CN104977342B - Graphene peels off houghite piece composite ankyrin modified electrode and its preparation method and application - Google Patents
Graphene peels off houghite piece composite ankyrin modified electrode and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 102000008102 Ankyrins Human genes 0.000 title claims abstract description 26
- 108010049777 Ankyrins Proteins 0.000 title claims abstract description 26
- 238000001548 drop coating Methods 0.000 claims abstract description 22
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 102000001554 Hemoglobins Human genes 0.000 claims abstract description 9
- 108010054147 Hemoglobins Proteins 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 8
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- 239000002608 ionic liquid Substances 0.000 claims abstract description 6
- 150000001721 carbon Chemical class 0.000 claims abstract description 3
- 238000009830 intercalation Methods 0.000 claims description 41
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- 239000000463 material Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 19
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- 238000000967 suction filtration Methods 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
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- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 235000014103 egg white Nutrition 0.000 claims description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
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- Inert Electrodes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Houghite piece (ELDH) composite ankyrin modified electrode and its preparation method and application is peeled off the invention discloses a kind of graphene (GR).The features such as present invention is using ELDH positively chargeds and big specific surface area, is combined, then with hydrazine hydrate reduction, GR ELDH hybrids have been made by electrostatic attraction with electronegative stripping stannic oxide/graphene nano piece (GO).GR ELDH, hemoglobin and chitosan are fixed on Ionic Liquid Modified carbon paste electrode successively using drop-coating, graphene is prepared for and peels off houghite piece composite ankyrin modified electrode.Gained modified electrode of the invention has played individual layer GR nanometer sheets and ELDH cooperative effect, and GR nanometer sheets add ELDH electric conductivity, it is suppressed that it is assembled and accumulated；ELDH effectively inhibits the stacking again of GR lamellas, reduce the contact resistance of piece interlayer, the electron transport rate of composite is improved, the third generation trichloroacetic acid sensor based on CTS/GR ELDH Hb composite membranes constructed has the advantages that test limit is low, detection range is wide and Michaelis constant is small.
Description
Technical field：
The present invention relates to a kind of graphene-stripping houghite piece composite ankyrin modified electrode；The present invention is also
It is related to the preparation method of the modified electrode and its application in electrochemical sensing context of detection.
Background technology：
Biology sensor is to be filled with reference to the sensing element of biological or biological derivative with an alanysis of physics and chemistry transducer
Put, it can produce interruption or continuous signal according to the concentration of analyte, and signal strength is directly proportional to concentration and [opened first
Grace, biology sensor [M], Beijing:Chemical Industry Press, 2006,16-40.].Wherein, enzyme electrochemical sensor is in recent years
Cause great concern.Bovine hemoglobin enzyme (Hb) is simple in construction and representative, it is easy to accomplish large-scale production, therefore
By the ideal model as Direct Electrochemistry.Research simultaneously for Hb Direct electron transfers can also promote people to organism
The understanding of electron transport mechanism.However, Hb activated centre generally buries relatively deep, in electrode surface it is difficult to occur direct electrification
Learn, and they directly adsorb in bare electrode surface and easily fall off denaturation.Therefore, find the activity that can keep enzyme and promote
The material of direct electron transfer, it has also become the important topic of bioelectrochemical sensing area research.
Graphene nanometer sheet due to remarkable chemical property, such as excellent electric conductivity, big specific surface area and
Good mechanical performance etc., in recent years turn into build electrochemica biological sensor common used material [K.S.Novoselov,
A.K.Geim,S.V.Morozov,D.Jiang,Y.Zhang,S.V.Dubonos,I.V.Grigorieva,A.A.Firsov,
Science 306(2004)666.].At present, due to low cost and be easy to large-scale production etc. advantage, people's generally useization
Learn redox graphene (GO) and prepare graphene (GR).However, in this preparation process, graphene film interlayer easily occurs not
It is reversible to stack and reassemble, dispersed individual layer GR nanometer sheets well can not be obtained, so as to can not play to greatest extent
The excellent electrochemical performance of graphene, expands its potential application [X.C.Dong, H.Xu, X.W.Wang.3D in every field
graphene-cobalt oxide electrode for high-performance supercapacitor and
enzymeless glucose detection.ACS nano,2012,6:3206~3213.].Research find, by by other
Nano material intercalation layer by layer can be dispersed in other nano materials effectively to solve above-mentioned ask well between GR monolithics
Topic, while the electric conductivity of composite can also be strengthened.Therefore, find a kind of suitable stratified material and be intercalated into GR interlayers,
It is to expand the effective means that GR different fields are deeply applied to prepare GR nano-complexes.
