CN109100400B - Sensor and its preparation method and application for detecting concanavalin A - Google Patents
Sensor and its preparation method and application for detecting concanavalin A Download PDFInfo
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- CN109100400B CN109100400B CN201810783531.0A CN201810783531A CN109100400B CN 109100400 B CN109100400 B CN 109100400B CN 201810783531 A CN201810783531 A CN 201810783531A CN 109100400 B CN109100400 B CN 109100400B
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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
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/38—Cleaning of electrodes
Abstract
The present invention relates to Electrochemiluminescsensor sensor technical fields, more particularly, to a kind of sensor and its preparation method and application for detecting concanavalin A.The sensor for being used to detect concanavalin A, including cathodoluminescence body, anode light body and coreaction reagent, the cathodoluminescence body includes the cadmium telluride quantum dot of graphene oxide modification, and the anode light body includes N- (aminobutyl)-N- (ethyl different luminol) of nanogold and Platinum Nanoparticles modification.The preparation method include: graphene oxide modification cadmium telluride quantum dot and recognition unit by pi-pi accumulation in conjunction with, and modification is in pretreated electrode surface；The anode light body for being combined with recognition unit is modified again, and incubation obtains the sensor.The present invention is based on the electrogenerated chemiluminescence systems of competition consumption oxygen building Ratio-type, improve signal-to-noise ratio, make the high reliablity of testing result.
Description
Technical field
The present invention relates to Electrochemiluminescsensor sensor technical fields, more particularly, to one kind for detecting concanavalin A
Sensor and its preparation method and application.
Background technique
Electrogenerated chemiluminescence (Electrogenerated Chemiluminescence, ECL) is electrochemistry and spectroscopy
Method combine a kind of novel detection technique, have it is versatile, Optical devices are simple, good time and space controlling etc.
Advantage, thus the detection of metal ion, the identification of molecule, the detection of DNA and in terms of obtained answering extensively
With.
Currently, ECL detection is largely all based on mono signal detection.These mono signal detection methods become vulnerable to electrode surface
Change and the dissociation of non-targeted object induction agent etc. influence and result are caused to be distorted, the especially life in the complexity such as cell and body fluid
In substance environment.Therefore, overcome environmental factor to interfere, improve sensitivity for analysis and reliability, to clinical micro and trace analysis
It is most important.
Concanavalin A (Concanavalin A, Con A) is a kind of carbohydrate binding protein matter, is a kind of phytohemagglutin phytolectin,
Mitogenesis effect with strength plays the role of preferably promoting lymphocyte transformation reaction, can precipitate hepatic glycogen, agglutination
The animals such as sheep, horse, dog, rabbit, pig, rat, mouse, cavy and human red blood cells, moreover it is possible to it is thin to selectively activate suppressor T lymphocyte (Ts)
Born of the same parents play a significant role to organism immune response is adjusted.As the agglutination prime model of a kind of mediated pathology and physiological reaction, Con
A is typically chosen as further clinical detection.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of for detecting the sensor of concanavalin A, and the sensor is base
In the electrogenerated chemiluminescence system of the Ratio-type of competition consumption oxygen building, signal-to-noise ratio is improved, is detected relative to single signal
Means effectively avoid the interference as caused by instrument, environmental factor and some artificial operation factors to detection, tie detection
The high reliablity of fruit.
The second object of the present invention is to provide for detecting the preparation method of the sensor of concanavalin A described in one kind,
The simple process of the preparation method, reaction condition is mild, strong operability.
The third object of the present invention is to provide described in one kind for detecting the sensor of concanavalin A in detection sword bean egg
Application in white A, the sensor are high to the detection sensitivity of concanavalin A, and detection limit is low, can be to the sword bean egg in sample
White A carries out ultramicron detection, with a high credibility.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
It is a kind of for detecting the sensor of concanavalin A, including cathodoluminescence body, anode light body and coreaction reagent,
The cathodoluminescence body includes the cadmium telluride quantum dot of graphene oxide modification, and the anode light body includes nanogold and nanometer
N- (aminobutyl)-N- (ethyl different luminol) of platinum modification.
