CN103387564A - Phenols electrochemical sensor based on ionic liquid-graphene oxide sensitive membrane - Google Patents
Phenols electrochemical sensor based on ionic liquid-graphene oxide sensitive membrane Download PDFInfo
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Abstract
The invention belongs to the technical field of electroanalytical chemistry and specifically discloses a novel ionic liquid 4-hydroxy-1-methyl-1-(3-pyrrole propyl)-piperidine bromine salt and an electrochemical sensor based on an ionic liquid-graphene oxide composite nanometer material modified electrode. According to the invention, interface characteristics of the modified electrode are inspected by AC (alternating current) impedance spectroscopy and electrochemical behaviors of honokiol on the modified electrode are researched by voltammetry. As shown by the result, honokiol has a pair of reversible redox peaks on the modified electrode. Compared with a bare glassy carbon electrode, the modified electrode has the advantages that the peak current of the redox peaks of the honokiol on the modified electrode is greatly reinforced, a good linear relation is built between the peak current and honokiol of which the concentration is between 3.0*10<-8> and 1.0*10<-5> mol.L-1, and the detection limit is low. The electrochemical sensor prepared by the invention is successfully applied to the detection of honokiol in traditional Chinese medicine cortex magnoliae officinalis, so that the industrial prospect is good.
Description
Technical field
The present invention relates to the electroanalytical chemistry technical field, be specifically related to that a kind of new ionic liquid is synthetic, this ionic liquid-graphene oxide composite nano materials and the application in electrochemical sensor thereof, this electrochemical sensor is highly sensitive to the mensuration of Honokiol, selectivity good, credible result.
Background technology
Honokiol is the main effective constituent of Cortex Magnoliae Officinalis, formal name used at school 3,5-diallyl-2,4-dihydroxybiphenyl.It is of flaccid muscles that Honokiol has obvious, lasting central, the nervus centralis restraining effect, also have anti-inflammatory, antibiotic, resisting pathogenic microbes, antiulcer agent, anti-oxidant, anti-ageing, antitumor, reduce the pharmacological actions such as cholesterol, be usually used in treating acute enteritis, bacillary or amebic dysentery, chronic gastritis etc.
Owing to all containing the bark of official magnolia in many Chinese patent medicines, make bark of official magnolia Raw Material Demand amount increase, its certified products wild resource is closely exhausted, thereby the different surrogate of various degree appears in various places, causes on market magnolia medicament quite chaotic, difficult quality guarantee.To the evaluation of effective constituent in herbal medicine with quantize very urgent.Because Chinese medicine preparation often comprises the multi-flavor medicinal material, and the composition of every Herba indigoferae Pseudotinctoriae is all very complicated, and the activeconstituents in Identification chinese herbs medicine is an abnormal hard numerous and diverse job.Therefore we are badly in need of the detection method of a Honokiol that cover efficiency is high, selectivity is strong, and quality and the rational use of drug of guaranteeing magnolia medicament had important directive significance.
The method of measuring at present Honokiol mainly contains: high performance liquid chromatography (HPLC), liquid chromatography/mass spectrometry coupling method (LC/MS), capillary electrophoresis (CE), ultraviolet spectrophotometry etc.Yet these methods maybe need to use the instrument of complex and expensive, need the professional to operate, or complex operation, consuming time, and when detecting the low concentration Honokiol, there is no higher sensitivity and selectivity.So, find a kind of method that detects the easy sensitivity of Honokiol, be vital.Electrochemical method, because of its potential advantage, more and more causes the concern of researcher, such as fast response time, easy to operate, low-cost, save time, durable, portability, highly sensitive, selectivity good and can the real-time online detection etc.
Graphene oxide (GO) is the important growth of Graphene, and its structure is substantially identical with Graphene, just is connected with the functional groups such as carboxyl, hydroxyl, epoxy group(ing) on hexagonal annular plates carbon atom.The special construction of graphene oxide makes it have the performance of many uniquenesses, and is as large in good electroconductibility and good mechanical property, specific surface area, synthetic method is simple, raw materials used price is low, is easy to modify etc.Compare with Graphene, due to the graphene oxide surface,, with a large amount of hydrophilic functional groups, therefore have certain wettability and surfactivity, it can disperse preferably in water, and the compatible performance of polymkeric substance also increases.
