CN105758911A - Gold electrode based on nanocellulose and cysteine modification and application thereof - Google Patents
Gold electrode based on nanocellulose and cysteine modification and application thereof Download PDFInfo
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Abstract
The invention discloses a gold electrode based on nanocellulose and cysteine modification.A preparation method of the electrode includes the steps that microcrystalline cellulose is prepared into nanocellulose through an acid hydrolysis method, nanocellulose oxide is prepared through a 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO) oxidation method, the nanocellulose oxide is prepared into a nanocellulose oxide water solution with the mass concentration being 0.01 g/mL, and the product is stored at 5 DEG C; a cleaned gold electrode is soaked in a cysteine water solution of 0.01-0.05 M to be subjected to self-assembly for 8-16 hours, so that a cysteine self-assembly gold electrode is obtained; hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride are added into the nanocellulose oxide water solution with the mass concentration being 0.01 g/mL to obtain a mixed solution; the cysteine self-assembly gold electrode is soaked into the mixed solution, and the gold electrode based on nanocellulose and cysteine modification is obtained after the mixture is subjected to stirring reaction for 18-30 hours at room temperature.With cellulose and cysteine being main raw materials, the preparation cost is low.
Description
Technical field
The present invention relates to a kind of based on nano-cellulose and the gold electrode of cysteine modified and application, belong to analysisization
Learn a skill detection field.
Background technology
Cellulose is natural chiral polymer, especially common for the cellulose research in chiral separation analysis direction.Will
After cellulose nanorize, obtain bar-shaped, high crystalline cellulose, widened the range of application of nano-cellulose especially.Nanofiber
Have the most superior physicochemical properties, such as: bigger the ratio of width to height and specific surface area, preferable biocompatibility, unique
Optical characteristics etc..These superior character make nano-cellulose have huge application potential at biochemical analysis detection field.
The application have studied preparation and the application of nano-cellulose modified electrode.Owing to nano-cellulose is not easy to be fixed on
Electrode surface, needs to aoxidize nano-cellulose in terms of modified electrode, generates carboxyl, introduce good biocompatibility and with appearance
Easily the cysteine of the functional group of bonding is as the medium between nano-cellulose and electrode, and cysteine low cost, with work
Property functional groups amino and sulfydryl.
Summary of the invention
It is an object of the invention to provide a kind of based on nano-cellulose and the gold electrode of cysteine modified and application.Will
This application of electrode is in measuring chiral amino acid, and experimental implementation is simple, it is quick and highly sensitive to detect, and electrochemical response is good.
A kind of based on nano-cellulose with the gold electrode of cysteine modified, it is characterised in that this electrode is by the following method
Prepare:
1) preparation of oxidation nanometer cellulose
Nano-cellulose acid hydrolysis method is prepared by microcrystalline Cellulose, prepares oxidation nanometer cellulose by TEMPO oxidizing process, and
Being made into the oxidation nanometer cellulose aqueous solution that mass concentration is 0.01g/mL, product is placed in 5 DEG C of storages；
2) preparation of cysteine self assembly gold electrode
The gold electrode cleaned up is immersed in self assembly in 0.01 ~ 0.05M aqueous cystein solution and within 8 ~ 16 hours, i.e. obtains half Guang
Propylhomoserin self assembly gold electrode；
3) preparation of oxidation nanometer cellulose/cysteine/gold electrode
Hydroxysuccinimide, 1-ethyl-(3-is added in the oxidation nanometer cellulose aqueous solution that mass concentration is 0.01g/mL
Dimethylaminopropyl) carbodiimide hydrochloride obtains mixed solution；Described cysteine self assembly gold electrode is immersed in mixed
Close in solution, stir reaction under room temperature and within 18 ~ 30 hours, i.e. obtain the gold electrode based on nano-cellulose and cysteine modified.
Described oxidation nanometer cellulose aqueous solution, hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl) carbonization
The amount ratio of diimmonium salt hydrochlorate is 10 g:0.2 ~ 0.4, mL:0.01 ~ 0.02 g.
The application in chiral amino acid detects of the above-mentioned gold electrode based on nano-cellulose and cysteine modified.
