CN108802124A - A kind of detection method and sensor of the l-cysteine based on glutathione composite membrane grid gold electrode - Google Patents
A kind of detection method and sensor of the l-cysteine based on glutathione composite membrane grid gold electrode Download PDFInfo
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Abstract
The invention discloses a kind of detection methods and sensor of the l-cysteine based on the complex film modified grid gold electrode of glutathione, it will be on dibutyl phthalate/graphene oxide/glutathione (DBP/GO/GSH) composite material modification extended grid golden membranous layer of scene effect transistor, form a kind of novel DBP/GO/GSH self assembly grid gold electrodes (GGE), Sensitive Detection is realized to l-cysteine using field-effect transistor signals in situ amplification, wherein, glutathione composite membrane is adsorbed by electrostatic interaction and combines positively charged object l-cysteine, it forms double electrical layers and generates the film potential for identifying monovalence organoammonium ions.The sensor has this special response relation of good energy to l-cysteine, and the range of linearity is 2.5 × 10‑6—1.0×10‑4Mol/L, response sensitivity are 55.72 ± 1.5mV/-pC (25 DEG C), and detection is limited to 1.02 × 10‑ 6mol/L.Its preparation process is simple and convenient, and the response time is fast, has potential application prospect.
Description
Technical field
The invention belongs to chemical/biological field of sensing technologies, and in particular to one kind is based on glutathione composite membrane grid gold
The detection method and sensor of the l-cysteine of electrode, i.e., a kind of selective membrane Copper diethlydithiocarbamate, be suitable for healthy aquaculture with
Detection in terms of life science.
Background technology
Dibutyl phthalate (Dibutyl phthalic, DBP), which is one kind, can make product have improved flexibility
Colourless oil liquid, stability, resistance to deflection, cohesiveness and water resistance are excellent so being used as polyvinyl acetate, alcohol
The plasticizer of acid resin, NC Nitroncellulose, ethyl cellulose and neoprene, nitrile rubber.
Graphene oxide (Graphene oxide, GO) is the derivative of graphene, and structure is substantially the same with graphene, only
It is to be connected with a large amount of oxygen-containing groups on basal plane that the two-dimensional space constituted in one layer of carbon atom infinitely extends, contains-OH in plane
And C-O-O, and contain C=O and-COOH at its lamella edge.Graphene oxide has some excellent property compared with graphene
Can, there are good wettability and surface-active, and prodigious work is played on the mechanics for improving material, electric property
With.
In recent years, many electrochemical research in relation to the composite modified material of graphene oxide, Ya etc. are aoxidized using N doping
Graphene modified glass-carbon electrode detects the carbendazim in food, which shows carbendazim excellent electrocatalytic oxidation
Performance, detection range are 5.0-850 μ g/L, and Monitoring lower-cut is 1.0 μ g/L；Shen etc. by nickel nano material, attapulgite with
And the dilute composite material modification of reduction-oxidation graphite is used for detecting glucose on glass-carbon electrode, inspection of the sensor for glucose
Survey shows the features such as high sensitivity and fast response, Monitoring lower-cut 0.37mM；Hadi Beitollahi etc. are in screen printing
Graphene oxide/zinc oxide (GO/ZnO) composite material is modified on brush electrode to be used for while detecting levodopa and tyrosine, this
Two kinds of detection substances of electrode pair show high sensitivity, and highly selective, Monitoring lower-cut is respectively 4.5 × 10-7M and 3.4 × 10-7M；Rao etc., which has studied two on p-type nitrophenols, has electroactive functional group on the dilute modified glassy carbon electrode of reduction-oxidation graphite
Electrochemical behavior, which is 0.55mM to the Monitoring lower-cut of PNP；Li Junhua etc. repaiies GO/MWCNT nanocomposites
It adorns on glass-carbon electrode, constructing a kind of novel L-Trp sensor that has good stability, detection range is 1.0 × 10-6—1.0×10-4Mol/L, Monitoring lower-cut are 3.5 × 10-7mol/L；Liu little Hua etc. is prepared for for measuring catechol
Single-walled carbon nanotube-graphene oxide composite modified glassy carbon electrode, the modified electrode have good electro-catalysis to catechol
Activity, detection are limited to 4 × 10-7M。
GSH is formed by peptide bond by glutamic acid, cysteine and glycine, there is the γ-COOH by glutamic acid in molecule
With the α-NH of cysteine2Special γ-the peptide bond being condensed into.Glutathione has antioxidation and integrates detoxication also
The function of normal immune system can be assisted in keeping.Antioxidation due to glutathione and integration detoxication so that its
It is widely used, cannot be only used for drug, more can be used as the base-material of functional food, in anti-aging, strengthen immunity, antitumor
Extensive use in equal functional foods.