The cadmium telluride quantum dot of graphene oxide modification is respectively adopted as cathodoluminescence body, the modification of nanogold platinum in the present invention
N- (aminobutyl)-N- (ethyl different luminol) be used as anode light body, modification can identify object on cathodoluminescence body
The recognition unit of concanavalin A, is used for combining target object, and the cadmium telluride quantum dot of graphene modified is single with identification as matrix
Member is combined by pi-pi accumulation effect, so as to solid by the biologic specificity effect between carbohydrate and protein
Carry target determinand Con A；Equally modification can identify the recognition unit of object concanavalin A on anode light body, into one
Walk the specificity by the recognition unit in target determinand Con A and anode light body immobilized in cathodoluminescence nanocrystal composition
It identifies and realizes the immobilized of anode light body.With the increase of target determinand Con A concentration, the supported quantity of anode light body with
Increase, due to cathodoluminescence body and anode light body competition coreaction reagent and cause the ECL signal of cathodoluminescence body to reduce,
The ECL signal enhancing of anode light body, to obtain the inverse variation of two ECL signals, it is to be measured to detect target by signal ratio
The concentration of object Con A.
The nanogold and N- (aminobutyl)-N- (ethyl different luminol) of Platinum Nanoparticles modification can enhance its own
ECL signal while, reduce the ECL signal of graphene quantum dot, according under different potentials present inverse variation two ECL believe
Number ratio realize Ratio-type detection.
Preferably, the coreaction reagent includes oxygen.It is furthermore preferred that the oxygen is dissolved oxygen.
Sensor of the present invention, anode light body and cathodoluminescence body competition process, only in consumption detection solution
Dissolved oxygen is not necessarily to additional H2O2Equal coreactions reagent, it is easy to detect.
Preferably, the sensor further includes being modified respectively in the recognition unit of cathodoluminescence body and anode light body, institute
State recognition unit concanavalin A for identification.
Preferably, the recognition unit includes phenoxylation glucan.
Preferably, by cathodoluminescence body and the modification of anode light body in glassy carbon electrode surface.
The present invention also provides the preparation methods of the sensor described in one kind for detecting concanavalin A, including walk as follows
It is rapid:
Cadmium telluride quantum dot and the recognition unit of graphene oxide modification by pi-pi accumulation in conjunction with, and modification is in pretreatment
Electrode surface；The anode light body for being combined with recognition unit is modified again, and incubation obtains the sensor.
The preparation method of the sensor of the present invention for being used to detect concanavalin A, simple process, reaction condition temperature
With strong operability.
Preferably, the cadmium telluride quantum dot that the graphene oxide is modified is dispersed in water, dispersion concentration 0.5-
2.0mg/mL, preferably 1.0mg/mL.
Preferably, the recognition unit includes phenoxylation glucan.
Preferably, the concentration of the phenoxylation glucan be 5-30mg/mL, preferably 10-20mg/mL, more preferably
15mg/mL.It is furthermore preferred that the phenoxylation glucan to be made to the aqueous solution of phenoxylation glucan.
Preferably, the dispersion liquid and the phenoxylation glucan of the cadmium telluride quantum dot of the graphene oxide modification
The volume ratio of solution is 1 ﹕ (0.8-1.2), preferably 1 ﹕ 1.
Preferably, the preparation method of the anode light body includes: by HAuCl4, (the different Shandong of ethyl N- (aminobutyl)-N-
Minot) and H2PtCl6Hybrid reaction stirs to get the anode light body.
Preferably, the preparation method of the anode light body includes:
By HAuCl4Solution be added N- (aminobutyl)-N- (ethyl different luminol) solution in, reaction is stirred at room temperature
1-3h；H is added2PtCl6Solution, 1-3h is stirred at room temperature, obtains mixed solution, solid is collected by centrifugation.
Preferably, anode light body is mixed with the solution of phenoxylation glucan, and anode light body is made to be combined with phenoxy group
Change glucan.It is furthermore preferred that anode light body is dispersed in water, the solution of phenoxylation glucan is added, stirs 1-3h.
Preferably, the HAuCl4Solution mass concentration be 0.5-2%, preferably 1%.It is furthermore preferred that described
HAuCl4Solution be HAuCl4Aqueous solution.
Preferably, the H2PtCl6Solution mass concentration be 0.5-2%, preferably 1%.It is furthermore preferred that described
H2PtCl6Solution be H2PtCl6Aqueous solution.
Preferably, the concentration of the solution of N- (the aminobutyl)-N- (ethyl different luminol) is 5-15mmol/L, preferably
10mmol/L.It is furthermore preferred that the solution of N- (the aminobutyl)-N- (ethyl different luminol) is N- (aminobutyl)-N- (second
Base different luminol) aqueous solution.