Described chiral amino acid is phenylalanine enantiomer, leucine enantiomer or valine enantiomerism
Body.
The step of gold electrode based on nano-cellulose and cysteine modified detection chiral amino acid is:
With oxidation nanometer cellulose/cysteine/gold electrode as working electrode, silver/silver chloride is as reference electrode, platinum filament electricity
Pole as forming three electrode detection systems to electrode, at the 5mM K containing appropriate amino acid enantiomer3[Fe(CN)6]/K4
[Fe(CN)6], supporting electrolyte is in 0.1M Klorvess Liquid, use cyclic voltammetric send out with differential pulse voltametry 0.6 to-
0.2V is scanned, and according to the linear relationship between peak height and the aminoacid concentration in the solution of current peak, carries out in sample
The mensuration of amino acid concentration.
Above-mentioned modified electrode is when detecting L-phenylalanine, 1 × 10-5~5×10-3M detects linearly, and detection is limited to
5.6×10-6M。
Above-mentioned modified electrode is when detecting D-phenylalanine, 1 × 10-5~5×10-3M detects linearly, and detection is limited to
9.0×10-6M。
The present invention compared with prior art has the advantage that:
Nano-cellulose is introduced electrochemical sensor by the present invention, has expanded the application of nano-cellulose；Use cellulose, half Guang
Propylhomoserin is as primary raw material, and preparation cost is low；Can be used for the detection of several amino acids enantiomer, applied range.
Accompanying drawing explanation
Fig. 1 is based on unmodified gold electrode (a), nano-cellulose modified gold electrode (b), oxidation nanometer cellulose modifying gold
Electrode (c), cysteine modified gold electrode (d) and the electrochemical response of oxidation nanometer cellulose/cysteine/gold electrode (e)
The cyclic voltammogram obtained.
Fig. 2 is modified electrode to L-phenylalanine (a) and the cyclic voltammogram (A) of D-phenylalanine (b) and differential pulse
Voltammogram (B).
Fig. 3 is modified electrode to L-Leu (a) and the cyclic voltammogram (A) of D-Leu (b) and differential pulse volt-ampere
Figure (B).
Fig. 4 is modified electrode to Valine (a) and the cyclic voltammogram (A) of D-Val (b) and differential pulse volt-ampere
Figure (B).
Detailed description of the invention
Embodiment 1
(1) preparation of nano-cellulose/gold electrode:
Nano-cellulose acid hydrolysis method is prepared by microcrystalline Cellulose, and preparation mass concentration is the nano-cellulose of 0.01g/mL
Aqueous solution, takes 20 μ L drop coatings in the gold electrode surfaces cleaned up, and is dried, obtains nano-cellulose/gold electrode at 50 DEG C.
(2) modified electrode is in the application of electrochemical signals:
Using the gold electrode modified is 5mM K at electrolyte3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is 0.1M chlorination
Potassium obtains cyclic voltammogram.Location parameter is:
INSTRUMENT MODEL: CHI660
Starting point position (Init E) (V)=0.6
High potential (High E) (V)=0.6
Electronegative potential (Low E) (V)=-0.2
Preliminary sweep polarity (Init P/N)=negative electrode
Sweep speed (Scan Rate) (V/s)=0.05
Scanning times (Segment)=2
Sample room is every (Sample Interval (V))=0.001
Quiescent time (Quite Time) (sec)=2
Sensitivity (Sensitivity) (A/V)=1e-5
Obtaining cyclic voltammogram as shown in Figure 1, abscissa Potential represents that electromotive force, vertical coordinate Current represent electric current,
Wherein (b) represents electrochemical response volt-ampere curve based on nano-cellulose/gold electrode, and (a) represents the gold electrode of unmodified
Electrochemical response volt-ampere curve.Electrode before and after being modified by contrast, it can be seen that the current-responsive value of modified electrode is less, says
Bright nano-cellulose is successfully modified in gold electrode surfaces.But the nano-cellulose thin layer of electrode surface is easy to fall off, stability
Poor.
