CN103412021B - Functionalized ionic liquid-hydrotalcite-like composite material fixed protein modified electrode as well as preparation method and application thereof - Google Patents
Functionalized ionic liquid-hydrotalcite-like composite material fixed protein modified electrode as well as preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 14
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000975 co-precipitation Methods 0.000 claims abstract description 11
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- 108010054147 Hemoglobins Proteins 0.000 claims abstract description 8
- 238000001514 detection method Methods 0.000 claims abstract description 7
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 150000002500 ions Chemical class 0.000 claims description 42
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- 238000005406 washing Methods 0.000 claims description 11
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- 238000012986 modification Methods 0.000 claims description 4
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- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical group [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052599 brucite Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
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- 108010015776 Glucose oxidase Proteins 0.000 description 2
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- 230000002776 aggregation Effects 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- Battery Electrode And Active Subsutance (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a functionalized ionic liquid-hydrotalcite-like composite material fixed protein modified electrode as well as a preparation method and an application thereof. According to the technical scheme provided by the invention, firstly the fixation of an ionic liquid-hydrotalcite-like composite material to hemoglobin is realized by utilizing a coprecipitation method, then obtained hemoglobin-functionalized ionic liquid-hydrotalcite-like composite material is prepared into a solution which is dropwise coated on the surface of a preprocessed glassy carbon electrode, and the functionalized ionic liquid-hydrotalcite-like composite material fixed protein modified electrode is obtained after natural drying. According to the obtained composite modified electrode, the superiorities of functionalized ionic liquid and layered inorganic materials in the aspect of electrode modified materials are adequately combined, so that the modified electrode has high electrical conductivity and good dispersibility and enzyme fixation capacity. A hydrogen peroxide electrochemical sensor based on the modified electrode has the advantages of simplicity in operation, mild condition, low detection limit, high sensitivity, wide linear range and the like.
Description
Technical field
The present invention relates to a kind of functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode; The invention still further relates to the preparation method of described modified electrode and the application in electrochemical sensing context of detection thereof.
Background technology
The Direct Electrochemistry research of the biomacromolecules such as redox protein matter and enzyme, people can not only be helped deeply to be familiar with the electron mechanism of biosystem, important theoretical foundation and technical support can also to be provided for development of new biology sensor, novel biological fuel battery etc.But their activated centre is buried comparatively dark usually, is difficult to Direct Electrochemistry occurs at electrode surface, and they are directly adsorbed on the easy sex change that comes off in bare electrode surface.Therefore, find and can keep the activity of enzyme and the material promoting direct electron transfer, become the important topic of bioelectrochemical sensing area research.Recent research shows, inorganic lamellar material has adjustable open lamellar structure, make it in machinery, chemistry and thermal stability, have obvious advantage, and the effect of its nano-scale gives material itself some New function (as performances such as electric conductivity, optical, electrical, magnetic), therefore fixes at biology enzyme and promotes to show the performance more superior than organic material in electron transmission.
Class neatly (being abbreviated as LDH) is a class two-dimensional nanometer anionic clay, and composition general formula can be expressed as [M
1-x 2+m
x 3+(OH)
2]
x+(A
n-)
x/nmH
2o, has hydrotalcite layered structure, and lamella band structure positive charge, interlayer exists tradable negative ion.The biomolecule such as electronegative amino acid, DNA, protein, polypeptide and enzyme can insert LDH interlayer, formation biomolecule-LDH nano hybrid [Zhan Tianrong, Hou Wanguo. the application of layered double hydroxide in green material field.
chemistry circular,
2010, 73 (7): 608 ~ 615.].At present, researcher achieves biology enzyme fixing on LDH by softening methods such as absorption, stripping restructuring, co-precipitation, electro-deposition, the Direct Electrochemistry result of study of corresponding biology enzyme shows, the nano-lamellar structure of LDH had both maintained the activity of biology enzyme, facilitated again the transmission of electronics.But when LDH is as electrode modified material immobilized enzyme, due to itself bad dispersibility and easy agglomeration traits, electrode surface is easily caused to occur protuberance, embrittlement, even phenomenon [the Han E such as to come off, Shan D, Xue H G, Cosnier S. Hybrid material based on chitosan and layered double hydroxides:characterization and application to the design of amperometric phenol biosensor.
biomacromolecules,
2007, 8:971 ~ 975.].
