CN102305821A - Electrochemical sensor electrode with integrated functions of enriching and detecting 1-hydroxypyrene, and preparation method of electrochemical sensor electrode - Google Patents
Electrochemical sensor electrode with integrated functions of enriching and detecting 1-hydroxypyrene, and preparation method of electrochemical sensor electrode Download PDFInfo
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Abstract
The invention relates to an electrochemical sensor electrode with integrated functions of enriching and detecting 1-hydroxypyrene, and a preparation method of the electrochemical sensor electrode. Cage polyhedral oligomeric silsesquioxane is used as a supporting skeleton of a graphene oxide three-dimensional spiral structure, and a graphene/polyhedral oligomeric silsesquioxane three-dimensional composite material is controllably synthesized on the electrode by an electrostatic layer-by-layer self-assembly technology, so that the graphene agglomeration is avoided and the specific surface area of the composite material is enlarged; 1-hydroxypyrene is selectively enriched under the pi-pi conjugation gathering action, and the 1-hydroxypyrene is determined in situ by an electrochemical sensing technology. The electrode integrates the functions of enriching and detecting the 1-hydroxypyrene and has the advantages of high stability and sensitivity, low cost and the like and is convenient to use.
Description
Technical field:
The invention belongs to sensor field, relate to a kind of enrichment detection 1-hydroxyl pyrene that is used in the electrochemical sensor electrodes and the preparation method of one.
Background technology:
Palycyclic aromatic (Polycyclic Aromatic Hydrocarbons; PAHs) be the persistence organic pollutant of a quasi-representative; Be distributed widely in atmosphere, water, the soil; Be important environment and food contaminant; Long-time exposure can be brought out cancers such as lung cancer, cutaneum carcinoma, has been classified as the pollutant of preferential control by various countries.1-hydroxyl pyrene is a kind of ubiquitous PAHs metabolic product; A large amount of experiments show: the concentration of 1-hydroxyl pyrene (1-OHP) contacts with human body has tangible dose-effect relationship between the PAHs dosage, so the biomarker that 1-OHP exposes as PAHs comes the comprehensive evaluation human body that multipath interior exposure situation of PAHs and degree of risk are accepted extensively by international research.
Yet current China mainly concentrates on the assay of PAHs in the environment to the research of PAHs, and very few to human body PAHs exposure level evaluation study, the detection technique of 1-OHP is a main restricting factor.From document analysis, there are following two aspect problems in the detection technique of 1-OHP: the one, and shortage has the selective enrichment material to 1-OHP; It two is detection methods of 1-OHP.
Aspect the selective enrichment material, the little column solid phase extraction of C18 is adopted in most at present researchs, though this method can improve detection level to a certain extent, lacks selectivity.In order to improve selectivity, the antibody through preparation OH-PAHs utilizes the immune affinity column beneficiation technologies, can improve adsorptive selectivity to a certain extent, but false positive and higher cost issues make Antibody Preparation fail practical application.
In the 1-OHP context of detection, mainly contain high performance liquid chromatography-fluorescence detector method, synchronous fluorimetry, liquid matter/gas chromatography mass spectrometry method, chemiluminescence enzyme immunoassay and enzyme-linked immunosorbent assay at present.Though high performance liquid chromatography-fluorescence detector method, synchronous fluorimetry, liquid matter/gas chromatography mass spectrometry method are highly sensitive, sample pre-treatments is complicated, length consuming time.The more important thing is these instrument expensive, the threshold that analytical approach requires is too high, makes these methods be difficult to popularize.And chemiluminescence enzyme immunoassay and enzyme-linked immunosorbent assay be because the instability of enzyme itself, and complex sample is disturbed, and accuracy in detection is not high.
Summary of the invention
One of the object of the invention is the deficiency to prior art, provides a kind of and is used for the electrochemical sensor electrodes of 1-hydroxyl pyrene selective enrichment and in-site detecting based on graphene oxide-six complex film modified electrodes of silsesquioxane of cage shape.
Another object of the present invention is to provide a kind of and is used for the preparation method that enrichment detects the electrochemical sensor electrodes of 1-hydroxyl pyrene based on graphene oxide-six complex film modified electrodes of silsesquioxane of cage shape.
These purposes of the present invention will further embody and set forth through following detailed description and explanation.