Embodiment 2
(1) prepared by oxidation nanometer cellulose/gold electrode:
Prepare oxidation nanometer cellulose: take containing 1g nano-cellulose suspension 100mL, be separately added into sodium bromide, TEMPO and
Liquor natrii hypochloritis.It is diluted to 200 mL, with ultrasonic Treatment with the sodium carbonate-bicarbonate buffer solution of pH=10.2
5min, stirs reaction 2 hours at a temperature of controlling, and is subsequently adding 10 mL dehydrated alcohol and terminates reaction, and regulation pH value, to 7, is dialysed
5 days, obtaining oxidation nanometer cellulose aqueous solution, product is placed in 5 DEG C of storages.
Preparation mass concentration is that the oxidation nanometer cellulose aqueous solution drop coating of 0.02g/mL is at the gold electrode table cleaned up
Face, is dried at 50 DEG C, obtains oxidation nanometer cellulose/gold electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1, obtains cyclic voltammogram as shown in Figure 1, wherein (c) represent based on
The electrochemical response volt-ampere curve of oxidation nanometer cellulose/gold electrode, (a) represents the electrochemical response volt of the gold electrode of unmodified
Peace curve.Electrode before and after being modified by contrast, it can be seen that the current-responsive value of modified electrode is less, and oxidation nanometer is described
Cellulose is successfully modified in gold electrode surfaces.But the oxidation nanometer cellulose layer of electrode surface is easy to fall off, and stability is relatively
Difference.
Embodiment 3
(1) prepared by cysteine/gold electrode:
The gold electrode cleaned up is immersed in 0.01M aqueous cystein solution 12 hours, obtains cysteine self assembly gold
Electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1, obtains cyclic voltammogram as shown in Figure 1, and wherein (d) represents half Guang ammonia
The electrochemical response volt-ampere curve of acid/gold electrode, (a) represents the electrochemical response volt-ampere curve of the gold electrode of unmodified.Pass through
Electrode before and after contrast modification, it can be seen that the current-responsive value of modified electrode is relatively big, illustrates that cysteine is successfully modified
Gold electrode surfaces.
Embodiment 4
(1) prepared by cysteine/gold electrode:
The gold electrode cleaned up is immersed in 0.02M aqueous cystein solution 8 hours, obtains cysteine self assembly gold electricity
Pole.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.Comparing with the modified electrode in embodiment 3, its peak current is relatively low, explanation
In the cysteine amount of self assembly relatively embodiment 3 less.
Embodiment 5
(1) prepared by cysteine/gold electrode:
The gold electrode cleaned up is immersed in 0.03M aqueous cystein solution 10 hours, obtains cysteine self assembly gold
Electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.Compare with the modified electrode in embodiment 3, the basic phase of its peak point current
With.
Embodiment 6
(1) prepared by cysteine/gold electrode:
The gold electrode cleaned up is immersed in 0.04M aqueous cystein solution 14 hours, obtains cysteine self assembly gold
Electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.Compare with the modified electrode in embodiment 3, the basic phase of its peak point current
With, illustrate that cysteine assembling amount on gold electrode is the most saturated.
Embodiment 7
(1) prepared by cysteine/gold electrode:
The gold electrode cleaned up is immersed in 0.05M aqueous cystein solution 16 hours, obtains cysteine self assembly gold
Electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.Compare with the modified electrode in embodiment 3, the basic phase of its peak point current
With, illustrate that cysteine assembling amount on gold electrode is the most saturated.
Embodiment 8
(1) preparation of oxidation nanometer cellulose/cysteine/gold electrode:
The preparation method of oxidation nanometer cellulose is identical with embodiment 2.
The gold electrode cleaned up is immersed in 0.01M aqueous cystein solution 12 hours, obtains cysteine from group
Dress gold electrode.
Prepare the oxidation nanometer cellulose aqueous solution that 10 mL mass concentrations are 0.01g/mL, add hydroxysuccinimide
0.018g, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride 0.27g, stirs.Put into cysteine certainly
Assemble gold electrode, react 24 hours, cleaning-drying after taking-up, obtain oxidation nanometer cellulose/cysteine/gold electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1, obtains cyclic voltammogram as shown in Figure 1, and wherein (e) represents based on oxygen
Changing the electrochemical response volt-ampere curve of nano-cellulose/cysteine/gold electrode, (a) represents the electrification of the gold electrode of unmodified
Learn response volt-ampere curve.Electrode before and after being modified by contrast, it can be seen that the current-responsive value of modified electrode is less, explanation
Oxidation nanometer cellulose and cysteine are successfully modified in gold electrode surfaces.