Class neatly (being abbreviated as LDH) is class two-dimensional nanometer anionic clay, and composition formula is represented by [M1-x 2+Mx 3+
(OH)2]x+(An-)x/n·mH2O, with hydrotalcite layered structure, lamella band structure positive charge, interlayer exist it is tradable it is cloudy from
Son.The pluggable LDH interlayers of the biomolecule such as negatively charged amino acid, DNA, protein, polypeptide and enzyme, formation biomolecule-
[application chemistry of Zhan Tianrong, Hou Wan state the layered double hydroxides in green material field is logical for LDH nano hybrids
Report, 2010,73 (7)：608~615.].At present, researcher is learned by softenings such as absorption, stripping restructuring, co-precipitation, electro-deposition
Method realizes fixation of the biology enzyme on LDH, and the Direct Electrochemistry result of study of corresponding biology enzyme shows, LDH nanometer sheet
Rotating fields had both maintained the activity of biology enzyme, and the transmission of electronics is promoted again.But when LDH is as electrode modified material immobilized enzyme,
Not only its own conductive poor shortcoming, and due to its bad dispersibility and easy agglomeration traits, is also easy to cause electrode table
There is protuberance, embrittlement in face, phenomenon [Han E, Shan D, Xue H G, the Cosnier S.Hybrid material such as even come off
based on chitosan and layered double hydroxides:characterization and
application to the design of amperometric phenol biosensor.Biomacromolecules,
2007,8:971~975.].
The aggregation that exists and the shortcomings of stacking during in order to solve that GR and LDH is used alone, researcher is by positively charged LDH
It is combined with GR, but the research of this respect at present mainly prepares LDH in GO dispersion mediums situ, and such as Gao is in list
Ureal antigen Vacuum-assisted method GNS-NiAl-LDH is used to answer in the water dispersion medium of the graphene film (GNS) of atomic layer
Compound [Z.Gao, J.Wang, Z.Li, W.Yang, B.Wang, M.Hou, Y.He, Q.Liu, T.Mann, P.Yang, M.Zhang,
L.Liu,Chem.Mater.2011,23；3509-3516.], Li etc. uses ureal antigen in the GO water dispersion mediums of stripping
Vacuum-assisted method GR-NiFe-LDH compounds [H.Li, G.Zhu, Z.-H.Liu, Z.Yang, Z.Wang, Carbon
2010,48:4391-4396.], LDH in obtained compound but is studied above still with multilayer form to exist, although certain
The problem of GR accumulations are solved in degree and are assembled, but LDH still can not reach good dispersion effect.The houghite of stripping
Nanometer sheet (ELDH) refers to the colloid that monolithic is peeled off into by LDH, with bigger specific surface area and super good dispersive property, and
And be especially advantageous for the property such as positive charge acting on compound by electrostatic attraction with negatively charged GO on its lamella, by two kinds of differences
The mutual intercalation of nanometer sheet in respective interlayer, effectively ELDH nanometer sheets and GO nanometer sheets can be kept apart, prepared corresponding
GO-ELDH nano-complexes, then it is reduced with reducing agent again, prepare GR-ELDH nano-complexes.At present by
Negatively charged GO is combined by electrostatic attraction effect with positively charged ELDH, then prepares GR-ELDH compounds through reduction, and is adopted
GR-ELDH- protein modifications electrode is prepared with drop method fixing protein and its yet there are no in the research of hydrogen peroxide context of detection
Report.The present invention will prepare GR-ELDH compounds using electrostatic assembly and drop-coating and fix protein on the composite,
Prepare corresponding bio-modification electrode and tentatively examine or check its detection to trichloroacetic acid.
GR-ELDH compounds are prepared using electrostatic assembly and drop-coating and fix protein on the composite, are prepared
Corresponding bio-modification electrode, is conducive to GR nanometer sheets and ELDH nanometer sheets being dispersed in each other in the middle of respective lamella, effectively
Suppress the shortcomings of accumulation and aggregation for existing when two kinds of nanometer sheets are used alone, and can fully combine GR nanometer sheets and ELDH nanometers
Advantage of the piece in terms of electrode modified material, makes up the defect existed when they are used alone, will be provided for composite modified electrode
More avtive spots, higher electric conductivity, more preferable biocompatibility and dispersiveness and to the crystallized ability of enzyme, play two
The synergy advantage of person, so that Direct Electrochemistry and electrocatalysis characteristic of the biomolecule in modified electrode are improved, it is new to setting up
The high sensitive electrochemical detection method of type is significant.
The content of the invention：
In view of the shortcomings of the prior art and this area research and application demand, an object of the present invention is to provide one
Plant graphene-stripping houghite piece composite ankyrin modified electrode；It is i.e. by electrostatic attraction that two dimension is electronegative
GO nanometer sheets are combined with ELDH nanoscale twins, are then prepared GR-ELDH compounds through reduction again, are eventually used for the fixation of protein
With the preparation of corresponding modified electrode.