Finishing is carried out to LDH and can not only improve it to the macromolecular intercalation ability of three dimensional biological, and be solve its effective ways as bad dispersibility during electrode modified material and easy agglomeration traits.As the LDH after DDS modifies has better fixed performance to hemoglobinase (Hb), and improve its electron transmission ability; Shitosan-LDH hybrid is used for electrode modified material, and result shows that the existence of shitosan overcomes inorganic nano material and easily swells and the defect such as embrittlement, and improve the electrocatalysis characteristic of enzyme, the detection limit of modified electrode to tea phenol reaches 0.36 nmol/L.The NiAl-LDH/CNT compound substance that employing coprecipitation obtains is as dispersion stabilization during electrode modified material, the electrocatalysis characteristic of gained modified electrode is than simple LDH or CNT modified electrode high octuple [Wang H, Xiang X, Li F. Facile synthesis and novel electrocatalytic performance of nanostructured Ni – Al layered double hydroxide/carbon nanotube composites.
j. Mater. Chem.,
2010 , 20:3944 ~ 3952.].This shows, the finishing suitable to LDH, decorative material can be improved at the dispersiveness of electrode surface, stability and biocompatibility, be conducive to improving it to the fixed performance of biomolecule and interfacial electrochemistry performance.
Functionalized ion liquid (Functionalized Ionic Liquid, FIL) refer to by negative ion or (with) cationic moiety introduces structural functionality group, and the class formed has the ionic liquid of specific physics, chemical property, it is except having conventional ionic liquid (Ionic Liquid, IL) electrochemical window is wide, electric conductivity is strong, volatility is low, outside stability high, due to the introducing of structural functionality group, additionally provide more reaction site, modify inorganic nano material for it and create advantage.At present, (functionalization) ion liquid modified nano composite material is made modified electrode and is obtained successful Application in electrochemical sensing field, as ionic liquid is done to be combined in the nano composite material formed with carbon nano-tube by the interaction force of " cation-π " key, ionic liquid improves the dispersiveness of nano composite material, the reunion of carbon nano-tube and wrapping phenomena are effectively suppressed, compound substance modified electrode show excellent chemical property [Zhang Xuzhi. the electrochemica biological sensor based on carbon nano-tube and ionic liquid enhancement effect: development, representation and application. Qingdao University of Science and Technology Ph.D. Dissertation,
2009.], after amino functional Ionic Liquid Modified Graphene, improve the dispersive property of the latter, gained composite modified electrode substantially increases direct electron transfer [Shan, the C.S. of glucose oxidase, Yang, H.F., Song, J.F., Han, D.X., Ivaska, A., Niu, L. Direct electrochemistry of glucose oxidase and biosensing for glucose based on graphene.
anal. Chem.
2009,
81, 2378-2382.], the existence of Carboxyl-functional Ionic Liquid-LDH compound substance intermediate ion liquid, for myoglobins (Mb) provides the microenvironment of biocompatibility, effectively improves Direct Electrochemistry and electrocatalysis characteristic [Zhan, the T. of protein, Guo, Y., Xu, L., Sun, W., Hou, W. Direct electron transfer and electrocatalysis of myoglobin intercalated into Mg
2al-Cl layered double hydroxide (LDH) on carbon ionic liquid electrode.
talanta 2012,
94, 189-194.].Although the research of functionalized ion liquid-inorganic nano composite material modified electrode is more active, but majority prepares composite modified electrode after directly functionalized ion liquid, inorganic nano material and biology enzyme direct physical being mixed, at present and have no the modified electrode that adopts coprecipitation to be prepared in functionalized ion liquid-LDH compound substance by proteinaceous solid and the report in hydrogen peroxide context of detection thereof.Here proteinaceous solid is prepared corresponding bio-modification electrode by employing coprecipitation by us after functionalized ion liquid-LDH compound substance, and the detection of preliminary its hydrogen peroxide of examination.
Adopt coprecipitation that proteinaceous solid is prepared corresponding bio-modification electrode after functionalized ion liquid-LDH compound substance, be conducive to abundant binding function ionic liquid and the advantage of layered inorganic material in electrode modified material, make up their defects in this respect, more avtive spot will be provided for composite modified electrode, higher electric conductivity, dispersiveness and the crystallized ability to enzyme, the synergy advantage of both performances, thus improve biomolecule at the Direct Electrochemistry of modified electrode and electrocatalysis characteristic, to setting up, novel high sensitive electrochemical detection method is significant.