(3) oxidation nanometer cellulose/cysteine/gold electrode is identifying the application of phenylalanine enantiomer:
The 5mM K of 5mM L-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is to obtain in 0.1M Klorvess Liquid
To cyclic voltammogram, method is same as in Example 1 with step.Obtaining cyclic voltammogram as shown in Figure 2 A, wherein (a) expression is repaiied
The decorations electrode response curve to L-phenylalanine.
Material is identical with cyclic voltammetry method with step, is only changed to differential pulse volt-ampere method of testing, records differential
Pulse Voltammetry figure, as shown in Figure 3 B, wherein the parameter in test process and value are:
INSTRUMENT MODEL: CHI660
Starting point position (Init E (V))=0.6
Terminate current potential (Final E (V))=-0..2
Step height (Incr E (V))=0.004
Amplitude (Amplitude) (V)=0.05
Pulse width (Pulse Width (sec))=0.05
Sampling interval (Sample Width (sec))=0.005
Pulse period (Pulse Period (sec))=0.5
Quiescent time (Quiet time) (sec)=2
Sensitivity (Sensitivity (A/V))=1e-5
As shown in Figure 3 B, wherein (a) represents the modified electrode response curve to L-phenylalanine.
The method of the cyclic voltammetric of 5mM D-phenylalanine and the test of differential pulse volt-ampere and step and L-phenylalanine phase
With.Obtaining cyclic voltammetric (A) as shown in Figure 2 and differential pulse voltammogram (B), wherein (b) represents that modified electrode is to D-phenylpropyl alcohol
The response curve of propylhomoserin.Finding out from differential pulse voltammogram, compared with L-phenylalanine, the peak current of D-phenylalanine is relatively
Low, peak current ratio (L/D) is 1.55.Illustrate that modified electrode has recognition effect to phenylalanine enantiomer.
Embodiment 9
(1) preparation of oxidation nanometer cellulose/cysteine/gold electrode:
The preparation method of oxidation nanometer cellulose is identical with embodiment 2.
The gold electrode cleaned up is immersed in 0.01M aqueous cystein solution 12 hours, obtains cysteine from group
Dress gold electrode.
Prepared by oxidation nanometer cellulose TEMPO oxidizing process, preparing 10 mL mass concentrations is the oxidation nanometer of 0.01g/mL
Cellulose aqueous solution.Above-mentioned solution is added hydroxysuccinimide 0.010g, 1-ethyl-(3-dimethylaminopropyl) carbonization
Diimmonium salt hydrochlorate 0.20g, stirs.Put into cysteine self assembly gold electrode, react 18 hours, clean dry after taking-up
Dry, obtain oxidation nanometer cellulose/cysteine/gold electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.
(3) oxidation nanometer cellulose/cysteine/gold electrode is identifying the application of phenylalanine enantiomer:
The 5mM K of 5mM L-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is to obtain in 0.1M Klorvess Liquid
To cyclic voltammogram and differential pulse voltammogram, method is the same as in Example 8 with step.
The 5mM K of 5mM L-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is 0.1M Klorvess Liquid
In obtain cyclic voltammogram and differential pulse voltammogram, method is the same as in Example 8 with step.Compared with L-phenylalanine, D-
The peak current of the differential pulse volt-ampere curve of phenylalanine is relatively low, and peak current ratio (L/D) is 1.21.Illustrate that modified electrode is to benzene
Alanine enantiomer has recognition effect.
Embodiment 10
(1) preparation of oxidation nanometer cellulose/cysteine/gold electrode:
The preparation method of oxidation nanometer cellulose is identical with embodiment 2.
The gold electrode cleaned up is immersed in 0.01M aqueous cystein solution 12 hours, obtains cysteine from group
Dress gold electrode.