A kind of graphene that the present invention is provided-stripping houghite piece composite ankyrin modified electrode, its feature
It is that it includes basal electrode layer and graphene-stripping houghite piece composite ankyrin layer；Graphene-the stripping
Houghite piece composite is to be attracted each other by the graphite oxide nanometer sheet peeled off and the houghite piece of stripping by electrostatic
Effect assembling, then be made through hydrazine hydrate reduction；Protein is fixed on graphene-stripping houghite piece hydridization material by drop-coating
Compound protein layer is formed on material；Wherein graphene is designated as GR, peels off houghite piece and is designated as ELDH；
The graphene-stripping houghite piece composite ankyrin modified electrode, it is characterised in that the stripping
Houghite piece is cobalt aluminium profiles；The protein is bovine hemoglobin, is designated as Hb；The basal electrode is Ionic Liquid Modified carbon
Paste electrode, is designated as CILE；
The two of the object of the invention are to provide a kind of graphene-stripping houghite piece composite ankyrin modified electrode
Preparation method, including step in detail below：
(a) ELDH preparation
By divalent metal salt CoCl2·6H2O, trivalent metal salt AlCl3·6H2O and urea are added to dress by a certain percentage
In the round-bottomed flask for having certain volume deionized water, total concentration of metal ions is 0.15mol/L, 60~98 DEG C be stirred at reflux 10~
36 hours, suction filtration, filter cake use distillation water washing 3~5 times, dried 48 hours, obtain carbonate intercalation at room temperature after completion of the reaction
LDH；
The LDH of a certain amount of carbonate intercalation is weighed, NaCl and 3.3mmol/L that concentration is respectively 1mol/L is scattered in
HCl mixed aqueous solutions in, N2Stirred 12 hours under atmosphere, drying at room temperature 12 hours after suction filtration obtain chlorion intercalation
LDH；
The LDH of a certain amount of chlorion intercalation is weighed, the NaNO that concentration is 0.1mol/L is scattered in3The aqueous solution in, N2
Stirred 12 hours under atmosphere, drying at room temperature 12 hours after suction filtration obtain the LDH of nitrate anion intercalation；
The LDH for weighing a certain amount of nitrate anion intercalation is scattered in formamide, and it is 1mg/mL, N to make its concentration2Stirred under atmosphere
24 hours, the mixed liquor is centrifuged into 10min under the conditions of 2000rpm, precipitation is discarded to remove unstripped product, what is obtained is clear
Clear liquid is to peel off product ELDH colloids；
(b) preparation of GR-ELDH nano-hybrid materials
Graphene oxide is prepared using hummer methods, GO is designated as, and a certain amount of GO is scattered in formamide, makes its dense
Spend and remove unstripped GO, the GO dispersion liquids peeled off for 1mg/mL, ultrasonic disperse 1 hour, 3000rpm centrifugations 10min；Will
The GO dispersion liquids ELDH colloidal solution isometric with gained in (a) is sufficiently mixed, and room temperature is stirred 12 hours under confined conditions,
After 5000rpm centrifugations 10min, gained brownish black precipitation is scattered in deionized water again, adds a certain amount of hydrazine hydrate in 80
DEG C stirring reaction 2.5 hours, 4000rpm centrifugations 10min obtains GR-ELDH hybrid materials；
(c) CILE preparation
By graphite powder and ionic liquid BPPF6With 2:1 mass ratio is added in mortar, is uniformly mixed under the conditions of being heated to 80 DEG C
Close, 1mL atoleines are added dropwise into the powder mixture and insert glass as adhesive, then after mixture is fully ground
The solid mixture in glass tube is compacted as wire, CILE is obtained, using preceding by the electrode by insertion copper wire in Guan Zhong, pipe
Surface is polished smooth；
(d) preparation of GR-ELDH composites ankyrin modified electrode
The GR-ELDH hybrid materials obtained in step (b) are configured to the pulpous state liquid that concentration is 1mg/mL with deionized water,
The CILE surfaces of 8 μ L pulpous state drop-coateds gained in step (c) are taken, the μ L concentration of drop coating 8 is on electrode again after drying naturally
The 10mg/mL Hb aqueous solution, after drying naturally, continues the chitosan CTS acetums that the μ L concentration of drop coating 6 is 1.0mg/mL, from
CTS/GR-ELDH-Hb/CILE bio-modification electrodes are obtained after so drying.
Divalent metal salt CoCl wherein described in step (a)2·6H2O, trivalent metal salt AlCl3·6H2O and urea rub
You are than being 2：1：7；The deionized water of certain volume is 400mL；The LDH of the carbonate intercalation weighed the and LDH of chlorion intercalation
Amount is quality of the compound concentration required for 1mg/mL suspension；The quality such as the consumption of hydrazine hydrate and GO in step (b)；Step
(b) the GR-ELDH hybrid materials obtained by are composited by the GR of individual layer and the ELDH nanometer sheets of individual layer, and its thickness is about 0.85-
1nm。
The three of the object of the invention are to provide a kind of graphene-stripping hydrotalcite-like composite material ankyrin modified electrode and existed
Prepare the application in terms of electrochemical sensor.
Specifically, the graphene-stripping hydrotalcite-like composite material ankyrin modified electrode is detected in trichloroacetic acid
The application of aspect.
The advantages of present invention utilizes ELDH positively charged and big specific surface area, passes through electrostatic attraction and is peeled off with electronegative
GO nanometer sheets are combined, and are then reduced compound by hydrazine hydrate, GR-ELDH nano hybrids are prepared, using drop-coating
GR-ELDH, hemoglobin and chitosan are fixed on CILE successively, graphene-stripping houghite has been prepared and has been combined
Material ankyrin modified electrode, to improve direct electron transfer of the hemoglobin on modified electrode, is constructed based on CTS/GR-
The third generation trichloroacetic acid sensor of ELDH-Hb composite membranes.The biology sensor for detection trichloroacetic acid have test limit it is low,
The advantages of detection range is wide and Michaelis constant is small.