Ionic liquid (Ionic Liguid, be called for short IL) has the peculiar property that the ordinary organic solvents such as fusing point is low, stability is high, dissolving power is strong, electroconductibility is high, steam forces down, the electromotive force window is wide and water all do not possess, and has been widely used in electrochemical field.In addition, ionic liquid also has good biocompatibility, is the perfect medium in some biomolecules electrocatalysis processes.
Stannic oxide/graphene nano particle and ionic liquid are combined together to form matrix material and are expected to further improve the performance of electrochemical sensor, be used for building the model electrochemical sensor of sensitive determination Honokiol, having potential using value, is the problem of a worth further investigated.
Summary of the invention
, in order to overcome above-mentioned the deficiencies in the prior art, the object of the invention is to:
The first, a kind of novel ion liquid is provided;
The second, the composite nano materials of a kind of carboxylated graphene oxide and above-mentioned ionic liquid is provided;
The 3rd, a kind of electrochemical sensor based on above-mentioned composite nano materials modified glassy carbon electrode is provided.
The 4th, the application of above-mentioned electrochemical sensor in measuring Honokiol is provided.
In order to realize above-mentioned all goals of the invention, the present invention has taked following technical measures:
At first, a kind of ionic liquid, its synthesis step is as follows:
4-hydroxy-n-methyl piperidine is dissolved in toluene; add again the 1-(3-bromopropyl) pyrroles; 4-hydroxy-n-methyl piperidine and 1-(3-bromopropyl) pyrroles's mol ratio is 1:1.1; 80 ℃ of oil baths; under nitrogen protection, condensing reflux reaction 15h, obtain yellow oil product 4-hydroxyl-1-methyl isophthalic acid-(3-pyrroles's propyl group)-piperidines bromine salt ion liquid.
Secondly, a kind of carboxylated graphene oxide-ionic liquid composite nano materials, its preparation methods steps is as follows:
(1) with graphene oxide (GO), solid sodium hydroxide (NaOH) and Mono Chloro Acetic Acid (ClCH
2COOH) water-soluble, graphene oxide, solid sodium hydroxide, Mono Chloro Acetic Acid three's mass ratio is (5-20): (400-600): (400-600), ultrasonic even, stirring reaction 2 hours, be converted into carboxyl with the hydroxyl on graphene oxide and epoxy group(ing).Centrifugation, solid wash with water to neutrality, and 60 ℃ of lower vacuum-dryings, namely obtain carboxylated graphene oxide, is denoted as GO-COOH.The carboxylated graphene oxide of gained is joined 0.01molL
-1In NaOH solution, solid-to-liquid ratio is (0.8-1.2) mg:1mL, stirs 2h, and centrifugal, solid washes with water to neutrality, and 60 ℃ of lower vacuum-dryings namely obtain the carboxylated graphene oxide of the form of alkalizing, and are denoted as GO-COONa.
(2) gained is alkalized carboxylated graphene oxide (GO-COONa) and 4-hydroxyl of the present invention-1-methyl isophthalic acid-(3-pyrroles's propyl group)-piperidines bromine salt ion liquid of form is added in water, GO-COONa and ionic liquid mass ratio are 9:(150-250), stirring reaction 1h under 40 ℃ of conditions, centrifugation, solid washes to remove excessive ionic liquid and the Sodium Bromide of generation with water, then, 60 ℃ of lower vacuum-dryings, namely obtain carboxylated graphene oxide-ionic liquid composite nano materials (GO-COO-IL).
Further, a kind of electrochemical sensor based on above-mentioned composite nano materials modified glassy carbon electrode, its preparation method comprises the following steps:
(1) pretreatment of glassy carbon electrode: first with aluminum oxide polishing powder, glass-carbon electrode is polished, after water rinses, then with nitric acid, second alcohol and water, glass-carbon electrode is carried out ultrasonic cleaning successively.