Preferably, the HAuCl4Solution, the H2PtCl6Solution, (the different Shandong of ethyl the N- (aminobutyl)-N-
Minot) solution volume ratio be 1 ﹕ (1 ﹕ 2 of 0.8-1.2) ﹕ (1-3), preferably 1 ﹕.
Preferably, the condition of the centrifugation include: 10000 ± 2000rpm/min revolving speed under be centrifuged 10-20min.
Preferably, the preparation method of the sensor, includes the following steps:
It is dry in the cadmium telluride quantum dot of electrode surface drop coating graphene oxide modification, recognition unit is added dropwise and forms π-π heap
Product.
Preferably, after forming pi-pi accumulation, in the solution of electrode surface drop coating bovine serum albumin(BSA).It is furthermore preferred that the ox
The mass fraction of sero-abluminous solution be 0.5-1.5%, preferably 1%.
Preferably, the dispersion of the solution of the bovine serum albumin(BSA) and the cadmium telluride quantum dot of graphene oxide modification
The volume ratio of liquid is 1 ﹕ (1-1.5).
Preferably, after the solution of drop coating bovine serum albumin(BSA), the prepare liquid containing concanavalin A is added dropwise and is incubated for.
Preferably, the anode light that modification after the prepare liquid containing concanavalin A is incubated for is combined with recognition unit is added dropwise
Body.It is furthermore preferred that the method for modifying the anode light body for being combined with recognition unit includes: that will be combined with the sun of recognition unit
Electrode surface of the pole illuminator drop coating after incubation, 1-3h is incubated under the conditions of 0-10 DEG C, is preferably incubated under the conditions of 4 DEG C
2h。
Preferably, in the prepare liquid, concentration >=3.0 × 10 of concanavalin A-5Ng/mL, preferably 3.0 × 10-5-
10ng/mL。
Preferably, the preparation method of the cadmium telluride quantum dot of the graphene oxide modification includes: mixing CdCl2Solution
With graphene oxide, Na is added2TeO3、C6H5Na3O7, mercaptopropionic acid and NaBH4, in 120-140 DEG C of back flow reaction 8-12h, adopt
Solid is collected by centrifugation with ethyl alcohol and water washing, is dispersed in water, obtains the cadmium telluride quantum dot of the graphene oxide modification.More
Preferably, the dispersion concentration of the cadmium telluride quantum dot of the graphene oxide modification is 1mg/mL.
Preferably, the preprocess method of electrode surface includes: by glass-carbon electrode respectively through 0.25-0.35 μm and 0.45-
0.55 μm of alumina powder polishing, is cleaned in water and ethyl alcohol, dry.
The present invention also provides detecting answering in concanavalin A for detecting the sensor of concanavalin A described in one kind
With.
Preferably, the method for detecting concanavalin A includes the following steps:
(1) after being incubated for the sensor using the solution of the standard concanavalin A containing various concentration, cathodoluminescence is acquired
The luminous signal of body and anode light body is dense by the intensity rate of two kinds of luminous signals and the solution of the standard concanavalin A
The logarithm of degree carries out linear fit, obtains working curve；
(2) sensor is incubated for using prepare liquid, acquires the luminous signal of cathodoluminescence body and anode light body, passes through
The concentration of concanavalin A in the prepare liquid is calculated in working curve.
