CN110146699A - A kind of bi-component Ratio-type electrochemical immunosensor and preparation method thereof - Google Patents
A kind of bi-component Ratio-type electrochemical immunosensor and preparation method thereof Download PDFInfo
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- CN110146699A CN110146699A CN201910473262.2A CN201910473262A CN110146699A CN 110146699 A CN110146699 A CN 110146699A CN 201910473262 A CN201910473262 A CN 201910473262A CN 110146699 A CN110146699 A CN 110146699A
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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
- G01N33/558—Immunoassay; Biospecific binding assay; Materials therefor using diffusion or migration of antigen or antibody
- G01N33/559—Immunoassay; Biospecific binding assay; Materials therefor using diffusion or migration of antigen or antibody through a gel, e.g. Ouchterlony technique
Abstract
The invention discloses a kind of bi-component Ratio-type electrochemical immunosensors and preparation method thereof, building and soft core-hard-shell type colloid body including sensing interface, and the sensing interface is to be made in base electrode surface modification N, S codope graphene；The soft core-hard-shell type colloid body is MB@PbS colloid body and AQ@CdS colloid body；Its bi-component Ratio-type analysis method are as follows: using NaAc_HAc buffer solution as supporting electrolyte solution, Differential Pulse Voltammetry scanning gained peak current carries out quantitative analysis, wherein the ratio between oxidation current of MB and Pb is analyzed for HE4, and the ratio between oxidation current of AQ and Cd is analyzed for CA125.Bi-component Ratio-type electrochemical immunosensor of the present invention can be used for measurement while people's epididymal proteins 4 and carbohydrate antigen 125.
Description
Technical field
The invention belongs to electrochemical analysis techniques field, be related to a kind of bi-component Ratio-type electrochemical immunosensor and its
Preparation method, specially a kind of bi-component Ratio-type electrochemical sensor based on metal sulfide colloid body label.
Background technique
Electrochemistry immuno-sensing is analyzed the highly sensitive phase of the specific reaction of Ag-Ab and electrochemical analysis method
In conjunction with, be complex sample system be immunized related-substance analysis important method.In recent years, in clinical diagnosis, food analysis etc.
Field is widely used research.These application fields are frequently necessary to the content of various ingredients in test sample.Such as in ring
In the monitoring of border, it is often necessary to while the concentration index of a variety of Insecticides (tech) & Herbicides (tech)s etc. in water body is monitored, it is dirty with overall merit environment
Dye is horizontal.And in clinical diagnosis, although it have been found that disease marker huge number, but actually enter the clinical diagnosis stage
It is very few.Medical expert thinks, by several tumor markers of joint-detection, diagnoses for improving in clinical tumor diagnosis
Accuracy, promote its clinical diagnosis application have very great help.Such as CA125 is in oophoroma clinical diagnosis, therapeutic response
Application in evaluation, prognosis evaluation and recurrence monitoring is up to more than 30 years, it is considered to be oophoroma biological marker analyte detection at present
" goldstandard ".However CA125 positive rate in I phase oophoroma is very low, it is poor there is also tissue specificity the disadvantages of.HE4 is a kind of
Newfound ovary carcinoma marker, the specificity in ovarian cancer diagnosis is higher than CA125, but it is used alone and sieves in oophoroma
The application looked into diagnosis still remains the biggish limitation such as false negative.Therefore, U.S. Food and Drug Administration in 2011
Have approved the progression of disease by CA125 and HE4 joint-detection diagnostic monitoring oophoroma and recurrence.The enzyme clinically generally used
Linked immune analysis is based primarily upon HRP label, microplate reader detection, and sensitivity is often limited.Although and electrochemical immunosensor
Detection sensitivity is relatively high, but there is a problem of being affected by sample matrices, accuracy it is not high.This patent utilizes MB@
PbS, two kinds of AQ@CdS soft cores-monocoque metal sulfide colloid body construct a kind of while detecting the double of HE4 and CA125
Component Ratio-type electrochemical immunosensor.
Summary of the invention
It is an object of the invention to solve the problems, such as that above two disease marker is highly sensitive while detecting, design and preparing
It is a kind of electrochemical based on MB@PbS, two kinds of AQ@CdS soft cores-monocoque metal sulfide colloid body label bi-component Ratio-type
Immunosensor is learned, can be used for measurement while HE4 and CA125.
