CN102426181B - Application of electrochemical sensor with magnetic conductive porous material as carrier in detection - Google Patents
Application of electrochemical sensor with magnetic conductive porous material as carrier in detection Download PDFInfo
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- CN102426181B CN102426181B CN201110256990.1A CN201110256990A CN102426181B CN 102426181 B CN102426181 B CN 102426181B CN 201110256990 A CN201110256990 A CN 201110256990A CN 102426181 B CN102426181 B CN 102426181B
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Abstract
The invention relates to application of an electrochemical sensor with a magnetic conductive porous material as a carrier in detection. According to the invention, the magnetic conductive porous material is adsorbed onto the surface of an electrode through an electromagnet so as to prepare the electrochemical sensor which carries out a series of electrochemical detection. The magnetic conductive porous material prepared by using the method has good paramagnetism and conductive performance and has a great potential application value and immerse market benefits in the fields of separation, enrichment and electrochemical detection of biological anti-oxidants, heavy metal ions and organic micromoleculal environmental pollutants. When the magnetic conductive porous material is fixed on the surface of the electrode by the magnet, time for surface modification of the electrode is substantially shortened, and the surface of the electrode can be renewed at any time, which enables time for cleaning the electrode to be saved.
Description
Technical field
The invention belongs to a kind of novel detection method, a kind ofly especially take the electrochemical sensor detection method that the magnetic conductive porous material of tool is carrier.
Background technology
The magnetic conductive porous material of tool refers to the material that has magnetic and can conduct electricity of the pore texture with certain size and quantity, and the common factor of porosity of this class material is larger, and pore texture exists as useful structure.The size of the power of magnetic, conductive capability, hole, quantity and distribution are the principal elements that affects magnetic conductive porosint performance, and these features can be adjusted control by preparation technology.
The application of conductive porous material in electrochemica biological sensing and bio-reactor, that has reported has the film modified glass-carbon electrode of Graphene-Nafion for the detection of heavy metal lead and chromium, experimental result shows, conductive porous material film not only shows sensitivity and significantly improves in heavy metal detects, and has alleviated the interference of conductive porous material film.
Oxidation reaction in human body and food is the research topic of people's extensive concern, and the energy that oxidative metabolism produces is of great significance for the survival tool of cell, but oxidizing process can produce a series of oxyradical.If produce excessive free radical in biosome; break the balance of free radical and antioxidant; the damage capability of free radical will surpass the protective capability of antioxidant (as superoxide dismutase, hydrogen peroxidase, peroxidase etc.) in body and can, by the self-regeneration function of the block cells such as oxidation cell membrane, damage dna or enzyme itself, cause the damage of biomacromolecule function and structure, cytoclasis, apoptosis or death so.Therefore, set up antioxidant analytical approach fast and effectively and there is good theory and applied research value for life science and Food Science analysis.
Detection method for heavy metal has a variety of, maximum method of use is that electrochemical method detects at present, this is because electrochemical methods analyst cost is low, highly sensitive, simple to operate, can analyzes several one-tenth advantage of grading simultaneously, and electrochemical method becomes one of the most suitable method of heavy metal ion of measuring.Up to the present, various chemically modified electrodes have been in the news for measuring metallic ion, as self-assemble film pole forms the film with special properties at electrode surface, are widely used for measuring metallic ion.
The current analyzing detecting method of organic molecule environmental contaminants adopts spectrographic technique to detect mostly.Wherein some material with electrochemical activity can detect by electrochemical method.
Summary of the invention
The object of the invention is in order to overcome above-mentioned the deficiencies in the prior art, a kind of electrochemical sensor detection method that the magnetic conductive porous material of tool is carrier of take is provided.The method utilizes conductive porous material for template, to obtain good paramagnetism, the compound substance of satisfactory electrical conductivity.
For achieving the above object, the present invention adopts following technical proposals:
The present invention be take conductive porous material as template, preparation take the magnetic compound substance of tool that conductive porous material is carrier concrete grammar as:
A kind ofly take the magnetic conductive porous material of tool as the application of carrier in electrochemical sensor detects, its method is, by magnet, the magnetic conductive porous material of tool is adsorbed on to electrode surface, this electrode is prepared into electrochemical sensor, then solution to be measured is carried out to Electrochemical Detection, after detection finishes, magnet is removed, water rinses electrode surface, can remove this material, and electrode surface is processed without other.
The magnetic conductive porous material of described tool is the compound substance of nano ferriferrous oxide graphite oxide.
