CN103412021A - 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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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 in the application of electrochemical sensing context of detection.
Background technology
The Direct Electrochemistry research of the biomacromolecules such as redox protein matter and enzyme, can not only help people deeply to be familiar with the electronic transfer machine reason of biosystem, can also provide important theoretical foundation and technical support for development of new biology sensor, novel biological fuel battery etc.Yet it is darker that bury usually in their activated centre, at electrode surface, be difficult to occur Direct Electrochemistry, and they directly are adsorbed on the easy sex change that comes off in bare electrode surface.Therefore, searching can keep the active of enzyme and promote the material of direct electron transfer, has become the important topic of bioelectrochemical sensing area research.Recent research shows, inorganic lamellar material has adjustable open lamellar structure, make it aspect machinery, chemistry and thermal stability, have obvious advantage, and the effect of its nano-scale gives some new functions of material itself (as performances such as electric conductivity, light, electricity, magnetic), therefore fixing at biology enzyme and promote having shown the performance more superior than organic material aspect the electronics transmission.
Class neatly (being abbreviated as LDH) is a class two-dimensional nanometer anionic clay, forms general formula and can be expressed as [M
1-x 2+M
x 3+(OH)
2]
X+(A
N-)
x/nMH
2O, have hydrotalcite layered structure, lamella band structure positive charge, and there is tradable negative ion in interlayer.The biomolecule such as electronegative amino acid, DNA, protein, polypeptide and enzyme can be inserted the LDH interlayer, formation biomolecule-LDH nano hybrid [Zhan Tianrong, Hou Wanguo. the application of layered double hydroxide in the green material field.
The chemistry circular,
2010, 73 (7): 608 ~ 615.].At present, the researcher has realized biology enzyme fixing on LDH by adsorbing, peel off the softening methods such as restructuring, co-precipitation, electro-deposition, the Direct Electrochemistry result of study of corresponding biology enzyme shows, the nano-lamellar structure of LDH had both kept the activity of biology enzyme, had promoted again the transmission of electronics.But LDH is during as the electrode modified material immobilized enzyme, due to itself bad dispersibility and easy agglomeration traits, easily cause electrode surface protuberance, embrittlement, phenomenon [the Han E such as come off even to occur, 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.].
LDH is carried out to finishing and can not only improve its ability of intercalation to three-dimensional biomacromolecule, and be bad dispersibility and the easy effective ways of agglomeration traits while solving it as electrode modified material.LDH after modifying as DDS has better fixed performance to hemoglobinase (Hb), and has improved its electronics transmission capacity; Shitosan-LDH hybrid is for electrode modified material, and result shows that the existence of shitosan has overcome the easily defect such as protuberance and embrittlement of inorganic nano material, has improved the electrocatalysis characteristic of enzyme, and modified electrode has reached 0.36 nmol/L to the detection limit of tea phenol.Dispersion stabilization while adopting NiAl-LDH/CNT compound substance that coprecipitation makes as electrode modified material, the electrocatalysis characteristic of gained modified electrode is than simple LDH or the high octuple of CNT modified electrode [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, can improve dispersiveness, stability and the biocompatibility of decorative material at electrode surface, is conducive to improve its fixed performance to biomolecule and interfacial electrochemistry performance.
