CN106248656A - A kind of based on Ni nanoparticle Co2o4the preparation method and application of the electrochemiluminescence immunosensor of@AD bifunctional catalyst - Google Patents
A kind of based on Ni nanoparticle Co2o4the preparation method and application of the electrochemiluminescence immunosensor of@AD bifunctional catalyst Download PDFInfo
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- CN106248656A CN106248656A CN201610702017.0A CN201610702017A CN106248656A CN 106248656 A CN106248656 A CN 106248656A CN 201610702017 A CN201610702017 A CN 201610702017A CN 106248656 A CN106248656 A CN 106248656A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
Abstract
The present invention is open a kind of based on Ni nanoparticle Co2O4The preparation method and application of the electrochemiluminescence immunosensor of@AD bifunctional catalyst, feature is by diamantane (obsolete) is modified NiCo2O4Nanometer sheet surface and then prepared bifunctional catalyst NiCo2O4@AD, owing to having the NiCo of the electronic conduction ability of bigger serface and excellence2O4Cooperative effect between nanometer sheet and the diamantane (obsolete) with good power supply capacity, the electrode that this composite is modified significantly improves S2O8 2−The sensitivity of electrochemiluminescsystem system and stability.Based on NiCo2O4The bio-compatibility that@AD is good, is fixed to modified electrode surface by PGE1 antibody and PGE1, prepares PGE1 electrochemiluminescence immunosensor, for the detection of PGE1, detection range 0.1 fg/ml 1.0 ng/ml.There is the advantage such as high specificity, highly sensitive, good stability.
Description
Technical field
The invention belongs to new function material and bio-sensing detection technique field, be specifically related to a kind of based on nanometer
NiCo2O4The preparation method and application of the electrochemiluminescence immunosensor of@AD bifunctional catalyst.
Background technology
PGE1 (PGE1), is widely present in internal bioactive substance, is important in prostaglandin families
Member, it has diversified and powerful effect to cell function in multiple organ system.Semen arachidis hypogaeae four as a kind of cyclooxygenase
Olefin(e) acid metabolite, PGE1 to before inflammation and antiinflammatory action and osteoporosis relevant, some research find PGE1 can reduce spinal cord
Damage cause compression and its to osteoporosis treatment reason have certain beneficial effect.PGE1, has as one
The vasodilation of effect, has expansion blood vessel, improves peripheral circulation and suppress platelet aggregation, prevent thrombosis effect, its
By increasing cardiac output and reduction filling pressure and pulmonary vascular resistance, severe heart failure patient had useful hemodynamic
Learn effect.PGE1 is closely related with angiopathy and pulmonary disease, and it has in monitoring and quantization human prostate's element level
Crucial effect, therefore in clinical research, the detection method of the PGE1 developing a kind of quick, easy, sensitive and low cost has
Huge demand and important meaning.
Electrochemiluminescence immunosensor, utilizes the specific binding class biosensor between antigen and antibody,
Have highly sensitive, selectivity good, easy and simple to handle, be prone to miniaturization, the detection advantage such as analysis, tool can be changed the most fast and automatically
There is good application prospect.The present invention is prepared for a kind of based on NiCo2O4The electrochemiluminescence immunity of@AD bifunctional catalyst passes
Sensor, and realize the highly sensitive detection to PGE1.Existing document report has the hydrogen-oxygen of the transition metal of multiple valence state
Compound or oxide, such as Co3O4, NiO, Ni(OH)2 and NiCo2O4, oxygen evolution reaction process is had certain catalytic action.
Wherein, due to Ni2+/Ni3+And Co2+/Co3+The contribution of oxidation-reduction pair, NiCo2O4Have more preferable electronic conduction ability and
Electro-chemical activity.The present invention is by modifying NiCo by diamantane (obsolete)2O4Nanometer sheet surface and then prepared bifunctional catalyst
NiCo2O4@AD, owing to this complex has bigger serface and good biocompatibility, it is possible to provide more electroactive sites and
Biomolecule fixes site, and its modified electrode illustrates the catalytic performance of excellence and can significantly improve S oxygen evolution reaction process2O8 2 −The sensitivity of electrochemiluminescsystem system and stability.Based on NiCo2O4The biocompatibility of@AD excellence and high catalytic performance, institute
The immunosensor prepared has the advantages such as high specificity, highly sensitive, good stability, detection limit are low.