The magnetic conductive porous material preenrichment of tool after biological anti-oxidant oxidation probe, in the analytical applications of biological anti-oxidant context of detection.
Described biological anti-oxidant oxidation probe is guanine; The process of the magnetic conductive porous material preenrichment of tool guanine is: (1), in ice-water bath, utilizes the diazotizing method of nitrite, obtains the diazo salt of guanine; (2) add the zinc powder of 2-6 times of guanine quality, observe while having Bubble formation, the product that adds the step (1) of 3 times of guanine quality to obtain, continues to stir 6-12 hour; (3) last, dry the magnetic guanine derivatives of tool that can to obtain take Graphene be carrier.
The magnetic conductive porous material preenrichment of tool after biological anti-oxidant oxidation probe, its process in the analytical applications of biological anti-oxidant context of detection is, by the oxidation of preenrichment biological anti-oxidant on the magnetic conductive porous material of tool probe, detect respectively in the aqueous solution that does not add biological anti-oxidant, and be 80 μ M to 2mM ascorbic acid in concentration, reductive glutathione, watermiscible vitamin E, in the aqueous solution of the biological anti-oxidants such as gallic acid, after oxidation probe pre-oxidation 30min, square wave volt-ampere and the timing Ampere currents signal intensity situation of oxidation probe.Result shows, after adding biological anti-oxidant, the electric current of oxidation probe obviously increases.
The magnetic conductive porous material preenrichment of tool after biological anti-oxidant oxidation probe as the application of electrode face finish material.
The magnetic conductive porous material preenrichment of tool after heavy metal ion, in the analytical applications of detection of heavy metal ion.
It,, in the analytical applications of detection of heavy metal ion, is specially: by the method for pre-heavy metal-enriched ion on the magnetic conductive porous material of tool, detecting respectively in concentration is the Cd of 1 μ M
2+, Pb
2+, Cu
2+, Hg
2+aqueous solution in, and containing Cd
2+, Pb
2+, Cu
2+, Hg
2+aqueous solution in, differential pulse voltammetry anodic stripping voltammetry curve.Result shows, is adding Cd
2+, Pb
2+, Cu
2+, Hg
2+after, electrode material has shown sensitive response condition.
The magnetic conductive porous material preenrichment of tool after organic molecule environmental contaminants, the analytical applications detecting at organic molecule environmental contaminants
The analytical applications that it detects at organic molecule environmental contaminants, be specially: by be rich in advance the method for the little molecule environmental contaminants of machine on the magnetic conductive porous material of tool, in the aqueous solution of the parathion-methyl that detection is 1mg/ml in concentration, and not containing in the aqueous solution of parathion-methyl, differential pulse voltammetry anodic stripping voltammetry curve.Result shows, after adding parathion-methyl, electrode material has shown sensitive response condition.
Described " the magnetic conductive porous material of tool " refers to: the material that has magnetic and can conduct electricity with the pore texture of certain size and quantity, for example: tri-iron tetroxide oxidized graphite composite material, cobaltosic oxide oxidized graphite composite material, tri-iron tetroxide graphene composite material etc.
The step of described " Electrochemical Detection " is generally preparation electrolyte solution, selects suitable electrode system, determines electrochemical detection method and test parameters, carries out Electrochemical Scanning, save data.
Described " biological anti-oxidant oxidation probe " refers to: can react with oxygen radical, and in electrochemical oxidation process, can provide the molecule of respective electrical chemical signal, such as: guanine etc.
Described " organic molecule environmental contaminants " refer to: relative molecular mass, below 1000, makes normal composition and the character of environment change after entered environment, are directly or indirectly harmful to the mankind and biological organism.Parathion-methyl for example, heptachlor indenes, chlorination camphene etc.
This compound substance has very large potential using value and huge market efficiency in fields such as biological anti-oxidant detection, detection of heavy metal ion and the detections of organic molecule environmental contaminants.It is fixed on to electrode surface with magnet, electrode face finish process time is shortened greatly, and electrode surface can upgrade at any time, save the time of clearing electrode.
The magnetic conductive porous material enrichment of tool after test substance, by magnet, be fixed on electrochemical detector surface, after analyzing and testing completes, remove magnet, buffer solution rinses detecting device, thereby form the detection mode that electrochemical detector can immediate updating, omitted the treatment steps such as electrode dismounting, mechanical grinding.The speed of analyzing and testing and the reappearance of result have obviously been improved.
Accompanying drawing explanation
Fig. 1 is the building-up process schematic diagram of the magnetic conductive porous material of tool of the present invention.
