CN105949481A - Preparation method of novel conductive hydrogel and conductive hydrogel prepared through method - Google Patents
Preparation method of novel conductive hydrogel and conductive hydrogel prepared through method Download PDFInfo
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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Abstract
The invention provides a preparation method of novel conductive hydrogel. According to the method, chloroauric acid modified chitosan is adopted and then reacts with glutaraldehyde and organic dye small molecules, and finally hydrogel is formed. The method is short in reaction time and simple and has certain universality, that is, the method can be used for forming hydrogel by means of different organic dye small molecules. The prepared hydrogel has good mechanical properties, is large in specific surface area and good in three-dimensional mesh structure and conductivity, and has certain hydrogen peroxide catalyzing capacity.
Description
Technical field
The present invention relates to chemical material preparation field, in particular to a class novel conductive hydrogel
Preparation method.
Background technology
Conductive hydrogel by the biocompatibility of hydrogel, transmit the ability of little molecule, hyperhydrated effect with
The electric conductivity that conducting polymer is good combines, and is the composite biological material of a kind of novelty.It is significant
Electric conductivity, highly continuous print network structure and excellent biocompatibility make its Electrochemical enzyme biosensor,
In the fields such as electrochemical immunosensor and electric active molecule sensor, there is important utilization.
In recent years, the study hotspot of conductive hydrogel is from initial polyelectrolyte conductive hydrogel progressively transition
Adding conductive hydrogel and conductive polymer subbase conductive hydrogel for inorganic matter, this is primarily due to single
Mechanical strength and the stability of polyelectrolyte conductive hydrogel are the most not fully up to expectations, and add through inorganic matter
Or the conductive hydrogel that conducting polymer composite is combined not only has good electric conductivity and stability, with
Time also there is preferable mechanical strength, this just makes its more actual application value.At present, there is scholar
(Guiseppi-Elie A.Biomaterials, 2010,31:2701 2716) leads with conductive polymer subbase
Electricity hydrogel is prepared as electrode and records the electrochemistry feedback signal of sensitivity, not only has good biofacies
Capacitive, and the signal intensity of record can be strengthened.Conductive hydrogel is keeping solid phase dimensional stability
Under premise, having manifested the feature that different electrical conductivity is interval, it can be used in conductive film, sensing
All many-sides such as device, chemical valve, biomaterial.On the other hand, natural as one and artificial bio-membrane lives
Sexual system, the biocompatibility that it is had makes it have broad application prospects in terms of medical product.
Summary of the invention
According to an aspect of the present invention, an object of the present invention is to provide a kind of novel hydrogels
Preparation method, said method comprising the steps of:
1) chitosan of 1 weight portion is dispersed in the solvent of about 100 weight portions is formed dispersed
Chitosan dispersion；
2) chloroaurate of 1 weight portion is dispersed in the solvent of about 25 weight portions formation soluble chlorine
Auric acid solution；
3) then by step 1) in the chitosan dispersion that obtains join in reactor, stirring
Under, in reactor, be slowly added dropwise step 2) in the solubility chlorauric acid solution that obtains, described shell gathers
The weight ratio of sugared and described gold chloride is preferably 1:0.01-1:100, and reaction temperature is 20-240 DEG C,
Response time is 1 minute to 1.5 hours, can get the chitosan solution with gold grain doping.