(2) carboxylated graphene oxide of the present invention-ionic liquid composite nano materials is added to the water, ultra-sonic dispersion is even, obtains concentration and is (0.1-1.0) mgmL
-1Carboxylated graphene oxide-ionic liquid dispersion liquid.
(3) the above-mentioned carboxylated graphene oxide of 1-16 microlitre-ionic liquid dispersant liquid drop is coated onto the pretreated glass-carbon electrode surface of step (1), evaporating solvent, obtain carboxylated graphene oxide-Ionic Liquid Modified electrode.
Further again, above-mentioned modified electrode has been carried out conventional electrochemical property test, result is good; Then, use it for Honokiol is measured, sensitivity, accuracy, precision and selectivity are all good.
Compared with prior art, advantage of the present invention and beneficial effect are:
(1) sensitive material of carboxylated graphene oxide-ionic liquid composite nano materials as electrochemical sensor used in the present invention, this material has bigger serface, good electroconductibility and accumulation ability, can significantly improve the electrochemical response signal of Honokiol, realize highly sensitive detection, detecting of Honokiol is limited to 4.22 * 10
-9MolL
-1(S/N=3).
(2) do not contain poisonous, contaminate environment, harmful to person material preparing in material of electrochemical sensor of the present invention, healthy without impact on the operator, environmentally friendly.
(3) operating process of electrochemical sensor mensuration Honokiol of the present invention is easy, does not need special experiment condition, and instrument requires simple.
Description of drawings
Fig. 1 is the synthetic route chart of ionic liquid 4-hydroxyl-1-methyl isophthalic acid-(3-pyrroles's propyl group)-piperidines bromine salt.
Fig. 2 is the carboxylated graphene oxide (a) of embodiment 2 and the transmission electron microscope picture (TEM) of carboxylated graphene oxide-ionic liquid composite nano materials (b).
Fig. 3 is the infrared spectra stacking diagram of carboxylated graphene oxide (a), ionic liquid (b) and the carboxylated graphene oxide-ionic liquid composite nano materials (c) of embodiment 2.
Fig. 4 is the structural representation of the carboxylated graphene oxide-ionic liquid nano material complex film modified electrode of embodiment 3.
Fig. 5 is naked glass-carbon electrode (a), the carboxylated graphene oxide modified electrode (b) of embodiment 4, the alternating-current impedance figure of the complex film modified electrode of carboxylated graphene oxide-ionic liquid (c).
Fig. 6 is that (concentration is 1.0 * 10 for the Honokiol of embodiment 5
-5MolL
-1, the pH5.5) cyclic voltammogram (CV) on naked glass-carbon electrode (a), carboxylated graphene oxide modified electrode (b), the complex film modified electrode of carboxylated graphene oxide-ionic liquid (c).
Fig. 7 is the differentiated pulse volt-ampere curve (DPV) of different concns Honokiol on the complex film modified electrode of carboxylated graphene oxide-ionic liquid of embodiment 5.
Embodiment
, below in conjunction with accompanying drawing, by specific embodiment, each technical scheme of the present invention is described in further detail:
In following examples, in embodiment 1, water is first water, and in all the other embodiment, water is redistilled water.
A kind of novel ion liquid 4-hydroxyl-1-methyl isophthalic acid-(3-pyrroles's propyl group)-piperidines bromine salt, its synthetic method step is as follows:
Take 4-hydroxy-n-methyl piperidine (0.4549g; 3mmol) in the 50mL three-necked flask; add 15mL toluene and make solvent; with the 1-(3-bromopropyl) pyrroles (0.5640g; 3.3mmol) be added drop-wise in three-necked flask, after adding, be placed in 80 ℃ of oil baths; stirring reaction 15h under nitrogen protection, generate yellow oily an insoluble liq.Be cooled to room temperature, separation of methylbenzene layer, the yellow oily liquid that is dissolved in water, extracted with diethyl ether.The water layer solvent evaporated obtains yellow oily liquid, obtains product 4-hydroxyl of the present invention-1-methyl isophthalic acid-(3-pyrroles's propyl group)-piperidines bromine salt ion liquid 0.8510g (productive rate 93.9%),
1H NMR(D
2O) δ: 6.76(d, 2H), 6.11(d, 2H), 3.98(t, 2H) and, 3.89(d, 1H) 3.38(t, 2H), 3.20(d, 2H) and, 3.12(d, 2H), 2.92(s, 3H) and, 2.16(t, 2H), 1.96(d, 2H) and, 1.74(d, 2H); M/z=222.92.