Compared with prior art, major advantage is the present invention：Pass through electrostatic attraction and electronegative stripping GO nanometer sheets
It is combined, then by hydrazine hydrate by composite reduction, GR-ELDH is prepared, using drop-coating successively by GR-ELDH, blood red egg
White and chitosan is fixed on CILE, is prepared for graphene-stripping hydrotalcite-like composite material ankyrin modified electrode；This hair
Bright gained composite modified electrode has played individual layer GR nanometer sheets in terms of hemoglobin Direct Electrochemistry and electrocatalysis characteristic is improved
With ELDH cooperative effect, graphene sheet layer adds ELDH electric conductivity, it is suppressed that it is assembled and accumulated；And ELDH is incorporated into
On GR nanoscale twins, the stacking again of GR lamellas is effectively inhibited, the contact resistance of piece interlayer is reduced, improves composite
Electron transport rate；Specifically, unexpected technique effect, this hair are generated to the effect that the direct fax of hemoglobin is passed
Bright gained composite modified electrode is acted on hemoglobin direct electron transfer, and single LDH or GR, or with passing through letter
The GR-LDH compounds that single physical mixed is obtained are compared, and all tool is significantly improved.The inventive method is simple to operate, condition temperature
With, prepare cost it is low.
Brief description of the drawings：
Fig. 1 is the IR spectrograms for the composite GR-ELDH-Hb (b) that Hb (a) is loaded with Hb with the gained of embodiment 1.
Fig. 2 is GR-ELDH atomic force microscopy.
Fig. 3 is embodiment 4 (e) with being repaiied obtained by comparative example 1 (a), comparative example 2 (b), comparative example 3 (c) and comparative example 4 (d)
Adorn electrode in pH=4 B-R cushioning liquid, sweep speed be 0.1V/s when cyclic voltammogram.
Fig. 4 is to be repaiied obtained by embodiment 4 (e), comparative example 1 (a), comparative example 2 (b), comparative example 3 (c) and comparative example 4 (d)
Decorations electrode is containing 10.0mmol/L [Fe (CN)6]-3/-4With the electrochemical impedance figure in 0.1mol/L KCl solution.
Fig. 5 be by the gained of embodiment 4 CTS/GR-ELDH-Hb/CILE under nitrogen protection, buffered in pH=4 B-R
The cyclic voltammetry curve of the trichloroacetic acid of different volumes is added in solution, it is 100mV/s to sweep speed, illustration is reduction peak current and three
The linear relationship of chloroethene acid concentration.
Fig. 6 is comparative example 1 is obtained in embodiment 5 CTS/GR-LDH-Hbmix/ CILE under nitrogen protection, in pH
The cyclic voltammetry curve of the trichloroacetic acid of different volumes is added in=4 B-R cushioning liquid, it is 100mV/s to sweep speed, and illustration is also
Parent peak electric current and the linear relationship of trichloroacetic acid concentration.
Embodiment：
To further understand the present invention, the invention will be further described with reference to the accompanying drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1：
(a) ELDH preparation
By divalent metal salt CoCl2·6H2O, trivalent metal salt AlCl3·6H2O and urea in molar ratio 2：1：7 ratio
It is added in the round-bottomed flask equipped with certain volume deionized water, total concentration of metal ions is 0.15mol/L, and 85 DEG C are stirred at reflux
18 hours, suction filtration, filter cake use distillation water washing 3~5 times, dried 48 hours, obtain carbonate intercalation at room temperature after completion of the reaction
LDH；The LDH of 100mg carbonate intercalations is weighed, NaCl and 3.3mmol/L that concentration is respectively 1mol/L is scattered in
In HCl mixed aqueous solutions, N2Stirred 12 hours under atmosphere, drying at room temperature 12 hours after suction filtration obtain the LDH of chlorion intercalation；
The LDH of 60mg chlorion intercalations is weighed, the NaNO that 60mL concentration is 0.1mol/L is scattered in3The aqueous solution in, N2Under atmosphere
Stirring 12 hours, drying at room temperature 12 hours after suction filtration obtain the LDH of nitrate anion intercalation；Weigh LDH points of 50mg nitrate anion intercalations
Dissipate in formamide, it is 1mg/mL, N to make its concentration2Under atmosphere stir 24 hours, by the mixed liquor under the conditions of 2000rpm from
Heart 10min, discards precipitation to remove unstripped product, and obtained clarified solution is to peel off product ELDH colloids.
(b) preparation of GR-ELDH nano-hybrid materials
Graphene oxide is prepared using hummer methods, GO is designated as, and 50mg GO are scattered in formamide, makes its concentration
For 1mg/mL, ultrasonic disperse 1 hour, 3000rpm centrifugations 10min removes unstripped GO, the GO dispersion liquids peeled off；Should
The GO dispersion liquids ELDH colloidal solution isometric with gained in (a) is sufficiently mixed, and room temperature is stirred 12 hours under confined conditions,
After 5000rpm centrifugations 10min, gained brownish black precipitation is scattered in deionized water again, is added 50mg hydrazine hydrates and is stirred in 80 DEG C
Reaction 2.5 hours is mixed, 4000rpm centrifugations 10min obtains GR-ELDH hybrid materials；
(c) CILE preparation
By graphite powder and ionic liquid (BPPF6) with 2:1 mass ratio is added in mortar, uniform under the conditions of being heated to 80 DEG C
Mixing, into the powder mixture 1mL atoleines are added dropwise inserts glass as adhesive, then after mixture is fully ground
In glass pipe, the solid mixture in glass tube is compacted as wire, CILE is obtained, using preceding by the electricity by insertion copper wire in pipe
Pole surface is polished smooth；
(d) preparation of GR-ELDH composites ankyrin modified electrode
The GR-ELDH hybrid materials obtained in step (b) are configured to the pulpous state liquid that concentration is 1mg/mL with deionized water,
The CILE surfaces of 8 μ L pulpous state drop-coateds gained in step (c) are taken, the μ L concentration of drop coating 8 is on electrode again after drying naturally
The 10mg/mL Hb aqueous solution, after drying naturally, continues the CTS acetums that the μ L concentration of drop coating 6 is 1.0mg/mL, spontaneously dries
After obtain CTS/GR-ELDH-Hb/CILE bio-modification electrodes.