In order to achieve the above technical purposes, the present invention is realized especially by following technical scheme:
A kind of bi-component Ratio-type electrochemical immunosensor, the immunosensor include sensing interface and electrochemistry
Marker, the sensing interface are to be made in base electrode surface modification N, S-rGO, and the electrochemical label object is metal sulphur
Compound colloid body.
Described matrix electrode is glass-carbon electrode, and the metal sulfide colloid body includes the MB@of soft core-monocoque
PbS and AQ@CdS colloid body.
MB and AQ are wrapped in PbS, CdS colloid body by reverse microemulsion process by the soft core-hard-shell type colloid body
It is obtained in cavity.Described two colloid body surfaces face is hydrolyzed by trimethoxy silane and introduces amino.
Immunosensor of the present invention further includes reference electrode, to electrode and supporting electrolyte solution, the ginseng
It is saturation calomel than electrode, described is platinum electrode to electrode, and the supporting electrolyte solution is Acetic acid-sodium acetate buffering
Solution.
In immunosensor of the present invention, soft core-hard-shell type colloid body utilizes four electrifications as semiochemicals
Learn Accurate Determining while signal realizes two kinds of antigen.
In another aspect of this invention, the preparation method of above-mentioned bi-component Ratio-type electrochemical immunosensor is provided,
By N, the base electrode surface of S doped graphene-chitosan dispersion drop coating after a polish resists the first of target analytes
Body crosslinking obtains sensing interface in electrode surface, is formed in sensing interface using interlayer type immune complex and introduces electrochemical label
Object.
The preparation method of the N, S doped graphene-chitosan dispersion is by N, and S doped graphene ultrasonic disperse is in shell
In the acetic acid solution of glycan.
In another aspect of this invention, the electrochemical immunosensor is to support with NaAc_HAc buffer solution
Electrolyte solution, differential plus Anodic Stripping Voltammetry scanning gained peak current carry out quantitative analysis.
Further, the first component analysis is used for the ratio between oxidation current of MB and Pb, the oxidation current of AQ and Cd it
Than being used for second of component analysis；The first described group is divided into HE4, and described second group is divided into CA125.
The invention has the benefit that
Bi-component Ratio-type electrochemical immunosensor provided by the invention is based on two kinds of MB@PbS, AQ@CdS soft cores-
Monocoque metal sulfide colloid body and construct.This core-shell structure colloid body can generate two kinds of electrochemical signals objects simultaneously
Matter, the ratio of two kinds of signals can be used as quantifiable signal, this ratio type analysis can greatly reduce nano material partial size it is uneven,
Electrode surface passivation and sensing interface are influenced to wait caused error by sample matrices.And two kinds of colloid bodies are used in combination, so that it may
Construct bi-component Ratio-type electrochemical immunosensor that is a kind of while detecting HE4 and CA125.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of PbS colloid body of the present invention；
Fig. 2 is the transmission electron microscope picture of CdS NPs and CdS colloid body of the present invention；Wherein A is CdS NPs；B is CdS；
Fig. 3 A is the scanning projection electron microscope figure of CdS colloid body of the present invention；B and C difference Cd element and S element
Face sweep figure；
Fig. 4 is that working electrode of the present invention is containing 10 μm of olL-1MB, AQ and 1.0 μm of olL-1Pb2+、Cd2+Branch
Hold the differentiated pulse voltammogram in electrolyte；
Fig. 5 is MB@PbS colloid body of the present invention with the photo that ethyl alcohol different time is added；
Fig. 6 is AQ CdS colloid body of the present invention with the ultraviolet-visible spectrogram that ethyl alcohol different time is added；
Fig. 7 is that MB@PbS and AQ@CdS colloid body of the present invention lies prostrate the differentiated pulse of ethyl alcohol, nitric acid control release
Antu；
Fig. 8 is the differentiated pulse voltammogram that electrochemical immunosensor of the present invention corresponds to that HE4 and CA125 is responded.
Specific embodiment
Below in conjunction with specific embodiment of the present invention, technical solution of the present invention is clearly and completely described, is shown
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Electrochemical immunosensor disclosed by the invention is prepared especially by following methods:
1) base electrode is processed by shot blasting；
2) by N, S-rGO dispersant liquid drop applies base electrode surface after a polish；
3) sensing interface is made to electrode surface by antibody linked；
4) interlayer type immune complex is formed in electrode surface；
5) Electrochemical Detection.
Preferably, 0.05 μm of Al is used in the step (1)2O3After powder is processed by shot blasting base electrode, super
It is ultrasonically treated 1min in pure water, dries at room temperature.