Compared with prior art, the invention has the benefit that
(1) particular cathode illuminator and anode light body is respectively adopted in the present invention, passes through mesh immobilized on cathodoluminescence body
Mark determinand Con A is combined with the phenoxylation glucosan specificity identification in anode light body；With target determinand
The increase of Con A concentration, the supported quantity of anode light body increase therewith, since cathodoluminescence body and the competition of anode light body are anti-altogether
It answers reagent and the ECL signal of cathodoluminescence body is caused to reduce, the ECL signal enhancing of anode light body, to obtain two ECL signals
Inverse variation, by signal ratio detect target determinand Con A concentration, thus realize by competition consumption oxygen building
The electrogenerated chemiluminescence system of Ratio-type the concentration of concanavalin A is detected, relative to single signal detection means, have
Effect avoids the interference as caused by instrument, environmental factor and some artificial operation factors to detection, makes the reliable of testing result
Property it is high；
(2) present invention also defines the usage ratio relationship of each substance, the sensor being prepared is further improved
Detection sensitivity reduces detection limit；
(3) of the present invention for detecting the preparation method of the sensor of concanavalin A, simple process, reaction condition
Mildly, strong operability；
(4) sensor of the present invention is used to detect the detection limit of concanavalin A up to 3.0 × 10-5ng/mL。
The description of division name involved in the present invention and abbreviation refer to as follows:
Graphene oxide: GO
The cadmium telluride quantum dot of graphene oxide modification: G-CdTe QDs
Phenoxylation glucan: Dexp
N- (aminobutyl)-N- (ethyl different luminol): ABEI
Nanogold and Platinum Nanoparticles modification N- (aminobutyl)-N- (ethyl different luminol): ABEI-Au-Pt
Glass-carbon electrode: GCE
Bovine serum albumin(BSA): BSA.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the preparation process and corresponding detection schematic diagram of sensor provided in an embodiment of the present invention；
Fig. 2 is the TEM image for the G-CdTe QDs that the embodiment of the present invention is prepared；
Fig. 3 is the enlarged drawing of TEM image shown in Fig. 2；
Fig. 4 is the SEM image for the ABEI-Au-Pt that the embodiment of the present invention is prepared；
The XPS figure that Fig. 5 is the ABEI-Au-Pt that the embodiment of the present invention is prepared,
Fig. 6 is the high-resolution curve that XPS shown in fig. 5 schemes corresponding each element, wherein Fig. 6 (a)-(d) is respectively N,
The high-resolution curve of C, Au and Pt；
The ultra-violet absorption spectrum of the ECL spectrum that Fig. 7 is ABEI and the G-CdTe QDs that the embodiment of the present invention is prepared；
Fig. 8 is the ECL response curve of the electrode for the different modifying that the embodiment of the present invention is prepared,
Wherein, a is the glass-carbon electrode for being modified with G-CdTe QDs；B is the glass carbon electricity for being modified with Dexp and G-CdTe QDs
Pole；C is the glass-carbon electrode for being modified with BSA, Dexp and G-CdTe QDs；D is to be modified with Con A, BSA, Dexp and G-CdTe
The glass-carbon electrode of QDs；E is the glass-carbon electrode for being modified with Dexp-ABE I-Au-Pt, Con A, BSA, Dexp and G-CdTe QDs；
Fig. 9 is the cyclic voltammetry curve of the electrode for the different modifying that the embodiment of the present invention is prepared,
Wherein, a is bare glassy carbon electrode；B is the glass-carbon electrode for being modified with G-CdTe QDs；C is to be modified with Dexp and G-
The glass-carbon electrode of CdTe QDs；D is the glass-carbon electrode for being modified with BSA, Dexp and G-CdTe QDs；E be modified with Con A,
The glass-carbon electrode of BSA, Dexp and G-CdTe QDs；F is to be modified with Dexp-ABEI-Au-Pt, Con A, BSA, Dexp and G-
The glass-carbon electrode of CdTe QDs；
Figure 10 be G-CdTe QDs of the present invention, ABEI ECL signal strength with pH variation diagram；
Figure 11 is ECL response curve of the sensor under the concentration of different Con A described in the embodiment of the present invention；
Figure 12 is the working curve that sensor described in the embodiment of the present invention detects Con A；
Figure 13 is the ECL signal of sensor described in the embodiment of the present invention with the change curve of cycle-index；
Figure 14 is selective figure of the sensor described in the embodiment of the present invention to Con A.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
The present invention provides a kind of for detecting the sensor of concanavalin A, including cathodoluminescence body, anode light body and
Coreaction reagent, the cathodoluminescence body include G-CdTe QDs, and the anode light body includes ABEI-Au-Pt.
In a preferred embodiment of the invention, the coreaction reagent includes oxygen.It is furthermore preferred that the oxygen is molten
Solve oxygen.
The cathodoluminescence body and anode light body that the present invention uses, under the conditions of existing for the coreaction reagent dissolved oxygen can
Energy luminescence mechanism is as follows:
G-CdTe QDs+e-→G-CdTe QDs·- (1)
O2+2G-CdTe QDs·-+2H+→H2O2+2G-CdTe QDs* (2)
G-CdTe QDs*→G-CdTe QDs+hν (3)
ABEI-e-→ABEI·+ (4)
O2+e-→O2 ·- (5)
ABEI·++O2 ·-→ABEI* (6)
ABEI*→ABEI+hν (7)
In a preferred embodiment of the invention, the sensor further includes being modified respectively in cathodoluminescence body and anode hair
The recognition unit of body of light, recognition unit concanavalin A for identification.Preferably, the recognition unit includes Dexp.