Summary of the invention
An object of the present invention is based on Ni nanoparticle Co2O4@AD material, builds a kind of unmarked, and good stability is sensitive
Spend the preparation of high electrochemiluminescence immunosensor.
The two of the purpose of the present invention are the highly sensitive inspections that this electrochemiluminescence immunosensor is applied to PGE1
Survey.
For realizing goal of the invention, the present invention adopts the following technical scheme that
1. one kind based on NiCo2O4The preparation method of the electrochemiluminescence immunosensor of@AD bifunctional catalyst:
(1) glass-carbon electrode (GCE) first mechanical grinding polishing on the chamois leather be covered with alumina powder, removes table with secondary washing
Face residual powder, then move into cleaning in ultrasonic water bath, until cleaning up, the most sequentially with ethanol, diluted acid and water thoroughly wash；
(2) NiCo that 3 μ L concentration are 0.5 mg/mL is dripped2O4@AD suspension is in clean glassy carbon electrode surface, infrared
Dry under lamp, be cooled to room temperature, prepare NiCo2O4@AD modified glassy carbon electrode；
(3) dripping 30 μ L concentration is that the glutaraldehyde solution of 2.0 wt% is in NiCo2O4@AD modified electrode surface active 1 h；
(4) drip 30 μ L PGE1 antibody (anti-PGE1) solution to hatch in modified electrode surface and in 4 ° of C refrigerators
40 min, are washed with deionized water the anti-PGE1 of physical absorption, prepare NiCo2O4@AD/ anti-PGE1 modifies glass carbon electricity
Pole；
(5) take the BSA that 40 μ L concentration are 1.0 wt.% to be added drop-wise in the C refrigerator of 4 ° of modified electrode surface hatch 1 h, to close
Nonspecific activity site on electrode surface, washes away physical absorption with deionized water rinsing electrode surface, and is saved in 4 ° of C refrigerators
In；
(6) take the PGE1 standard solution that 30 μ L concentration are 0.1 fg/ml 1.0 ng/ml to drip in NiCo2O4@AD/
40 min are also hatched in 4 ° of C refrigerators in anti-PGE1 modified electrode surface, rinse electrode table with the PBS buffer solution of pH7.5
Face, prepares a kind of based on Ni nanoparticle Co2O4The PGE1 electrochemiluminescence immunosensor of@AD dual catalyst.
The most above-mentioned NiCo2O4The preparation of@AD material: 1.0 mL concentration are the NiCo of 1.0 mg/mL2O4Dense with 1.0 mL
3-aminopropyl triethoxysilane (APTES) the mixing vibration 12h that degree is 1.0wt %, is centrifuged and collects amino functional
NiCo2O4Product is also dispersed in the deionized water of 2.0 mL again；Then by (1-(3-dimethylamino-propyl)-3-ethyl carbon two
Inferior amine salt hydrochlorate) NiCo of the 1-adamantanecarboxylic acid that activates of (EDC) and N-hydroxy-succinamide (NHS) and amino functional2O4
Product mixing vibration 2h, prepares the NiCo that diamantane (obsolete) is modified2O4 (NiCo2O4@AD), centrifugal collection NiCo2O4@AD product is laid equal stress on
Newly it is dispersed in the deionized water of 2.0 mL.
The most above-mentioned NiCo2O4The preparation of material: be 1 mmol with 20 mL ethanol and 40 mL deionized water compound concentrations
Ni (NO3)2·6H2O solution, concentration is the Co (NO of 2 mmol3)2·6H2O solution and six Asias that concentration is 4.5 mmol
The mixed solution of tetramine, transfers in 100 mL politef inner liner of reaction kettle, magnetic force under 90 C by mixed solution
It is cooled to room temperature after stirring 24 h, by centrifugal collecting precipitate and by deionized water and washing with alcohol for several times, in an oven 60
Drying 12 h under C, finally, 350 C calcine 2 h and obtain mesoporous NiCo in atmosphere2O4Nanometer sheet.