Preferably, N described in step (2), the preparation method of S-rGO dispersion liquid is:
1) it is synthesized in the aqueous dispersions of graphene oxide as chemical dopant by one pot of hydro-thermal method using thiocarbamide
N,S-rGO；
2) 5.0mg chitosan is dissolved in 1.0mL 0.1molL-1In acetic acid solution and it is stirred at room temperature until obtaining
Clear solution；
3) N prepared by step (1) is added into step (2) gained clear solution, S-rGO (1.0mg) is simultaneously ultrasonically treated
Until being uniformly dispersed.
Preferably, the construction method at immune sensing interface described in step (3) is:
1) by 6 μ L, 10 μ gmL-1Ab1-HE4And Ab1-CA125It mixes drop on the electrode and is placed in 4 DEG C of refrigerators
Overnight, the antibody of excess and weakly stable is washed away with PBS and PBST；
2) electrode surface reaction 1h, PBS and PBST that 6 μ L 1%BSA solution drip to step (1) are washed again, and will
It is placed in spare at 4 DEG C.
Preferably, it is the step of the formation of interlayer type immune complex in step (4):
1) HE4 the and CA125 mixed liquor of various concentration is incubated for 1h, PBS and PBST washing on immune sensing interface；
2) by 6 μ L MB@PbS-Ab2-HE4With AQ@CdS-Ab2-CA125Biological nano compound and obtained sensing interface exist
It is incubated for 45min at room temperature, carries out Electrochemical Detection after PBS washing.
Preferably, it is the step of Electrochemical Detection in step (5):
1) after electrode being immersed 200 μ L ethyl alcohol 10min, then 200 μ L HNO are immersed3Solution (1molL-1) in 10min, will
Acquired solution and HAc-NaAc buffer (0.1molL-1, pH 5.0) and mixing；
2) it is detected by DPASV differential pulse anodic stripping voltammetry.Potential range be -1.2V to 0.2V, sedimentation potential be -
1.2V, sedimentation time 300s, impulse amplitude 50mV, pulse width 50ms, quiescent time 2s.
Embodiment 1
1, the preparation of PbS, CdS nanoparticle
Entire synthesis is carried out in room temperature and in argon atmosphere.First by PbCl2(0.28g) and 5.0mL oleyl amine
(Oleylamine, OLA) is added in the three neck round bottom of 50mL, and flask is sealed and is deaerated 5min under vacuum, is then existed
It is heated to 90 DEG C under stirring and keeps constant temperature heating 1h to form uniform PbCl2- OLA dispersion liquid.Meanwhile at room temperature
Sulphur (0.83mmol) is dissolved in 2.5mL OLA, 30min is stirred, gained sulphur solution is rapidly joined into above-mentioned dispersion liquid,
And heat the mixture to 220 DEG C and continue 1h, obtaining black colloidal solution is PbS NPs.After being cooled to room temperature, second is added
Alcohol (100mL) washs PbS NPs, centrifugation, and obtained solid product can be well dispersed in heptane, toluene isopolarity solvent
In.
Using same preparation method, using Cd, S molar ratio for 2:1 reaction mixture as raw material, synthesized spherical
CdS NPs.Specifically, the OLA dispersion liquid comprising 0.75mmol sulphur is added rapidly to 160 DEG C of CdCl containing 1.5mmol2-
In OLA dispersion liquid, and continue 1h at 160 DEG C, the CdS NPs being centrifuged after ethyl alcohol is added.
2, the preparation of MB@PbS, AQ@CdS
10mg PbS NPs is added in 2mL toluene, 10min is ultrasonically treated.Then, by the 400 μ L comprising 4 μ L ammonium hydroxide
10mg·mL-1MB is added to (R in PbS NPs dispersion liquido/wAfter 5), being ultrasonically treated 1h formation Pickering lotion, then it is quiet
1h is set, 30 μ L 3- aminopropyl trimethoxysilanes are then added into lotion, stands reaction 20h, centrifugation again after being ultrasonically treated 1h
And it is washed with distilled water the aqueous dispersion liquid for obtaining MB@PbS three times.AQ@CdS is also prepared with identical method.