Embodiment 2：
(a) ELDH preparation
By divalent metal salt CoCl2·6H2O, trivalent metal salt AlCl3·6H2O and urea are by molar ratio 2：1：7 ratio
Example is added in the round-bottomed flask equipped with certain volume deionized water, and total concentration of metal ions is 0.15mol/L, and 90 DEG C are stirred back
Stream 24 hours, suction filtration after completion of the reaction, filter cake distillation water washing 3~5 times is dried 48 hours, obtains carbonate and insert at room temperature
The LDH of layer；The LDH of 100mg carbonate intercalations is weighed, NaCl and 3.3mmol/L that concentration is respectively 1mol/L is scattered in
HCl mixed aqueous solutions in, N2Stirred 12 hours under atmosphere, drying at room temperature 12 hours after suction filtration obtain chlorion intercalation
LDH；The LDH of 60mg chlorion intercalations is weighed, the NaNO that 60mL concentration is 0.1mol/L is scattered in3The aqueous solution in, N2Gas
Stirred 12 hours under atmosphere, drying at room temperature 12 hours after suction filtration obtain the LDH of nitrate anion intercalation；Weigh 50mg nitrate anion intercalations
LDH is scattered in formamide, and it is 1mg/mL, N to make its concentration2Stirred 24 hours under atmosphere, by the mixed liquor in 2000rpm conditions
Lower centrifugation 10min, discards precipitation to remove unstripped product, and obtained clarified solution is to peel off product ELDH colloids.
(b) preparation of GR-ELDH nano-hybrid materials
Prepared according to the method in step (b) in embodiment 1 and condition
(c) CILE preparation
It is prepared by method and condition on time in embodiment 1 in step (c)
(d) preparation of GR-ELDH composites ankyrin modified electrode
CTS/GR-ELDH-Hb/CILE biologies are prepared according to the method and condition in step (d) in embodiment to repair
Adorn electrode.
Embodiment 3：
(a) ELDH preparation
By divalent metal salt CoCl2·6H2O, trivalent metal salt AlCl3·6H2O and urea are by molar ratio 2：1：7 ratio
Example is added in the round-bottomed flask equipped with certain volume deionized water, and total concentration of metal ions is 0.15mol/L, and 95 DEG C are stirred back
Stream 32 hours, suction filtration after completion of the reaction, filter cake distillation water washing 3~5 times is dried 48 hours, obtains carbonate and insert at room temperature
The LDH of layer；The LDH of 100mg carbonate intercalations is weighed, NaCl and 3.3mmol/L that concentration is respectively 1mol/L is scattered in
HCl mixed aqueous solutions in, N2Stirred 12 hours under atmosphere, drying at room temperature 12 hours after suction filtration obtain chlorion intercalation
LDH；The LDH of 60mg chlorion intercalations is weighed, the NaNO that 60mL concentration is 0.1mol/L is scattered in3The aqueous solution in, N2Gas
Stirred 12 hours under atmosphere, drying at room temperature 12 hours after suction filtration obtain the LDH of nitrate anion intercalation；Weigh 50mg nitrate anion intercalations
LDH is scattered in formamide, and it is 1mg/mL, N to make its concentration2Stirred 24 hours under atmosphere, by the mixed liquor in 2000rpm conditions
Lower centrifugation 10min, discards precipitation to remove unstripped product, and obtained clarified solution is to peel off product ELDH colloids.
(b) preparation of GR-ELDH nano-hybrid materials
Prepared according to the method in step (b) in embodiment 1 and condition
(c) CILE preparation
Prepared according to the method in step (c) in embodiment 1 and condition
(d) preparation of GR-ELDH composites ankyrin modified electrode
CTS/GR-ELDH-Hb/CILE biologies are prepared according to the method and condition in step (d) in embodiment to repair
Adorn electrode.
Embodiment 4：
(a) ELDH preparation
By divalent metal salt CoCl2·6H2O, trivalent metal salt AlCl3·6H2O and urea are by molar ratio 2：1：7 ratio
Example is added in the round-bottomed flask equipped with certain volume deionized water, and total concentration of metal ions is 0.15mol/L, and 97 DEG C are stirred back
Stream 48 hours, suction filtration after completion of the reaction, filter cake distillation water washing 3~5 times is dried 48 hours, obtains carbonate and insert at room temperature
The LDH of layer；The LDH of 100mg carbonate intercalations is weighed, NaCl and 3.3mmol/L that concentration is respectively 1mol/L is scattered in
HCl mixed aqueous solutions in, N2Stirred 12 hours under atmosphere, drying at room temperature 12 hours after suction filtration obtain chlorion intercalation
LDH；The LDH of 60mg chlorion intercalations is weighed, the NaNO that 60mL concentration is 0.1mol/L is scattered in3The aqueous solution in, N2Gas
Stirred 12 hours under atmosphere, drying at room temperature 12 hours after suction filtration obtain the LDH of nitrate anion intercalation；Weigh 50mg nitrate anion intercalations
LDH is scattered in formamide, and it is 1mg/mL, N to make its concentration2Stirred 24 hours under atmosphere, by the mixed liquor in 2000rpm conditions
Lower centrifugation 10min, discards precipitation to remove unstripped product, and obtained clarified solution is to peel off product ELDH colloids.