Functionalized ion liquid (Functionalized Ionic Liquid, FIL) refer to by negative ion or (with) cationic moiety introduces the structure function group, and the ionic liquid that the class formed has specific physics, chemical property, it is except having conventional ion liquid (Ionic Liquid, IL) electrochemical window is wide, electric conductivity is strong, volatility is low, outside the stability high, introducing due to the structure function group, more reaction site also is provided, for it, has modified inorganic nano material and created advantage.At present, (functionalization) ion liquid modified nano composite material is made modified electrode and in the electrochemical sensing field, has been obtained successful Application, as ionic liquid, do to be combined by the interaction force of " cation-π " key with carbon nano-tube in the nano composite material formed, ionic liquid has improved the dispersiveness of nano composite material, reunion and the wrapping phenomena of carbon nano-tube are effectively suppressed, the compound substance modified electrode shown excellent chemical property [Zhang Xuzhi. based on the electrochemica biological sensor of carbon nano-tube and ionic liquid enhancement effect: development, representation and application. Qingdao University of Science and Technology's doctorate paper,
2009.], after amino functional Ionic Liquid Modified Graphene, improved the latter's dispersive property, the gained composite modified electrode has improved direct electron transfer [Shan, the C.S. of glucose oxidase greatly, 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, provide the microenvironment of biocompatibility for myoglobins (Mb), effectively improved 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 and comparison of functionalized ion liquid-inorganic nano composite material modified electrode is active, but majority is directly will functionalized ion liquid, inorganic nano material and biology enzyme direct physical prepare composite modified electrode after mixing, at present and have no and adopt modified electrode prepared proteinaceous solid in functionalized ion liquid-LDH compound substance by coprecipitation and at the report of hydrogen peroxide context of detection.Here we will adopt coprecipitation by proteinaceous solid corresponding bio-modification electrode of preparation after functionalized ion liquid-LDH compound substance, and tentatively examine or check the detection of its hydrogen peroxide.
Adopt coprecipitation by proteinaceous solid corresponding bio-modification electrode of preparation after functionalized ion liquid-LDH compound substance, be conducive to abundant binding function ionic liquid and the advantage of layered inorganic material aspect electrode modified material, make up their defects in this respect, to provide more avtive spot for composite modified electrode, higher electric conductivity, dispersed and to the crystallized ability of enzyme, bring into play both synergy advantages, thereby improve Direct Electrochemistry and the electrocatalysis characteristic of biomolecule at modified electrode, significant to setting up novel high sensitive electrochemical detection method.
Summary of the invention
For the demand of the deficiencies in the prior art and this area research and application, one of purpose 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, described functionalized ion liquid-hydrotalcite-like composite material ankyrin layer is fixed in protein molecule in functionalized ion liquid-hydrotalcite-like composite material by coprecipitation; 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, structure is similar to brucite, and it forms general formula and can be expressed as:
[M
1-x 2+M
x 3+(OH)
2]
x+(A
n-)
x/n·mH
2O，
M in following formula
2+Refer to divalent metal, M
3+Refer to trivalent metal cation, A
n-
But for the interlayer stable existence-n valency negative ion, n is the negative ion valence mumber, 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)
3By certain mol proportion, be made into mixing salt solution, total concentration of metal ions is 0.6 mol/L, adds the Hb of certain mass, then by IL
OHBy certain mol proportion, add in mixing salt solution, by the titration simultaneously of above-mentioned mixed solution and alkaline solution, control pH between 9.0 ~ 10.0, vigorous stirring, under room temperature aging 12 ~ 24 hours; Gained slurries suction filtration, filter cake washs 3 ~ 5 times with distilled water, and under room temperature, drying is 24 hours, obtains the IL that load has Hb
OH-LDH compound substance, learn that through the light absorption value at ultraviolet spectroscopy 406 nm places the haemoglobin more than 98% is fixed;
(b) preparation of decorating liquid
The compound substance Hb-IL that the load obtained in step (a) is had to haemoglobin
OH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, standby;
(c) pre-service of GCE
With conventional polishing and polishing process, pre-service is carried out in the GCE surface, then use successively the NaOH solution of 1 mol/L, the HNO of 1 mol/L
3Solution, acetone and redistilled water supersound washing;
(d) preparation of modified electrode
The modification drop that step (b) is made is coated in through the pretreated electrode surface of step (c), drips the painting amount and is 7 μ L, standing, and 4 ℃ of refrigerator overnight dryings form one deck Hb-IL on the glass-carbon electrode surface
OH-LDH film, then at Hb-IL
OHOn-LDH film, drip being coated with concentration is the chitosan-acetic acid solution of 1 mg/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.