4) the little molecular dispersion of organic dyestuff of 1 weight portion is formed in the solvent of about 100 weight portions
Homodisperse thionine dispersion liquid；
5) glutaraldehyde of 1 weight portion is dispersed in the solvent of about 20 weight portions formation glutaraldehyde solution；
6) then by step 4) in the little molecular dispersions of organic dyestuff that obtains join in reactor,
Under stirring, in reactor, be slowly added dropwise step 5) in the glutaraldehyde solution that obtains, described in have
The weight ratio of the little molecule of organic dye and described glutaraldehyde solution is 1:0.01-1:100, and reaction temperature is
0-160 DEG C, the response time is 3 seconds to 12 hours, the i.e. available thionine solution mixed with glutaraldehyde；
7) by above-mentioned steps 3) in obtain obtained gold grain doping chitosan solution join instead
Answer in device, in reactor, be slowly added dropwise step 6 the most again) in organic mixed with glutaraldehyde that obtain
Small molecule dyes solution, the chitosan solution of described gold grain doping and mixed with the organic dyestuff of glutaraldehyde
The weight ratio of small molecule solution is 1:0.01-1:100, and reaction temperature is 0-100 DEG C, and the response time is
1 second to 6 hours, i.e. can get thionine hydrogel；
8) by product through conventional post processing after reaction terminates, dialyse, be washed with deionized at least
Three times.
Wherein, described organic dyestuff little molecule autofluorescence Huang, methylene blue, Congo red, thionine,
Cresol-purple and toluidine blue etc., more preferably thionine, methylene blue and m-cresol purple.
The weight ratio of described chitosan and described gold chloride is preferably 1:0.05-1:50, further preferably
For 1:0.1-1:10.
The weight ratio of the little molecule of described organic dyestuff and described glutaraldehyde is preferably 1:0.05-1:50, enters
One step is preferably 1:0.1-1:10.
The chitosan solution of described gold grain doping and the weight ratio of the thionine solution mixed with glutaraldehyde
It is preferably 1:0.05-1:50, more preferably 1:0.1-1:10.
One or more in water, ethanol, propanol of described solvent, preferably water.
Preferably, described step 3) in reaction temperature be preferably 50-180 DEG C.
Preferably, described step 6) in reaction temperature be preferably 20-100 DEG C.
Preferably, described step 7) in reaction temperature be preferably 20-100 DEG C.
Preferably, described step 3) in response time be preferably 2 minutes to 60 minutes.
Preferably, described step 6) in response time be preferably 20 seconds to 80 minutes.
Preferably, described step 7) in response time be preferably 5 seconds to 90 minutes.
According to an aspect of the present invention, an object of the present invention is to provide a class novel hydrogels
Material, described novel hydrogels material is prepared by method made above.
Beneficial effect
The preparation method of hydrogel that the present invention provides has the advantage that the response time is short, preparation side
Method is simple and has certain universality (can molecule little from different organic dyestuff form hydrogel).Preparation
Novel hydrogels material have that good mechanical performance, specific surface area be big, three-dimensional net structure, lead
The best, possess certain catalyzing hydrogen peroxide ability.
Accompanying drawing explanation
Fig. 1 is sweeping of the chitosan solution of the gold grain doping according to preparation in embodiments of the invention 1
Retouch electron micrograph (SEM).
Fig. 2 is according to the scanning electron microscope of the thionine hydrogel of preparation in embodiments of the invention 1
Photo (SEM).
Fig. 3 is according to the digital photograph of the hydrogel of preparation in embodiments of the invention 1 to 3, wherein
Photo is the most successively the thionine hydrogel of preparation, methylene blue water in embodiment 1,2,3
Gel and m-cresol purple hydrogel.
Fig. 4 is the detection spectrum at the electrochemical oxidation peak of the thionine hydrogel obtained according to EXPERIMENTAL EXAMPLE 1
Figure.
Fig. 5 is the inspection at the electrochemical oxidation peak of the methylene blue hydrogel obtained according to EXPERIMENTAL EXAMPLE 2
Survey spectrogram.
Fig. 6 is the inspection at the electrochemical oxidation peak of the m-cresol purple hydrogel obtained according to EXPERIMENTAL EXAMPLE 3
Survey spectrogram.
Detailed description of the invention
The present inventor's molecule little to organic dyestuff, glutaraldehyde and the chitosan having gold grain to adulterate are molten
Liquid is prepared hydrogel and has been carried out careful research, by little for organic dyestuff molecule, glutaraldehyde with there is gold grain to mix
Miscellaneous chitosan solution reaction is prepared for a class novel hydrogels.