In a preferred embodiment of the invention, by cathodoluminescence body and the modification of anode light body in glassy carbon electrode surface.
The present invention also provides the preparation methods of the sensor described in one kind for detecting concanavalin A, including walk as follows
It is rapid:
G-CdTe QDs and recognition unit by pi-pi accumulation in conjunction with, and modify in pretreated electrode surface；Knot is modified again
The anode light body for having recognition unit is closed, incubation obtains the sensor.
In a preferred embodiment of the invention, the G-CdTe QDs is dispersed in water, dispersion concentration 0.5-
2.0mg/mL。
In a preferred embodiment of the invention, the recognition unit includes Dexp.Preferably, the concentration of the Dexp is
5-30mg/mL.It is furthermore preferred that the Dexp to be made to the aqueous solution of Dexp.
In a preferred embodiment of the invention, the volume of the solution of the dispersion liquid and Dexp of the G-CdTe QDs
Than for 1 ﹕ (0.8-1.2), preferably 1 ﹕ 1.
In a preferred embodiment of the invention, the preparation method of the anode light body includes: by HAuCl4, ABEI and
H2PtCl6Hybrid reaction stirs to get the anode light body.
In a preferred embodiment of the invention, the preparation method of the anode light body includes:
By HAuCl4Solution be added ABEI solution in, be stirred at room temperature reaction 1-3h；H is added2PtCl6Solution, room temperature
1-3h is stirred, mixed solution is obtained, solid is collected by centrifugation.
In a preferred embodiment of the invention, anode light body is mixed with the solution of phenoxylation glucan, makes anode
Illuminator is combined with phenoxylation glucan.Preferably, anode light body is dispersed in water, the solution of Dexp is added, stirred
1-3h.Preferably, the dispersion concentration of anode light body is 1-2mg/mL, preferably 1.5mg/mL.It is furthermore preferred that anode light body point
The volume ratio of the solution of the volume and Dexp of dispersion liquid is 1 ﹕ (0.8-1.2), preferably 1 ﹕ 1.
In a preferred embodiment of the invention, the HAuCl4Solution mass concentration be 0.5-2%, preferably
1%.It is furthermore preferred that the HAuCl4Solution be HAuCl4Aqueous solution.
In a preferred embodiment of the invention, the H2PtCl6Solution mass concentration be 0.5-2%, preferably
1%.It is furthermore preferred that the H2PtCl6Solution be H2PtCl6Aqueous solution.
In a preferred embodiment of the invention, the concentration of the solution of the ABEI is 5-15mmol/L, preferably 10mmol/
L.It is furthermore preferred that the solution of the ABEI is the aqueous solution of ABEI.
In a preferred embodiment of the invention, the HAuCl4Solution, the H2PtCl6Solution, the N- (ammonia
Base butyl)-N- (ethyl different luminol) solution volume ratio be 1 ﹕ (1 ﹕ 2 of 0.8-1.2) ﹕ (1-3), preferably 1 ﹕.
In a preferred embodiment of the invention, the condition of the centrifugation includes: the revolving speed of 10000 ± 2000rpm/min
Lower centrifugation 10-20min.
In a preferred embodiment of the invention, the preparation method of the sensor includes the following steps:
It is dry in electrode surface drop coating G-CdTe QDs, recognition unit Dexp is added dropwise and forms pi-pi accumulation.
In a preferred embodiment of the invention, after forming pi-pi accumulation, in the solution of electrode surface drop coating BSA.More preferably
, the mass fraction of the solution of the BSA is 0.5-1.5%, preferably 1%.
In a preferred embodiment of the invention, the volume of the dispersion liquid of the solution of the BSA and the G-CdTe QDs
Than for 1 ﹕ (1-1.5), preferably 1 ﹕ 1.
In a preferred embodiment of the invention, after the solution of drop coating BSA, the prepare liquid that the A containing Con is added dropwise is incubated for.
In a preferred embodiment of the invention, modification is combined with identification after the prepare liquid of dropwise addition A containing Con is incubated for
The anode light body of unit.It is furthermore preferred that described modify the method for being combined with the anode light body of recognition unit are as follows: send out anode
Electrode surface of the body of light drop coating after incubation, is incubated for 1-3h under the conditions of 0-10 DEG C, is preferably incubated for 2h under the conditions of 4 DEG C.