One prepared by said method the most of the present invention is based on Ni nanoparticle Co2O4The electrochemiluminescence of@AD bifunctional catalyst is exempted from
Epidemic disease sensor.
5. the detecting step of PGE1:
(1) electrochemical workstation is used to use three-electrode system to be measured, with the one of above-mentioned preparation based on nanometer
NiCo2O4The electrochemiluminescence immunosensor of@AD dual catalyst is working electrode, and Ag/AgCl is reference electrode, platinum electrode
For to electrode, at 0.1mol/ml K2S2O8PH 8.0 PBS buffer solution in test；
(2) using cyclic voltammetric voltage to detect the PGE1 standard solution of variable concentrations, scanning voltage scope is
0.8V-1.8 V, sweep speed is 100 mV/s, gathers electrochemiluminescence signal, photoelectricity by electrogenerated chemiluminescence equipment
Multiplier voltage is 900V, by the pass between electrogenerated chemiluminescence intensity and the PGE1 concentration of standard solution of gained
System, drawing curve；
(3) testing sample solution replaces PGE1 standard solution to detect, and the result of detection can be looked into by working curve
?.
The remarkable advantage of the present invention is:
(1) due to Ni2+/Ni3+And Co2+/Co3+The contribution of oxidation-reduction pair, NiCo2O4Have excellence electronic conductivity and
Electro-chemical activity, has the NiCo of bigger serface and meso-hole structure simultaneously2O4Nanometer sheet can provide more electroactive site and life
Thing molecule fixes site.Diamantane (obsolete) has bigger serface and preferable electron supplying capacity.The present invention is by modifying diamantane (obsolete)
To NiCo2O4Nanometer sheet surface prepares bifunctional catalyst NiCo2O4@AD, this complex modified electrode is to oxygen evolution reaction process exhibition
Show the catalytic performance of excellence and S can have been significantly improved2O8 2−The sensitivity of electrochemiluminescsystem system and stability, prepared by the present invention
Immunosensor there is higher sensitivity.
(2)NiCo2O4@AD has bigger serface and good bio-compatibility is conducive to antibody consolidating at electrode surface
Fixed, immunosensor prepared by the present invention has preferable stability.
(3) present invention utilizes the immunoreation of antigen, antibody, improves the specificity of detection method.
Accompanying drawing explanation
Figure 1A is NiCo2O4Electron emission scanning electron microscope (SEM) figure of nanometer sheet.
Figure 1B is NiCo2O4Transmission electron microscope (TEM) figure of nanometer sheet.
Figure 1B illustration is NiCo2O4High resolution transmission electron microscopy (HRTEM) figure of nanometer sheet.
Fig. 2 is NiCo2O4Infrared spectrum (IR) figure of@AD.
Fig. 3 is the electrochemiluminescence response signal linear pass with PGE1 concentration of standard solution of immune sensing electrode
System's figure.
Detailed description of the invention
Present invention the following example further illustrates the present invention, but protection scope of the present invention is not limited to following
Embodiment.
Embodiment 1
1. one kind based on Ni nanoparticle Co2O4The preparation of the electrochemiluminescence immunosensor of@AD bifunctional catalyst:
(1) glass-carbon electrode (GCE) first mechanical grinding polishing on the chamois leather be covered with alumina powder, removes table with secondary washing
Face residual powder, then move into cleaning in ultrasonic water bath, until cleaning up, the most sequentially with ethanol, diluted acid and water thoroughly wash；
(2) NiCo that 3 μ L concentration are 0.5 mg/mL is dripped2O4@AD suspension is in clean glassy carbon electrode surface, infrared
Dry under lamp, be cooled to room temperature, prepare NiCo2O4@AD modified glassy carbon electrode；
(3) dripping 30 μ L concentration is that the glutaraldehyde solution of 2.0wt % is in NiCo2O4@AD modified electrode surface active 1 h；
(4) drip 30 μ L PGE1 antibody (anti-PGE1) solution to hatch in modified electrode surface and in 4 ° of C refrigerators
40 min, are washed with deionized water the anti-PGE1 of physical absorption, prepare NiCo2O4@AD/ anti-PGE1 modifies glass carbon electricity
Pole；
(5) take the BSA that 40 μ L concentration are 1.0 wt.% to be added drop-wise in the C refrigerator of 4 ° of modified electrode surface hatch 1 h, to close
Nonspecific activity site on electrode surface, washes away physical absorption with deionized water rinsing electrode surface, and is saved in 4 ° of C refrigerators
In；
(6) take the PGE1 standard solution that 30 μ L concentration are 0.1 fg/ml 1.0 ng/ml to drip in NiCo2O4@AD/ anti-
40 min are also hatched in 4 ° of C refrigerators in PGE1 modified electrode surface, rinse electrode surface, system with the PBS buffer solution of pH7.5
Obtain a kind of based on Ni nanoparticle Co2O4The PGE1 electrochemiluminescence immunosensor of@AD dual catalyst.