The present invention is first prepared for organic dyestuff small molecule solution, glutaraldehyde solution and the shell having gold grain to adulterate
Polysaccharide solution, the most in the reactor hybrid reaction, it is thus achieved that the hydrogel that structural behaviour is stable.This
Bright feature is: preparation condition gentleness is easily-controllable, preparation process simple and fast, and the hydrogel of preparation has good
Good physical and mechanical properties, electric conductivity and certain catalytic capability, to the method preparing novel hydrogel
There is certain universality.
Using glutaraldehyde in preparation in accordance with the present invention, what it played in the formation of hydrogel is
The effect of cross-linking agent ,-OH the group of glutaraldehyde plays important crosslinked action, does not has glutaraldehyde then can not
Form gel.Additionally, the present inventor also attempt use benzaldehyde, acetaldehyde etc. as reactant,
All can not form gel, it can be seen that for the preparation method of the present invention, glutaraldehyde is most important
's.
By improving hydrogel with gold doping vario-property chitosan in preparation in accordance with the present invention
Although the amount of the gold chloride of electric conductivity doping is the most, electric conductivity more preferably, but can also have the upper limit.At root
According in the preparation method of the present invention, the weight ratio of described chitosan and described gold chloride is preferably
1:0.01-1:100, when the amount of described gold chloride is less than 0.01, the electric conductivity of end product may not
Foot, when described gold chloride amount more than 100 time, high cost, can hinder simultaneously later stage chitosan with
Glutaraldehyde or the crosslinking of the little molecule of organic dyestuff, and then affect the gel formation in later stage.
The corresponding electrochemistry of initiation that the little molecule of organic dyestuff plays in preparation in accordance with the present invention
The effect of signal, when the little molecule content of organic dyestuff is too low, it is impossible to effectively produce the electricity that intensity is enough
Chemical signal, when the little molecule content of organic dyestuff is too high, then due to the little molecule of organic dyestuff self
Soda acid character, may impact and the combination of chitosan.Therefore, in preparation in accordance with the present invention,
The chitosan solution of described gold grain doping and the weight ratio mixed with the thionine solution of glutaraldehyde are preferred
For 1:0.01-1:100.The little molecule of organic dyestuff is different, and the electrochemical signals that they are had is the most different,
That just can produce differentiable electrochemical signals in Electrochemical Detection.Therefore, the invention of the present invention
People also attempts using methyl orange, viride nitens, rhodamine as the little molecule of organic dyestuff, but this several has
The little molecule of organic dye can not be effectively formed gel, and this is likely due to the different little molecule of organic dyestuff
Structure different so that it can not produce what the reactions such as crosslinking effectively caused with glutaraldehyde, therefore selects
Select the little molecule of suitable organic dyestuff extremely important to the jel product forming the present invention.
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this theory
The term used in bright book and appending claims should not be construed as and is limited to general sense and dictionary contains
Justice, and should allow inventor suitably define term to carry out the principle of best interpretations on the basis of, root
Explain according to implication corresponding with the technical elements of the present invention and concept.Therefore, description presented herein
Merely for the sake of the preferred embodiment of illustration purpose, it is not meant to limit the scope of the present disclosure, thus should
When being understood by, in the case of without departing from the spirit and scope of the present invention, can by its obtain other etc.
Valency mode or improved procedure.
Following example are enumerated only as the example of embodiment of the present invention, do not constitute the present invention
Any restriction, it will be appreciated by those skilled in the art that without departing from the present invention essence and design in the range of
Amendment each fall within protection scope of the present invention.
Embodiment
Embodiment 1: the preparation of thionine hydrogel
1) chitosan of 1 weight portion is dispersed in the solvent of about 100 weight portions is formed dispersed
Chitosan dispersion, the chloroaurate of 1 weight portion is dispersed in the solvent of about 25 weight portions formation
Solubility chlorauric acid solution, then joins in reactor by chitosan dispersion, the most again to reaction
Device is slowly added dropwise solubility chlorauric acid solution, described chitosan dispersion and described chlorauric acid solution
Weight ratio is 10:1, and reaction temperature is 120 DEG C, and the response time is 10 minutes (under microwave condition).