Synthetic route as shown in Figure 1, adopts the synthetic 4-hydroxyl of single stage method-1-methyl isophthalic acid-(3-pyrroles's propyl group)-piperidines bromine salt ion liquid, and method is simple, and post-processing operation is easy, and productive rate is high.
A kind of carboxylated graphene oxide-ionic liquid composite nano materials, its preparation methods steps is as follows:
(1) with 10mg graphene oxide (GO), 0.5g sodium hydrate solid (NaOH) and 0.5g Mono Chloro Acetic Acid (ClCH
2COOH) be dissolved in 10mL water, ultrasonic even, stirring reaction is 2 hours on magnetic stirring apparatus.Centrifugation, solid wash with water to neutrality, and 60 ℃ of lower vacuum-dryings namely obtain carboxylated graphene oxide 9.5mg, are denoted as GO-COOH.The carboxylated graphene oxide of gained is all joined 10mL0.01molL
-1In NaOH solution, stirring reaction 2h on magnetic stirring apparatus, centrifugation, solid washes with water to neutrality, and 60 ℃ of lower vacuum-dryings namely obtain the carboxylated graphene oxide 9.0mg of the form of alkalizing, and are denoted as GO-COONa.
Graphene oxide used does not have particular requirement;
Concrete, the graphene oxide in the present embodiment is this laboratory self-control, the preparation method is as follows:
Under ice bath, the vitriol oil of 17mL98wt% is added drop-wise to 0.45g KNO
3In the mixture of 0.5g Graphite Powder 99, continue to stir, add 2.25g potassium permanganate in 1h, after stirring reaction 2h, reaction flask is moved to room temperature, stirred 5 days, obtain the black thick liquid; Under agitation condition, to the sulfuric acid that adds 50mL5wt% in this black thick liquid, stir 2h, the hydrogen peroxide that adds 15g30wt%, continue again to stir 2h, continuation is under agitation condition, to the mixing solutions (in mixing solutions, sulfuric acid concentration is 3wt%, and concentration of hydrogen peroxide is 0.5wt%) that adds 50mL sulfuric acid and hydrogen peroxide in the gained mixture, standing sedimentation 2 days, discard upper strata liquid, obtain the brownish black soup compound, be washed with water to neutrality, the ultrasonic 30min that peels off, the yellow solution that must clarify, be drying to obtain graphene oxide (GO).
(2) the carboxylated graphene oxide (GO-COONa) of gained 9.0mg alkalization form and the ionic liquid of 0.2g embodiment 1 preparation are added in 10mL water, stirring reaction 1h under 40 ℃ of conditions, centrifugation, the solid water cleans, to remove excessive ionic liquid and the Sodium Bromide of generation (NaBr), 60 ℃ of lower vacuum-dryings, namely obtain carboxylated graphene oxide-ionic liquid composite nano materials (GO-COO-IL) 8.0mg.
Fig. 2 (a) and (b) be respectively the carboxylated graphene oxide of the present embodiment preparation and the transmission electron microscope picture of carboxylated graphene oxide-ionic liquid composite nano materials.As can be seen from the figure, carboxylated graphene oxide (a) and carboxylated graphene oxide-ionic liquid composite nano materials (b) is typical lamella nanostructure, and its diameter is about the hundreds of nanometer, and thickness is about several nanometers.Relatively both topology discoverys, carboxylated graphene oxide surface is through transparent Ionic Liquid Modified, do not change the geometry of carboxylated graphene oxide, can keep the characteristics such as its bigger serface, high electronic conduction, be conducive to build the electrochemical sensor of excellent property.