Summary of the invention
For the demand of the deficiencies in the prior art and this area investigation and application, an object of the present invention is to provide a kind of functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode; Namely adopt coprecipitation by the corresponding modified electrode of proteinaceous solid rear preparation in functionalized ion liquid-hydrotalcite-like composite material.
A kind of functionalized ion liquid provided by the invention-hydrotalcite-like composite material ankyrin modified electrode, it is characterized in that it comprises basal electrode layer and functionalized ion liquid-hydrotalcite-like composite material ankyrin layer, protein molecule is fixed in functionalized ion liquid-hydrotalcite-like composite material by coprecipitation by described functionalized ion liquid-hydrotalcite-like composite material ankyrin layer; Wherein houghite is the double-metal hydroxide formed by positively charged laminate and interlayer anion ordered fabrication, metal cation and hydroxyl form the regular octahedron centered by metal cation by covalent bond, adjacent octahedron forms by sharing seamed edge the main body flaggy be parallel to each other, similar is in brucite, and its composition general formula can be expressed as:
[M
1-x 2+M
x 3+(OH)
2]
x+(A
n-)
x/n·mH
2O，
M in above formula
2+refer to divalent metal, M
3+refer to trivalent metal cation, A
n-
for-n valency the negative ion that interlayer Absorbable organic halogens exists, n is negative ion valence mumber, and x is M in every mole of houghite
3+molal quantity (0.20≤x≤0.33), m is the molal quantity of every mole of houghite interlayer water of crystallization;
Described functionalized ion liquid is that 1-methyl-3-hydroxypropyl tetrafluoroborate (is designated as IL
oH), its molecular structural formula is as follows:
。
Described a kind of functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode, is characterized in that described houghite is zinc-aluminum gavite, i.e. M in its general formula
3+for Al
3+, M
2+for Zn
2+, A
n-
for NO
3 -; Described protein molecule is haemoglobin (being designated as Hb); Described basal electrode is glass-carbon electrode (being designated as GCE).
Two of the object of the invention is to provide the preparation method of a kind of functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode, specifically comprises the following steps:
A () Hb is at IL
oHfixing on-LDH compound substance
By divalent metal salt Zn (NO
3)
2with trivalent metal salt Al (NO
3)
3be made into mixing salt solution by certain mol proportion, total concentration of metal ions is 0.6 mol/L, adds the Hb of certain mass, then by IL
oHadd in mixing salt solution by certain mol proportion, by the titration simultaneously of above-mentioned mixed solution and alkaline solution, control pH between 9.0 ~ 10.0, vigorous stirring, aged at room temperature 12 ~ 24 hours; Gained slurries suction filtration, filter cake distilled water washing 3 ~ 5 times, under room temperature, drying 24 hours, obtains the IL that load has Hb
oH-LDH compound substance, the light absorption value through ultraviolet spectroscopy 406 nm place learns that the haemoglobin of more than 98% is fixed;
The preparation of (b) decorating liquid
By the compound substance Hb-IL of negative loaded with hemoglobin obtained in step (a)
oH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, for subsequent use;
The pre-service of (c) GCE
With conventional polishing and polishing process, pre-service is carried out to GCE surface, then use the HNO of the NaOH solution of 1 mol/L, 1 mol/L successively
3solution, acetone and redistilled water supersound washing;
The preparation of (d) modified electrode
Be coated in by modification drop obtained for step (b) through the pretreated electrode surface of step (c), dripping painting amount is 7 μ L, and leave standstill, 4 DEG C of refrigerator overnight dryings, form one deck Hb-IL in glassy carbon electrode surface
oH-LDH film, then at Hb-IL
oH-LDH film drips and is coated with the chitosan-acetic acid solution that concentration is 1 mg/ml, form one deck chitosan film, dripping painting amount is 5 μ L, obtains Hb-IL after natural drying
oH-LDH/GCE modified electrode.
The wherein Zn of divalent metal salt described in step (a) (NO
3)
2with trivalent metal salt Al (NO
3)
3mol ratio be 2:1; IL
oHwith divalent metal salt Zn (NO
3)
2mol ratio be respectively 1:2; The mass ratio of Hb and LDH is respectively 0.05,0.25,0.5,1 and 2; Described alkaline solution is the sodium hydroxide solution of 2 mol/L.