3, the preparation of biological nano compound
100 μ LMB@PbS and 100 μ LAQ@CdS are mixed with the PBS buffer solution of 100 μ LpH 7.4 respectively, and 4 μ are added
L 1mg·mL-1Ab2- HE4 and 4 μ L 1mgmL-1Ab2- CA125 at 4 DEG C is overnight then added 20 μ L 1%BSA solution, shakes
1h is placed after even, is then centrifuged for and is washed with pH 7.4PBS buffer, obtains MB@PbS-Ab2- HE4 and AQ@CdS-Ab2-
CA125 biological nano compound is simultaneously scattered in for further use in the PBS buffer solution of 0.1mLpH 7.4.
4, the building at immune sensing interface
Firstly, glass-carbon electrode successively uses the Al of 0.3 μm and 0.05 μm2O3Powder polishes surface polishing, and uses dehydrated alcohol
The substance of electrode surface absorption is removed with distilled water ultrasound 1min.Then, by 6 μ L 1mgmL-1N, S-rGO dispersant liquid drop exist
It dries on electrode and at room temperature.After modified electrode is washed with water, 6 μ L, 5% glutaraldehyde is added dropwise, 2.5h is reacted at 4 DEG C and uses water
Washing is three times.Then by 6 μ L, 10 μ gmL-1Ab1- HE4 and Ab1- CA125 mixes drop on the electrode and is placed on 4 DEG C
Refrigerator overnight washes away the antibody of excess and weakly stable with PBS and PBST after taking-up.6 μ L 1%BSA solution are finally dripped into electricity
Pole surface reacts 1h to close non-specific sites, and PBS and PBST are washed again, and are placed it in spare at 4 DEG C.
The characterization of 2 metallic sulfide nano-particle of embodiment and metal sulfide colloid body
Fig. 1 show the scanning electron microscope (SEM) photograph of PbS colloid body, it can be observed that it is about tens to several that PbS colloid body, which is size,
Hundred nanometers of nano spherical particle.Fig. 2 is the transmission electron microscope picture of prepared CdSNPs and CdS colloid body, by Fig. 2A visible
The uniform particle sizes of the prepared CdSNPs of invention, show the spherical shape of uniform particle sizes, average grain diameter is about 10nm.It can be with from Fig. 2 B
Observe that CdS colloid body is the nano spherical particle that size is about 100nm.Amplify a CdS colloid body, it can be seen that it be by
The three-dimensional spherical structure that single nanoparticle assembles, illustrates that colloid body is assembled by a large amount of nanoparticle.Figure
3A is the scanning transmission electron microscope figure of CdS colloid body, and Fig. 3 B and C are respectively that figure is swept in the face of Cd element and S element, can be seen
Two kinds of elements are evenly distributed in the spherical structure of CdS colloid body out, illustrate that the basic chemical composition of colloid body includes CdS.
Embodiment 3
Fig. 4 is that working electrode is containing 10 μm of olL-1MB, AQ and 1.0 μm of olL-1Pb2+、Cd2+Supporting electrolyte in
Differentiated pulse voltammogram, specifically: N, S-rGO/GCE modified electrode are in pH 4.5HAc-NaAc buffer solution using micro-
Divide pulse voltammetry to 10 μm of olL-1MB, AQ and 1 μm of olL-1Pb2+、Cd2+It carries out while measuring.MB,AQ,Pb2+And Cd2+
The peak of four kinds of substances is located at -0.17V, -0.38V, -0.56V and -0.79V.The peak of four kinds of substances is not overlapped and peak-to-peak away from conjunction
It is suitable, tentatively illustrate that selected four kinds of semiochemicals can be used for the analysis of bi-component Ratio-type electrochemistry immuno-sensing.
Embodiment 4
MB@PbS of the present invention, AQ@CdS colloid body are using the silicon fiml that sol-gel method is formed as completed shell.It should
The silicon shell that method is formed includes a large amount of aperture, and the small molecules such as dyestuff when these apertures by being somewhat limited.It grinds
Study carefully discovery: the release of dye molecule in silicon cladding colloid body can be enhanced in ethyl alcohol.This may be to coagulate since ethyl alcohol can improve silicon
Wetability of the aperture of glue to water.Therefore, in order to control the electrochemical signals substance for discharging prepared colloid body, first to colloid
Ethyl alcohol is added in dispersion liquid.