Prepared by oxidation nanometer cellulose TEMPO oxidizing process, preparing 10 mL mass concentrations is the oxidation nanometer of 0.01g/mL
Cellulose aqueous solution.Above-mentioned solution is added hydroxysuccinimide 0.014g, 1-ethyl-(3-dimethylaminopropyl) carbonization
Diimmonium salt hydrochlorate 0.28g, stirs.Put into cysteine self assembly gold electrode, react 21 hours, clean dry after taking-up
Dry, obtain oxidation nanometer cellulose/cysteine/gold electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.
(3) oxidation nanometer cellulose/cysteine/gold electrode is identifying the application of phenylalanine enantiomer:
The 5mM K of 5mM L-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is to obtain in 0.1M Klorvess Liquid
To cyclic voltammogram and differential pulse voltammogram, method is the same as in Example 8 with step.
The 5mM K of 5mM L-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is 0.1M Klorvess Liquid
In obtain cyclic voltammogram and differential pulse voltammogram, method is the same as in Example 8 with step.Compared with L-phenylalanine, D-
The peak current of the differential pulse volt-ampere curve of phenylalanine is relatively low, and peak current ratio (L/D) is 1.37.Illustrate that modified electrode is to benzene
Alanine enantiomer has recognition effect.
Embodiment 11
(1) preparation of oxidation nanometer cellulose/cysteine/gold electrode:
The preparation method of oxidation nanometer cellulose is identical with embodiment 2.
The gold electrode cleaned up is immersed in 0.01M aqueous cystein solution 12 hours, obtains cysteine from group
Dress gold electrode.
Prepared by oxidation nanometer cellulose TEMPO oxidizing process, preparing 10 mL mass concentrations is the oxidation nanometer of 0.01g/mL
Cellulose aqueous solution.Above-mentioned solution is added hydroxysuccinimide 0.018g, 1-ethyl-(3-dimethylaminopropyl) carbonization
Diimmonium salt hydrochlorate 0.36g, stirs.Put into cysteine self assembly gold electrode, react 27 hours, clean dry after taking-up
Dry, obtain oxidation nanometer cellulose/cysteine/gold electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.
(3) oxidation nanometer cellulose/cysteine/gold electrode is identifying the application of phenylalanine enantiomer:
The 5mM K of 5mM L-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is to obtain in 0.1M Klorvess Liquid
To cyclic voltammogram and differential pulse voltammogram, method is the same as in Example 8 with step.
The 5mM K of 5mM L-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is 0.1M Klorvess Liquid
In obtain cyclic voltammogram and differential pulse voltammogram, method is the same as in Example 8 with step.Compared with L-phenylalanine, D-
The peak current of the differential pulse volt-ampere curve of phenylalanine is relatively low, and peak current ratio (L/D) is 1.53.Illustrate that modified electrode is to benzene
Alanine enantiomer has recognition effect.
Embodiment 12
(1) preparation of oxidation nanometer cellulose/cysteine/gold electrode:
The preparation method of oxidation nanometer cellulose is identical with embodiment 2.
The gold electrode cleaned up is immersed in 0.01M aqueous cystein solution 12 hours, obtains cysteine from group
Dress gold electrode.
Prepared by oxidation nanometer cellulose TEMPO oxidizing process, preparing 10 mL mass concentrations is the oxidation nanometer of 0.01g/mL
Cellulose aqueous solution.Above-mentioned solution is added hydroxysuccinimide 0.020g, 1-ethyl-(3-dimethylaminopropyl) carbonization
Diimmonium salt hydrochlorate 0.40g, stirs.Put into cysteine self assembly gold electrode, react 30 hours, clean dry after taking-up
Dry, obtain oxidation nanometer cellulose/cysteine/gold electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.
(3) oxidation nanometer cellulose/cysteine/gold electrode is identifying the application of phenylalanine enantiomer:
The 5mM K of 5mM L-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is to obtain in 0.1M Klorvess Liquid
To cyclic voltammogram and differential pulse voltammogram, method is the same as in Example 8 with step.
The 5mM K of 5mM L-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is 0.1M Klorvess Liquid
In obtain cyclic voltammogram and differential pulse voltammogram, method is the same as in Example 8 with step.Compared with L-phenylalanine, D-
The peak current of the differential pulse volt-ampere curve of phenylalanine is relatively low, and peak current ratio (L/D) is 1.54.Illustrate that modified electrode is to benzene
Alanine enantiomer has recognition effect.