Glutathione exists in human body in the form of two kinds, and one is reduced glutathione (GSH), another kind is oxidation
Type glutathione (GSSG), the reduced glutathione that the glutathione that usually we say refers to.Since glutathione contains mercapto
Base, therefore glutathione can self-assemble to gold electrode surfaces by-SH.There are many self-assemble to gold about glutathione
Electrode surface is used for detecting the report of metal ion.Zeng etc. is by the mixture self assembly of 3- mercaptopropionic acids and glutathione in gold
The surface of electrode is used for detecting Cu2+, studies have shown that the sensor is for Cu2+Excellent selectivity is shown, detection range is
0.1 μM~1mM；The self assembly of MPA-GSH systems is used for detecting Cd by Chow in gold electrode surfaces2+, repeatability is good for this electrode,
Monitoring lower-cut is 5nM.Decorative material of the glutathione as electrode not only has extensive effect in terms of detecting metal ion,
Some nitrogen-containing molecules are being detected, are also having important role in terms of organic matter.Vilian etc. repaiies RGO/L-P-GSH composite materials
For decorations on glass-carbon electrode, which shows 4- amino phenols excellent electrocatalysis characteristic, and detection range is 0.4~200 μ
M, Monitoring lower-cut have reached 0.03 μM (S/N=3), and selectivity is good, can be applied to the detection of actual sample；Pérez-
R à fols etc. are modified using GSH on screen printing electrode carbon nano-fiber, for detecting Cd2+And Pb2+, Monitoring lower-cut difference
It is 3.0 μ g/L and 3.2 μ g/L；Han etc. utilizes Fe3O4@Au-GSH molecularly imprinted polymer electrochemical methods detect estrogen, this
The detection range that sensor detects estrogen is 0.025~10 μM, and Monitoring lower-cut is 2.76 μM.
Cystine (L-cystine) is that containing disulfide bond, (sulfide linkage is exactly that two thiol molecules are connected using S -- S to one kind
Come structure) amino acid.The detection method of amino acid has very much, high performance liquid chromatography (HPLC), gas chromatography-mass spectrum
(GC-MS), capillary electrophoresis, fluorescence probe detection method etc..But these instrumental methods need costliness in the prevalence of of high cost
Precision instrument, complicated sample preparation flow and skilled operator, and cannot online or inconvenient to carry use etc. lack
It falls into, so exploring the important goal that a kind of analysis method of simple, fast amino acid of development is the area research.With other instrument
Device analysis method is compared, electrochemical method is simple with its, it is sensitive, without radiation, it is pollution-free the features such as increasingly closed by people
Note, is used not only for test in laboratory, and can be additionally used in field assay.Various electrochemical techniques such as Differential Pulse Voltammetry
(DPV), square wave voltammetry (SWV), electrochemical impedance spectroscopy (EIS) and fluorescence spectrophotometric method (ISEs), have been widely used for
Various fields.However, the method for electric potential type electrochemical sensing detection l-cysteine is not yet reported.
Invention content
The present invention is directed to overcome the deficiencies of the prior art and provide a kind of L- based on glutathione composite membrane grid gold electrode
The detection method and sensor of cystine.
In order to achieve the above object, technical solution provided by the invention is：
The detection method of the l-cysteine based on glutathione composite membrane grid gold electrode includes the following steps：
(1) p traps (2) and N-type substrate (3) are implanted on the Si basal layers (1) of scene effect transistor, using thermal evaporation and magnetic
Control sputtering technology builds source electrode (4) and drain electrode (5) at p traps (2), is then being implanted p traps (2) and N-type substrate (3) simultaneously
Structure silicon dioxide layer (6) on the Si basal layers (1) of active electrode (4) and drain electrode (5) is built, then uses thermal evaporation and magnetic control
Sputtering technology plates aluminum-copper alloy layer (8), chromium palladium alloy layer (9) and golden membranous layer successively on the basal layer of polysilicon gate (7)
(10), silicon nitride layer (11) is finally built on the basal layer of polysilicon gate (7) and silicon dioxide layer (6)；By grid part
Extend the distance of 0.1-500mm, the extension grid field effect transistor with grid gold electrode is made；
(2) the grid gold electrode of the extension grid field effect transistor after cleaning is soaked in dibutyl phthalate solution
In, after taking-up, by graphene oxide solution drop coating on grid gold electrode, after the drying of grid gold electrode, by grid gold electrode
It is soaked in glutathione solution, then cleans the grid gold electrode after impregnating, glutathione composite membrane (12) modification is made
Glutathione composite membrane grid gold electrode；The glutathione composite membrane is dibutyl phthalate, graphene oxide and paddy
The composite membrane of the sweet peptide composition of Guang；
(3) by reference electrode, glutathione composite membrane grid gold electrode and the electrode interface for extending grid field effect transistor
Double high resistant differential amplifier circuits are connected to form, reference electrode, glutathione composite membrane grid gold electrode are inserted into PBS buffer solutions
In, the power interface for extending grid field effect transistor is connected with the positive and negative anodes of regulated power supply respectively, it is brilliant by gate field-effect is extended
The signal output interface of body pipe is connected with the test port of universal meter, thus constitutes a complete sensing detection circuit；Profit
The signals in situ amplification of field-effect transistors, can Sensitive Detection system potential change；Paddy Guang as working electrode
Sweet peptide composite membrane grid gold electrode can be intended to stablize as time increases and gradually in the current potential of PBS buffer solutions, wait for electricity
The sample to be tested containing various concentration l-cysteine (13) is added in position after stablizing, and then obtains corresponding potential response data, complete
At the detection of l-cysteine in sample to be tested (13).