Graphene is a kind of novel two-dimentional carbon nanomaterial, is the basic building module of other all dimension graphite materials, is the another nanoscale functional material of carbon family after carbon nano-tube is found.It is reported that Graphene is the outstanding material of present known conductive performance; Its excellent conducting performance and macroscopical tunnel effect can make it become effective electron mediator between fixed compound and the electrode; Can improve the sensitivity and the response current of sensor; Shorten the response time; Improve detection limit, so Graphene has great application prospect in sensor field.In addition, Graphene contains a large amount of π systems, therefore can combine well through pi-pi accumulation effect and other π system (like 1-hydroxyl pyrene), thereby reach efficient, selective enrichment adsorption effect.In addition, Graphene also has the specific surface area of super large, therefore has very big adsorption capacity.Graphene oxide is the important growth of Graphene, except the character consistent with Graphene, because its surface is connected with functional groups such as a large amount of hydroxyls, carboxyl, epoxy radicals, thereby has better dispersiveness, water wettability and compatibility.In addition, the preparation cost of Graphene class material is lower, and this provides good basis for its practical application.
The present invention mainly prepares the enrichment material of 1-hydroxyl pyrene on electrode through controlled composite methods, form graphene oxide-six complex film modified electrodes of silsesquioxane of cage shape, adopts the electrochemical sensing technology that 1-hydroxyl pyrene is carried out in-site detecting.
Technical scheme
The purpose of invention realizes through following technical proposals:
1, the preparation method of graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane, preparation process is following:
(1) graphite oxide is added to ultrasonic dispersion in water or the alkaline solution, forms with the homodisperse graphene oxide solution of monolithic layer, subsequent use;
(2) select suitable polycation electrolyte to be mixed with aqueous solution, strut body electrode is carried out pre-service, be immersed in then in the polycation electrolyte, make the strut body electrode surface lotus that becomes positively charged;
(3) will after above-mentioned steps is handled, the become positively charged strut body electrode of lotus is alternately soaked graphene oxide solution and cage shape hexahedron silsesquioxane solution (1-100 time) repeatedly, can obtain graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane.
2, the graphene oxide-complex film modified electrode original position electrochemical sensing of cage shape hexahedron silsesquioxane 1-hydroxyl pyrene, its step is following:
(1) graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane for preparing is soaked in the solution that contains 1-hydroxyl pyrene, reaches the effect of enrichment 1-hydroxyl pyrene through the pi-pi accumulation effect.
(2) be working electrode with the graphene oxide behind the enrichment 1-hydroxyl pyrene-complex film modified electrode of cage shape hexahedron silsesquioxane; With Ag/AgCl electrode or mercurous chloride electrode is contrast electrode; Platinum electrode utilizes electrochemical workstation that 1-hydroxyl pyrene is measured for electrode is constructed three-electrode system.
Wherein said graphene oxide solution concentration is 0.01-5mg/mL, and cage shape hexahedron silsesquioxane solution concentration is 0.01-5mg/mL.
Wherein said polycation electrolyte is PAH salt, gather the diallyl alkyl dimethyl ammonium chloride, gather the dipropenyl dimethyl ammonium chloride, a kind of or wherein any two kinds potpourri in polyvinyl alcohol (PVA), collagen, shitosan, poly-D-lysine or the polyvinyl inferior amine salt hydrochlorate.Polycation electrolyte is mixed with aqueous solution, and concentration is 0.1-2wt%, and strut body electrode soak time in its aqueous solution is 1-30min.
The preferred multiplicity that wherein said strut body electrode is alternately soaked graphene oxide solution and cage shape hexahedron silsesquioxane solution is 5-40 time, and the soak time in graphene oxide solution and cage shape hexahedron silsesquioxane solution is respectively 2-60min.
It is 5-60min that wherein said graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane is soaked in the time of adsorbing in the solution that contains 1-hydroxyl pyrene.
Wherein said strut body electrode is glass-carbon electrode, graphite electrode, pencil-lead electrode or carbon paste electrode.