A kind of functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode, this composite modified electrode is prepared by above-mentioned any one method.
Three of the object of the invention is to provide a kind of functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode and is preparing the application in electrochemical sensor.
Particularly, described functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode is in the application of hydrogen peroxide context of detection.
The present invention utilizes houghite to have can the open lamellar structure of intercalant anion and the advantage such as specific surface area is large, by coprecipitation, itself and the Hydroxyl-functionalized Ionic Liquids 1-methyl-3-hydroxypropyl tetrafluoroborate and haemoglobin with good biocompatibility and electric conductivity are carried out compound, and prepare functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode, to improve the direct electron transfer of haemoglobin on composite modified electrode, construct based on Hb-IL
oHthe third generation hydrogen peroxide sensor of-LDH composite membrane.This biology sensor has highly sensitive, the advantage such as detectability is low and sensing range is wide for being detected hydrogen oxide.
Compared with prior art, major advantage is in the present invention: adopt coprecipitation that houghite and Hydroxyl-functionalized Ionic Liquids and haemoglobin are carried out compound, prepared functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode; Gained composite modified electrode of the present invention is held concurrently and has been played functionalized ion liquid and the houghite stuctures and properties advantage as electrode modified material aspect, is improving the collaborative advantage function that can play two kinds of functional materials in haemoglobin Direct Electrochemistry and electrocatalysis characteristic; Particularly, unexpected technique effect is created to the effect that the direct fax of haemoglobin is passed, no matter gained composite modified electrode of the present invention is that all tool is significantly improved compared with houghite or functionalized ion liquid to the effect of haemoglobin direct electron transfer.The inventive method is simple to operate, mild condition, preparation cost are low.
Accompanying drawing explanation
Fig. 1 is embodiment 4 (d), comparative example 1 (a), comparative example 2 (b) and comparative example 3 (c) the gained modified electrode cyclic voltammogram in the phosphate buffer solution of 0.05 mol/L, when to sweep speed be 0.1 V/s in embodiment 4.
Fig. 2 is that embodiment 4 (d), comparative example 1 (a), comparative example 2 (b) and comparative example 3 (c) gained modified electrode are containing 10.0 mmol/L [Fe (CN)
6]
3/ 4with the electrochemical impedance figure in 0.1 mol/L KCl solution.
Fig. 3 is the compound substance Hb-IL that Hb (a) and the load of embodiment 1 ~ 5 gained have Hb
oHthe IR spectrogram of-LDH (b ~ f).。
Fig. 4 is by the Hb-IL of embodiment 4 gained
oHunder nitrogen protection, in the phosphate buffer solution (pH 7.0) of 0.1 mol/L, add the cyclic voltammetry curve of the hydrogen peroxide of different volumes, sweep speed is 100 mV/s to-LDH/GCE, and illustration is the linear relationship of reduction peak current and concentration of hydrogen peroxide.
Fig. 5 for the Hb-LDH/GCE that obtained by comparative example 3 in embodiment 4 under nitrogen protection; the cyclic voltammetry curve of the hydrogen peroxide of different volumes is added in the phosphate buffer solution (pH 7.0) of 0.1 mol/L; sweeping speed is 100 mV/s, and illustration is the linear relationship of reduction peak current and concentration of hydrogen peroxide.
Embodiment
For understanding the present invention further, below in conjunction with drawings and Examples, the invention will be further described, but and do not limit the present invention in any way.
embodiment 1
By divalent metal salt Zn (NO
3)
2with trivalent metal salt Al (NO
3)
3be made into mixing salt solution by certain mol proportion 2:1, total concentration of metal ions is 0.6 mol/L, in mass ratio Hb:LDH be 0.05 amount add Hb in mixing salt solution, then by IL
oHby itself and divalent metal salt Zn (NO
3)
2mol ratio be that the amount of 1:2 is added in mixing salt solution, above-mentioned mixing salt solution and volumetric molar concentration are the sodium hydroxide solution titration simultaneously of 2 mol/L, control pH between 9.0 ~ 10.0, vigorous stirring, aged at room temperature 18 hours; Gained slurries suction filtration, filter cake distilled water washs 5 times, and under room temperature, drying 24 hours, obtains the compound substance Hb-IL that load has Hb
oH-LDH; Gained is born the compound substance Hb-IL of loaded with hemoglobin
oH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, get 7 μ L drip be coated in use 1 mol/L successively NaOH solution, 1 mol/L HNO
3the GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
oH-LDH film drips and is coated with the chitosan-acetic acid solution 5 μ L that concentration is 1 mg/ml, after natural drying, obtain Hb-IL
oH-LDH/GCE modified electrode.