Embodiment 2
NiCo2O4The preparation of material:
With 20 mL ethanol and Ni (NO that 40 mL deionized water compound concentrations are 1 mmol3)2·6H2O solution, concentration is
Co (the NO of 2 mmol3)2·6H2O solution and the mixed solution of hexamethylenetetramine that concentration is 4.5 mmol, will mixing
Solution is transferred to, in 100 mL politef inner liner of reaction kettle, be cooled to room temperature, pass through under 90 C after magnetic agitation 24 h
Centrifugal collecting precipitate by deionized water and washing with alcohol for several times, dries 12 h, in an oven finally, at air under 60 C
In 350 C calcine 2 h obtain mesoporous NiCo2O4Nanometer sheet.NiCo2O4The electron emission scanning electron microscope of nanometer sheet
(SEM) figure and transmission electron microscope (TEM) figure, as illustrated in figures ia and ib, show NiCo2O4Nanometer sheet is by NiCo2O4Receive
Rice corpuscles unit is interconnected to constitute, and forms substantial amounts of intergranular pore, and such loose structure will greatly increase electroactive position
Point.High resolution transmission electron microscopy (HRTEM) figure, as shown in illustration in Figure 1B, it is seen that the lattice bar of the most about 0.25 nm
Stricture of vagina, with spinelle NiCo2O4(311) crystal face is consistent.
Embodiment 3
NiCo2O4The preparation of@AD material:
1.0 mL concentration are the NiCo of 1.0 mg/mL2O4With the 3-aminopropyl-triethoxy that 1.0 mL concentration are 1.0 wt%
Silane (APTES) mixing vibration 12h, the centrifugal NiCo collecting amino functional2O4Product is also dispersed in going of 2.0 mL again
In ionized water；Then by sub-to (1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride) (EDC) and N-hydroxysuccinimidyl acyl
The 1-adamantanecarboxylic acid that amine (NHS) activates and the NiCo of amino functional2O4Product mixing vibration 2h, prepares what diamantane (obsolete) was modified
NiCo2O4 (NiCo2O4@AD), centrifugal collection NiCo2O4@AD product is also dispersed in the deionized water of 2.0 mL again.
NiCo2O4Infrared spectrum (IR) figure of@AD, as in figure 2 it is shown, at 1666 cm-1With 3185 cm-1Place has absworption peak to occur, this is
C=O and the stretching vibration absworption peak of N-H group in typical amide group, indicate NiCo2O4Prepared by the success of@AD.
Embodiment 4
The detecting step of PGE1:
(1) electrochemical workstation is used to use three-electrode system to be measured, with prepared one based on Ni nanoparticle Co2O4@
The electrochemiluminescence immunosensor of AD dual catalyst is working electrode, and Ag/AgCl is reference electrode, and platinum electrode is to electricity
Pole, at 0.1mol/ml K2S2O8PH 8.0 PBS buffer solution in test；
(2) using cyclic voltammetric voltage to detect the PGE1 standard solution of variable concentrations, scanning voltage scope is
0.8V-1.8 V, sweep speed is 100 mV/s, gathers electrochemiluminescence signal, photoelectricity by electrogenerated chemiluminescence equipment
Multiplier voltage is 900V, by the pass between electrogenerated chemiluminescence intensity and the PGE1 concentration of standard solution of gained
System, drawing curve, Fig. 3 is electrochemiluminescence response signal and the PGE1 concentration of standard solution of immune sensing electrode
Linear relationship chart；
(3) testing sample solution replaces PGE1 standard solution to detect, and the result of detection can be looked into by working curve
?.