Fig. 5 and Fig. 6 is respectively MB@PbS and AQ@CdS colloid body with the photo and UV, visible light that ethyl alcohol different time is added
Spectrogram, as seen from Figure 5, when ethyl alcohol is not added, MB@PbS colloid body near colorless, when illustrating that ethyl alcohol is not added, MB is difficult
It is infiltrated from the cavity of MB@PbS colloid body；After ethyl alcohol 10min is added, solution colour becomes blue, this is by colloid body
Caused by the MB released；When ethyl alcohol 30min is added, blue is slightly deepened.Since AQ color is unobvious, we are using purple
Outside-visible spectrum has studied ethyl alcohol and discharges to the control of AQ@CdS colloid body.As shown in fig. 6, being located at when ethyl alcohol 10min is added
The absorption peak strength of AQ obviously becomes larger at 256nm, illustrates that AQ is released from AQ@CdS colloid body, and when 30min absorbs
Peak intensity does not obviously increase, this shows to reach in 10min by the way that the dye molecule that ethyl alcohol controls inside colloid body is added
To substantially completely discharging.
Fig. 7 is the differentiated pulse voltammogram of MB@PbS and AQ@CdS colloid body for ethyl alcohol, nitric acid control release.We examine
It has examined addition ethyl alcohol and nitric acid destroys MB@PbS and AQ@CdS colloid body, mixed it with HAc-NaAc buffer solution after 10min
The DPASV of acquired solution is responded.As shown in fig. 7, extremely weak Cd can be observed on voltammogram when ethyl alcohol, nitric acid are not all added2+
Dissolution peak and more apparent Pb2+Dissolution peak, this may be CdS NPs and the PbS NPs due to colloid body shell layer the bottom of at
It is slightly dissolved in liquid HAc-NaAc buffer solution.When ethyl alcohol is only added, the oxidation peak of apparent MB and AQ can be observed；When only
When nitric acid is added, apparent Pb can be observed2+And Cd2+Dissolution peak.And when ethyl alcohol and nitric acid is successively added, gained dissolution
Occur the response of four kinds of semiochemicals on voltammogram simultaneously, explanation can be jointly controlled by ethyl alcohol and nitric acid release MB@PbS and
The electrochemical signals substance of AQ@CdS colloid body.
Embodiment 5
Fig. 8 is the differentiated pulse voltammogram that electrochemical immunosensor corresponds to that HE4 and CA125 is responded.It has investigated with N,
S-rGO/GCE be base electrode, with MB@PbS, AQ@CdS be mark for the immunosensor of object DPASV response.Such as Fig. 8
Shown, there is the faint peak Pb in the response (curve 1) of blank solution, this should be since MB@PbS is in electrode surface
There is faint non-specific adsorption.1U·mL-1CA125 (curve 2), it can be seen that except the signal of Pb caused by non-specific adsorption
Outside, more apparent AQ and Cd is produced2+Signal, this be by mark the AQ@CdS in CA125 secondary antibody discharge to obtain letter
Number substance generates.And to 1ngmL-1For HE4, the signal of Pb is obviously increased, while producing the oxidation peak (curve 3) of MB,
Illustrate that MB@PbS colloid body is bonded to sensing interface by the formation of sandwich immunoassay compound.When in solution to be measured simultaneously
Contain 1ngmL-1HE4 and 1UmL-1When CA125, it can be observed on the volt-ampere response curve (curve 4) of sensor while going out
MB, AQ, Pb are showed2+And Cd2+The peak of four kinds of semiochemicals.In addition, when to 100ngmL-1HE4 and 100UmL-1CA125 is (bent
Line 5) it carries out simultaneously when measuring, the peak current of four kinds of substances significantly increases, it was demonstrated that the peak current and HE4 and CA125 of four kinds of substances
Content it is related.Therefore, the analysis of bi-component Ratio-type electrochemistry immuno-sensing can be carried out based on MB@PbS, AQ@CdS colloid body.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understand without departing from the principles and spirit of the present invention can to these examples carry out it is a variety of variation, modification, replacement and
Modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of bi-component Ratio-type electrochemical immunosensor, which is characterized in that the immunosensor includes sensing circle
Face and electrochemical label object, the sensing interface are to be made in base electrode surface modification N, S-rGO, the electrochemical label
Object is metal sulfide colloid body.
2. a kind of bi-component Ratio-type electrochemical immunosensor according to claim 1, which is characterized in that described matrix
Electrode is glass-carbon electrode, and the metal sulfide colloid body includes MB@PbS and AQ the@CdS colloid body of soft core-monocoque.
3. a kind of bi-component Ratio-type electrochemical immunosensor according to claim 2, which is characterized in that described is soft
Core-hard-shell type colloid body MB and AQ are wrapped in the cavity of PbS, CdS colloid body by reverse microemulsion process it is obtained, it is described
Colloid body surface face is hydrolyzed by trimethoxy silane and introduces amino.