In Fig. 3, curve a, b, c are respectively the infrared spectrogram of the ionic liquid of carboxylated graphene oxide, embodiment 1 preparation of the present embodiment preparation and the carboxylated graphene oxide of the present embodiment preparation-ionic liquid composite nano materials.By curve a as can be known, there is O-H stretching vibration (ν in graphene oxide
O-H, 3411cm
-1); C=O stretching vibration (ν
C=O, 1735cm
-1), C=C stretching vibration (ν
C=C, 1627cm
-1) and C-O stretching vibration (ν
C-O, 1224cm
-1).Curve b is the infrared spectra curve of 4-hydroxyl-1-methyl isophthalic acid-(3-pyrroles's propyl group)-piperidines bromine salt ion liquid, the O-H stretching vibration (ν in piperidine alcohols in ionic liquid as can be observed from Figure
O-H, 3354cm
-1);-CH
3Antisymmetric stretching vibration (2946cm
-1); Skeleton stretching vibration (the 1630cm of pyrroles and piperidines heterocycle
-1, 1464cm
-1); Stretching vibration (the ν of C-N key on pyrroles and piperidines group
C-N, 1379cm
-1); Stretching vibration (the ν of C-O key on the piperidine alcohols group
C-O, 1280cm
-1); The out-of-plane bending of the pyrrole ring (1090cm that shakes
-1);-CH
2Rocking vibration (ν
C-H, 742cm
-1); Stretching vibration (the ν of C-H on pyrrole ring
C-H, 618cm
-1).Curve c is that carboxylated graphene oxide is combined the infrared spectrogram of later composite nano materials (GO-COO-IL) with ionic liquid, can find out 3399cm from curve c
-1O-H stretching vibration peak overlapping on place's graphene oxide and ionic liquid, and skew to some extent, the charateristic avsorption band of GO and IL all exists, and the Partial Feature absorption peak has slight movement, should be after both combinations, influence each other and cause, illustrate that success of ionic liquid combines with graphene oxide.
As shown in Figure 4, a kind of carboxylated graphene oxide-ionic liquid composite nanometer material modified electrode, comprise insulation layer 1, glass carbon substrate 3, the contact conductor 4 that is electrically connected to glass carbon substrate 3, glass carbon substrate 3 surfaces scribble the nano combined nano material film 2 of carboxylated graphene oxide-ionic liquid.The preparation method of above-mentioned carboxylated graphene oxide-Ionic Liquid Modified electrode comprises the following steps successively:
(1) pretreatment of glassy carbon electrode: first with the aluminum oxide polishing powder that particle diameter is 0.3 micron and 0.05 micron, glass-carbon electrode (3 millimeters of diameters) is polished successively, after water rinses, use successively salpeter solution (65wt% nitric acid and water equal-volume mixing solutions), ethanolic soln (95wt% ethanol and water equal-volume mixing solutions) and water to each ultrasonic cleaning of glass-carbon electrode 1 minute, cleaning temperature is 20～30 ℃ again.
(2) the carboxylated graphene oxide of embodiment 2 preparations-ionic liquid composite nano materials 2.0mg is joined in 4.0mL water, be uniformly dispersed in ultrasonic 25 minutes, obtaining concentration is 0.5mgmL
-1Carboxylated graphene oxide-ionic liquid dispersion liquid.
(3) the carboxylated graphene oxide that 8 microlitre steps (2) is obtained-ionic liquid dispersant liquid drop is coated onto the pretreated glass-carbon electrode surface of step (1), and evaporating solvent, obtain carboxylated graphene oxide-Ionic Liquid Modified electrode.
