ionic liquid/ K
aA, K
ionic liquid/ K
4-VP, K
ionic liquid/ K
mAAbe respectively 1.103,1.243 and 1.399.Result can draw to have larger current-responsive with ionic liquid as function monomer thus.The detection of the method gained BPA is limited to 0.005 μM (S/N=3), contrasts with pertinent literature report, as shown in table 2, and the detection of RGO-MIPs sensor to BPA has wider linearity range and higher sensitivity.
Table 2 present method and other electrochemical process measuring BPA contrast.
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12, modified electrode is to BPA and K
3[Fe (CN)
6] electrochemical behavior
In order to investigate trace and non-imprinted material to the absorption property of BPA, RGO-MIPs and RGO-NIPs is immersed the PBS (pH=8.0 containing 30 μMs of BPA, 0.1M) whip attachment 5min in solution, and in this adsorption liquid, carry out CV and DPV detection, experimental result is as shown in Figure 7.As can be seen from figure (A) we, BPA is an irreversible oxidation reaction process on modified electrode surface, reaction mechanism as figure (A) interior illustration shown in.According to the CV size of current of trace and non-trace electrode pair 30 μMs of BPA, can find out that the current-responsive of trace electrode is larger than non-trace electrode current response, this is owing to imprinted sites identification.Fig. 7 (B) is the DPV current-responsive size of trace and non-trace electrode pair 30 μMs of BPA, also further demonstrate trace electrode current larger than non-trace electric current, as can be seen from the figure the current-responsive size of RGO-MIPs to BPA is approximately 2.2 times of RGO-NIPs.This is because imprinted polymer material surface has the imprinted cavity of shape size the same as template molecule BPA, can to the BPA specific adsorption in solution.But not imprinted polymer does not have this imprinted cavity, thus fewer than imprinted polymer to the adsorptive capacity of BPA.
In order to study the electrochemical properties of material on modified electrode further, RGO, RGO-MIPs, RGO-NIPs and bare electrode as working electrode, are placed in the K containing 5mM by respectively
3[Fe (CN)
6] and 0.1M KCl mixing solutions in, measure its cyclic voltammetric spectrogram.As shown in Figure 8, the redox current response of RGO working electrode is maximum (curve a), this is because RGO has good electroconductibility, and its current-responsive slightly reduces (curve b) after connecting MIPs on RGO surface, this is because the electro catalytic activity of RGO is better than MIPs.RGO-NIPs electroconductibility is slightly better than naked glass-carbon electrode (curve c), and this is because RGO-NIPs is the matrix material of RGO, also has certain electroconductibility.And RGO-MIPs is larger than the current-responsive of RGO-NIPs, this is because RGO-MIPs has more site, hole, facilitate the electron transmission of electrode surface, illustrate that the recognition site of surface imprinted material can accelerate the diffusion of hexacyanoferrate at electrode surface, facilitate the carrying out of redox reaction.
Fig. 9 is the electrochemical alternate impedance spectrum figure of RGO, RGO-MIPs, RGO-NIPs and GCE.Its collection of illustrative plates is normally made up of semicircle and straight line two portions, and wherein half circular diameter represents electronics resistance to mass transfer, and half circular diameter is less just illustrates that resistance is less, and electroconductibility is better.As the impedance spectrogram that Fig. 9 (d) is naked glass-carbon electrode, its electronics resistance to mass transfer is about 350 Ω.When drip coat RGO-MIPs material after, electronics resistance to mass transfer has diminished, as shown in Fig. 9 (b).This illustrates that imprinted material accelerates [Fe (CN) 6]
3-/4-at the electron transmission of electrode surface, this may have good electroconductibility owing to Graphene.Compared with RGO-MIPs/GCE, the electronics resistance to mass transfer of RGO-NIPs modified electrode is a little slightly large than imprinted material, as shown in Fig. 9 (c).This is owing to not having specific hole in non-imprinted material, can not accelerate [Fe (CN)
6]
3-/4-at the electron transmission of electrode surface, but due to non-imprinted material be also the matrix material of RGO, thus its electronics resistance to mass transfer is better than bare electrode.And the impedance spectrum of RGO electrode almost becomes straight line, Fig. 9 (a), this is because RGO surface is better without MIPs material conductivity.EIS result and above-mentioned modified electrode are to K
3[Fe (CN)
6] electrochemical behavior result of study be also consistent.