Preferably, in step (1), with thermal evaporation and magnetron sputtering technique on the basal layer of polysilicon gate (7) successively
When plating aluminum-copper alloy layer (8), chromium palladium alloy layer (9) and golden membranous layer (10), using Si3N4It is passivated；Aluminum-copper alloy layer (8)
Include the component of following parts by weight：Al 40—68,Cu 30—60,Ni 2—12,Fe 1—8,Ti 1—6,Nb 0.01—
0.50；Chromium palladium alloy layer (9) includes the component of following parts by weight：Cr 40—80,Pd 10—40,Ni 2—12,Fe 1—8,
Ti 1—6,Nb 0.01—0.50；The thickness of aluminum-copper alloy layer (8) is 20-600nm, and the thickness of chromium palladium alloy layer (9) is
The thickness of 20-600nm, golden membranous layer (10) are 20-1000nm.
Preferably, dibutyl phthalate solution described in step (2) is dibutyl phthalate a concentration of 0.1-
The solution of 10.0mmol/L, the graphene oxide solution are the solution of a concentration of 0.1-10.0mg/mL of graphene oxide, institute
The ethanol solution for stating glutathione is the ethanol solution that glutathione concentrations are 0.1-10.0mmol/L.Step is successively in (2)
Extend the grid gold electrode of grid field effect transistor with ultra-pure water and washes of absolute alcohol.Grid gold electrode impregnates in step (2)
Time in dibutyl phthalate solution is 1.0-300min, by graphene oxide solution drop coating in grid gold electrode
The dosage of graphene oxide solution is 1.0-10.0 μ L when upper, and grid gold electrode is soaked in the ethanol solution of glutathione
Time be 1-72h.It is to clean the grid gold electrode after impregnating with absolute ethyl alcohol and ultra-pure water, and done in step (2)
Dry, preservation.
Preferably, the reference electrode in step (3) is the Ag/AgCl electricity of saturated calomel electrode or built-in saturation KCl solution
Pole, working electrode are glutathione composite membrane grid gold electrode.PBS buffer solutions in step (3) are pH3.0-8.0, concentration
For the phosphate buffer solution of 0.1mol/L, pH value is preferably 4.0, and preparation method is by a certain amount of NaH2PO4·2H2O、
Na2HPO4·12H2O, NaCl is dissolved in water by proper proportion mixing, its pH value is adjusted using the hydrochloric acid of 0.1mol/L.
The present invention also provides a kind of sensors of detection l-cysteine, and the sensor includes field-effect transistor, institute
It states field-effect transistor and is equipped with the extended gold electrode of grid, that is, grid gold electrode, in the extended gold electrode of grid, institute
The distance that grid part extends 0.1-500mm is stated, golden membranous layer (10) surface-assembled of gold electrode has glutathione composite membrane
(12)。
Wherein, the field-effect transistor includes Si basal layers (1) and the polysilicon gate on Si basal layers (1)
(7)；It is implanted into p traps (2) and N-type substrate (3) on the Si basal layers (1), source electrode (4) and drain electrode are equipped at the p traps (2)
(5), p traps (2) and N-type substrate (3) are implanted and the Si basal layers (1) for building active electrode (4) and drain electrode (5) are equipped with two
Silicon oxide layer (6)；Plated successively on the basal layer of the polysilicon gate (7) aluminum-copper alloy layer (8), chromium palladium alloy layer (9) and
Golden membranous layer (10)；It is additionally provided with silicon nitride layer (11) on the basal layer of polysilicon gate (7) and silicon dioxide layer (6).The aluminium
The thickness of copper alloy layer (8) is 20-600nm, and the thickness of chromium palladium alloy layer (9) is 20-600nm, the thickness of golden membranous layer (10)
For 20-1000nm.