In a preferred embodiment of the invention, in the prepare liquid, concentration >=3.0 × 10 of concanavalin A-5Ng/mL,
Preferably 3.0 × 10-5-10ng/mL。
In a preferred embodiment of the invention, the preparation method of the G-CdTe QDs includes: mixing CdCl2Solution
With GO, Na is added2TeO3、C6H5Na3O7, mercaptopropionic acid and NaBH4, in 120-140 DEG C of back flow reaction 8-12h, using ethyl alcohol and
Solid is collected by centrifugation in water washing, is dispersed in water, and obtains the G-CdTe QDs.It is furthermore preferred that the G-CdTe QDs's is dense
Degree is 0.5-2.0mg/mL, preferably 1mg/mL.
In a preferred embodiment of the invention, the preprocess method of electrode surface includes: to pass through glass-carbon electrode respectively
0.25-0.35 μm and 0.45-0.55 μm of alumina powder polishes, and cleans in water and ethyl alcohol, dry.
The present invention also provides detecting answering in concanavalin A for detecting the sensor of concanavalin A described in one kind
With.
In a preferred embodiment of the invention, the method for detecting concanavalin A includes the following steps:
(1) after being incubated for the sensor using the solution of the standard concanavalin A containing various concentration, cathodoluminescence is acquired
The luminous signal of body and anode light body is dense by the intensity rate of two kinds of luminous signals and the solution of the standard concanavalin A
The logarithm of degree carries out linear fit, obtains working curve；
(2) sensor is incubated for using prepare liquid, acquires the luminous signal of cathodoluminescence body and anode light body, passes through
The concentration of concanavalin A in the prepare liquid is calculated in working curve.
The reagent and device information that various embodiments of the present invention use are as follows:
1, reagent
Sodium tellurite (Na2TeO3) He Banwu water caddy (CdCl2·2.5H2O AlfaAesar (China) limited public affairs) are purchased from
Department；
GO is provided by Nanjing pioneer's nanosecond science and technology company；
ABEI is purchased from TCL Development Co., Ltd (Shanghai, China)；
Con A comes from CanaValia ensiformis jack bean；
3- mercaptopropionic acid (MPA) is provided by Sigma Chemical Co., Ltd. (St.Louis, MO, USA)；
Dexp comes from Aladdin Shanghai Co., Ltd；
Gold chloride (HAuCl4·4H2) and chloroplatinic acid (H O2PtCl6) purchase from Solution on Chemical Reagents in Shanghai Co., Ltd；
Bovine serum albumin(BSA) is bought from the Shanghai Sigma-Aldrich Co., Ltd；
Use Na2HPO4(0.10mol/L) and KH2PO4(0.10mol/L) preparation has the phosphate-buffered of various pH value
Solution (PBS, 0.10mol/L), KCl (0.10mol/L) are used as supporting electrolyte；
All chemical reagent are that analysis is pure；
All experimental waters are secondary distilled water.
2, instrument
ECL signal detection: MPI-A Electrochemiluminescprocess process instrument, Xi'an Rui Mai Electronic Science and Technology Co., Ltd.；Entire detection
All at room temperature, the voltage of photomultiplier tube is set as 800V to process, and scanning range is -1.7V to+0.6V, sweep speed
For 0.5V/s；Using three-electrode system, the glass-carbon electrode that the present invention modifies is as working electrode, and Ag/AgCl electrode is as reference
Electrode, Pt is as auxiliary electrode；
Cyclic voltammetric detection: CHI600D electrochemical workstation, Shanghai CH instrument company；Using three-electrode system, the present invention
The glass-carbon electrode of modification is as working electrode, and Ag/AgCl electrode is as reference electrode, and Pt is as auxiliary electrode；
Ultra-violet absorption spectrum test: UV-2450 ultraviolet specrophotometer, Shimadzu Co., Ltd；
Scanning electron microscopy picture: scanning electron microscope, Hitachi；
Transmission electron microscope image: transmission electron microscope H-800, Hitachi；
XPS test: 250 spectrometer of Thermo ESCALAB, SID-Molecular.