embodiment 2
By divalent metal salt Zn (NO
3)
2with trivalent metal salt Al (NO
3)
3be made into mixing salt solution by certain mol proportion 2:1, total concentration of metal ions is 0.6 mol/L, in mass ratio Hb:LDH be 0.25 amount add Hb in mixing salt solution, then by IL
oHby itself and divalent metal salt Zn (NO
3)
2mol ratio be that the amount of 1:2 is added in mixing salt solution, above-mentioned mixing salt solution and volumetric molar concentration are the sodium hydroxide solution titration simultaneously of 2 mol/L, control pH between 9.0 ~ 10.0, vigorous stirring, aged at room temperature 20 hours; Gained slurries suction filtration, filter cake distilled water washs 5 times, and under room temperature, drying 24 hours, obtains the compound substance Hb-IL that load has Hb
oH-LDH; Gained is born the compound substance Hb-IL of loaded with hemoglobin
oH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, get 7 μ L drip be coated in use 1 mol/L successively NaOH solution, 1 mol/L HNO
3the GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
oH-LDH film drips and is coated with the chitosan-acetic acid solution 5 μ L that concentration is 1 mg/ml, after natural drying, obtain Hb-IL
oH-LDH/GCE modified electrode.
embodiment 3
By divalent metal salt Zn (NO
3)
2with trivalent metal salt Al (NO
3)
3be made into mixing salt solution by certain mol proportion 2:1, total concentration of metal ions is 0.6 mol/L, in mass ratio Hb:LDH be 0.5 amount add Hb in mixing salt solution, then by IL
oHby itself and divalent metal salt Zn (NO
3)
2mol ratio be that the amount of 1:2 is added in mixing salt solution, above-mentioned mixing salt solution and volumetric molar concentration are the sodium hydroxide solution titration simultaneously of 2 mol/L, control pH between 9.0 ~ 10.0, vigorous stirring, aged at room temperature 22 hours; Gained slurries suction filtration, filter cake distilled water washs 5 times, and under room temperature, drying 24 hours, obtains the compound substance Hb-IL that load has Hb
oH-LDH; Gained is born the compound substance Hb-IL of loaded with hemoglobin
oH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, get 7 μ L drip be coated in use 1 mol/L successively NaOH solution, 1 mol/L HNO
3the GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
oH-LDH film drips and is coated with the chitosan-acetic acid solution 5 μ L that concentration is 1 mg/ml, after natural drying, obtain Hb-IL
oH-LDH/GCE modified electrode.
embodiment 4
By divalent metal salt Zn (NO
3)
2with trivalent metal salt Al (NO
3)
3be made into mixing salt solution by certain mol proportion 2:1, total concentration of metal ions is 0.6 mol/L, in mass ratio Hb:LDH be 1 amount add Hb in mixing salt solution, then by IL
oHby itself and divalent metal salt Zn (NO
3)
2mol ratio be that the amount of 1:2 is added in mixing salt solution, above-mentioned mixing salt solution and volumetric molar concentration are the sodium hydroxide solution titration simultaneously of 2 mol/L, control pH between 9.0 ~ 10.0, vigorous stirring, aged at room temperature 22 hours; Gained slurries suction filtration, filter cake distilled water washs 5 times, and under room temperature, drying 24 hours, obtains the compound substance Hb-IL that load has Hb
oH-LDH; Gained is born the compound substance Hb-IL of loaded with hemoglobin
oH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, get 7 μ L drip be coated in use 1 mol/L successively NaOH solution, 1 mol/L HNO
3the GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
oH-LDH film drips and is coated with the chitosan-acetic acid solution 5 μ L that concentration is 1 mg/ml, after natural drying, obtain Hb-IL
oH-LDH/GCE modified electrode.
comparative example 1
With reference to the above-mentioned method preparing modified electrode, be directly mixed with the decorating liquid that Hb content is 20 μ g/ μ L, get 7 μ L drip be coated in use 1 mol/L successively NaOH solution, 1 mol/L HNO
3the GCE surface of solution, acetone and redistilled water supersound washing, and then drip on Hb film and be coated with the chitosan-acetic acid solution 5 μ L that concentration is 1 mg/ml, obtain Hb/GCE modified electrode after natural drying.