The present invention compared with prior art, its remarkable advantage:
(1) the super large specific surface area that makes full use of with the graphene oxide of monolithic layer stable existence improves electro catalytic activity and adsorptive power to 1-hydroxyl pyrene;
(2) utilize the graphene oxide surface to attend oxy radicals such as institute's hydroxyl, carboxyl and form binding site; Organically combine through electrostatic adsorption and positively charged cage shape hexahedron silsesquioxane support frame; Form graphene oxide-cage shape hexahedron silsesquioxane composite membrane; Make each item performance of combination electrode material improve greatly, especially improved the sensitivity of sensor;
(3) the present invention is based on the static layer-by-layer; Its film forming driving force derives from the electrostatic adsorption between the positive and negative charge; Mutually combine with ionic link; Acting force is stronger; Can control thickness through number of times and filmogen concentration that Control Circulation is alternately soaked film forming, really reach from the molecular level control membrane material and membrane structure;
(4) utilize the contained π system in graphene oxide surface, can be through the pi-pi accumulation effect with other π system materials, firmly adsorb like 1-hydroxyl pyrene and to reach inrichment, thereby effectively reduce detectability, improved sensitivity and stability thereof.
(5) composite membrane of the present invention's preparation, in conjunction with the characteristic of graphene oxide, cage shape hexahedron silsesquioxane and nano material, and required cost is lower.
(6) modified electrode of the present invention has excellent electrocatalysis characteristic.Behind enrichment 1-hydroxyl pyrene, very high to the peak current response of 1-hydroxyl pyrene, be 125 times that naked glass-carbon electrode peak current responds, so high peak current response can't see on other modified electrodes.
(7) testing process is simple, and is highly sensitive.
Description of drawings
Fig. 1 is the uv-spectrogram of the resultant graphene oxide of different cycle indexes-cage shape hexahedron silsesquioxane composite membrane.
Fig. 2 is the differential pulse voltammetry curve map of the prepared graphene oxide-complex film modified electrode pair variable concentrations of cage shape hexahedron silsesquioxane 1-hydroxyl pyrene; Wherein horizontal ordinate is a galvanochemistry scanning current potential (E/V vs Ag/AgCl), and ordinate is the response current (unit is μ A) under the corresponding current potential.
Fig. 3 is the response curve of the prepared graphene oxide-complex film modified electrode pair variable concentrations of cage shape hexahedron silsesquioxane 1-hydroxyl pyrene, and wherein transverse axis is represented the concentration (unit is μ M) of 1-hydroxyl pyrene, vertical axis represents current response intensity (unit is μ A)
Embodiment 1:
1, graphene oxide is synthetic:
Take by weighing 150mg multi-walled carbon nano-tubes (MWCNTs) in the dense H of 150mL
2SO
4In, ultrasound suspending.Add 750mg KMnO then
4, 60 ℃ of water-baths heating behind the stirring 1h obtain the sepia product under the room temperature until reacting completely.When reaction is increased to 70 ℃ with temperature when complete or complete, treat behind the temperature stabilization reactant to be taken out, be cooled to room temperature, pour 400mL then into and contain 5mL30% H
2O
2Ice in cessation reaction.Put into hydro-extractor, 6, centrifugal 10min under the 000rpm rotating speed goes to dissolve with the 150mL ultrapure water behind the supernatant, and the HCl that adds 30mL 20% then behind magnetic stirring 30min, the ultrasonic 20min makes its flocculation sediment.This flocculate is put into hydro-extractor, and 6, centrifugal 10min under the 000rpm rotating speed goes to use the 150mL anhydrous alcohol solution behind the supernatant, and magnetic adds the 150mL absolute ether after stirring 30min, ultrasonic 20min then.Put into hydro-extractor, 10, centrifugal 10min under the 000rpm rotating speed, supernatant are with 0.45 μ m PTFE membrane filtration, and centrifugal sediment and filtration back solid are washed twice with the 50mL absolute ether.At last absolute ether is volatilized the back in 40 ℃ of vacuum drying chamber inner drying 12h,
Preserve for use in the exsiccator.Get a certain amount of products therefrom and be scattered in water or the alkaline solution, ultrasonic then 10-120min peels off the oxidation product lamella, can obtain stable graphene oxide dispersion liquid.
2, cage shape hexahedron silsesquioxane is synthetic:
Under intense agitation, with 20mL3-aminopropyl triethoxysilane and 160mL methanol mixed.After mixing, add 27mL concentrated hydrochloric acid (36.5%).Then, at room temperature stir a week up to cage shape hexahedron silsesquioxane-NH
3 +Stop reaction after being precipitated as white powder.Resulting product filters earlier, then with ice washed with methanol, vacuum drying chamber inner drying.Last reusable heat methyl alcohol carries out recrystallization to it, preserves for use after the vacuum drying in the exsiccator.