Claims (5)
1. one kind based on Ni nanoparticle Co2O4The preparation method of the electrochemiluminescence immunosensor of@AD bifunctional catalyst, it is special
Levy and be, comprise the following steps:
Glass-carbon electrode (GCE) first mechanical grinding polishing on the chamois leather be covered with alumina powder, goes to surface residual with secondary washing
Staying powder, then move into cleaning in ultrasonic water bath, until cleaning up, the most sequentially with ethanol, diluted acid and water thoroughly wash；
Drip the NiCo that 3 μ L concentration are 0.5 mg/mL2O4@AD suspension, in clean glassy carbon electrode surface, dries under infrared lamp
Dry, it is cooled to room temperature, prepares NiCo2O4@AD modified glassy carbon electrode；
Dripping 30 μ L concentration is that the glutaraldehyde solution of 2.0 wt% is in NiCo2O4@AD modified electrode surface active 1 h；
Drip 30 μ L PGE1 antibody (anti-PGE1) solution and hatch 40 in modified electrode surface and in 4 ° of C refrigerators
Min, is washed with deionized water the anti-PGE1 of physical absorption, prepares NiCo2O4@AD/ anti-PGE1 modified glassy carbon electrode；
Take the BSA that 40 μ L concentration are 1.0 wt.% to be added drop-wise in the C refrigerator of 4 ° of modified electrode surface hatch 1 h, with enclosed-electrode
Nonspecific activity site on surface, washes away physical absorption with deionized water rinsing electrode surface, and is saved in 4 ° of C refrigerators；
Take the PGE1 standard solution that 30 μ L concentration are 0.1 fg/ml 1.0 ng/ml to drip in NiCo2O4@AD/ anti-
40 min are also hatched in 4 ° of C refrigerators in PGE1 modified electrode surface, rinse electrode surface, system with the PBS buffer solution of pH7.5
Obtain a kind of based on Ni nanoparticle Co2O4The PGE1 electrochemiluminescence immunosensor of@AD bifunctional catalyst.
Method the most according to claim 1, it is characterised in that described NiCo2O4Being prepared by following method of@AD material
: 1.0 mL concentration are the NiCo of 1.0 mg/mL2O4With the 3-aminopropyl-triethoxy silicon that 1.0 mL concentration are 1.0 wt%
Alkane (APTES) mixing vibration 12h, the centrifugal NiCo collecting amino functional2O4Product and be again dispersed in 2.0 mL go from
In sub-water；Then by (1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride) (EDC) and N-hydroxy-succinamide
(NHS) the 1-adamantanecarboxylic acid activated and the NiCo of amino functional2O4Product mixing vibration 2h, prepares what diamantane (obsolete) was modified
NiCo2O4 (NiCo2O4@AD), centrifugal collection NiCo2O4@AD product is also dispersed in the deionized water of 2.0 mL again.
Method the most according to claim 1 and 2, it is characterised in that described NiCo2O4Being prepared by following method of material
: with 20 mL ethanol and Ni (NO that 40 mL deionized water compound concentrations are 1 mmol3)2·6H2O solution, concentration is 2
Co (the NO of mmol3)2·6H2O solution and the mixed solution of hexamethylenetetramine that concentration is 4.5 mmol, by mixed solution
Transfer to, in 100 mL politef inner liner of reaction kettle, under 90 C, after magnetic agitation 24 h, be cooled to room temperature, by centrifugal
Collect precipitate by deionized water and washing with alcohol for several times, under 60 C, dry 12 h in an oven, finally, in atmosphere 350
C calcines 2 h and obtains mesoporous NiCo2O4Nanometer sheet.
4. the one that prepared by the arbitrary described method of claim 1-3 is based on Ni nanoparticle Co2O4The electrification of@AD bifunctional catalyst
Learn electrochemiluminescent immunoassay sensor.