13, condition determination optimization
In order to obtain optimum testing conditions, our adopted DPV the to investigate concentration of RGO-MIPs, adsorption time and pH value of solution is on the impact of RGO-MIPs modified electrode for the current-responsive of 5 μMs of BPA.Figure 10 A is that the concentration of RGO-MIPs is on the impact of BPA size of current, find that DPV current-responsive is maximum when 2.5mg/mL, when concentration is less than 2.5mg/mL, less owing to dripping the RGO-MIPs being coated onto electrode surface, so corresponding imprinted sites is also few, electric current and diminishing; And when concentration is greater than 2.5mg/mL, the too thick obstruction electron transmission of modified membrane of RGO-MIPs is to the surface of electrode, therefore corresponding electric current also diminishes thereupon; So select RGO-MIPs concentration to be 2.5mg/mL herein.Figure 10 B is the impact of adsorption time on size of current, adsorption time electric current when 5min reaches maximum as can be seen from Fig., illustrate that RGO-MIPs electrode has the shorter time of response, embody surface imprinted superiority, the adsorption time therefore selected herein is 5min.Figure 10 C be the PBS solution of different pH on the impact of BPA size of current, when pH is from 5.0-8.0, electric current along with the change of pH large and increase; As pH=8.0, response current is maximum.Therefore, pH is selected to be 8.0.
14, sensor selectivity
The object of the surface imprinted material RGO-MIPs synthesized by this experiment is the selectivity improving electrochemical sensor, and therefore our electrochemical sensor of having investigated RGO-MIPs and RGO-NIPs is to the selectivity of the phenol (PhOH) of BPA and its structural similitude, 4-nitrophenols (4-NP), p-tert-butylphenol (PTBP), bisphenol AF (BPF), meta-cresol (MC), paracetamol (APAP), 2-nitrophenols (2-NP).As shown in figure 11, we find that RGO-MIPs modified electrode is PhOH, 4-NP, PTBP, BPF, MC, APAP, 2-NP under the same terms 3.79,2.46,4.47,2.70,5.47,7.09,5.30 times to the current-responsive of BPA respectively.And the response current difference of RGO-NIPs modified electrode to BPA, PhOH, 4-NP, PTBP, BPF, MC, APAP and 2-NP is little.This result shows, RGO-MIPs surface imprinted material has good adsorptivity to BPA, and this defines the imprinted cavity identical with BPA size owing to RGO-MIPs material, can produce specific adsorption to template molecule BPA.
15, linearity range, detectability, circulation ratio and stability
DPV method is adopted to have studied the electrochemical sensor of RGO-MIPs to the linearity range of BPA and detectability.As illustrated in fig. 12, along with the increase of BPA concentration, also increase at the oxidation peak current at 0.424V place thereupon, its oxidation peak current size and BPA concentration have good linear relationship within the scope of 0.01 ~ 50.0 μM, linear equation is I (μ A)=0.13911C (μM)+0.1483, typical curve is as shown in Figure 12 B (a), and its linearly dependent coefficient is 0.9951.
In order to confirm the superiority of RGO-MIPs/GCE, we have also been made the linear of RGO-NIPs/GCE, and linear equation is I (μ A)=0.0680C (μM)-0.044.We are by K
rGO-MIPswith K
rGO-NIPsrepresent the slope of RGO-MIPs and RGO-NIPs sensor respectively, then K
rGO-MIPswith K
rGO-NIPsbe 0.13911 and 0.0680, the ratio of slope is 2.046, illustrates that RGO-MIPs/GCE has higher current-responsive, and this is because the imprinted cavity of RGO-MIPs has good adsorptivity.
Meanwhile, measure by continuous 5 times the circulation ratio that the current-responsive of RGO-MIPs sensor to 10.0 μMs of BPA investigates this modified electrode, its relative standard deviation is 4.2%.RGO-MIPs electrode is deposited after 2 weeks and is measured 10.0 μMs of BPA in 4 DEG C, and sensor remains 91.8% of primary current.Result shows that RGO-MIPs sensor has good circulation ratio and stability.