3, the processing of bare electrode:
Before using, glass-carbon electrode is used the aluminium oxide slurry polishing of 4000 order sand paper and 1.0,0.3,0.05 μ m successively, uses absolute ethyl alcohol and ultrapure water ultrasonic cleaning then, and is subsequent use with drying up in the nitrogen subsequently.
4, the preparation of graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane:
(1) graphene oxide is added to ultrasonic dispersion 10-120min in 1% ammoniacal liquor, forms with the homodisperse graphene oxide solution of monolithic layer (1mg/mL), subsequent use;
(2) the 0.5mol/L NaCl solution of the glass-carbon electrode of handling well being put into 1wt%PDDA soaks 20min, takes out the back with drying under careful flushing of a large amount of ultrapure waters and the infrared lamp;
(3) electrode alternately soaks graphene oxide solution repeatedly (1mg/mL, 30min) (1mg/mL 30min) 20 times, can obtain the graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane of 20 bed thickness with cage shape hexahedron silsesquioxane aqueous solution.Wherein, before changing soaking solution, need with the ultrapure water flushing, to remove the graphene oxide or the cage shape hexahedron silsesquioxane of not absorption at every turn.
5, the enrichment based on graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane detects 1-hydroxyl pyrene
After graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane placed 1-hydroxyl pyrene solution absorption 40min; In the phosphate buffer that contains 0.2M NaOH of 50mM pH=2.0; (graphene oxide-complex film modified glass-carbon electrode of cage shape hexahedron silsesquioxane is a working electrode with three-electrode system with the CHI660c electrochemical workstation; Platinum electrode is to electrode; The Ag/AgCl electrode is a contrast electrode), in-0.3～0.8V scope, carry out differential pulse voltammetry (DPV) and measure.Compare with naked glass-carbon electrode, the graphene oxide-complex film modified electrode pair 1-of cage shape hexahedron silsesquioxane hydroxyl pyrene has unusual electro-catalysis ability, and 1-hydroxyl pyrene is had very strong adsorptive power.In 0.1～12.55 μ M scope, have good linear relationship between the peak point current of 1-hydroxyl pyrene and its concentration, detect and be limited to 0.04 μ M.With graphene oxide-cage shape hexahedron silsesquioxane composite membrane electrochemical sensor 1-hydroxyl pyrene is measured 13 times repeatedly, peak point current does not almost change, and illustrates that the reappearance of electrode is good.
Embodiment 2:
Graphene oxide and cage shape hexahedron silsesquioxane are mixed with the aqueous solution of 0.5mg/mL respectively, with the ultrasonic hydrotropy of Ultrasound Instrument; The glass-carbon electrode that pre-service is good soaks 15min in the 1.0mol/L of 0.5wt%PDDA NaCl solution, take out the back with drying under careful flushing of a large amount of ultrapure waters and the infrared lamp; Then, electrode alternately soaks graphene oxide solution (30min) and cage shape hexahedron silsesquioxane aqueous solution (30min) 25 times repeatedly.
Embodiment 3:
Graphene oxide and cage shape hexahedron silsesquioxane are mixed with the aqueous solution of 2.0mg/mL respectively, with the ultrasonic hydrotropy of Ultrasound Instrument; The glass-carbon electrode that pre-service is good soaks 30min in the 0.5mol/L of 1.5wt%PDDA NaCl solution, the taking-up back is carefully washed with a large amount of ultrapure waters and under infrared lamp, dried; Then, electrode alternately soaks graphene oxide solution (45min) and cage shape hexahedron silsesquioxane aqueous solution (45min) 15 times repeatedly.
Claims (9)
1. an enrichment detects 1-hydroxyl pyrene in the electrochemical sensor electrodes of one; It is characterized in that based on the graphene composite material modified electrode; Comprise strut body electrode, polycation electrolyte and graphene complex modified membrane; Wherein the graphene complex film is graphene oxide-cage shape hexahedron silsesquioxane compound, and the number of plies of compound is the 1-100 layer.
2. a kind of enrichment described in claim 1 detects 1-hydroxyl pyrene in the electrochemical sensor electrodes of one, it is characterized in that:
(1) graphene oxide provides big π system;
(2) cage shape hexahedron silsesquioxane avoids graphene oxide to reunite as the supporter of setting up the three-dimensional framework structure, and keeps the graphene oxide bigger serface;
(3) 1-hydroxyl pyrene interacts through pi-pi accumulation and graphene oxide, thereby plays concentration effect, and adsorption time is 5-60min.