The sensor has this special response relation of good energy to l-cysteine (13), and the range of linearity is 2.5 × 10-6—
1.0×10-4Mol/L, response sensitivity are 55.72 ± 1.5mV/-pC (25 DEG C), and detection is limited to 1.02 × 10-6mol/L。
The invention will be further described below：
The grid gold electrode (GGE) of field-effect transistor (FET) is extended certain distance by the present invention, such as extends 0.1-
500mm modifies field-effect using dibutyl phthalate/graphene oxide/glutathione (DBP/GO/GSH) composite material
The extended grid gold electrode (GGE) of transistor constructs a kind of novel electric potential type electrochemical sensor of detection l-cysteine.It passes
Electro-chemical test, the XPS analysis at sense interface show trim GSH, and two carboxyls are negatively charged in the solution, contain ammonia with object
In gold electrode surfaces variation of the Electrostatic Absorption so as to cause electrode surface film potential occurs for the l-cysteine of base band positive electricity.The electrode
There are good potential response, linear response model of the electrode to l-cysteine to l-cysteine in the PBS buffer solutions of pH=4.0
Enclose is 5.00 × 10-6—1.00×10-4Mol/L, response sensitivity are 54.16 ± 1.5mV/-pC (25 DEG C), and detection is limited to
1.02×10-6Mol/L, response time are 76 seconds.The electrode has relatively good reproducibility and stability, and the electrode has well
Selectivity, L- glycine (L-Gly), L-threonine (L-Thy), L-phenylalanine (L-Phe), Pidolidone (L-Glu), L-
Alanine (L-Ala), L-Aspartic acid (L-Asp), l-Isoleucine (L-Lle), L-Histidine (L-His), L-PROLINE (L-
Pro), L-lysine (L-Lys), l-methionine (L-Met), L-cysteine (L-Cys) and five metal ion species such as Fe3 +、Zn2+、Cu2+、Ca2+、Ni2+Deng the measurement for not interfering l-cysteine.In addition, the electrode can be used for practical Swine serum, pig urcine
The measurement of l-cysteine in sample, the rate of recovery illustrate that the potentiometric sensor is expected to become l-cysteine up to 99.5-105.7%
A kind of easy, quick new tool of analysis.
In short, the present invention develops a kind of selective membrane electric potential type electrochemical sensor of simplicity, provide a kind of new
The detection method of l-cysteine exists dibutyl phthalate/graphene oxide/glutathione (DBP/GO/GSH) modification
On the extended grid golden membranous layer of field-effect transistor, a kind of novel DBP/GO/GSH self assembly grid gold electrodes (GGE) are formed,
Sensitive Detection is realized to l-cysteine using field-effect transistor signals in situ amplification, wherein glutathione composite membrane is logical
It crosses electrostatic interaction absorption and combines positively charged object l-cysteine, form double electrical layers and generate identification monovalence organic ammonium
The film potential of ion.Experimental results show that the sensor is in l-cysteine a concentration of 5.00 × 10-6—1.00×10- 4Shown within the scope of mol/L it is good can this special response relation, and its preparation process is simple and convenient, and the response time is fast, has
Potential application prospect.
Description of the drawings
Fig. 1 is the design diagram for extending gate field effect transistor；In figure：1, Si basal layers, 2, source electrode, 3, electric leakage
Pole, 4, p traps, 5, N-type substrate, 6, silicon dioxide layer, 7, polysilicon gate, 8, aluminum-copper alloy layer, 9, chromium palladium alloy layer, 10, gold
Film layer, 11, silicon nitride layer, 12, glutathione composite membrane；
Fig. 2 is the identification response theory schematic diagram of DBP/GO/GSH molecule combination l-cysteine molecules；In figure：10, golden film
Layer, 12, glutathione composite membrane, 13, l-cysteine；
Fig. 3：Fig. 3 A and Fig. 3 B be respectively electrode in potassium ferricyanide solution (containing 2.0mmol/LK3[Fe(CN)6],
2.0mmol/L K4[Fe(CN)6], 0.2mol/LNa2SO4) in AC impedance figure and cyclic voltammogram；In Fig. 3 A and Fig. 3 B：
A, GGE, b, GGE/DBP/GO/GSH, c, GGE/DBP/GO/GSH/L-cystine；
Fig. 4 is the full spectrograms of XPS on Different electrodes surface；In figure：A, GGE, b, GGE/DBP/GO/GSH, c, GGE/DBP/
GO/GSH/L-cystine；
Fig. 5 be the complex film modified GGE electrodes of DBP/GO/GSH glutathione slope with pH variation (pH 3.0,3.5,
4.0,4.5,5.0,5.5,6.0,6.5,7.0) relational graph；
Fig. 6 be GGE/DBP/GO/GSH electrodes in the PBS buffer solutions of pH=4.0, in conjunction with various concentration l-cysteine
The potential response curve graph obtained afterwards；
Fig. 7：Fig. 7 A are that various concentration L- Guangs are added in GGE/DBP/GO/GSH electrodes in the PBS buffer solutions of pH=4.0
When m- current potential dynamic curve diagram after propylhomoserin；Fig. 7 B are that l-cysteine (10 is added-4Mol/L the dynamic response curve figure after)；
Fig. 8 is influence of the common amino acid to GGE/DBP/GO/GSH electrode detection l-cysteine.
Specific implementation mode
One, experimentation
1, the preparation of DBP/GO/GSH self-assembled films gold electrode
The preparation process of DBP/GO/GSH self-assembled films：Ultra-pure water and ethyl alcohol cleaning electrode are first used successively；Then GGE is soaked
Bubble 1h in the DBP solution of 1mmol/L；Electrode is taken out after 1h, then 5 μ L of graphene oxide (1mg/mL) solution drop coating exist
On electrode；After pole drying, it is immersed in the GSH/ ethanol solutions of 1mmol/L；The GGE that finally self-assembled film is modified
Taking-up ethyl alcohol and ultra-pure water cleaning, drying preserve, and obtain the self-assembled film gold electrode of composite material.