Wherein 1. conductive porous materials, 2. conductive porous material and magnetic nanoparticle compound substance.
Fig. 2 is the building-up process schematic diagram that load of the present invention has the magnetic conductive porous material of tool of oxidation probe.
1. conductive porous materials wherein, 2. conductive porous material and magnetic nanoparticle compound substance, 3. load has the magnetic conductive porosint of oxidation probe.
Fig. 3 a be take the magnetic guanine derivatives of tool that Graphene is carrier for application is of the present invention, be applied to the antioxidant square wave volt-ampere testing result of embodiment 3-gallic acid system.
Fig. 3 b be take the magnetic guanine derivatives of tool that Graphene is carrier for application is of the present invention, be applied to the antioxidant timing ampere testing result of embodiment 3-gallic acid system.
Fig. 4 a be take the magnetic guanine derivatives of tool that Graphene is carrier for application is of the present invention, be applied to the antioxidant square wave volt-ampere testing result of embodiment 4-ascorbic acid system.
Fig. 4 b be take the magnetic guanine derivatives of tool that Graphene is carrier for application is of the present invention, be applied to the antioxidant timing ampere testing result of embodiment 4-ascorbic acid system.
Fig. 5 a be take the magnetic guanine derivatives of tool that Graphene is carrier for application is of the present invention, be applied to the antioxidant timing ampere testing result of embodiment 5-watermiscible vitamin E system.
Fig. 5 b be take the magnetic guanine derivatives of tool that Graphene is carrier for application is of the present invention, be applied to the antioxidant square wave volt-ampere testing result of embodiment 5-watermiscible vitamin E system.
Fig. 6 a be take the magnetic guanine derivatives of tool that Graphene is carrier for application is of the present invention, be applied to the antioxidant square wave volt-ampere testing result of embodiment 6-glutathione system.
Fig. 6 b be take the magnetic guanine derivatives of tool that Graphene is carrier for application is of the present invention, be applied to the antioxidant timing ampere testing result of embodiment 6-glutathione system.
Fig. 7 be take the magnetic guanine derivatives of tool that Graphene is carrier for application is of the present invention, on glass-carbon electrode, and the square wave volt-ampere curve of continuous several times revision test.
Fig. 8 is application nano ferriferrous oxide combined oxidation graphite of the present invention, is applied to the heavy metal ion differential pulse voltammetry anodic stripping voltammetry testing result of embodiment 8-cadmium carbonate system.
Wherein, curve a is not for adding heavy metal ion Cd
2+differential pulse voltammetry anodic stripping voltammetry curve, curve b is for adding heavy metal ion Cd
2+differential pulse voltammetry anodic stripping voltammetry curve.
Fig. 9 is application nano ferriferrous oxide combined oxidation graphite of the present invention, is applied to the heavy metal ion differential pulse voltammetry anodic stripping voltammetry testing result of embodiment 9-lead acetate system.
Wherein, curve a is not for adding heavy metal ion Pb
2+differential pulse voltammetry anodic stripping voltammetry curve, curve b is for adding heavy metal ion Pb
2+differential pulse voltammetry anodic stripping voltammetry curve.
Figure 10 is application nano ferriferrous oxide combined oxidation graphite of the present invention, is applied to the heavy metal ion differential pulse voltammetry anodic stripping voltammetry testing result of embodiment 10-copper sulphate system.
Wherein, curve a is not for adding heavy metal ion Cu
2+differential pulse voltammetry anodic stripping voltammetry curve, curve b is for adding heavy metal ion Cu
2+differential pulse voltammetry anodic stripping voltammetry curve.
Figure 11 is application nano ferriferrous oxide combined oxidation graphite of the present invention, is applied to the heavy metal ion differential pulse voltammetry anodic stripping voltammetry testing result of embodiment 11-mercuric nitrate system.
Wherein, curve a is not for adding heavy metal ion Hg
2+differential pulse voltammetry anodic stripping voltammetry curve, curve b is for adding heavy metal ion Hg
2+differential pulse voltammetry anodic stripping voltammetry curve.
Figure 12 is application nano ferriferrous oxide combined oxidation graphite of the present invention, is applied to the square wave volt-ampere testing result of the organic molecule environmental contaminants of embodiment 12-parathion-methyl system.
Wherein, curve b is not for adding the square wave volt-ampere curve of parathion-methyl, and curve a is the square wave volt-ampere curve adding after parathion-methyl.
Figure 13 magnetic conductive porosint is applied to the testing process of heavy metal ion system.