Divalent metal salt Zn (NO described in step (a) wherein
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, prepared by above-mentioned any one method by this composite modified electrode.
Three of the object of the invention is to provide a kind of functionalized ion liquid-hydrotalcite-like composite material ankyrin modified electrode in the application prepared aspect 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 advantage such as but the present invention utilizes houghite to have the open lamellar structure of intercalant anion and specific surface area is large, by coprecipitation, undertaken itself and the Hydroxyl-functionalized Ionic Liquids 1-methyl with good biocompatibility and electric conductivity-3-hydroxypropyl tetrafluoroborate and haemoglobin 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 the advantages such as highly sensitive, that detectability is low and sensing range is wide for detecting hydrogen peroxide.
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 double has brought into play functionalized ion liquid and houghite structure and the performance advantage as the electrode modified material aspect, is improving aspect haemoglobin Direct Electrochemistry and electrocatalysis characteristic the collaborative advantage function that can bring into play two kinds of functional materials; Particularly, the effect that direct fax is passed to haemoglobin has produced unexpected technique effect, no matter gained composite modified electrode of the present invention is to compare with houghite or functionalized ion liquid to the effect of haemoglobin direct electron transfer, all has obvious raising.The inventive method is simple to operate, mild condition, preparation cost are low.
The accompanying drawing explanation
Fig. 1 be Comparative Examples 1 (a) in embodiment 4 (d), embodiment 4, Comparative Examples 2 (b) and Comparative Examples 3 (c) gained modified electrode in the phosphate buffer solution of 0.05 mol/L, sweep the cyclic voltammogram of speed while being 0.1 V/s.
Fig. 2 is that embodiment 4 (d), Comparative Examples 1 (a), Comparative Examples 2 (b) and Comparative Examples 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 embodiment 1 ~ 5 gained load have Hb
OH-LDH (the IR spectrogram of b ~ f).。
Fig. 4 is the Hb-IL by embodiment 4 gained
OH-LDH/GCE, under nitrogen protection, adds the cyclic voltammetry curve of the hydrogen peroxide of different volumes 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.
Fig. 5 for Comparative Examples 3 obtains in embodiment 4 Hb-LDH/GCE under nitrogen protection; the cyclic voltammetry curve that adds the hydrogen peroxide of different volumes 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 further understanding the present invention, the invention will be further described below in conjunction with drawings and Examples, but and do not limit the present invention in any way.
By divalent metal salt Zn (NO
3)
2With trivalent metal salt Al (NO
3)
32:1 is made into mixing salt solution by certain mol proportion, and total concentration of metal ions is 0.6 mol/L, and Hb:LDH is that 0.05 amount adds Hb in mixing salt solution in mass ratio, 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, under room temperature aging 18 hours; Gained slurries suction filtration, filter cake washs 5 times with distilled water, and under room temperature, drying is 24 hours, obtains the compound substance Hb-IL that load has Hb
OH-LDH; The compound substance Hb-IL that the gained load is had to haemoglobin
OH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, gets 7 μ L and drips and be coated in the NaOH solution of using successively 1 mol/L, the HNO of 1 mol/L
3The GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
OHOn-LDH film, drip being coated with concentration is the chitosan-acetic acid solution 5 μ L of 1 mg/ml, obtains Hb-IL after natural drying
OH-LDH/GCE modified electrode.
By divalent metal salt Zn (NO
3)
2With trivalent metal salt Al (NO
3)
32:1 is made into mixing salt solution by certain mol proportion, and total concentration of metal ions is 0.6 mol/L, and Hb:LDH is that 0.25 amount adds Hb in mixing salt solution in mass ratio, 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, under room temperature aging 20 hours; Gained slurries suction filtration, filter cake washs 5 times with distilled water, and under room temperature, drying is 24 hours, obtains the compound substance Hb-IL that load has Hb
OH-LDH; The compound substance Hb-IL that the gained load is had to haemoglobin
OH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, gets 7 μ L and drips and be coated in the NaOH solution of using successively 1 mol/L, the HNO of 1 mol/L
3The GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
OHOn-LDH film, drip being coated with concentration is the chitosan-acetic acid solution 5 μ L of 1 mg/ml, obtains Hb-IL after natural drying
OH-LDH/GCE modified electrode.