comparative example 2
With reference to the above-mentioned method preparing modified electrode, be directly mixed with IL
oHthe decorating liquid of mass percent to be 10%, Hb content be 20 μ g/ μ L, get 7 μ L drip be coated in use 1 mol/L successively NaOH solution, 1 mol/L HNO
3the GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
oHfilm drips and is coated with the chitosan-acetic acid solution 5 μ L that concentration is 1 mg/ml, after natural drying, obtain Hb-IL
oH/ GCE modified electrode.
comparative example 3
Prepare the method for modified electrode with reference to above-described embodiment 4, do not add IL
oH, preparation Hb-LDH/GCE modified electrode.
Fig. 1 is embodiment 4 (d), comparative example 1 (a), comparative example 2 (b) and comparative example 3 (c) the gained modified electrode cyclic voltammogram in the phosphate buffer solution of 0.05 mol/L, when to sweep speed be 0.1 V/s.As seen from the figure, Hb/GCE (curve a) on there is a pair very weak asymmetric redox peak, illustrate and electrode there occurs slowly electronic transfer process; At Hb-IL
oHon/GCE (curve b), redox current does not significantly change, and shows IL
oHexistence do not improve the electron transfer rate of Hb.On Hb-LDH/GCE (curve c), redox current increases, and this shows that LDH improves electron transfer rate in the existence of electrode surface, adds electrochemical response signal.And at Hb-IL
oHon-LDH/GCE (curve d), redox peak current strengthens further and peak type is better, and IL is described
oH-LDH composite membrane can greatly improve the Direct electron transfer speed of Hb, and this is due to IL
oHhigh conductivity and the nanometer laminated structure of LDH work in coordination with the electro transfer accelerating Hb.As can be seen from curve d, reduction peak and oxidation peak current potential are respectively-0.384 V and-0.2664 V (vs. SCE), Middle Eocene is-0.298 V (vs. SCE), and this is the characteristic peak of prosthetic heme group Fe (II) in Hb/Fe (III) oxidation-reduction pair.Result shows at Hb-IL
oH-LDH/GCE can realize the Direct electron transfer of Hb.
Fig. 2 is that embodiment 4 (d), comparative example 1 (a), comparative example 2 (b) and comparative example 3 (c) gained modified electrode are containing 10.0 mmol/L [Fe (CN)
6]
3/ 4with the electrochemical impedance figure in 0.1 mol/L KCl solution.In figure, the diameter of each bar curve medium-high frequency region semi arch is the resistance of electron transmission, can reflect the electron transport rate of redox probe.As can be seen from the figure, (a) above the resistance of electron transmission is maximum, when there being IL for curve for Hb/GCE
oH(Hb-IL
oH/ GCE, curve b) or LDH (Hb-LDH/GCE, curve c) exists time, on corresponding modified electrode, the resistance of electron transmission has obvious reduction, and this result shows IL
oHall electron transport rate can be accelerated with the existence of LDH.And Hb-IL
oHthe resistance of the upper electron transmission of-LDH/GCE (curve d) is minimum, and IL is described
oHthe existence of-LDH composite membrane improves electric conductivity, adds effective electrode area, makes more [Fe (CN)
6]
3/ 4participate in electrochemical reaction, thus improve the transfer rate of electronics.
embodiment 5
By divalent metal salt Zn (NO
3)
2with trivalent metal salt Al (NO
3)
3be made into mixing salt solution by certain mol proportion 2:1, total concentration of metal ions is 0.6 mol/L, in mass ratio Hb:LDH be 2 amount add Hb in mixing salt solution, then by IL
oHby itself and divalent metal salt Zn (NO
3)
2mol ratio be that the amount of 1:2 is added in mixing salt solution, above-mentioned mixing salt solution and volumetric molar concentration are the sodium hydroxide solution titration simultaneously of 2 mol/L, control pH between 9.0 ~ 10.0, vigorous stirring, aged at room temperature 24 hours; Gained slurries suction filtration, filter cake distilled water washs 5 times, and under room temperature, drying 24 hours, obtains the compound substance Hb-IL that load has Hb
oH-LDH; Gained is born the compound substance Hb-IL of loaded with hemoglobin
oH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, get 7 μ L drip be coated in use 1 mol/L successively NaOH solution, 1 mol/L HNO
3the GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
oH-LDH film drips and is coated with the chitosan-acetic acid solution 5 μ L that concentration is 1 mg/ml, after natural drying, obtain Hb-IL
oH-LDH/GCE modified electrode.