Figure 14 load has the magnetic conductive porosint of oxidation probe to be applied to the testing process of biological anti-oxidant system.
Embodiment
Below by instantiation, this detection method is further elaborated, should be noted that following explanation is only in order to explain this detection method, does not limit its content.In embodiment, raw materials used and reagent, except particularly pointing out, is commercially available prod.
Embodiment 1: the synthetic method of a kind of concrete conductive porous material of the present invention and magnetic nanoparticle compound substance-nano ferriferrous oxide combined oxidation graphite
Utilize improved Hummer ' s method to obtain graphite oxide (GO) by oxidation crystalline flake graphite.Concrete preparation process is as follows: (1) preoxidation process: 3g crystalline flake graphite joins in the mixed solution of the 12ml concentrated sulphuric acid, 2.5g potassium persulfate, 2.5g phosphorus pentoxide, heats 4.5 hours under the condition of 80 ℃.Potpourri is cooled to after room temperature with the dilution of 0.5L deionized water, filters after placing a liquid, and wash and remove unnecessary acid with deionized water with the nylon leaching film of 0.2 μ m, and room temperature is dried.(2) further oxidation: the dag of pre-oxidation joins (0 ℃) in the 120ml concentrated sulphuric acid, adds potassium permanganate 15g, and make its temperature lower than 20 ℃ under the condition stirring under condition by amount.Potpourri stirs after 2h under 35 ℃ of conditions, under ice-water bath condition, slowly add 250ml water, continue to stir 2h, with after the dilution of 700ml deionized water, add 20ml superoxol (30wt.%), solution colour is become glassy yellow and is produced bubble from black.(3) process: the graphite of oxidation is collected after by centrifugal washing, and stores for future use under 4 ℃ of conditions.
In 200ml water, add 2g graphite oxide, vigorous stirring one hour, obtains homogeneous phase solution, adds the NaOH solution of 1M, regulates pH to neutrality or alkalescent, 50 ℃ of constant temperature.Under argon atmosphere protection, add 4165.2mgNH
4fe (SO
4)
212H
2o and 1693.7mg (NH
4)
2fe (SO
4)
26H
2o, is stirred to completely and dissolves, and continues to stir 30min.Dropwise add 50ml 5M ammoniacal liquor, final pH is 11-12.Under 50 ℃ of constant temperatures, continue to stir 5h.After product filters, in baking oven, vacuum drying spends the night, and obtains the compound substance of nano ferriferrous oxide combined oxidation graphite.
Embodiment 2: a kind of concrete load of the present invention has the synthetic method of magnetic conductive porosint (being specifically designed to biological anti-oxidant the detects)-magnetic guanine derivatives of tool that the Graphene of take is carrier of oxidation probe
In concentrated hydrochloric acid, add 10mg guanine, be placed in ice-water bath, adding 0.1ml concentration is the NaNO of 1M
2solution, continues reaction 30min.Add 30mg zinc powder, while having observed Bubble formation, add the compound substance of the nano ferriferrous oxide combined oxidation graphite obtaining in 30mg embodiment 1, continue to stir 8h.After the washing of water, ethanol, in vacuum drying oven, dry the magnetic guanine derivatives of tool that can to obtain take Graphene be carrier.
Embodiment 3: a kind of concrete load of the present invention has the synthetic method of magnetic conductive porosint (being specifically designed to biological anti-oxidant the detects)-magnetic guanine derivatives of tool that the Graphene of take is carrier of oxidation probe
5mg graphite oxide (commercially available) is dissolved in 10ml dry DMF, is transferred in round-bottomed flask, be heated to 70 ℃, adding 1ml concentration is the manganese acetate aqueous solution of 0.2mol/l.Keep 70 ℃ of constant temperature 1 hour.By after precipitation and centrifugal separation, wash.This precipitation is dispersed in 10ml water, is transferred in reactor, 180 ℃ of heating 5 hours.Precipitate centrifugal after, wash with water ,-50 ℃ of freeze dryings 10 hours, have obtained mangano-manganic oxide-oxidized graphite composite material.
In concentrated hydrochloric acid, add 10mg guanine, be placed in ice-water bath, adding 0.1ml concentration is the NaNO of 1M
2solution, continues reaction 30min.Add 30mg zinc powder, while having observed Bubble formation, add 30mg mangano-manganic oxide-oxidized graphite composite material, continue to stir 8h.After the washing of water, ethanol, in vacuum drying oven, dry the magnetic guanine derivatives of tool that can to obtain take Graphene be carrier.