Embodiment 1
Present embodiments provide a kind of for detecting the preparation method of the sensor of concanavalin A, steps are as follows:
1, G-CdTe QDs is prepared
Weigh the CdCl of 36.89mg2·2.5H2O is dissolved in the deionized water of 50mL, and the GO of the 1mg/mL of 220 μ L is existed
It is added under stirring condition in above-mentioned solution and continues to stir 1h.Then it is gradually added into the Na that 1mL concentration is 0.01M2TeO3, 50mg
C6H5Na3O7·2H2O, the NaBH of the MPA and 100mg of 33 μ L4And continue to stir, after being heated to reflux 10h under the conditions of 130 DEG C,
It is collected obtained G-CdTe QDs three times with the ethyl alcohol and distillation water washing centrifugation that volume ratio is 1 ﹕ 1, dispersed in deionized water in 4
It is stored for future use under the conditions of DEG C, dispersion concentration 1mg/mL.
2, the preparation of anode light body Dexp-ABEI-Au-Pt
The HAuCl for being 1% by 1mL mass fraction4Solution be added drop-wise under agitation 2mL 10mmol/L ABEI
In solution, it is stirred to react 2h at room temperature.Then the H for being 1% by 1mL mass fraction2PtCl6Solution is under agitation
It is added drop-wise in above-mentioned mixed solution and continues to stir 2h.Then above-mentioned mixed solution is centrifuged 15min under the conditions of 10000rpm, and
And be washed with deionized three times, obtained anode light body ABEI-Au-Pt is distributed in secondary distilled water, dispersion concentration
For 1.5mg/mL, 1mL is added, concentration is the Dexp solution of 15mg/mL, obtains the anode hair for being combined with recognition unit after stirring 2h
Body of light Dexp-ABEI-Au-Pt is stored under the conditions of 4 DEG C with spare.
3, sensor is prepared
Referring to Fig. 1, it is the preparation process and the signal of corresponding testing principle of sensor provided in an embodiment of the present invention
Figure.Steps are as follows for the preparation process:
Bare glassy carbon electrode (φ=4.0mm) is polished through 0.3 μm and 0.5 μm of alumina powder respectively, successively uses ultrapure water
It is cleaned with EtOH Sonicate, after being dried in air, the ready G-CdTe QDs of 10 μ L is added dropwise in electrode surface, is done in air
It is dry；Then 10 μ L, the Dexp solution that concentration is 15mg/mL are added drop-wise to the electrode surface for being modified with G-CdTe QDs, pass through G-
Pi-pi accumulation combination between CdTe QDs and Dexp, by Dexp modification to electrode surface；Then it is by 10 μ L mass fractions
1% BSA solution is added drop-wise to the electrode surface for being modified with Dexp, to block the nonspecific binding site of modified electrode；Pass through
The 10 μ L Con A for containing determinand is incubated for electrode surface, incubates by the biospecific sexual reaction between Con A and Dexp
Educating the time is 1h；Then Dexp-ABEI-Au-Pt is added drop-wise to electrode surface, is incubated for 2h under the conditions of 4 DEG C, obtain the sensing
Device.
Embodiment 2
Present embodiments provide a kind of for detecting the preparation method of the sensor of concanavalin A, steps are as follows:
1, G-CdTe QDs is prepared
With embodiment 1
2, the preparation of anode light body Dexp-ABEI-Au-Pt
The HAuCl for being 1% by 1mL mass fraction4Solution be added drop-wise under agitation 2mL 10mmol/L ABEI
In solution, it is stirred to react 2h at room temperature.Then the H for being 1% by 1mL mass fraction2PtCl6Solution is under agitation
It is added drop-wise in above-mentioned mixed solution and continues to stir 2h.Then above-mentioned mixed solution is centrifuged 15min under the conditions of 10000rpm, and
And be washed with deionized three times, obtained anode light body ABEI-Au-Pt is distributed in secondary distilled water, dispersion concentration
For 1.5mg/mL, 1mL is added, concentration is the Dexp solution of 15mg/mL, obtains the anode hair for being combined with recognition unit after stirring 2h
Body of light Dexp-ABEI-Au-Pt is stored under the conditions of 4 DEG C with spare.