About step (2), drip the concentration of the carboxylated graphene oxide be coated in the glass-carbon electrode surface-ionic liquid dispersion liquid, be the response current relation curve by dispersion liquid concentration and Honokiol, definite optimum concn.Configure respectively 0.1,0.3,0.5,0.8,1.0mgmL
-1Carboxylated graphene oxide-ionic liquid dispersant liquid drop is applied to pretreated glass-carbon electrode surface, drips the amount of being coated with and is 8 microlitres, to 1.0 * 10
-5MolL
-1Honokiol carry out differentiated pulse volt-ampere scanning, find when dispersion liquid concentration 0.1 to 0.5mgL
-1Between, the oxidation peak peak current increases gradually, to concentration 0.5mgmL
-1The time reach maximum, after this, increase with dispersion liquid concentration, the oxidation peak peak current descends on the contrary, may be because concentration is too large, causes electrode surface film too thick, hinder on the contrary the electronics transmission, therefore, follow-up detection to Honokiol, drip the carboxylated graphene oxide be applied to the glass carbon surface-ionic liquid dispersion liquid concentration and be 0.5mgmL
-1
About step (3), drip the amount of being coated with of dripping of the carboxylated graphene oxide be coated in the glass-carbon electrode surface-ionic liquid dispersion liquid, be to be coated with the volume of dispersion liquid and the response current relation curve of Honokiol by dripping, definite the best is dripped the amount of being coated with.Drip respectively and be coated with Isosorbide-5-Nitrae, 6,8,10,12,14,16 microlitre 0.5mgmL
-1Carboxylated graphene oxide-ionic liquid dispersion liquid in pretreated glass-carbon electrode surface, to 1.0 * 10
-5MolL
-1Honokiol carry out differentiated pulse volt-ampere scanning, find when the dispersant liquid drop amount of being coated with is between 1 to 8 microlitre, the oxidation peak peak current increases gradually, when being 8 microlitre, volume reaches maximum, after this, increase with the dispersant liquid drop amount of being coated with, the oxidation peak peak current descends on the contrary, may be that to be coated with volume too large because drip, cause electrode surface film too thick, hinder on the contrary the electronics transmission, therefore, follow-up detection to Honokiol, drip the carboxylated graphene oxide be applied to the glass carbon surface-ionic liquid dispersion liquid volume and be 8 microlitres.
As shown in Figure 5, the carboxylated graphene oxide that embodiment 3 is made-Ionic Liquid Modified electrode carries out electrochemical AC impedance spectrum (EIS) and characterizes, and EIS is one of effective tool of exploring the chemically modified electrode interfacial property.Its spectrogram generally is divided into HFS and low frequency part, and wherein HFS is the kinetic control zone, and low frequency part is the diffusion control zone.With 5.0mmolL
-1K
3[Fe (CN)
6]/K
4[Fe (CN)
6] (1:1) be probe, at 0.1molL
-1PBS (pH=7.0) and 0.1molL
-1Carry out alternating-current impedance in KCl solution and characterize, and calculated the charge-transfer resistance of electrode interface with Randles circuit fitting circuit, in Randles circuit fitting circuit, interfacial charge is transmitted resistance (Rct), diffusion resistance (Z
W) in parallel with interface capacitance (Cdl), the diameter of semicircle transmits electricity (Rct) corresponding to interfacial charge.The Nyquist curve as shown in Figure 5, can find out that the ac impedance spectroscopy of bare electrode GCE (a) is larger at the semicircle of HFS, through its Rct of analog calculation, is 1158.0 Ω; When carboxylated stannic oxide/graphene nano material is modified to electrode surface, because graphene oxide has promoter action to the transmission of electronics, half circular diameter of its HFS reduces (b), and impedance diminishes, and interfacial charge is transmitted resistance and reduced to 683.5 Ω; Figure (c) is the nanometer-material-modified alternating-current impedance spectrogram to electrode interface of carboxylated graphene oxide-ionic liquid, because having of ionic liquid helps the electronics transmission, it has promoted the electronics transmission at interface equally, and interfacial charge is transmitted resistance and is reduced to once again 233.7 Ω.By the comparison of three resistance values, as can be known the present invention preparation carboxylated graphene oxide-ionic liquid nano material electroconductibility is fine.
Embodiment 5
As shown in Figure 6, take the prepared modified electrode of embodiment 3 in-0.2～0.8V potential range to concentration as 1.0 * 10
-5MolL
-1Honokiol carry out cyclic voltammetry scan (CV), sweep velocity is 0.1Vs
-1, supporting electrolyte is 0.1molL
-1Phosphate buffer soln (pH5.5), accumulating potential are 0.0V, and enrichment time is 240s, the results are shown in Figure 6 curve c, and (curve a), cyclic voltammetric behavior on carboxylated graphene oxide modified electrode (curve b) compares with naked glass-carbon electrode.As seen from the figure, when from-when 0.20V carries out Anodization scan to 0.8V, can observe an oxidation peak on three kinds of electrodes, to the process of negative pole scanning, also can be observed the reduction peak corresponding with it, the mensuration process of this explanation Honokiol is a reversible process.The redox peak to peak current of curve c is maximum, shows that carboxylated graphene oxide-ionic liquid composite nano materials has significant enhancement effect and accumulation ability to Honokiol, can obviously improve the detection sensitivity of Honokiol.