(b) preparation of GR-ELDH nano-hybrid materials
Prepared according to the method in step (b) in embodiment 1 and condition
(c) CILE preparation
Prepared according to the method in step (c) in embodiment 1 and condition
(d) preparation of GR-ELDH composites ankyrin modified electrode
CTS/GR-ELDH-Hb/CILE biologies are prepared according to the method and condition in step (d) in embodiment to repair
Adorn electrode.
Comparative example 1：
With reference to the above-mentioned method for preparing modified electrode, the decorating liquid that Hb contents are 10 μ g/ μ L is formulated directly into, 8 μ L drops are taken
The CILE surfaces polished are coated in, then drop coating concentration is the 1mg/ml μ L of CTS acetums 6 on Hb films again, is spontaneously dried
After obtain CTS/Hb/CILE modified electrodes.
Comparative example 2：
With reference to the above-mentioned method for preparing modified electrode, it is 0.5mg/mL suspension directly to prepare LDH contents, takes 8 μ L drop coatings
On the CILE surfaces polished, again in the Hb aqueous solution that the μ L concentration of electrode surface drop coating 8 is 10mg/mL after drying naturally, again
Naturally dry, finally drop coating concentration is the 1mg/ml μ L of CTS acetums 6 on LDH-Hb films again, is obtained after natural drying
CTS/LDH-Hb/CILE modified electrodes.
Comparative example 3：
With reference to the method for above-mentioned modified electrode, the GR hanging drops for taking 8 μ L concentration to be 0.5mg/mL are coated in, polished
CILE surfaces, dry, most naturally again in the Hb aqueous solution that the μ L concentration of electrode surface drop coating 8 is 10mg/mL again after drying naturally
Drop coating concentration is the 1mg/ml μ L of CTS acetums 6 afterwards, and CTS/GR-Hb/CILE modified electrodes are obtained after natural drying.
Comparative example 4：
With reference to the method for above-mentioned modified electrode, using physical mixed method, the mixing directly prepared simultaneously containing LDH and GR is molten
Liquid, its content is 0.5mg/mL, takes 8 μ L drop coatings on CILE surfaces, and the μ L concentration of drop coating 8 is on electrode after drying naturally
The 10mg/mL Hb aqueous solution, dries the μ L of CTS acetums 6 that rear drop coating concentration is 1mg/ml, is obtained after natural drying naturally
CTS/GR-LDH-Hbmix/ CILE modified electrodes.
Fig. 1 is Hb (a) and the gained GR-ELDH-Hb composites (b) of embodiment 4 IR spectrograms.Infra-red sepectrometry can use
In characterizing Secondary structure, the amide I absorption band of protein is located at (1700-1600cm-1) region, this is by protein
In peptide backbone caused by the C=O of peptide fragment junction stretching vibration；Acid amides II absorption bands are located at (1620-1500cm-1) area
Domain, this is as caused by N-H bendings and C-N stretching vibrations.If protein denaturation, two absorption bands of acid amides I and acid amides II
Can occur notable displacement or even disappearance.It can be seen that the acid amides I and acid amides II absorption bands of GR-ELDH-Hb hybrid materials
It is located at 1652cm respectively-1With 1534cm-1Place, with free Hb (1647 and 1533cm-1) spectrogram it is similar, show Hb in composite membrane
Its native conformation is inside maintained substantially, and acid amides I and acid amides II slight displacement may be considered and deposited between Hb and nano material
In interaction, this active force is probably hydrogen bond or electrostatic interaction, so GR-ELDH-Hb lifes could be formed well
Thing composite.
Fig. 2 is the atomic force microscopy and lamellar spacing figure of GR-ELDH nano hybrids, as a result shows GR nanometer sheets
It is about 0.85-1nm with its nano combined rear thickness of ELDH, shows its GR (0.4nm) and the ELDH of monolithic by monolithic
(0.48nm) is composited by electrostatic attraction.