The most available chitosan solution with gold grain doping.
2) thionine of 1 weight portion is dispersed in the solvent of about 100 weight portions is formed homodisperse
Thionine dispersion liquid, the glutaraldehyde of 1 weight portion is dispersed in the solvent of about 20 weight portions formation glutaraldehyde
Solution, then joins in reactor by thionine dispersion liquid, is slowly added dropwise penta the most again in reactor
Dialdehyde solution, the weight ratio of described thionine and described glutaraldehyde solution is 3:1, and reaction temperature is 35
DEG C, the response time is 5 minutes.The most available thionine solution mixed with glutaraldehyde.
3) chitosan solution of above-mentioned obtained gold grain doping is joined in reactor, the most again to instead
Answer and device be slowly added dropwise the thionine solution mixed with glutaraldehyde, described gold grain doping chitosan solution and mix
The weight ratio having the thionine solution of glutaraldehyde is 1:1, and reaction temperature is 35 DEG C, and the response time is 20 points
Clock.The most just can get thionine hydrogel.
Embodiment 2: the preparation of methylene blue hydrogel
1) chitosan of 1 weight portion is dispersed in the solvent of about 100 weight portions is formed dispersed
Chitosan dispersion, the chloroaurate of 1 weight portion is dispersed in the solvent of about 25 weight portions formation
Solubility chlorauric acid solution, then joins in reactor by chitosan dispersion, the most again to reaction
Device is slowly added dropwise solubility chlorauric acid solution, described chitosan dispersion and described chlorauric acid solution
Weight ratio is 10:1, and reaction temperature is 120 DEG C, 10 minutes response time.The most just can get
Chitosan solution with gold grain doping.
2) methylene blue of 1 weight portion is dispersed in the solvent of about 100 weight portions formation uniformly to divide
The methylene blue dispersion liquid dissipated, the glutaraldehyde of 1 weight portion is dispersed in the solvent of about 20 weight portions formation
Glutaraldehyde solution, then joins in reactor by methylene blue dispersion liquid, the most again in reactor
Being slowly added dropwise glutaraldehyde solution, the weight ratio of described methylene blue and described glutaraldehyde solution is 3:1,
Reaction temperature is 35 DEG C, and the response time is 5 minutes.The most available methylene mixed with glutaraldehyde
Base indigo plant solution.
3) chitosan solution of above-mentioned obtained gold grain doping is joined in reactor, the most again
Being slowly added dropwise the methylene blue solution mixed with glutaraldehyde in reactor, the shell of described gold grain doping gathers
Sugar juice and the weight ratio mixed with the methylene blue solution of glutaraldehyde are 1:1, and reaction temperature is 35 DEG C,
Response time is 20 minutes.The most just can get methylene blue hydrogel.
Embodiment 3: the preparation of m-cresol purple hydrogel
1) chitosan of 1 weight portion is dispersed in the solvent of about 100 weight portions is formed dispersed
Chitosan dispersion, the chloroaurate of 1 weight portion is dispersed in the solvent of about 25 weight portions formation
Solubility chlorauric acid solution, then joins in reactor by chitosan dispersion, the most again to reaction
Device is slowly added dropwise solubility chlorauric acid solution, described chitosan dispersion and described chlorauric acid solution
Weight ratio is 10:1, and reaction temperature is 120 DEG C, and the response time is 10 minutes.The most just can obtain
To the chitosan solution with gold grain doping.