Fig. 3 is the compound substance Hb-IL that Hb (a) and the load of embodiment 1 ~ 5 gained have Hb
oHthe IR spectrogram of-LDH (b ~ f).Infrared spectrum (IR) is the important responsive instrument of Study on Protein structure, and the I level amine of protein and II level amine can provide the details of polypeptied chain secondary structure, and protein structure degenerative condition can be reflected in their intensity and peak position.Compound substance Hb-IL in figure
oHall occurred the I level amine of Hb and the absorption band of II level amine in-LDH (b ~ f) curve, absorption peak lays respectively at 1647 ~ 1655 cm
-1between and 1538 ~ 1545 cm
-1between, with I level amine (1653 cm of free Hb
-1) and II level amine (1545 cm
-1) absorption peak position substantially identical, illustrate and be fixed on IL
oHhb in-LDH compound substance maintains its native secondary structure well, but in Hb, the slight change of I level amine and II level amine peak intensity and absorption peak position illustrates and there is certain interaction, so could form Hb-IL well between protein and nano composite material in compound substance
oH-LDH Biocomposite material.
embodiment 6
By the Hb-IL obtained by embodiment 4
oH-LDH/GCE modified electrode is as working electrode, and platinum filament is to electrode, and Ag/AgCl is contrast electrode, adopts three-electrode system to carry out the mensuration of hydrogen peroxide.The hydrogen peroxide of different volumes is added in the phosphate buffer solution (pH 7.0) of 0.1 mol/L, draw circulation volt curve during variable concentrations concentration of hydrogen peroxide, record the change of reduction peak current during the increase along with concentration of hydrogen peroxide, and with reduction peak current to adding concentration of hydrogen peroxide mapping in electrolytic cell, solve correlation parameter.Within 30 minutes, remove oxygen with high pure nitrogen to bubbling in solution before test, during test, get rid of the interference of oxygen with nitrogen protection.
comparative example 1
According to the method described above, Hb-LDH/GCE modified electrode comparative example 3 in embodiment 4 obtained carries out the electro-chemical test of hydrogen peroxide as working electrode.
Fig. 4 shows Hb-IL
oH-LDH/GCE is along with the increase of concentration of hydrogen peroxide, and its reduction peak current constantly increases, show in illustration its parent peak electric current and concentration of hydrogen peroxide linear, the range of linearity of its detectable concentration is 0.99 × 10
-8~ 1.19 × 10
-7mol/L, sensitivity is 30.63 μ A/mM, and minimal detectable concentration is 0.99 × 10
-8mol/L, and Hb-LDH/GCE is detected the linear concentration scope (1.99 ~ 7.94) × 10 of hydrogen oxide
-8mol/L(is shown in Fig. 5), sensitivity is 15.78 μ A/mM, and minimal detectable concentration is 1.99 × 10
-8mol/L.Can find out, Hb-IL
oHthe electrochemical catalysis performance of-LDH/GCE to hydrogen peroxide is obviously better than Hb-LDH/GCE, and IL is described
oHexistence further increase the electric conductivity of composite membrane, improve the catalytic performance of combination electrode.Above experimental result shows prepared based on Hb-IL
oHthe hydrogen peroxide sensor detectability of-LDH/GCE is lower, and sensitivity is higher, and the range of linearity is wider.