Embodiment 4: a kind of concrete load of the present invention has the synthetic method of magnetic conductive porosint (being specifically designed to biological anti-oxidant the detects)-magnetic guanine derivatives of tool that the Graphene of take is carrier of oxidation probe
Take 288.4mg lauryl sodium sulfate, be dissolved in 2ml water, be then transferred in 28ml ethylene glycol.Add 50mg graphite oxide (commercially available), it was uniformly dispersed in ultrasonic 30 minutes.In vigorous stirring, add 582mg Co (NO
3)
2.6H
2o, then adds 180mg oxalic acid.Solution stirs 15 hours at 40 ℃.Solid product obtains by centrifuging, and with ethanol and water washing several, in baking oven, 50 ℃ of oven dry are spent the night, and under argon shield, 500 ℃ of calcinings can obtain cobaltosic oxide-oxidized graphite composite material in 3 hours.
In concentrated hydrochloric acid, add 10mg guanine, be placed in ice-water bath, adding 0.1ml concentration is the NaNO of 1M
2solution, continues reaction 30min.Add 30mg zinc powder, while having observed Bubble formation, add 30mg cobaltosic oxide-oxidized graphite composite material, continue to stir 8h.After the washing of water, ethanol, in vacuum drying oven, dry the magnetic guanine derivatives of tool that can to obtain take Graphene be carrier.
Embodiment 5: a kind of concrete load of the present invention has the synthetic method of magnetic conductive porosint (being specifically designed to biological anti-oxidant the detects)-magnetic guanine derivatives of tool that the Graphene of take is carrier of oxidation probe
Getting 1g graphene oxide (commercially available) is dissolved in 400ml deionized water.350mg (C
2h
3o
2)
2co4H
2o is dissolved in 400ml deionized water, dropwise joins in the aqueous solution of graphene oxide, then adds 4ml ammoniacal liquor, 1ml hydrazine.Solution stirs 8 hours at 90 ℃, and precipitation obtains by isolated by filtration.Use deionized water washing precipitation, then, 180 ℃ of heating 10 hours, obtain cobaltosic oxide-graphene composite material.
In concentrated hydrochloric acid, add 10mg guanine, be placed in ice-water bath, adding 0.1ml concentration is the NaNO of 1M
2solution, continues reaction 30min.Add 30mg zinc powder, while having observed Bubble formation, add 30mg cobaltosic oxide-oxidized graphite composite material, continue to stir 8h.After the washing of water, ethanol, in vacuum drying oven, dry the magnetic guanine derivatives of tool that can to obtain take Graphene be carrier.
Embodiment 6: the antioxidant that the magnetic guanine derivatives of tool that the Graphene of take is carrier is applied to gallic acid system detects
By synthetic, take the magnetic guanine derivatives of tool that Graphene is carrier and be dispersed in water, be designated as dispersion liquid A.Take 15mgEDTA and 12mgFeSO
47H
2o, is dissolved in 10ml water, is designated as solution B.Take 936mgNaH
2pO
42H
2o and 573mg Na
2hPO
412H
2o, is dissolved in 200ml water, is designated as solution C.By 1.2mg gallic acid, be dissolved in 1.5ml water, be designated as solution D.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, under-0.3V constant potential, process 30min, then by solution C, displace solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 1ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 2ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 5ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 10ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 25ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 50ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 75ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 100ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Experimental result records as Fig. 3 a, Fig. 3 b.From figure, square wave volt-ampere curve result can be found out, if do not add gallic acid,, after oxidation, the signal of oxidation probe guanine can be down to very low level.And after adding gallic acid, the signal of the oxidation probe guanine of oxidation can rise to some extent, and along with the increase of gallic acid addition, the signal of oxidation rear oxidation probe guanine rises and also obviously increases.The result of chronoamperometry detection curve is consistent with the result that square wave volt-ampere curve obtains.
Embodiment 7: the antioxidant that the magnetic guanine derivatives of tool that the Graphene of take is carrier is applied to ascorbic acid system detects
By synthetic, take the magnetic guanine derivatives of tool that Graphene is carrier and be dispersed in water, be designated as dispersion liquid A.Take 15mgEDTA and 12mgFeSO
47H
2o, is dissolved in 10ml water, is designated as solution B.Take 936mgNaH
2pO
42H
2o and 573mg Na
2hPO
412H
2o, is dissolved in 200ml water, is designated as solution C.By 1.0mg ascorbic acid, be dissolved in 1.5ml water, be designated as solution D.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, under-0.3V constant potential, process 30min, then by solution C, displace solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 1ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 2ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 5ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 10ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 25ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 50ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 75ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 100ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Experimental result records as Fig. 4 a, Fig. 4 b.From figure, square wave volt-ampere curve result can be found out, if do not add ascorbic acid,, after oxidation, the signal of oxidation probe guanine can be down to very low level.And after adding ascorbic acid, the signal of the oxidation probe guanine of oxidation can rise to some extent, and along with the increase of ascorbic acid addition, the signal of oxidation rear oxidation probe guanine rises and also obviously increases.The result of chronoamperometry detection curve is consistent with the result that square wave volt-ampere curve obtains.