4. a kind of bi-component Ratio-type electrochemical immunosensor according to claim 1, which is characterized in that described exempts from
Epidemic disease sensor further includes reference electrode, to electrode and supporting electrolyte solution, and the reference electrode is saturation calomel, described
It is platinum electrode to electrode, the supporting electrolyte solution is NaAc_HAc buffer solution.
5. the preparation method of electrochemical immunosensor described in claim 1, which is characterized in that by N, S doped graphene-shell
Glycan dispersant liquid drop applies base electrode surface after a polish, and the first antibody of target analytes is crosslinked and is obtained in electrode surface
To sensing interface, sensing interface is formed in using interlayer type immune complex and introduces electrochemical label object.
6. preparation method according to claim 5, which is characterized in that the N, S doped graphene-chitosan dispersion
Preparation method is by N, and S doped graphene ultrasonic disperse is in the acetic acid solution of chitosan.
7. the analysis method of electrochemical immunosensor described in claim 1, which is characterized in that buffered with Acetic acid-sodium acetate
Solution is supporting electrolyte solution, and differential plus Anodic Stripping Voltammetry scanning gained peak current carries out quantitative analysis.
8. analysis method according to claim 7, which is characterized in that be used for the first with the ratio between oxidation current of MB and Pb
The ratio between oxidation current of component analysis, AQ and Cd is used for second of component analysis.
9. analysis method according to claim 8, which is characterized in that the first described group is divided into HE4, and described second
Kind group is divided into CA125.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102980925A (en) * | 2012-11-26 | 2013-03-20 | 济南大学 | Sandwich type electrochemical immunosensor, preparation method and application thereof |
| CN104192830A (en) * | 2014-05-20 | 2014-12-10 | 江苏欧力特能源科技有限公司 | Preparing method of nitrogen-sulfur co-doped graphene by hydrothermal method |
| CN106442665A (en) * | 2016-12-22 | 2017-02-22 | 山东理工大学 | Preparation method of ratio-dependent adapter sensor for detecting antibiotic residues based on screen-printed electrodes |
| CN106660807A (en) * | 2014-07-09 | 2017-05-10 | 阿尔托大学基金会 | Method for forming a graphene based material and a product |
| CN106629678A (en) * | 2016-12-12 | 2017-05-10 | 天津师范大学 | Method for preparing multi-element co-doped graphene by hydrothermal method |
| CN107328930A (en) * | 2017-05-09 | 2017-11-07 | 济南大学 | A kind of preparation and application based on dual signal response ratio type screen printing electrode immunosensor |
| CN107389772A (en) * | 2017-06-21 | 2017-11-24 | 安徽师范大学 | Ratio-type electrochemical sensor and its preparation method and application |
-
2019
- 2019-05-31 CN CN201910473262.2A patent/CN110146699B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102980925A (en) * | 2012-11-26 | 2013-03-20 | 济南大学 | Sandwich type electrochemical immunosensor, preparation method and application thereof |
| CN104192830A (en) * | 2014-05-20 | 2014-12-10 | 江苏欧力特能源科技有限公司 | Preparing method of nitrogen-sulfur co-doped graphene by hydrothermal method |
| CN106660807A (en) * | 2014-07-09 | 2017-05-10 | 阿尔托大学基金会 | Method for forming a graphene based material and a product |
| CN106629678A (en) * | 2016-12-12 | 2017-05-10 | 天津师范大学 | Method for preparing multi-element co-doped graphene by hydrothermal method |
| CN106442665A (en) * | 2016-12-22 | 2017-02-22 | 山东理工大学 | Preparation method of ratio-dependent adapter sensor for detecting antibiotic residues based on screen-printed electrodes |
| CN107328930A (en) * | 2017-05-09 | 2017-11-07 | 济南大学 | A kind of preparation and application based on dual signal response ratio type screen printing electrode immunosensor |
| CN107389772A (en) * | 2017-06-21 | 2017-11-24 | 安徽师范大学 | Ratio-type electrochemical sensor and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| LILI XIAO ET AL.: "Facile one-pot synthesis and application of nitrogen and sulfur-doped activated graphene in simultaneous electrochemical determination of hydroquinone and catechol", 《ANALYST》 * |
| XIUJUAN HAN ET AL.: "Ultrasensitive Electrochemical Immunoassay Based on Cargo Release from Nanosized PbS Colloidosomes", 《ANAL. CHEM.》 * |
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