2, extend the design of gate field effect transistor and the preparation of grid gold electrode
Fig. 1 is the schematic diagram for extending gate field effect transistor, in conjunction with metal-oxide semiconductor fieldeffect transistor
(MOSFET) basic structure, implantation p traps 2 and N-type substrate 3 on the Si basal layers 1 of scene effect transistor, using thermal evaporation and
Magnetron sputtering technique builds source electrode 4 and drain electrode 5 at p traps 2, is then being implanted p traps 2 and N-type substrate 3 and is building active
Silicon dioxide layer 6 is built on the Si basal layers 1 of electrode 4 and drain electrode 5, then using thermal evaporation and magnetron sputtering technique in polysilicon
Aluminum-copper alloy layer 8, chromium palladium alloy layer 9 and golden membranous layer 10 are plated on the basal layer of grid 7 successively, finally in polysilicon gate 7
Silicon nitride layer 11 is built on basal layer and silicon dioxide layer 6；Aluminum-copper alloy layer 8 includes the component of following parts by weight：Al 40—
68,Cu 30—60,Ni 2—12,Fe 1—8,Ti 1—6,Nb 0.01—0.50；Chromium palladium alloy layer 9 includes following parts by weight
Component：Cr 40—80,Pd 10—40,Ni 2—12,Fe 1—8,Ti 1—6,Nb 0.01—0.50；Aluminum-copper alloy layer 8
Thickness be 20-600nm, the thickness of chromium palladium alloy layer 9 is 20-600nm, and the thickness of golden membranous layer 10 is 20-1000nm；It will
The gold electrode of grid part extends the distance of 200mm, and utilizes SiO2And Si3N4It is passivated field-effect transistor chip, it is therefore an objective to
It prevents part of the chip in addition to Au from being contacted with solution, extends gate field effect transistor (EGFET) to be formed.To EGFET's
Extend grid gold electrode (GGE) film surface and carry out different physical/chemical moditied processings, forms sensitive membrane to realize to mesh to be measured
Mark the Sensitive Detection of object.Gluathione is made by the self assembly of glutathione composite membrane on the surface of grid gold electrode by preceding method
The glutathione composite membrane grid gold electrode that peptide composite membrane 12 is modified.
3, the test of self-assembled film grid gold electrode
The electrode potential test phosphate buffer solution (PBS, 0.1mol/L) that buffer system is pH3.0-8.0, matches
Method processed is by a certain amount of NaCl, NaH2PO4·2H2O and Na2HPO4·12H2O is dissolved in water by proper proportion mixing, uses
The hydrochloric acid of 0.1mol/L adjusts its pH value.First, by the good grid gold electrode (GGE) of calomel electrode, self assembly and this laboratory
The extension gate field effect transistor (EGFET) of design is connected to form double high resistant differential amplifier circuits, inserts electrodes into PBS bufferings
In solution, the power interface of EGFET is connected with the positive and negative anodes of regulated power supply respectively, the survey of signal output interface and universal meter
It tries port to be connected, thus constitutes a complete sensing detection circuit.Using the signals in situ amplification of field-effect transistor,
Can Sensitive Detection system potential change.Working electrode GGE can be as time increases and gradual in the current potential of PBS buffer solutions
It is intended to stablize, determinand l-cysteine is added after current potential is stablized, and then obtain corresponding potential response data.
Two, experimental result and analysis
1, the Response Mechanism and electrochemical Characterization of GGE/DBP/GO/GSH electrodes
Glutathione (GSH) is a kind of a kind of substance containing sulfydryl end group, and the sulphur in sulfydryl can form Au- with Au
On golden plate electrode surface, the carboxyl of glutathione dissociates H for S keys and self assembly+And in negatively charged and l-cysteine-
NH3 +Between electrostatic attraction occurs, so as to cause the variation of film potential；And glutathione contain there are two-COOH, and l-cysteine contains
There are two amino, a glutathione molecules combine a l-cysteine molecule, therefore are in the response characteristic of monovalence cation,
It is as shown in Figure 2 to respond identification process.
For the interaction of checking carrier and l-cysteine, the present invention is investigated using AC impedance and cyclic voltammetric method
The electrochemical behavior of above-mentioned different modifying electrode, as shown in Figure 3.Fig. 3 is AC impedance of the electrode in potassium ferricyanide solution
Scheme (A) and cyclic voltammogram (B).A represents naked gold electrode in Fig. 3 A, impedance value very little, and it is compound to represent DBP-GO-GSH by b in Fig. 3 A
The gold electrode of material modification, compared with naked gold electrode, there is small semicircle and illustrates that impedance value becomes larger in high frequency section, and illustrates that this is compound
Material reduces the electric conductivity of gold electrode.In conjunction with l-cysteine (1.0 × 10-5Mol/L after), the semicircle of high frequency section becomes larger, and says
Bright impedance value is increased again (as shown in curve c in Fig. 3 A), this is because with l-cysteine suction-operated occurs for GSH, is reduced
Electronic conductivity, so that the gold electrode impedance value for having modified GSH increases, the variation tendency of impedance can also be followed from accordingly
It is confirmed in ring voltammetric behaviors (Fig. 3 B).