Embodiment 13
(1) preparation of oxidation nanometer cellulose/cysteine/gold electrode:
The preparation method of oxidation nanometer cellulose is identical with embodiment 2.
The gold electrode cleaned up is immersed in 0.01M aqueous cystein solution 12 hours, obtains cysteine from group
Dress gold electrode.
Prepared by oxidation nanometer cellulose TEMPO oxidizing process, preparing 10 mL mass concentrations is the oxidation nanometer of 0.01g/mL
Cellulose aqueous solution.Above-mentioned solution is added hydroxysuccinimide 0.018g, 1-ethyl-(3-dimethylaminopropyl) carbonization
Diimmonium salt hydrochlorate 0.27g, stirs.Put into cysteine self assembly gold electrode, react 24 hours, clean dry after taking-up
Dry, obtain oxidation nanometer cellulose/cysteine/gold electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.
(3) oxidation nanometer cellulose/cysteine/gold electrode is identifying the application of leucine enantiomer:
The 5mM K of 5mM L-Leu3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is to obtain in 0.1M Klorvess Liquid
Cyclic voltammogram and differential pulse voltammogram, method is the same as in Example 8 with step.Obtain cyclic voltammogram as shown in Figure 3
(A) and differential pulse voltammogram (B), wherein (a) represents the modified electrode response curve to L-Leu.
The method that the cyclic voltammetric of 5mM D-Leu characterizes with differential pulse volt-ampere is identical with L-Leu with step.?
To cyclic voltammogram (A) as shown in Figure 3 and differential pulse voltammogram (B), wherein (b) represents that modified electrode is to D-Leu
Response curve.Compared with L-Leu, its peak current is relatively low.Illustrate that modified electrode has identification effect to leucine enantiomer
Really.
Embodiment 14
(1) preparation of oxidation nanometer cellulose/cysteine/gold electrode:
The preparation method of oxidation nanometer cellulose is identical with embodiment 2.
The gold electrode cleaned up is immersed in 0.01M aqueous cystein solution 12 hours, obtains cysteine from group
Dress gold electrode.
Prepared by oxidation nanometer cellulose TEMPO oxidizing process, preparing 10 mL mass concentrations is the oxidation nanometer of 0.01g/mL
Cellulose aqueous solution.Above-mentioned solution is added hydroxysuccinimide 0.018g, 1-ethyl-(3-dimethylaminopropyl) carbonization
Diimmonium salt hydrochlorate 0.33g, stirs.Put into cysteine self assembly gold electrode, react 24 hours, clean dry after taking-up
Dry, obtain oxidation nanometer cellulose/cysteine/gold electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.
(3) oxidation nanometer cellulose/cysteine/gold electrode is identifying the application of valine enantiomer:
The 5mM K of 5mM Valine3[Fe(CN)6]/K4[Fe(CN)6], in supporting electrolyte is 0.1M Klorvess Liquid
The same as in Example 8 with step to the method for cyclic voltammetric and differential pulse voltammogram.Obtain cyclic voltammogram as shown in Figure 4
(A) and differential pulse voltammogram (B), wherein (a) represents the modified electrode response curve to Valine.
The cyclic voltammogram of 5mM D-Val is identical with Valine with step with the method for differential pulse voltammogram.?
To cyclic voltammogram (A) as shown in Figure 4 and differential pulse voltammogram (B), wherein (b) represents that modified electrode is to D-Val
Response curve.Compared with Valine, its peak current is relatively low.Illustrate that modified electrode has identification effect to valine enantiomer
Really.
Embodiment 15
(1) preparation of oxidation nanometer cellulose/cysteine/gold electrode:
The preparation method of oxidation nanometer cellulose is identical with embodiment 2.
The gold electrode cleaned up is immersed in 0.01M aqueous cystein solution 12 hours, obtains cysteine from group
Dress gold electrode.