16, interference experiment
Table 3 is that some interfering ions and organism are to the maximum limitation of RGO-MIPs sensor determination 5.0 μMs of BPA.These interfering ions are all the materials that may exist in environmental water sample.Interference volume is allowed to be that this amount causes peak current size to change in ± 5% scope.As can be seen from Table 3, Cl
-, NO
3 -, 5O
4 2-, PO
4 3-, Br
-, CO
3 2-, Na
+, K
+within 500 times, interference is not produced to detection system; And Cu
2+and Co
2+within 100 times, interference is not produced to detection system; Mg
2+and Mn
2+then within 50 times, do not produce interference to detection system, benzene, toluene, oil of mirbane do not produce interference to detection system in 20 times.These results show, RGO-MIPs sensor has good selectivity, measure interference smaller.
Table 3 RGO-MIPs sensor DPV measures the permission interference volume of BPA;
Condition determination: BPA concentration: 5.0 μMs; Supporting electrolyte: 0.1M PBS (pH 8.0); Adsorption time: 5min.
17, the detection of BPA in actual sample
Take commercially available various material Plastic Bottle 5.0g, shred and add 25mL ethanol after cleaning, 50 DEG C of heating 3h, and soak 48h, evaporate to dryness ethanol, and adding 0.1M PBS (pH 8.0), to be settled to 10.0mL to be measured.Water sample is taken from laboratory from the beginning, without any need for process.RGO-MIPs sensor application measured in actual sample, replicate(determination) 5 times, we find the current-responsive of not BPA in actual each sample, therefore adopt standard addition method to obtain the rate of recovery, check the feasibility of present method with this.
The assay (each sample surveys 5 times) of BPA in table 4 plastics and from the beginning water sample;
Condition determination: supporting electrolyte: 0.1M PBS (pH 8.0), adsorption time: 5min.
Experimental result is as shown in table 4, and the rate of recovery that present method obtains is at 97.3%-105.7%, and relative standard deviation, at 3.8%-4.8%, illustrates that RGO-MIPs sensor can be used for the mensuration of BPA in plastics and water sample, and achieves gratifying result.
Claims (9)
1. the surface molecule print poly ion liquid of redox graphene, it is polymerized under initiator effect by redox graphene, function monomer, linking agent and template molecule formed and remove the matrix material of template molecule, it is characterized in that, described function monomer is 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate; Described linking agent is ethylene glycol dimethacrylate and Isosorbide-5-Nitrae-butane-3,3 '-bis--1-vinyl imidazole hexafluorophosphate; Described template molecule is dihydroxyphenyl propane.
2. the surface molecule print poly ion liquid of redox graphene as claimed in claim 1, it is characterized in that, described initiator is Diisopropyl azodicarboxylate.
3. the surface molecule print poly ion liquid of redox graphene as claimed in claim 1, it is characterized in that, described 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, ethylene glycol dimethacrylate, 1, the mol ratio of 4-butane-3,3 '-bis--1-vinyl imidazole hexafluorophosphate is 1 ~ 3: 4 ~ 6: 4 ~ 6.
4. the surface molecule print poly ion liquid of redox graphene as claimed in claim 1, it is characterized in that, described redox graphene is 0.1 ~ 0.2g: 0.1mmol with the molal ratio of template molecule.
5. the surface molecule print poly ion liquid of redox graphene as claimed in claim 1, it is characterized in that, the mol ratio of described function monomer and initiator is 1 ~ 3: 1.
6. the preparation method of the surface molecule print poly ion liquid of redox graphene as described in as arbitrary in claim 1-5, comprise the following steps: template molecule is added in solvent, add function monomer, linking agent, initiator and redox graphene again, mix and carry out polyreaction, react rear collection product, remove the template molecule in product, final drying obtains the surface molecule print poly ion liquid of described redox graphene.
7. preparation method as claimed in claim 6, it is characterized in that, the temperature of described polyreaction is 60 ~ 80 DEG C, and the time is 12 ~ 36h.
8. utilize as arbitrary in claim 1-5 as described in the electrochemical sensor made of the surface molecule print poly ion liquid of redox graphene.
9. electrochemical sensor is detecting the application in dihydroxyphenyl propane as claimed in claim 8.
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