Claims (4)
1. functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode, it is characterized in that it comprises basal electrode layer and functionalized ion liquid-hydrotalcite-like composite material ankyrin layer, protein molecule is fixed in functionalized ion liquid-hydrotalcite-like composite material by coprecipitation by described functionalized ion liquid-hydrotalcite-like composite material ankyrin layer; Wherein houghite, be designated as LDH, it is the double-metal hydroxide formed by positively charged laminate and interlayer anion ordered fabrication, metal cation and hydroxyl form the regular octahedron centered by metal cation by covalent bond, adjacent octahedron forms by sharing seamed edge the main body flaggy be parallel to each other, similar is in brucite, and its composition general formula can be expressed as:
[M
1-x 2+M
x 3+(OH)
2]
x+(A
n-)
x/n·mH
2O，
M in above formula
2+refer to divalent metal, M
3+refer to trivalent metal cation, A
n-for-n valency the negative ion that interlayer Absorbable organic halogens exists, n is negative ion valence mumber, and x is M in every mole of houghite
3+molal quantity, 0.20≤x≤0.33, m is the molal quantity of every mole of houghite interlayer water of crystallization;
Described functionalized ion liquid is 1-methyl-3-hydroxypropyl tetrafluoroborate, is designated as IL
oH, its molecular structural formula is as follows:
Described functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode, is characterized in that described houghite is zinc-aluminum gavite, i.e. M in its general formula
3+for Al
3+, M
2+for Zn
2+, A
n-for NO
3 -; Described protein molecule is haemoglobin, is designated as Hb; Described basal electrode is glass-carbon electrode, is designated as GCE;
The preparation method of described functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode, is characterized in that comprising following concrete steps:
A () Hb is at IL
oHfixing on-LDH compound substance
By divalent metal salt Zn (NO
3)
2with trivalent metal salt Al (NO
3)
3be made into mixing salt solution by certain mol proportion, total concentration of metal ions is 0.6mol/L, adds the Hb of certain mass, then by IL
oHadd in mixing salt solution by certain mol proportion, by the titration simultaneously of above-mentioned mixed solution and alkaline solution, control pH between 9.0 ~ 10.0, vigorous stirring, aged at room temperature 12 ~ 24 hours; Gained slurries suction filtration, filter cake distilled water washing 3 ~ 5 times, under room temperature, drying 24 hours, obtains the IL that load has Hb
oH-LDH compound substance, the light absorption value through ultraviolet spectroscopy 406nm place learns that the haemoglobin of more than 98% is fixed;
The preparation of (b) decorating liquid
By the compound substance Hb-IL of negative loaded with hemoglobin obtained in step (a)
oH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, for subsequent use;
The pre-service of (c) GCE
With conventional polishing and polishing process, pre-service is carried out to GCE surface, then use the NaOH solution of 1mol/L, the HNO of 1mol/L successively
3solution, acetone and redistilled water supersound washing;
The preparation of (d) modified electrode
Be coated in by modification drop obtained for step (b) through the pretreated electrode surface of step (c), dripping painting amount is 7 μ L, and leave standstill, 4 DEG C of refrigerator overnight dryings, form one deck Hb-IL in glassy carbon electrode surface
oH-LDH film, then at Hb-IL
oH-LDH film dripping painting concentration is the chitosan-acetic acid solution of 1mg/ml, forms one deck chitosan film, and dripping a painting amount is 5 μ L, obtains Hb-IL after natural drying
oH-LDH/GCE modified electrode.
2. the preparation method of a kind of functionalized ion liquid according to claim 1-hydrotalcite-like composite material ankyrin modified electrode, is characterized in that the Zn of divalent metal salt described in step (a) (NO
3)
2with trivalent metal salt Al (NO
3)
3mol ratio be 2:1; IL
oHwith divalent metal salt Zn (NO
3)
2mol ratio be respectively 1:2; The mass ratio of Hb and LDH is respectively 0.05,0.25,0.5,1 and 2; Described alkaline solution is the sodium hydroxide solution of 2mol/L.
3. a kind of functionalized ion liquid described in claim 1-hydrotalcite-like composite material ankyrin modified electrode is preparing the application in electrochemical sensor.
4. the application of a kind of functionalized ion liquid according to claim 3-hydrotalcite-like composite material ankyrin modified electrode, is characterized in that this modified electrode can be used for the detection of hydrogen peroxide.
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| CN104034778A (en) * | 2014-06-18 | 2014-09-10 | 武汉工程大学 | Chitosan-ionic liquid-graphene-enzyme composite membrane modified electrode and preparation method thereof |
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| CN105784807A (en) * | 2015-11-28 | 2016-07-20 | 青岛科技大学 | Ionic liquid covalent-modified graphene-hydrotalcite-like composite membrane fixed protein-modified electrode, and preparation method and detection application thereof |
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| CN109100404B (en) * | 2018-08-14 | 2020-08-18 | 青岛科技大学 | Hydrotalcite-like nanosheet @ ZIF-67 composite material modified electrode and preparation method and detection application thereof |
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