Embodiment 8: the antioxidant that the magnetic guanine derivatives of tool that the Graphene of take is carrier is applied to watermiscible vitamin E system detects
By synthetic, take the magnetic guanine derivatives of tool that Graphene is carrier and be dispersed in water, be designated as dispersion liquid A.Take 15mgEDTA and 12mgFeSO
47H
2o, is dissolved in 10ml water, is designated as solution B.Take 936mgNaH
2pO
42H
2o and 573mg Na
2hPO
412H
2o, is dissolved in 200ml water, is designated as solution C.By 1.0mg watermiscible vitamin E, be dissolved in 1.5ml water, be designated as solution D.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, under-0.3V constant potential, process 30min, then by solution C, displace solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 1ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 2ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 5ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 10ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 25ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 50ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 75ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 100ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Experimental result records as Fig. 5 a, Fig. 5 b.From figure, square wave volt-ampere curve result can be found out, if adding water soluble vitamin E not,, after oxidation, the signal of oxidation probe guanine can be down to very low level.And after adding watermiscible vitamin E, the signal of the oxidation probe guanine of oxidation can rise to some extent, and along with the increase of watermiscible vitamin E addition, the signal of oxidation rear oxidation probe guanine rises and also obviously increases.The result of chronoamperometry detection curve is consistent with the result that square wave volt-ampere curve obtains.
Embodiment 9: the antioxidant that the magnetic guanine derivatives of tool that the Graphene of take is carrier is applied to glutathione system detects
By synthetic, take the magnetic guanine derivatives of tool that Graphene is carrier and be dispersed in water, be designated as dispersion liquid A.Take 15mgEDTA and 12mgFeSO
47H
2o, is dissolved in 10ml water, is designated as solution B.Take 936mgNaH
2pO
42H
2o and 573mg Na
2hPO
412H
2o, is dissolved in 200ml water, is designated as solution C.By 1.2mg glutathione, be dissolved in 1ml water, be designated as solution D.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, under-0.3V constant potential, process 30min, then by solution C, displace solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 1ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 2ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 5ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 10ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 25ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 50ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 75ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, to fix, take the magnetic guanine derivatives of tool that Graphene is carrier.Add 100ul solution B, 100ul solution D is processed 30min under-0.3V constant potential, then by solution C, displaces solution B, at the timing ampere curve of 0V-1.0V test square wave volt-ampere curve and 0V-0.9V.
Experimental result records as Fig. 6 a, Fig. 6 b.From figure, square wave volt-ampere curve result can be found out, if do not add glutathione,, after oxidation, the signal of oxidation probe guanine can be down to very low level.And after adding glutathione, the signal of the oxidation probe guanine of oxidation can rise to some extent, and along with the increase of glutathione addition, the signal of oxidation rear oxidation probe guanine rises and also obviously increases.The result of chronoamperometry detection curve is consistent with the result that square wave volt-ampere curve obtains.
Embodiment 10: by synthetic in this patent, take the magnetic guanine derivatives of tool that Graphene is carrier and be applied to electrode face finish material, can save in test the processing time of electrode.
By synthetic, take the magnetic guanine derivatives of tool that Graphene is carrier and be dispersed in water, be designated as dispersion liquid A.Take 936mgNaH
2pO
42H
2o and 573mg Na
2hPO
412H
2o, is dissolved in 200ml water, is designated as solution B.
Get 4ul dispersion liquid A, drip on glass-carbon electrode surface magnet adsorption dispersion liquid A for glass-carbon electrode bottom.Add 300ul solution B.At 0V-1.0V test square wave volt-ampere curve.After having tested, with deionized water, solution is rinsed well, electrode is left intact, and continues to add 4ul dispersion liquid A, magnet adsorption dispersion liquid A for glass-carbon electrode bottom.Add 300ul solution B, at 0V-1.0V test square wave volt-ampere curve, then with deionized water, rinse out solution.This process repeats 9 times.