A represents naked gold electrode in Fig. 3 B, there is apparent oxidation peak and reduction peak, illustrates that pretreated naked gold electrode is transmitted
Electronic capability is stronger.B represents the gold electrode of DBP-GO-GSH composite materials modification in Fig. 3 B, and redox peaks are compared with naked gold electrode
It is small much compared to apparent, illustrate that this composite material forms nonconducting unimolecule self assembly by sulfydryl on a gold surface
Film layer hinders [Fe (CN)6]3-/4-It is conducted in the electronics of electrode surface.Combining l-cysteine (1.0 × 10-5Mol/L after),
It redox peaks (as shown in curve c in Fig. 3 B) and reduces, this is because having modified on the gold electrode of composite material again
Continue to have adsorbed cystine, reduce electronic conductivity, to reduce electrochemical transduction electric current, illustrates that DBP-GO-GSH is compound
The gold electrode of material modification has good coordination combination with l-cysteine, shows identification of this method for l-cysteine
Detection is feasible.
2, the XPS characterizations of GGE/DBP/GO/GSH electrodes
Using interaction situation of the x-ray photoelectron spectroscopy (XPS) between modified electrode and object ion done into
One pacing is taken temperature sign, and the full spectrograms of XPS on above-mentioned Different electrodes surface are as shown in Figure 4.As shown in Figure 4, (bent compared to naked gold electrode
Line a), modified the gold electrode after DBP-GO-GSH (curve b) combination can to there is the characteristic peak of S2p at 162.71eV,
Show the electrode surface composite material successfully self assembly in gold electrode surfaces.Curve c represents GGE/DBP/GO/
Surface XPS collection of illustrative plates after GSH electrode detection l-cysteine, modified electrode react l-cysteine after carbon, oxygen element and
The peak intensity of element sulphur is above the peak intensity of electrode before reaction, and different atomic binding energy data can be found that O1s's from table 1
0.31eV is changed in conjunction with that can survey before and after l-cysteine, has been that there are electrostatic adsorptions with l-cysteine due to glutathione, makes
It obtains electronegative GSH originally and has adsorbed positively charged l-cysteine, can be deviated to low energy so it is combined.The combination of S2p can be
To high energy offset by 0.93eV after detection l-cysteine, this is because-the COOH on GSH slough hydrogen and with-NH3 +Electrostatic occurs to inhale
Draw causes its combination that can increase so as to cause the cloud density reduction of S.From table 2 it is also seen that before electrode combination l-cysteine
The variation of C, O, S element highest CPS can also prove that GSH and l-cysteine have occurred the effect of Electrostatic Absorption and make electrode table afterwards
Face is changed.
The different atomic binding energies of table 1
The not homoatomic highest CPS of table 2
3, the selection of Optimal pH
Experiment has studied electrode under the conditions of pH is 3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0 respectively, electricity
Electrode potential with tested solion concentration variation relation, and find out according to this can this special response slope, then make slope and pH
Relational graph, as shown in Figure 5.As can be seen from Figure 5：Electrode response maximum slope when pH=4.0, and its slope value is
55.72 ± 1.5mV/-pC (25 DEG C), the theoretical value of this special response slope close to energy.This explanation, when pH=4.0, electrode response is most
It is good, it is 4.0 to obtain best pH value.
4, GGE/DBP/GO/GSH Responsibility of the electrode
Experiment exam test response performance of the electrode to l-cysteine, Fig. 6 are that PBS buffering of the electrode in pH=4.0 is molten
In liquid, in conjunction with the potential response curve graph obtained after various concentration l-cysteine.As seen from the figure, with the increasing of l-cysteine concentration
Add, electrode potential also gradually increases, and illustrates that the l-cysteine of modified electrode surface bond increases, and the electrode is pH=4.0's
It is 2.5 × 10 to the linear response range of l-cysteine ion in PBS buffer solutions-6mol/L—1.0×10-4mol/L.Together
When, using Least Square in Processing, electrode potential linear response figure is obtained after fitting, the linear equation of electrode is Δ E=
324.40+55.72log10C.Its detection limit can be obtained according to graphing method, and value is about 1.02 × 10-6mol/L.It is responded
Slope is nernst theory response slope values of the 55.72mV/-pC close to monovalence cation, further proves to speculate before us
A glutathione molecules combine a l-cysteine molecule reasonability.
5, the measurement of response time, stability and reproducibility
Response time and the stability of DBP/GO/GSH composite material modified gold electrodes detection l-cysteine have been investigated in experiment.