Embodiment 3
By divalent metal salt Zn (NO
3)
2With trivalent metal salt Al (NO
3)
32:1 is made into mixing salt solution by certain mol proportion, and total concentration of metal ions is 0.6 mol/L, and Hb:LDH is that 0.5 amount adds Hb in mixing salt solution in mass ratio, 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, under room temperature aging 22 hours; Gained slurries suction filtration, filter cake washs 5 times with distilled water, and under room temperature, drying is 24 hours, obtains the compound substance Hb-IL that load has Hb
OH-LDH; The compound substance Hb-IL that the gained load is had to haemoglobin
OH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, gets 7 μ L and drips and be coated in the NaOH solution of using successively 1 mol/L, the HNO of 1 mol/L
3The GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
OHOn-LDH film, drip being coated with concentration is the chitosan-acetic acid solution 5 μ L of 1 mg/ml, obtains Hb-IL after natural drying
OH-LDH/GCE modified electrode.
By divalent metal salt Zn (NO
3)
2With trivalent metal salt Al (NO
3)
32:1 is made into mixing salt solution by certain mol proportion, and total concentration of metal ions is 0.6 mol/L, and Hb:LDH is that 1 amount adds Hb in mixing salt solution in mass ratio, 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, under room temperature aging 22 hours; Gained slurries suction filtration, filter cake washs 5 times with distilled water, and under room temperature, drying is 24 hours, obtains the compound substance Hb-IL that load has Hb
OH-LDH; The compound substance Hb-IL that the gained load is had to haemoglobin
OH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, gets 7 μ L and drips and be coated in the NaOH solution of using successively 1 mol/L, the HNO of 1 mol/L
3The GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
OHOn-LDH film, drip being coated with concentration is the chitosan-acetic acid solution 5 μ L of 1 mg/ml, obtains Hb-IL after natural drying
OH-LDH/GCE modified electrode.
Comparative Examples 1
With reference to the above-mentioned method for preparing modified electrode, directly being mixed with Hb content is the decorating liquid of 20 μ g/ μ L, gets 7 μ L and drips and be coated in the NaOH solution of using successively 1 mol/L, the HNO of 1 mol/L
3The GCE surface of solution, acetone and redistilled water supersound washing, and then drip to be coated with concentration on the Hb film be the chitosan-acetic acid solution 5 μ L of 1 mg/ml, obtain the Hb/GCE modified electrode after natural drying.
Comparative Examples 2
With reference to the above-mentioned method for preparing modified electrode, directly be mixed with IL
OHMass percent is that 10%, Hb content is the decorating liquid of 20 μ g/ μ L, gets 7 μ L and drips and be coated in the NaOH solution of using successively 1 mol/L, the HNO of 1 mol/L
3The GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
OHOn film, drip being coated with concentration is the chitosan-acetic acid solution 5 μ L of 1 mg/ml, obtains Hb-IL after natural drying
OH/ GCE modified electrode.
Comparative Examples 3
The method for preparing modified electrode with reference to above-described embodiment 4, do not add IL
OH, preparation Hb-LDH/GCE modified electrode.