5. the one described in claim 4 is based on Ni nanoparticle Co2O4The electrochemiluminescence immunosensor of@AD bifunctional catalyst,
It is characterized in that, for the detection of PGE1, detecting step is as follows:
(1) electrochemical workstation is used to use three-electrode system to be measured, with the one described in claim 4 based on nanometer
NiCo2O4The electrochemiluminescence immunosensor of@AD bifunctional catalyst is working electrode, and Ag/AgCl is reference electrode, platinum filament
Electrode is to electrode, at 0.1mol/ml K2S2O8PH 8.0 PBS buffer solution in test；
(2) using cyclic voltammetric voltage to detect the PGE1 standard solution of variable concentrations, scanning voltage scope is
0.8V-1.8 V, sweep speed is 100 mV/s, gathers electrochemiluminescence signal, photoelectricity by electrogenerated chemiluminescence equipment
Multiplier voltage is 900V, by the pass between electrogenerated chemiluminescence intensity and the PGE1 concentration of standard solution of gained
System, drawing curve；
(3) testing sample solution replaces PGE1 standard solution to detect, and the result of detection can be looked into by working curve
?.
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Cited By (6)
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| CN107256972A (en) * | 2017-05-27 | 2017-10-17 | 武汉理工大学 | A kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth |
| CN108318477A (en) * | 2018-02-05 | 2018-07-24 | 福建省妇幼保健院 | Based on TiO2Electrogenerated chemiluminescence probe prepared by metal organic frame and its competitive type immuno-sensing method to vomitoxin |
| CN108445062A (en) * | 2018-03-22 | 2018-08-24 | 福建医科大学附属第医院 | One kind being based on NiCo2O4The structure of nano lamellar material and the trypsase electrochemical sensing platform of peptide chain cutting effect |
| CN109799273A (en) * | 2019-03-04 | 2019-05-24 | 福建师范大学 | One kind being based on nano Co3O4The zearalenone impedance transducer of the double amplifications of the signal of mimetic enzyme catalysis effect |
| CN110031529A (en) * | 2019-05-18 | 2019-07-19 | 福建师范大学 | One kind being based on NiCo2O4Device is immunized in the thermotropic sensitizing type thyroglobulin electrogenerated chemiluminescence of nanometer sheet |
| CN111766288A (en) * | 2020-06-22 | 2020-10-13 | 济南大学 | Based on oxygen boosting vacancy NiCo2O4Preparation method and application of electrochemiluminescence sensor |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107256972A (en) * | 2017-05-27 | 2017-10-17 | 武汉理工大学 | A kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth |
| CN108318477A (en) * | 2018-02-05 | 2018-07-24 | 福建省妇幼保健院 | Based on TiO2Electrogenerated chemiluminescence probe prepared by metal organic frame and its competitive type immuno-sensing method to vomitoxin |
| CN108318477B (en) * | 2018-02-05 | 2020-06-26 | 福建省妇幼保健院 | Based on TiO2Electrochemiluminescence probe prepared by metal organic framework and competitive immunosensing method of electrochemiluminescence probe for vomitoxin |
| CN108445062A (en) * | 2018-03-22 | 2018-08-24 | 福建医科大学附属第医院 | One kind being based on NiCo2O4The structure of nano lamellar material and the trypsase electrochemical sensing platform of peptide chain cutting effect |
| CN108445062B (en) * | 2018-03-22 | 2020-05-19 | 福建医科大学附属第一医院 | Based on NiCo2O4Construction of nano sheet material and trypsin electrochemical sensing platform with peptide chain cleavage effect |
| CN109799273A (en) * | 2019-03-04 | 2019-05-24 | 福建师范大学 | One kind being based on nano Co3O4The zearalenone impedance transducer of the double amplifications of the signal of mimetic enzyme catalysis effect |
| CN110031529A (en) * | 2019-05-18 | 2019-07-19 | 福建师范大学 | One kind being based on NiCo2O4Device is immunized in the thermotropic sensitizing type thyroglobulin electrogenerated chemiluminescence of nanometer sheet |
| CN111766288A (en) * | 2020-06-22 | 2020-10-13 | 济南大学 | Based on oxygen boosting vacancy NiCo2O4Preparation method and application of electrochemiluminescence sensor |
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