2) m-cresol purple of 1 weight portion is dispersed in the solvent of about 100 weight portions formation uniformly to divide
The m-cresol purple dispersion liquid dissipated, the glutaraldehyde of 1 weight portion is dispersed in shape in the solvent of about 20 weight portions
Become glutaraldehyde solution, then m-cresol purple dispersion liquid is joined in reactor, the most again to reactor
In be slowly added dropwise glutaraldehyde solution, the weight ratio of described m-cresol purple and described glutaraldehyde solution is
3:1, reaction temperature is 35 DEG C, and the response time is 5 minutes.The most available mixed with glutaraldehyde
M-cresol purple solution.
3) chitosan solution of above-mentioned obtained gold grain doping is joined in reactor, the most again
Being slowly added dropwise the m-cresol purple solution mixed with glutaraldehyde in reactor, the shell of described gold grain doping gathers
Sugar juice and the weight ratio mixed with the m-cresol purple solution of glutaraldehyde are 1:1, and reaction temperature is 35 DEG C,
Response time is 20 minutes.The most just can get m-cresol purple hydrogel.
EXPERIMENTAL EXAMPLE: the detection of electrochemical signals
EXPERIMENTAL EXAMPLE 1
Electrode pretreatment: by glass-carbon electrode successively with the Al that particle diameter is 1.0,0.3 and 0.05 μm2O3
Powder polishes so that it is become minute surface, the most successively with ethanol, acetone and water ultrasonic cleaning, and by being dried
Nitrogen dry up.The electrode that physical method is handled well puts into 0.5mol L-1H2SO4In-0.3
Enclose by electrochemical method further to electricity with cyclic voltammetry scanning 3 in V-1.5V potential range
Pole surface cleaning and activation, the electrode handled well is placed in secondary water standby.
Afterwards, by 15 μ L embodiments 1 preparation thionine hydrogel and glassy carbon electrode surface, 30 DEG C
After conditioned response 30 minutes, clean surface with deionized water.At selected supporting electrolyte, (phosphoric acid delays
Dissolved liquid: 0.1mol L-1, pH 7.0), measure under room temperature condition.All of electrochemical meter
Device is the CHI832 electrochemical analyser being connected with computer, the three-electrode system by traditional:
Root platinum electrode as to electrode, Ag/AgCl electrode saturated for KCl as reference electrode and
Sensor measures as working electrode.
The detection at the electrochemical oxidation peak of the thionine hydrogel that according to Fig. 4, this EXPERIMENTAL EXAMPLE 1 obtains
Spectrogram.By in figure it can be seen that the electrochemistry oxygen of thionine hydrogel prepared of the method according to this invention
The position changing signal peak is-0.12V.
EXPERIMENTAL EXAMPLE 2
Electrode pretreatment: by glass-carbon electrode successively with the Al that particle diameter is 1.0,0.3 and 0.05 μm2O3
Powder polishes so that it is become minute surface, the most successively with ethanol, acetone and water ultrasonic cleaning, and by being dried
Nitrogen dry up.The electrode that physical method is handled well puts into 0.5mol L-1H2SO4In-0.3
Enclose by electrochemical method further to electricity with cyclic voltammetry scanning 3 in V-1.5V potential range
Pole surface cleaning and activation, the electrode handled well is placed in secondary water standby.
Afterwards, by the methylene blue hydrogel prepared in 15 μ L embodiments 2 and glassy carbon electrode surface,
30 DEG C of conditioned responses, after 30 minutes, clean surface with deionized water.At selected supporting electrolyte (phosphorus
Acid buffering solution: 0.1mol L-1, pH 7.0), measure under room temperature condition.All of electrochemistry is surveyed
Measuring appratus is the CHI832 electrochemical analyser being connected with computer, the three-electrode system by traditional:
Piece platinum electrode as to electrode, Ag/AgCl electrode saturated for KCl as reference electrode, with
And sensor measures as working electrode.
The electrochemical oxidation peak of the methylene blue hydrogel that according to Fig. 5, this EXPERIMENTAL EXAMPLE 2 obtains
Detection spectrogram.By in figure it can be seen that the electricity of prepared according to the methods of the invention methylene blue hydrogel
The position of chemical oxidation signal peak is-0.25V.