Fig. 1 be embodiment 4 (d), Comparative Examples 1 (a), Comparative Examples 2 (b) and Comparative Examples 3 (c) gained modified electrode in the phosphate buffer solution of 0.05 mol/L, sweep the cyclic voltammogram of speed while being 0.1 V/s.As seen from the figure, (curve a pair of very weak asymmetric redox peak occurred on a), illustrates on electrode electronic transfer process has very slowly occurred at Hb/GCE; At Hb-IL
OH/ GCE (curve b) is upper, and the redox electric current does not significantly change, and shows IL
OHExistence do not improve the electron transfer rate of Hb.Upper at Hb-LDH/GCE (curve c), the redox electric current increases, and this shows that LDH has improved electron transfer rate in the existence of electrode surface, has increased the electrochemical response signal.And at Hb-IL
OH-LDH/GCE (curve d) is upper, and the further enhancing of redox peak current and peak type are 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 collaborative electronics of having accelerated Hb of the nanometer laminated structure of LDH shift.From curve d, finding out, reduction peak and oxidation peak current potential are respectively-0.384 V and-0.2664 V (vs. SCE), the formula current potential is-0.298 V (vs. SCE), and this is the characteristic peak of protoheme prothetic group Fe (II) in Hb/Fe (III) oxidation-reduction pair.Result shows at Hb-IL
OHThe upper Direct electron transfer that can realize Hb of-LDH/GCE.
Fig. 2 is that embodiment 4 (d), Comparative Examples 1 (a), Comparative Examples 2 (b) and Comparative Examples 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 curve medium-high frequency zone semi arch is the resistance that electronics transmits, and can reflect the electronics transfer rate of redox probe.As can be seen from the figure, (curve is the resistance maximum of upper electronics transmission a), when IL is arranged for Hb/GCE
OH(Hb-IL
OH/ GCE, curve b) or LDH (Hb-LDH/GCE, curve c) while existing, on corresponding modified electrode, the resistance of electronics transmission has obvious reduction, this result shows IL
OHWith the existence of LDH, all can accelerate the electronics transfer rate.And Hb-IL
OHThe resistance minimum that the upper electronics of-LDH/GCE (curve d) transmits, illustrate IL
OHThe existence of-LDH composite membrane has improved electric conductivity, has increased effective electrode area, makes more [Fe (CN)
6]
3/ 4Participate in electrochemical reaction, thereby improved the transfer rate of electronics.
Embodiment 5
By divalent metal salt Zn (NO
3)
2With trivalent metal salt Al (NO
3)
32:1 is made into mixing salt solution by certain mol proportion, and total concentration of metal ions is 0.6 mol/L, and Hb:LDH is that 2 amount adds Hb in mixing salt solution in mass ratio, 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, under room temperature aging 24 hours; Gained slurries suction filtration, filter cake washs 5 times with distilled water, and under room temperature, drying is 24 hours, obtains the compound substance Hb-IL that load has Hb
OH-LDH; The compound substance Hb-IL that the gained load is had to haemoglobin
OH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, gets 7 μ L and drips and be coated in the NaOH solution of using successively 1 mol/L, the HNO of 1 mol/L
3The GCE surface of solution, acetone and redistilled water supersound washing, and then at Hb-IL
OHOn-LDH film, drip being coated with concentration is the chitosan-acetic acid solution 5 μ L of 1 mg/ml, obtains Hb-IL after natural drying
OH-LDH/GCE modified electrode.
Fig. 3 is the compound substance Hb-IL that Hb (a) and embodiment 1 ~ 5 gained load have Hb
OH-LDH (the IR spectrogram of 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 the protein structure degenerative condition can be reflected in their intensity and peak position.Compound substance Hb-IL in figure
OH(absorption band of I level amine and the II level amine of Hb in the curve of b ~ f), all occurred, absorption peak lays respectively at 1647 ~ 1655 cm to-LDH
-1Between and 1538 ~ 1545 cm
-1Between, with I level amine (1653 cm of free Hb
-1) and II level amine (1545 cm
-1) the absorption peak position basic identical, illustrate and be fixed on IL
OHHb in-LDH compound substance has kept its natural secondary structure well, but in compound substance, between the slight change of I level amine and II level amine peak intensity and absorption peak position explanation protein and nano composite material, exist certain interaction in Hb, so could form well Hb-IL
OH-LDH Biocomposite material.