Experimental result is recorded in Figure of description 7.From figure, square wave volt-ampere curve can be found out, electrode is used ten times continuously, and the peak position that goes out of oxidation probe guanine is offset a little to positive potential, peak current slight reduction, but in the scope all allowing in galvanochemistry.This shows, the material that this patent is synthetic is applied to electrode face finish material, can save the processing time of electrode in test.
Embodiment 11: nano ferriferrous oxide combined oxidation graphite is applied to the detection of heavy metal ion of cadmium carbonate system
Synthetic nano ferriferrous oxide combined oxidation graphite is dispersed in water, is designated as dispersion liquid A.Sodium acetate-hac buffer (pH 4.4 for HAc-NaAc, 50mM), as electrolyte solution, is designated as solution B.Take 0.172mgCdCO
3be dissolved in 1000ml water, be designated as solution C.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, with fixing nano ferriferrous oxide combined oxidation graphite.Add 100ul solution B, adopt differential pulse polarography an odic stripping voltammetry, (amplitude 50mV, pulse width 10ms, recurrence interval 0.2s, step electromotive force 2mV), sweep record voltammogram.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, with fixing nano ferriferrous oxide combined oxidation graphite.Add 100ul solution C, standing adsorption 10min, then displaces solution C by solution B, adopts differential pulse polarography an odic stripping voltammetry, (amplitude 50mV, pulse width 10ms, recurrence interval 0.2s, step electromotive force 2mV), sweep record voltammogram.
Experimental result is as Fig. 8.As seen from Figure 8, after adding solution C, differential pulse voltammetry anodic stripping voltammetry curve demonstrates near-0.73V and occurs an obvious peak, and this is corresponding to Cd
2+stripping peak.
Embodiment 12: nano ferriferrous oxide combined oxidation graphite is applied to the detection of heavy metal ion of lead acetate system
Synthetic nano ferriferrous oxide combined oxidation graphite is dispersed in water, is designated as dispersion liquid A.Sodium acetate-hac buffer (pH 4.4 for HAc-NaAc, 50mM), as electrolyte solution, is designated as solution B.Take 0.379mgPb (CH
3cOO)
23H
2o is dissolved in 1000ml water, is designated as solution C.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, with fixing nano ferriferrous oxide combined oxidation graphite.Add 100ul solution B, adopt differential pulse polarography an odic stripping voltammetry, (amplitude 50mV, pulse width 10ms, recurrence interval 0.2s, step electromotive force 2mV), sweep record voltammogram.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, with fixing nano ferriferrous oxide combined oxidation graphite.Add 100ul solution C, standing adsorption 10min, then displaces solution C by solution B, adopts differential pulse polarography an odic stripping voltammetry, (amplitude 50mV, pulse width 10ms, recurrence interval 0.2s, step electromotive force 2mV), sweep record voltammogram.
Experimental result is as Fig. 9.As seen from Figure 9, after adding solution C, differential pulse voltammetry anodic stripping voltammetry curve demonstrates near-0.55V and occurs an obvious peak, and this is corresponding to pb
2+stripping peak.
Embodiment 13: nano ferriferrous oxide combined oxidation graphite is applied to the detection of heavy metal ion of copper sulphate system
Synthetic nano ferriferrous oxide combined oxidation graphite is dispersed in water, is designated as dispersion liquid A.Sodium acetate-hac buffer (pH 4.4 for HAc-NaAc, 50mM), as electrolyte solution, is designated as solution B.Take 0.25mgCuSO
45H
2o is dissolved in 1000ml water, is designated as solution C.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, with fixing nano ferriferrous oxide combined oxidation graphite.Add 100ul solution B, adopt differential pulse polarography an odic stripping voltammetry, (amplitude 50mV, pulse width 10ms, recurrence interval 0.2s, step electromotive force 2mV), sweep record voltammogram.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, with fixing nano ferriferrous oxide combined oxidation graphite.Add 100ul solution C, standing adsorption 10min, then displaces solution C by solution B, adopts differential pulse polarography an odic stripping voltammetry, (amplitude 50mV, pulse width 10ms, recurrence interval 0.2s, step electromotive force 2mV), sweep record voltammogram.
Experimental result is as Figure 10.As seen from Figure 10, after adding solution C, differential pulse voltammetry anodic stripping voltammetry curve demonstrates near-0.07V and occurs an obvious peak, and this is corresponding to Cu
2+stripping peak.