Prepared by oxidation nanometer cellulose TEMPO oxidizing process, preparing 10 mL mass concentrations is the oxidation nanometer of 0.01g/mL
Cellulose aqueous solution.Above-mentioned solution is added hydroxysuccinimide 0.012g, 1-ethyl-(3-dimethylaminopropyl) carbonization
Diimmonium salt hydrochlorate 0.31g, stirs.Put into cysteine self assembly gold electrode, react 24 hours, clean dry after taking-up
Dry, obtain oxidation nanometer cellulose/cysteine/gold electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.
(3) oxidation nanometer cellulose/cysteine/gold electrode application in detection L-phenylalanine:
Concentration is from the 5mM K of 0.01 ~ 5mM L-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is 0.1M chlorine
Changing in potassium solution and obtain differential pulse voltammogram, method is the same as in Example 8 with step.Obtain peak current dense with L-phenylalanine
The linear relationship of degree.And the detection limit calculating L-phenylalanine is 5.6 × 10-6M。
Embodiment 16
(1) preparation of oxidation nanometer cellulose/cysteine/gold electrode:
The preparation method of oxidation nanometer cellulose is identical with embodiment 2.
The gold electrode cleaned up is immersed in 0.01M aqueous cystein solution 12 hours, obtains cysteine from group
Dress gold electrode.
Prepared by oxidation nanometer cellulose TEMPO oxidizing process, preparing 10 mL mass concentrations is the oxidation nanometer of 0.01g/mL
Cellulose aqueous solution.Above-mentioned solution is added hydroxysuccinimide 0.016g, 1-ethyl-(3-dimethylaminopropyl) carbonization
Diimmonium salt hydrochlorate 0.29g, stirs.Put into cysteine self assembly gold electrode, react 24 hours, clean dry after taking-up
Dry, obtain oxidation nanometer cellulose/cysteine/gold electrode.
(2) modified electrode is in the application of electrochemical signals:
Cyclic voltammetry method is same as in Example 1.
(3) oxidation nanometer cellulose/cysteine/gold electrode application in detection D-phenylalanine:
Concentration is from the 5mM K of 0.01 ~ 5mM D-phenylalanine3[Fe(CN)6]/K4[Fe(CN)6], supporting electrolyte is 0.1M chlorine
Changing in potassium solution and obtain differential pulse voltammogram, method is the same as in Example 8 with step.Obtain peak current dense with D-phenylalanine
The linear relationship of degree.And the detection limit calculating D-phenylalanine is 9.0 × 10-6M。
Claims (4)
1. one kind based on nano-cellulose and the gold electrode of cysteine modified, it is characterised in that this electrode is made by the following method
For obtaining:
1) preparation of oxidation nanometer cellulose
Nano-cellulose acid hydrolysis method is prepared by microcrystalline Cellulose, prepares oxidation nanometer cellulose by TEMPO oxidizing process, and
Being made into the oxidation nanometer cellulose aqueous solution that mass concentration is 0.01g/mL, product is placed in 5 DEG C of storages；
2) preparation of cysteine self assembly gold electrode
The gold electrode cleaned up is immersed in self assembly in 0.01 ~ 0.05M aqueous cystein solution and within 8 ~ 16 hours, i.e. obtains half Guang
Propylhomoserin self assembly gold electrode；
3) preparation of oxidation nanometer cellulose/cysteine/gold electrode
Hydroxysuccinimide, 1-ethyl-(3-is added in the oxidation nanometer cellulose aqueous solution that mass concentration is 0.01g/mL
Dimethylaminopropyl) carbodiimide hydrochloride obtains mixed solution；Described cysteine self assembly gold electrode is immersed in mixed
Close in solution, stir reaction under room temperature and within 18 ~ 30 hours, i.e. obtain the gold electrode based on nano-cellulose and cysteine modified.
2. gold electrode as claimed in claim 1, it is characterised in that described oxidation nanometer cellulose aqueous solution, maloyl are sub-
The amount ratio of amine, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride be 10 mL:0.01 ~ 0.02 g:0.2 ~
0.4 g。
3. gold electrode based on nano-cellulose and cysteine modified detects at chiral amino acid as claimed in claim 1 or 2
In application.
Apply the most as claimed in claim 3, it is characterised in that described chiral amino acid is phenylalanine enantiomer, bright ammonia
Acid enantiomer or valine enantiomer.
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