Fig. 7 A are the when m- current potential dynamic response figures being added in PBS buffer solutions after various concentration l-cysteine, by 1.0 ×
10-6—1.0×10-4Its current potential changed over time is continuously measured and recorded within the scope of mol/L from low concentration to high concentration
Value, it can be seen that in entire concentration range electrode reach balance reaction time it is very short, to reach potential response maximum value
95% calculates response time, as 76s, shows that the electrode can have l-cysteine response speed quickly；Fig. 7 B are to add again
Enter 10-4Dynamic response curve after mol/L l-cysteine, the response performance for further demonstrating the electrode are stablized.By the electricity
Extremely to 1.0 × 10-5Mol/L l-cysteine samples follow-on test 35 days, response slope variation is 45.36mV/-pC, is had dropped
18.59%, illustrate that the potentiometric sensor can about use 1 month or more, service life is longer.
The reproducibility of 3 GGE/DBP/GO/GSH electrodes of table
The experiment exam electricity of GGE/DBP/GO/GSH composite material modified electrode combination various concentration l-cysteine samples
Position response reproducibility, i.e., to 1 × 10-5Mol/L and 1 × 10-4The l-cysteine standard items of mol/L measure their current potential back and forth
Value, it is each to survey 10 times (as shown in table 3).By the analysis and processing of data, it is found that relative standard deviation is respectively 1.39% He
2.45%, and relative standard deviation is smaller, illustrates that reproducibility of the electrode in the l-cysteine of two various concentrations is preferable.
6, the selectivity of electrode
One of key property of ion selective electrode is exactly that its selectivity is good, is only had to a certain specific substance
There is response.Therefore, in the PBS buffer solutions of the pH=4.0 containing modified electrode, 10 μM of l-cysteine, chaff interferent is added
10 times of a concentration of test substance concentration, i.e., 100 μM, wherein examining L- glycine (L-Gly), L-threonine (L-Thy), L-
Phenylalanine (L-Phe), Pidolidone (L-Glu), l-Alanine (L-Ala), L-Aspartic acid (L-Asp), l-Isoleucine
(L-Lle), L-Histidine (L-His), L-PROLINE (L-Pro), L-lysine (L-Lys), l-methionine (L-Met), L-
Cysteine (L-Cys) and five metal ion species such as iron, zinc, copper, calcium, nickel plasma (shown in Fig. 8).The result shows that removing L-
The interference unobvious of other 17 kinds of interfering substances except cysteine to test substance l-cysteine, it may be said that the bright sensing
Device has good selectivity.
7, the measurement of the rate of recovery is applied with analysis
Under the conditions of Optimal Experimental, grid gold electrode is modified to L- Guangs in actual sample using DB/GO/GSH composite materials
Propylhomoserin concentration is measured.When measurement, actual sample Swine serum 1,2 is acquired respectively and pig urcine 3,4 centrifuges, supernatant is taken, uses
The PBS buffer solution that pH is 4.0 dilutes 10 times, and the l-cysteine that known concentration is added in the sample is measured by standard addition method
For the rate of recovery between 99.5-105.7%, experimental result illustrates that the electrode can be used for the detection of l-cysteine in actual sample.
In short, the present invention provides a kind of electrodes selective for modifying extension grid golden film based on DBP/GO/GSH, experiment
The result shows that the electrode is in the PBS buffer solutions of pH=4.0, highly sensitive energy this spy is shown to l-cysteine and is responded
Relationship, linear response range are 2.5 × 10-6—1.0×10-4Mol/L, detection are limited to 1.02 × 10-6mol/L.The electrode is rung
(about 76 seconds) short between seasonable, and have good selectivity, reproducibility and the features such as stability.In addition, the electrode can be used for
The detection of l-cysteine in actual sample is expected to the novel means as on-line checking l-cysteine.
Claims (10)
1. a kind of detection method of the l-cysteine based on glutathione composite membrane grid gold electrode, which is characterized in that the side
Method includes the following steps：
(1) it is implanted into p traps (2) and N-type substrate (3) on the Si basal layers (1) of scene effect transistor, is splashed using thermal evaporation and magnetic control
It penetrates technology and builds source electrode (4) and drain electrode (5) at p traps (2), be then implanted p traps (2) and N-type substrate (3) and building
Silicon dioxide layer (6) is built on the Si basal layers (1) of active electrode (4) and drain electrode (5), then uses thermal evaporation and magnetron sputtering
Technology plates aluminum-copper alloy layer (8), chromium palladium alloy layer (9) and golden membranous layer (10) successively on the basal layer of polysilicon gate (7),
Silicon nitride layer (11) is finally built on the basal layer of polysilicon gate (7) and silicon dioxide layer (6)；Grid part is extended
The extension grid field effect transistor with grid gold electrode is made in the distance of 0.1-500mm；
(2) the grid gold electrode of the extension grid field effect transistor after cleaning is soaked in dibutyl phthalate solution,
After taking-up, by graphene oxide solution drop coating on grid gold electrode, after the drying of grid gold electrode, grid gold electrode is impregnated
In glutathione solution, the grid gold electrode after impregnating then is cleaned, the paddy Guang of glutathione composite membrane (12) modification is made
Sweet peptide composite membrane grid gold electrode；The glutathione composite membrane is dibutyl phthalate, graphene oxide and gluathione
The composite membrane of peptide composition；
(3) reference electrode, glutathione composite membrane grid gold electrode are connected with the electrode interface for extending grid field effect transistor
Double high resistant differential amplifier circuits are formed, reference electrode, glutathione composite membrane grid gold electrode are inserted into PBS buffer solutions,
The power interface for extending grid field effect transistor is connected with the positive and negative anodes of regulated power supply respectively, grid field effect transistor will be extended
Signal output interface be connected with the test port of universal meter, thus constitute a complete sensing detection circuit；Utilize field
The signals in situ amplification of effect transistor, can Sensitive Detection system potential change；Glutathione as working electrode
Composite membrane grid gold electrode can be intended to stablize as time increases and gradually in the current potential of PBS buffer solutions, wait for that current potential is steady
The sample to be tested containing various concentration l-cysteine (13) is added after fixed, and then obtains corresponding potential response data, completes to wait for
The detection of l-cysteine (13) in sample.