(4) utilize the electroactive of 1-hydroxyl pyrene, the 1-hydroxyl pyrene that is enriched in through the pi-pi accumulation effect on graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane is carried out the electrochemical in-situ detection.
3. the preparation method of graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane, preparation process is following:
(1) graphite oxide is added to ultrasonic dispersion in water or the alkaline solution, forms with the homodisperse graphene oxide solution of monolithic layer, subsequent use;
(2) select suitable polycation electrolyte to be mixed with aqueous solution, strut body electrode is carried out pre-service, be immersed in then in the polycation electrolyte, make the strut body electrode surface lotus that becomes positively charged;
(3) will after above-mentioned steps is handled, the become positively charged strut body electrode of lotus is alternately soaked graphene oxide solution and cage shape hexahedron silsesquioxane solution (1-100 time) repeatedly, can obtain graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane.
4. the preparation method described in claim 3, it is characterized in that described polycation electrolyte be PAH salt, gather the diallyl alkyl dimethyl ammonium chloride, gather the dipropenyl dimethyl ammonium chloride, a kind of or wherein any two kinds potpourri in polyvinyl alcohol (PVA), collagen, shitosan, poly-D-lysine or the polyvinyl inferior amine salt hydrochlorate.
5. the preparation method described in claim 3 is characterized in that described polycation electrolyte is mixed with aqueous solution, and concentration is 0.1-2wt%, and strut body electrode soak time in its aqueous solution is 1-30min.
6. the preparation method described in claim 3 is characterized in that described strut body electrode is glass-carbon electrode, graphite electrode, pencil-lead electrode or carbon paste electrode.
7. the preparation method described in claim 3 is characterized in that described graphene oxide solution concentration is 0.01-5mg/mL, and cage shape hexahedron silsesquioxane solution concentration is 0.01-5mg/mL.
8. the preparation method described in claim 3; It is characterized in that it is 5-40 time that described strut body electrode is alternately soaked the preferred multiplicity of graphene oxide solution and cage shape hexahedron silsesquioxane solution, obtains graphene oxide-complex film modified electrode of cage shape hexahedron silsesquioxane.
9. the preparation method described in claim 3 is characterized in that the soak time that described strut body electrode replaces in graphene oxide solution and cage shape hexahedron silsesquioxane solution is respectively 2-60min.
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| CN104181258A (en) * | 2013-05-24 | 2014-12-03 | 北京蛋白质组研究中心 | Glycoprotein N-carbohydrate chain one-step enrichment-derivation processing method based on graphene and MALDI-TOF-MS analysis method |
| CN105758920A (en) * | 2015-11-05 | 2016-07-13 | 佳木斯大学 | Preparation method of electrochemical micro-detection system based on disposable pipette tip and lead core electrode array |
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| CN103972481A (en) * | 2013-01-24 | 2014-08-06 | 黄炳照 | Manufacturing method for composite material |
| CN104181258A (en) * | 2013-05-24 | 2014-12-03 | 北京蛋白质组研究中心 | Glycoprotein N-carbohydrate chain one-step enrichment-derivation processing method based on graphene and MALDI-TOF-MS analysis method |
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| CN103343424A (en) * | 2013-07-25 | 2013-10-09 | 中国科学院新疆理化技术研究所 | Fluorescent nano mesh fiber film for detecting nitro explosive steam and preparation method thereof |
| CN103343424B (en) * | 2013-07-25 | 2015-08-12 | 中国科学院新疆理化技术研究所 | Nitro explosive steam detects by fluorescence nano reticular fibre film and preparation method |
| CN105758920A (en) * | 2015-11-05 | 2016-07-13 | 佳木斯大学 | Preparation method of electrochemical micro-detection system based on disposable pipette tip and lead core electrode array |
| CN105758920B (en) * | 2015-11-05 | 2019-06-14 | 佳木斯大学 | A kind of preparation method of the micro- detection system of electrochemistry based on disposable liquid transfer gun head and lead for retractable pencil electrod-array |
| CN106159240A (en) * | 2016-08-30 | 2016-11-23 | 安徽师范大学 | The preparation method of a kind of sulfur/graphene nanocomposite material, lithium ion cell positive, lithium ion battery |
| CN106159240B (en) * | 2016-08-30 | 2019-06-25 | 安徽师范大学 | A kind of preparation method of sulphur/graphene nanocomposite material, lithium ion cell positive, lithium ion battery |
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Application publication date: 20120104 |