EXPERIMENTAL EXAMPLE 3
Electrode pretreatment: by glass-carbon electrode successively with the Al that particle diameter is 1.0,0.3 and 0.05 μm2O3
Powder polishes so that it is become minute surface, the most successively with ethanol, acetone and water ultrasonic cleaning, and by being dried
Nitrogen dry up.The electrode that physical method is handled well puts into 0.5mol L-1H2SO4In-0.3
Enclose by electrochemical method further to electricity with cyclic voltammetry scanning 3 in V-1.5V potential range
Pole surface cleaning and activation, the electrode handled well is placed in secondary water standby.
Afterwards, by the m-cresol purple hydrogel prepared in 15 μ L embodiments 3 and glassy carbon electrode surface,
30 DEG C of conditioned responses, after 30 minutes, clean surface with deionized water.At selected supporting electrolyte (phosphorus
Acid buffering solution: 0.1mol L-1, pH 7.0), measure under room temperature condition.All of electrochemistry is surveyed
Measuring appratus is the CHI832 electrochemical analyser being connected with computer, the three-electrode system by traditional:
Piece platinum electrode as to electrode, Ag/AgCl electrode saturated for KCl as reference electrode, with
And sensor measures as working electrode.
The electrochemical oxidation peak of the m-cresol purple hydrogel that according to Fig. 6, this EXPERIMENTAL EXAMPLE 3 obtains
Detection spectrogram.By in figure it can be seen that the electricity of prepared according to the methods of the invention m-cresol purple hydrogel
The position of chemical oxidation signal peak is-0.78V.
Preparation in accordance with the present invention condition is easy, it is not necessary to the instrument of external costliness.Previously reported
The preparation method of hydrogel is to be interacted reacted by monomer, cross-linking agent, initiator, and preparation process is loaded down with trivial details.
The hydrogel preparing phytic acid and metal ion according to the present invention did not met report at pertinent literature.According to this
The hydrogel that the preparation method of invention obtains belongs to physical hydrogel, (such as executes under the change of external condition
Add certain external force) transformation of gel and colloidal sol can occur.Change based on this character can be equal it
Even drop coating is on the surface of electrode, it is achieved the application in electrochemica biological sensor.
Claims (8)
1. a preparation method for novel hydrogels, described preparation method comprises the following steps:
1) chitosan of 1 weight portion is dispersed in the solvent of about 100 weight portions is formed dispersed
Chitosan dispersion；
2) chloroaurate of 1 weight portion is dispersed in the solvent of about 25 weight portions formation soluble chlorine
Auric acid solution；
3) then by step 1) in the chitosan dispersion that obtains join in reactor, stirring
Under, in reactor, be slowly added dropwise step 2) in the solubility chlorauric acid solution that obtains, described shell gathers
The weight ratio of sugared and described gold chloride is preferably 1:0.01-1:100, and reaction temperature is 20-240 DEG C,
Response time is 1 minute to 1.5 hours, can get the chitosan solution with gold grain doping；
4) the little molecular dispersion of organic dyestuff of 1 weight portion is formed in the solvent of about 100 weight portions
Homodisperse thionine dispersion liquid；
5) glutaraldehyde of 1 weight portion is dispersed in the solvent of about 20 weight portions formation glutaraldehyde solution；
6) then by step 4) in the little molecular dispersions of organic dyestuff that obtains join in reactor,
Under stirring, in reactor, be slowly added dropwise step 5) in the glutaraldehyde solution that obtains, described in have
The weight ratio of the little molecule of organic dye and described glutaraldehyde solution is 1:0.01-1:100, and reaction temperature is
0-160 DEG C, the response time is 3 seconds to 12 hours, the i.e. available thionine solution mixed with glutaraldehyde；
7) by above-mentioned steps 3) in obtain obtained gold grain doping chitosan solution join instead
Answer in device, in reactor, be slowly added dropwise step 6 the most again) in organic mixed with glutaraldehyde that obtain
Small molecule dyes solution, the chitosan solution of described gold grain doping and mixed with the organic dyestuff of glutaraldehyde
The weight ratio of small molecule solution is 1:0.01-1:100, and reaction temperature is 0-100 DEG C, and the response time is
1 second to 6 hours, i.e. can get thionine hydrogel；
8) by product through conventional post processing after reaction terminates, dialyse, be washed with deionized at least
Three times.