Embodiment 14: nano ferriferrous oxide combined oxidation graphite is applied to the detection of heavy metal ion of mercuric nitrate system
Synthetic nano ferriferrous oxide combined oxidation graphite is dispersed in water, is designated as dispersion liquid A.Sodium acetate-hac buffer (pH 4.4 for HAc-NaAc, 50mM), as electrolyte solution, is designated as solution B.Take 0.34mg Hg (NO
3)
2h
2o is dissolved in 1000ml water, is designated as solution C.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, with fixing nano ferriferrous oxide combined oxidation graphite.Add 100ul solution B, adopt differential pulse polarography an odic stripping voltammetry, (amplitude 50mV, pulse width 10ms, recurrence interval 0.2s, step electromotive force 2mV), sweep record voltammogram.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, with fixing nano ferriferrous oxide combined oxidation graphite.Add 100ul solution C, standing adsorption 10min, then displaces solution C by solution B, adopts differential pulse polarography an odic stripping voltammetry, (amplitude 50mV, pulse width 10ms, recurrence interval 0.2s, step electromotive force 2mV), sweep record voltammogram.
Experimental result is as Figure 11.As seen from Figure 11, after adding solution C, differential pulse voltammetry anodic stripping voltammetry curve demonstrates and near 0.27V, occurs an obvious peak, and this is corresponding to Hg
2+stripping peak.
Embodiment 15: the organic molecule environmental contaminants that nano ferriferrous oxide combined oxidation graphite is applied to parathion-methyl system detect
Synthetic nano ferriferrous oxide combined oxidation graphite is dispersed in water, is designated as dispersion liquid A.Sodium acetate-hac buffer (pH 4.4 for HAc-NaAc, 50mM), as electrolyte solution, is designated as solution B.Take 1mg parathion-methyl and be dissolved in 1ml solution B, be designated as solution C.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, with fixing nano ferriferrous oxide combined oxidation graphite.Add 100ul solution B, adopt square wave voltammetry, (take-off potential-0.5V stops current potential 0.3V, current potential increment 0.005V, frequency 10Hz), sweep record voltammogram.
Get 4ul solution A and drip on the glass-carbon electrode surface of handling well, electrode bottom adds magnet, with fixing nano ferriferrous oxide combined oxidation graphite.Add 100ul solution C, standing adsorption 10min, then displaces solution C by solution B, adopts square wave voltammetry, (take-off potential-0.5V stops current potential 0.3V, current potential increment 0.005V, frequency 10Hz), sweep record voltammogram.
Experimental result is as Figure 12.As seen from Figure 12, after adding solution C, square wave volt-ampere curve demonstrates near-0.05V and occurs an obvious peak, and this is corresponding to the oxidation peak of parathion-methyl.
Claims (5)
1. take the magnetic conductive porous material of tool as the application of carrier in electrochemical sensor detects for one kind, its method is, by magnet, the magnetic conductive porous material of tool is adsorbed on to electrode surface, this electrode is prepared into electrochemical sensor, then solution to be measured is carried out to Electrochemical Detection, after detection finishes, magnet is removed, water rinses electrode surface, can remove this material;
The magnetic conductive porous material of described tool is the compound substance of nano ferriferrous oxide graphite oxide;
The magnetic conductive porous material preenrichment of tool after biological anti-oxidant oxidation probe, in the analytical applications of biological anti-oxidant context of detection.
2. application according to claim 1, is characterized in that: described biological anti-oxidant oxidation probe is guanine; The process of the magnetic conductive porous material preenrichment of tool guanine is: (1), in ice-water bath, utilizes the diazotizing method of nitrite, obtains the diazo salt of guanine; (2) add the zinc powder of 2-6 times of guanine quality, observe while having Bubble formation, add the magnetic conductive porosint of 3 times of guanine quality, continue to stir 6-12 hour; (3) last, dry, the magnetic guanine derivatives of tool that can to obtain take Graphene be carrier, described magnetic conductive porosint is a kind of in tri-iron tetroxide combined oxidation graphite, mangano-manganic oxide-oxidized graphite composite material, cobaltosic oxide-oxidized graphite composite material or cobaltosic oxide-graphene composite material.
3. application according to claim 1, is characterized in that: the magnetic conductive porous material preenrichment of tool after biological anti-oxidant oxidation probe as the application of electrode face finish material.
4. application according to claim 1, is characterized in that: also comprised the magnetic conductive porous material preenrichment of tool after heavy metal ion, in the analytical applications of detection of heavy metal ion.
5. application according to claim 1, is characterized in that: also comprised the magnetic conductive porous material preenrichment of tool after organic molecule environmental contaminants, the analytical applications detecting at organic molecule environmental contaminants.
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