Fig. 3 is to be repaiied obtained by embodiment 4 (e), comparative example 1 (a), comparative example 2 (b), comparative example 3 (c) and comparative example 4 (d)
Adorn electrode in pH=4 B-R cushioning liquid, sweep speed be 0.1V/s when cyclic voltammogram.As seen from the figure, pure Hb modifications
(curve a) has a pair of peak shapes smaller and irreversible redox peaks to electrode, shows that Hb electro transfer is obtained on bare electrode
It is preliminary to realize.After GR or LDH is added (curve b or c), the redox peak current of bioelectrode has different degrees of rise, peak
Deformation is defined reversible, and this explanation LDH and GR presence promotes Hb Direct Electrochemistry behavior.As can be seen from the figure CTS/
(curve e) occurs in that a pair of obvious redox peaks to GR-ELDH-Hb/CILE, and electrochemical signals are significantly stronger than mixed by physics
It is legal obtain CTS/GR-LDH-Hb/CILE (curve d), show GR-ELDH hybrid materials can efficiently promote Hb with
Electron transfer rate between CILE, because GR nanometer sheets and ELDH nanometer sheets are preferably disperseed in GR-ELDH hybrid materials
In the composite, after two kinds of nanometer sheets with different electric charges are by electrostatic attraction effect assembling, intercalation each other is received respective
In the middle of rice lamella, the accumulation and accumulation of two kinds of laminar nano pieces are inhibited well, each of which has been given full play to and has been received with individual layer
The premium properties having in the presence of rice, GR nanometer sheets improve the electric conductivity of composite nano materials, and ELDH intercalation is effective
The aggregation of GR accumulation is inhibited, makes composite that both there is good electric conductivity and larger specific surface area, while also making a living
The fixation of thing enzyme provides good biocompatibility and microenvironment.
Fig. 4 is to be repaiied obtained by embodiment 4 (e), comparative example 1 (a), comparative example 2 (b), comparative example 3 (c) and comparative example 4 (d)
Decorations electrode is containing 10.0mmol/L [Fe (CN)6]-3/-4With the electrochemical impedance figure in the 0.1mol/L KCl aqueous solution.From figure
As can be seen that spectrogram is divided into two parts, its corresponding effective electron transfer process of the semicircle wherein under high frequency condition, and low-frequency range
Linear segment is due to the diffusion process of electronics.Electrochemical impedance result shows, the electrochemical impedance size of different modifying electrode
Order is followed successively by CTS/Hb/CILE (curve a) ＞ CTS/LDH-Hb/CILE (curve b) ＞ CTS/GR-Hb/CILE (curve c) ＞
CTS/GR-LDH-Hbmix((curve e) shows that GR or LDH can be with after adding to curve d) ＞ CTS/GR-ELDH-Hb/CILE to/CILE
Promote the electron transmission of biology enzyme, and work as the GR-LDH-Hb that physical mixed is obtainedmixIn the presence of, further speed up electronics and turned
Move, and during for obtaining GR-ELDH by the way that electrostatic attraction effect is compound and be used as decorative material, disperse excellent GR nanometer sheets and
ELDH nanometer sheets, until synergy, add effective electrode area to Hb electron transmission so that more [Fe (CN)6
]-3/-4Electrochemical reaction has been participated in, so that the transfer rate of electronics is improved, therefore CTS/GR-ELDH-Hb/CILE is shown
Minimum electrochemical impedance, is conducive to the structure of biology sensor.
Embodiment 5：
Using the CTS/GR-ELDH-Hb/CILE modified electrodes obtained by embodiment 4 as working electrode, platinum filament is to electricity
Pole, saturated calomel electrode is reference electrode, and the measure of trichloroacetic acid is carried out using three-electrode system.It is molten to pH=4 B-R bufferings
The trichloroacetic acid of different volumes is added in liquid, circulation volt curve during different trichloroacetic acid concentration is drawn, records with three chloroethenes
The change of reduction peak current during the increase of acid concentration, and mapped with reduction peak current to adding trichloroacetic acid concentration in electrolytic cell,
Solve relevant parameter.With high pure nitrogen, into solution, bubbling removes oxygen in 30 minutes before test, is protected and excluded with nitrogen during test
The interference of oxygen.
Comparative example 1：
According to the method described above, by comparative example 4 is obtained in embodiment 1 CTS/GR-LDH-Hbmix/ CILE modified electrodes are made
The electro-chemical test of trichloroacetic acid is carried out for working electrode.
Fig. 5 shows that CTS/GR-ELDH-Hb/CILE is added after TCA in pH 4.0 B-R cushioning liquid, can be observed
In -0.301V or so, with the increase of TCA additions, reduction peak current is significantly increased, and oxidation peak fades away, and this is typical case
TCA reduction processes.With the further increase of TCA concentration, occurs a new reduction peak at -0.551V.This reduction
The appearance at peak is probably because high reduction-state HbFeIFormation make TCA dechlorinations again.Urged when TCA concentration is 5-135mmol/L
Galvanic current and TCA concentration are linear, as shown in the illustration in Fig. 5, and its equation of linear regression is Ip (μ A)=0.272C
(mmol/L)+5.25 (n=15, γ=0.992), detection is limited to 1.5mmol/L (3 σ), and Michaelis constant is 5.25mmol/L.And
CTS/GR-LDH-Hb in Fig. 6mix/ CILE detects the linear concentration scope 10-130mmol/L of trichloroacetic acid, minimal detectable concentration
For 3.7mmol/L, Michaelis constant is 33.8mmol/L.As can be seen that CTS/GR-ELDH-Hb/CILE modified electrodes are to three chloroethenes
The electrochemical catalysis performance of acid is substantially better than CTS/GR-LDH-Hbmix/ CILE modified electrodes, illustrate GR nanometer sheets and ELDH nanometers
The synergy of piece further increases the electric conductivity of composite membrane, improves the catalytic performance of combination electrode.Above experimental result
Show that the prepared trichloroacetic acid sensor test limit based on CTS/GR-ELDH-Hb/CILE modified electrodes is lower, linear model
Enclose wider, Michaelis constant is smaller.