As shown in Figure 7, with the prepared modified electrode of embodiment 3, the Honokiol of different concns is carried out differential pulse voltammetry scanning (DPV) at 0.0～0.8V, pulse width 0.05s, amplitude 0.05V, sweep velocity is 0.05Vs
-1Built-in figure is the linear relationship curve of concentration and electric current, 3.0 * 10
-8～1.0 * 10
-5MolL
-1In scope, the oxidation peak current of Honokiol and its concentration have good linear relationship, and equation of linear regression is I (μ A)=4.2955C (molL
-1)+9.0 * 10
-7(R
2=0.9985), detect and be limited to 4.22 * 10
-9MolL
-1(S/N=3).This shows that the electrochemical sensor based on carboxylated graphene oxide-ionic liquid composite nano materials film can be used for the Sensitive Detection of Honokiol.
In embodiment 5, measure the pH of the supporting electrolyte of Honokiol, be by different pH, the response current of Honokiol to be affected relation curve to obtain.Investigate pH and be respectively 4.0,4.5,5.0,5.5,6.0,6.5,7.0 phosphate buffer soln is to 1.0 * 10
-5MolL
-1The impact of the differentiated pulse volt-ampere peak current of Honokiol.Research shows, variation along with the pH value, the oxidation peak peak current size of Honokiol can change thereupon, when pH increased to 5.5 by 4.0, the oxidation peak peak current of Honokiol increased gradually, as pH greater than 5.5 the time, the oxidation peak peak current of Honokiol reduces gradually, show that best pH is 5.5, therefore, best pH5.5 is all selected in the detection to Honokiol in the present invention.
In embodiment 5, Honokiol selected accumulating potential and enrichment time on modified electrode, be to determine by the differentiated pulse volt-ampere response current size of different accumulating potentials and enrichment time and Honokiol.Different accumulating potentials-0.2 ,-0.1,0.0,0.1,0.2V, when accumulating potential from-when 0.2V changes to 0V, 1.0 * 10
-5MolL
-1The oxidation peak peak current of Honokiol on modified electrode increases gradually.After accumulating potential surpassed 0V, the oxidation peak peak current descended on the contrary.Therefore selecting best accumulating potential is 0V.Different enrichment time 60,120,180,240,300,360,400s, from 60 to 240s the time, the oxidation peak peak current significantly increases along with the increase of time when enrichment time.After enrichment time surpassed 240s, the oxidation peak peak current, along with the increase of time, slowly increased, and keeps finally a platform, illustrates that the absorption of Honokiol on the modified electrode surface has been tending towards saturated, therefore select best enrichment time, is 240s.
Embodiment 6
Measure the selectivity of embodiment 3 prepared modified electrodes, interference free performance is one of the important indicator of weighing the practicality of electrochemical sensor.The Cd of 100 times is found in experiment
2+, Pb
2+, Cu
2+, Fe
3+, Mg
2+, proline(Pro), Methionin, L-glutamic acid, Histidine, halfcystine, p-NP, Resorcinol, ethyl naphthol, xitix, uric acid, VITMAIN B1 etc. do not produce interference to the electrochemical oxidation of Honokiol, illustrate that the electrochemical sensor selectivity of the present invention's preparation is better.