By the prepared Hb-IL of 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.To the hydrogen peroxide that adds different volumes in the phosphate buffer solution (pH 7.0) of 0.1 mol/L, circulation volt curve while drawing the variable concentrations concentration of hydrogen peroxide, the variation of record reduction peak current during along with the increase of concentration of hydrogen peroxide, and with reduction peak current to adding in electrolytic cell the concentration of hydrogen peroxide mapping, solve correlation parameter.Before test with high pure nitrogen to bubbling in solution 30 minutes except oxygen, during test, get rid of the interference of oxygen with nitrogen protection.
Comparative Examples 1
According to the method described above, Hb-LDH/GCE modified electrode Comparative Examples 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, and in illustration, shows that its former peak current and concentration of hydrogen peroxide are linear, and 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, minimal detectable concentration is 0.99 * 10
-8Mol/L, and Hb-LDH/GCE detects the linear concentration range (1.99 ~ 7.94) * 10 of hydrogen peroxide
-8Mol/L(is shown in Fig. 5), sensitivity is 15.78 μ A/mM, minimal detectable concentration is 1.99 * 10
-8Mol/L.Can find out Hb-IL
OH-LDH/GCE obviously is better than Hb-LDH/GCE to the electrochemical catalysis performance of hydrogen peroxide, and IL is described
OHExistence further increased the electric conductivity of composite membrane, improved 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 (6)
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, described functionalized ion liquid-hydrotalcite-like composite material ankyrin layer is fixed in protein molecule in functionalized ion liquid-hydrotalcite-like composite material by coprecipitation; Wherein houghite (being designated as LDH) 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, structure is similar to brucite, and it forms general formula and can be expressed as:
[M
1-x 2+M
x 3+(OH)
2]
x+(A
n-)
x/n·mH
2O，
M in following formula
2+Refer to divalent metal, M
3+Refer to trivalent metal cation, A
n-
But for the interlayer stable existence-n valency negative ion, n is the negative ion valence mumber, 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:
2. a kind of functionalized ion liquid according to claim 1-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).
3. the preparation method of a kind of functionalized ion liquid according to claim 1 and 2-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)
3By certain mol proportion, be made into mixing salt solution, total concentration of metal ions is 0.6 mol/L, adds the Hb of certain mass, then by IL
OHBy certain mol proportion, add in mixing salt solution, by the titration simultaneously of above-mentioned mixed solution and alkaline solution, control pH between 9.0 ~ 10.0, vigorous stirring, under room temperature aging 12 ~ 24 hours; Gained slurries suction filtration, filter cake washs 3 ~ 5 times with distilled water, and under room temperature, drying is 24 hours, obtains the IL that load has Hb
OH-LDH compound substance, learn that through the light absorption value at ultraviolet spectroscopy 406 nm places the haemoglobin more than 98% is fixed;
(b) preparation of decorating liquid
The compound substance Hb-IL that the load obtained in step (a) is had to haemoglobin
OH-LDH is mixed with the decorating liquid that Hb content is 20 μ g/ μ L, standby;
(c) pre-service of GCE
With conventional polishing and polishing process, pre-service is carried out in the GCE surface, then use successively the NaOH solution of 1 mol/L, the HNO of 1 mol/L
3Solution, acetone and redistilled water supersound washing;
(d) preparation of modified electrode
The modification drop that step (b) is made is coated in through the pretreated electrode surface of step (c), drips the painting amount and is 7 μ L, standing, and 4 ℃ of refrigerator overnight dryings form one deck Hb-IL on the glass-carbon electrode surface
OH-LDH film, then at Hb-IL
OHOn-LDH film, drip being coated with concentration is the chitosan-acetic acid solution of 1 mg/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.
4. the preparation method of a kind of functionalized ion liquid according to claim 3-hydrotalcite-like composite material ankyrin modified electrode, is characterized in that divalent metal salt Zn (NO described in step (a)
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.
5. the described a kind of functionalized ion liquid of claim 1 or 2-hydrotalcite-like composite material ankyrin modified electrode is in the application prepared aspect electrochemical sensor.
6. the application of a kind of functionalized ion liquid according to claim 5-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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