Claims (2)
1. a kind of graphene-stripping houghite piece composite ankyrin modified electrode, it is characterised in that it includes substrate
Electrode layer and graphene-stripping houghite piece composite ankyrin layer；The graphene-stripping houghite piece is combined
Material is to be assembled by the graphite oxide nanometer sheet peeled off and the houghite piece of stripping by electrostatic adelphotaxy, then through water
Hydrazine reduction is closed to be made；Protein is fixed on graphene-stripping houghite piece composite by drop-coating and forms compound egg
White；Wherein graphene is designated as GR, peels off houghite piece and is designated as ELDH；
The graphene-stripping houghite piece composite ankyrin modified electrode, wherein the stripping houghite piece
For cobalt aluminium profiles；The protein is bovine hemoglobin, is designated as Hb；The basal electrode is Ionic Liquid Modified carbon paste electrode, note
For CILE；
The preparation method of the graphene-stripping houghite piece composite ankyrin modified electrode, including in detail below
Step：
(a) ELDH preparation
By divalent metal salt CoCl2·6H2O, trivalent metal salt AlCl3·6H2O and urea are added to equipped with one by certain mol proportion
In the round-bottomed flask for determining volumes of deionized water, total concentration of metal ions is 0.15mol/L, and 60~98 DEG C to be stirred at reflux 10~36 small
When, suction filtration, filter cake use distillation water washing 3~5 times, dry 48 hours, obtain carbonate intercalation at room temperature after completion of the reaction
LDH；
The LDH of a certain amount of carbonate intercalation is weighed, NaCl and 3.3mmol/L that concentration is respectively 1mol/L is scattered in
In HCl mixed aqueous solutions, N2Stirred 12 hours under atmosphere, drying at room temperature 12 hours after suction filtration obtain the LDH of chlorion intercalation；
The LDH of a certain amount of chlorion intercalation is weighed, the NaNO that concentration is 0.1mol/L is scattered in3The aqueous solution in, N2Atmosphere
Lower stirring 12 hours, drying at room temperature 12 hours after suction filtration obtain the LDH of nitrate anion intercalation；
The LDH for weighing a certain amount of nitrate anion intercalation is scattered in formamide, and it is 1mg/mL, N to make its concentration2Stirring 24 is small under atmosphere
When, the mixed liquor is centrifuged into 10min under the conditions of 2000rpm, precipitation is discarded to remove unstripped product, obtained clarified solution
As peel off product ELDH colloids；
(b) preparation of GR-ELDH composites
Graphene oxide is prepared using hummer methods, GO is designated as, and a certain amount of GO is scattered in formamide, makes its concentration be
1mg/mL, ultrasonic disperse 1 hour, 3000rpm centrifugations 10min removes unstripped GO, the GO dispersion liquids peeled off；By the GO
The dispersion liquid ELDH colloidal solution isometric with gained in (a) is sufficiently mixed, and room temperature is stirred 12 hours under confined conditions,
After 5000rpm centrifugations 10min, gained brownish black precipitation is scattered in deionized water again, adds a certain amount of hydrazine hydrate in 80
DEG C stirring reaction 2.5 hours, 4000rpm centrifugations 10min obtains GR-ELDH composites；
(c) CILE preparation
By graphite powder and ionic liquid BPPF6With 2:1 mass ratio is added in mortar, is uniformly mixed under the conditions of being heated to 80 DEG C, to
1mL atoleines are added dropwise in the powder mixture to insert in glass tube as adhesive, then after mixture is fully ground,
The solid mixture in glass tube is compacted as wire, obtains CILE, beaten the electrode surface using preceding by insertion copper wire in pipe
Ground smooth；
(d) preparation of GR-ELDH composites ankyrin modified electrode
The GR-ELDH composites obtained in step (b) are configured to the pulpous state liquid that concentration is 1mg/mL with deionized water, 8 μ are taken
The CILE surfaces of L pulpous state drop-coateds gained in step (c), the μ L concentration of drop coating 8 is 10mg/ on electrode again after drying naturally
The mL Hb aqueous solution, after drying naturally, continues the chitosan acetic acid CTS solution that the μ L concentration of drop coating 6 is 1.0mg/mL, spontaneously dries
After obtain CTS/GR-ELDH-Hb/CILE bio-modification electrodes；
The preparation method of the graphene-stripping houghite piece composite ankyrin modified electrode, wherein in step (a)
The divalent metal salt CoCl2·6H2O, trivalent metal salt AlCl3·6H2The mol ratio of O and urea is 2：1：7；Certain volume
Deionized water be 400mL；The LDH of the carbonate intercalation weighed and the LDH amounts of chlorion intercalation are that compound concentration is 1mg/
Quality required for mL suspension；The quality such as the consumption of hydrazine hydrate and GO in step (b)；GR-ELDH obtained by step (b) is combined
Material is composited by the GR of individual layer and the ELDH nanometer sheets of individual layer, and its thickness is 0.85-1nm.
2. a kind of graphene described in claim 1-stripping houghite piece composite ankyrin modified electrode is preparing electricity
Application in terms of chemical sensor, it is characterised in that the modified electrode can be used for the detection of trichloroacetic acid.
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