2. the method as described in claim 1, which is characterized in that in step (1), with thermal evaporation and magnetron sputtering technique in polycrystalline
When plating aluminum-copper alloy layer (8), chromium palladium alloy layer (9) and golden membranous layer (10) on the basal layer of silicon gate (7) successively, using Si3N4
It is passivated；Aluminum-copper alloy layer (8) includes the component of following parts by weight：Al 40—68,Cu 30—60,Ni 2—12,Fe
1—8,Ti 1—6,Nb 0.01—0.50；Chromium palladium alloy layer (9) includes the component of following parts by weight：Cr 40—80,Pd
10—40,Ni 2—12,Fe 1—8,Ti 1—6,Nb 0.01—0.50；The thickness of aluminum-copper alloy layer (8) is 20-600nm,
The thickness of chromium palladium alloy layer (9) is 20-600nm, and the thickness of golden membranous layer (10) is 20-1000nm.
3. the method as described in claim 1, which is characterized in that dibutyl phthalate solution described in step (2) is neighbour
The solution of a concentration of 0.1-10.0mmol/L of dibatyl phithalate, the graphene oxide solution are graphene oxide concentration
For the solution of 0.1-10.0mg/mL, it is 0.1-10.0mmol/L that the ethanol solution of the glutathione, which is glutathione concentrations,
Ethanol solution.
4. the method as described in claim 1, which is characterized in that grid gold electrode is soaked in phthalic acid two in step (2)
Time in butyl acetate solution is 1.0-300min, by graphene oxide solution drop coating when on grid gold electrode graphene oxide
The dosage of solution is 1.0-10.0 μ L, and grid gold electrode is soaked in the time in the ethanol solution of glutathione as 1-72h.
5. the method as described in claim 1, which is characterized in that the reference electrode in step (3) is saturated calomel electrode or interior
The Ag/AgCl electrodes of saturation KCl solution are set, working electrode is glutathione composite membrane grid gold electrode.
6. the method as described in claim 1, which is characterized in that PBS buffer solutions in step (3) are pH3.0-8.0, dense
Degree is the phosphate buffer solution of 0.1mol/L.
7. a kind of sensor of detection l-cysteine, the sensor includes field-effect transistor, on the field-effect transistor
Equipped with the extended gold electrode of grid, which is characterized in that in the extended gold electrode of grid, the grid part extends 0.1-
Golden membranous layer (10) surface-assembled of the distance of 500mm, gold electrode has glutathione composite membrane (12)；The glutathione composite membrane
For the composite membrane of dibutyl phthalate, graphene oxide and glutathione composition.
8. sensor as claimed in claim 7, which is characterized in that the field-effect transistor includes Si basal layers (1) and sets
In the polysilicon gate (7) on Si basal layers (1)；P traps (2) and N-type substrate (3), the p are implanted on the Si basal layers (1)
It is equipped with source electrode (4) and drain electrode (5) at trap (2), be implanted p traps (2) and N-type substrate (3) and builds active electrode (4) and leakage
The Si basal layers (1) of electrode (5) are equipped with silicon dioxide layer (6)；Plated aluminum successively on the basal layer of the polysilicon gate (7)
Copper alloy layer (8), chromium palladium alloy layer (9) and golden membranous layer (10)；In the basal layer and silicon dioxide layer (6) of polysilicon gate (7)
On be additionally provided with silicon nitride layer (11).
9. sensor as claimed in claim 8, which is characterized in that the thickness of the aluminum-copper alloy layer (8) is 20-600nm,
The thickness of chromium palladium alloy layer (9) is 20-600nm, and the thickness of golden membranous layer (10) is 20-1000nm.
10. such as claim 7 to 9 any one of them sensor, which is characterized in that the sensor has l-cysteine (13)
There is this special response relation of good energy, the range of linearity is 2.5 × 10-6—1.0×10-4Mol/L, response sensitivity be 55.72 ±
1.5mV/-pC (25 DEG C), detection are limited to 1.02 × 10-6mol/L。
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