Actual sample is measured, and Cortex Magnoliae Officinalis is bought in local hospital.Bark of official magnolia sample is being pulverized after dry 4h under 60 ℃.The extraction process of Honokiol carries out according to following steps: the powder that weighing 2.0g is ground, add 100.0mL methyl alcohol, and 60 ℃ of standing 3h, be cooled to room temperature, and ultrasonic 30min filters, and collects filtrate.Get 50 microlitre filtrates, add 0.1molL
-1PBS buffered soln (pH5.5) is diluted to 10mL solution, at optimum experimental condition (accumulating potential 0.0V, enrichment time 240s, pH5.5, sweep velocity 0.1Vs
-1) under, the content of Honokiol in actual sample is measured, replicate(determination) three times, its concentration is obtained according to calibration curve method, the results are shown in Table 1.Add a certain amount of Honokiol standard substance to carry out recovery testu in sample, replicate(determination) three times, average recovery rate is 99.5%, the results are shown in Table 2, illustrates that the measuring method accuracy of setting up is good.Utilize the classical measuring method high performance liquid chromatography of measuring Honokiol to test the mark-on sample, and with the inventive method measurement result, compare, relative deviation is less, the results are shown in Table 3, shows that the present invention measures the Honokiol method reliable.
The detection of Honokiol in table 1 actual sample
In table 2 actual sample, the rate of recovery of Honokiol detects
Two kinds of methods of table 3 are measured in the mark-on sample and the comparative analysis as a result of Determination of Magnolol
Claims (5)
1. ionic liquid 4-hydroxyl-1-methyl isophthalic acid-(3-pyrroles's propyl group)-piperidines bromine salt; its preparation method is as follows: 4-hydroxy-n-methyl piperidine is dissolved in toluene; add again the 1-(3-bromopropyl) pyrroles; 4-hydroxy-n-methyl piperidine and 1-(3-bromopropyl) pyrroles's mol ratio is 1:1.1; 80 ℃ of oil baths; under nitrogen protection, condensing reflux reaction 15h, obtain.
2. carboxylated graphene oxide-ionic liquid composite nano materials, its preparation methods steps is as follows:
(1) graphene oxide, solid sodium hydroxide and Mono Chloro Acetic Acid is water-soluble, graphene oxide, solid sodium hydroxide, Mono Chloro Acetic Acid three's mass ratio is (5-20): (400-600): (400-600), ultrasonic even, stirring reaction 2 hours, centrifugation, solid wash with water to neutrality, 60 ℃ of lower vacuum-dryings, namely obtain carboxylated graphene oxide, the carboxylated graphene oxide of gained is joined 0.01molL
-1In NaOH solution, solid-to-liquid ratio is (0.8-1.2) mg:1mL, stirs 2h, and centrifugal, solid washes with water to neutrality, and 60 ℃ of lower vacuum-dryings namely obtain the carboxylated graphene oxide of the form of alkalizing;
(2) will alkalize the carboxylated graphene oxide of form and ionic liquid 4-hydroxyl claimed in claim 1-1-methyl isophthalic acid-(3-pyrroles's propyl group)-piperidines bromine salt with 9:(150-250) mass ratio be added in water, at 40 ℃ of lower stirring reaction 1h, centrifugation, solid washes with water, then, 60 ℃ of lower vacuum-dryings, obtain.
3. an electrochemical sensor, comprise glass-carbon electrode, it is characterized in that: the glass-carbon electrode surface scribbles carboxylated graphene oxide claimed in claim 2-ionic liquid composite nano materials.
4. electrochemical sensor according to claim 3, is characterized in that, the modification of described glass-carbon electrode is as follows:
(1) pretreatment of glassy carbon electrode: first with aluminum oxide polishing powder, glass-carbon electrode is polished, after water rinses, then with nitric acid, second alcohol and water, glass-carbon electrode is carried out ultrasonic cleaning successively.
(2) carboxylated graphene oxide claimed in claim 2-ionic liquid composite nano materials is added to the water, ultra-sonic dispersion is even, obtains concentration and is (0.1-1.0) mgmL
-1Carboxylated graphene oxide-ionic liquid dispersion liquid.
(3) the carboxylated graphene oxide of 1-16 microlitre step (2)-ionic liquid dispersant liquid drop is coated onto the pretreated glass-carbon electrode surface of step (1), evaporating solvent, obtain carboxylated graphene oxide-Ionic Liquid Modified electrode.
5. the application of the described electrochemical sensor of claim 3 or 4 in measuring Honokiol.
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