The preparation method of novel hydrogels the most according to claim 1, it is characterised in that institute
State organic dyestuff little molecule autofluorescence Huang, methylene blue, Congo red, thionine, m-cresol purple and toluene
Amine is blue, more preferably thionine, methylene blue and m-cresol purple.
The preparation method of novel hydrogels the most according to claim 1, it is characterised in that step
Rapid 3) weight ratio of chitosan and described gold chloride described in is 1:0.05-1:50, further preferably
For 1:0.1-1:10.
The preparation method of novel hydrogels the most according to claim 1, it is characterised in that step
Rapid 6) weight ratio of the little molecule of organic dyestuff described in and described glutaraldehyde is 1:0.05-1:50, enters
One step is preferably 1:0.1-1:10.
The preparation method of novel hydrogels the most according to claim 1, it is characterised in that step
Rapid 7) gold grain described in doping chitosan solution and mixed with glutaraldehyde thionine solution weight it
Ratio is 1:0.05-1:50, more preferably 1:0.1-1:10.
The preparation method of novel hydrogels the most according to claim 1, it is characterised in that institute
State one or more in water, ethanol, propanol of solvent, preferably water.
The preparation method of novel hydrogels the most according to claim 1, it is characterised in that institute
State step 3) in reaction temperature be preferably 50-180 DEG C；Described step 6) in reaction temperature excellent
Elect 20-100 DEG C as；Described step 7) in reaction temperature be preferably 20-100 DEG C；Described step 3)
In response time be preferably 2 minutes to 60 minutes；Described step 6) in response time preferred
It it is 20 seconds to 80 minutes；Described step 7) in response time be preferably 5 seconds to 90 minutes.
8. a novel hydrogels material, described hydrogel material is by according in claim 1 to 9
Preparation method described in any one prepares.
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| CN109021258A (en) * | 2018-07-12 | 2018-12-18 | 首都师范大学 | A kind of preparation method for the novel conductive hydrogel that electrochemical signals are overstable |
| CN110591166A (en) * | 2019-08-20 | 2019-12-20 | 华南农业大学 | Self-driven artificial intelligence material, preparation method and application in imaging analysis and detection and drug controlled release |
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| CN103454426A (en) * | 2013-09-10 | 2013-12-18 | 山东理工大学 | Preparation method of nanogold/chitosan-graphene-methylene blue modified immunosensor |
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| CN103454426A (en) * | 2013-09-10 | 2013-12-18 | 山东理工大学 | Preparation method of nanogold/chitosan-graphene-methylene blue modified immunosensor |
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| GUO-SONG LAI ET AL.: ""Amperometric hydrogen peroxide biosensor based on the immobilization of horseradish peroxidase by carbon-coated iron nanoparticles in combination with chitosan and cross-linking of glutaraldehyde"", 《MICROCHIM ACTA》 * |
| YAXI LIU ET AL.: ""Preparation of a composite film electrochemically deposited with chitosan and gold nanoparticles for the determination of a-1-fetoprotein"", 《BIOPROCESS BIOSYST ENG》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021258A (en) * | 2018-07-12 | 2018-12-18 | 首都师范大学 | A kind of preparation method for the novel conductive hydrogel that electrochemical signals are overstable |
| CN110591166A (en) * | 2019-08-20 | 2019-12-20 | 华南农业大学 | Self-driven artificial intelligence material, preparation method and application in imaging analysis and detection and drug controlled release |
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