3, sensor is prepared
Bare glassy carbon electrode (φ=4.0mm) is polished through 0.3 μm and 0.5 μm of alumina powder respectively, successively uses ultrapure water
It is cleaned with EtOH Sonicate, after being dried in air, the ready G-CdTe QDs of 10 μ L is added dropwise in electrode surface, is done in air
It is dry；Then 12 μ L, the Dexp solution that concentration is 15mg/mL are added drop-wise to the electrode surface for being modified with G-CdTe QDs, pass through G-
Pi-pi accumulation combination between CdTe QDs and Dexp, by Dexp modification to electrode surface；Then it is by 8 μ L mass fractions
1% BSA solution is added drop-wise to the electrode surface for being modified with Dexp, to block the nonspecific binding site of modified electrode；Pass through
The 10 μ L Con A for containing determinand is incubated for electrode surface, incubates by the biospecific sexual reaction between Con A and Dexp
Educating the time is 1h；Then Dexp-ABEI-Au-Pt is added drop-wise to electrode surface, is incubated for 2h under the conditions of 4 DEG C, obtain the sensing
Device.
Embodiment 3
The preparation method of the present embodiment reference implementation example 1, difference be when step 3 prepares sensor, by Con A and
A series of Con A standard solution containing various concentration of 10 μ L are incubated for by the biospecific sexual reaction between Dexp respectively
To electrode surface, incubation time 1h.
The series of concentrations of Con A standard solution is respectively as follows: 1.0 × 10-4ng/mL、1.0×10-3ng/mL、1.0×10- 2Ng/mL, 0.1ng/mL, 1ng/mL and 10ng/mL, the standard solution are the pH=7.4's that Con A is dissolved in 0.1mol/L
Obtained in PBS buffer solution.
Experimental example 1
In order to further confirm to illustrate preparation process of the invention, by taking embodiment 1 as an example, to the sensor preparation process
In each substance carry out characterization test etc., it is specific as follows.
Fig. 2 and 3 are please referred to, is the TEM image that G-CdTe QDs is prepared in the embodiment of the present invention 1, it can be with from figure
See and be scattered with many granular cadmium telluride quantum dots in surface of graphene oxide, and quantum dot can be observed from Fig. 3
Size about 2.2nm.
Referring to Fig. 4, it is the SEM image for the ABEI-Au-Pt that the embodiment of the present invention 1 is prepared, Cong Tuzhong observable
To flower-shaped pattern, and it is to be stacked up in layer that each, which is spent, further illustrates ABEI and passes through in-situ reducing
HAuCl4And H2PtCl6Obtain ABEI-Au-Pt composite nano materials.
Please refer to Fig. 5 and Fig. 6, be respectively the ABEI-Au-Pt that the embodiment of the present invention 1 is prepared XPS figure and
The high-resolution curve of corresponding each element.From XPS figure it is found that the characteristic peak occurred in 398.3eV and 293.9eV from
The N 1s (corresponding diagram 6 (a)) and C 1s (corresponding diagram 6 (b)) of ABEI, the characteristic peak of Au 4f (corresponding diagram 6 (c)) appear in
84.25eV and 87.75eV, the characteristic peak in 72.1eV then belong to Pt 4f (corresponding diagram 6 (d)), these characteristic peaks illustrate
The successful preparation of ABEI-Au-Pt nanocomposite.
Referring to Fig. 7, it is ECL spectrum and the ultraviolet suction of G-CdTe QDs that is prepared of the embodiment of the present invention of ABEI
Spectrum is received, it can be seen that there is no lap, explanations for the ultra-violet absorption spectrum of the ECL spectrum of ABEI and G-CdTe QDs
ECL energy transfer is not present between ABEI and G-CdTe QDs.
Experimental example 2
ECL the and CV performance for the sensor being prepared in order to further illustrate the present invention, to modifying G- on bare electrode
CdTe QDs, each step progress ECL response for successively modifying Dexp, BSA, determinand Con A and Dexp-ABEI-Au-Pt again
Signal and cyclic voltammetry curve test, test result are shown in Fig. 8 and Fig. 9.
The test method of specific ECL response signal are as follows: PBS (pH 7.4) solution of the 0.10mol/L of 3mL is as test bottom
Liquid tests the ECL response signal of each step different modifying electrode respectively；
As can be known from Fig. 8, the modified electrode that each step obtains respectively corresponds the a-e in Fig. 8；When bare electrode modifies upper G-
CdTe QDs (curve 8a) occurs a very strong cathode ECL signal at -1.7V current potential, does not occur in anode at this time
ECL transmitting.After electrode is successively modified with Dexp (curve 8b) and BSA (curve 8c), compared with curve 8a, the ECL of cathode is sent out
Signal is penetrated to be gradually reduced.When determinand Con A (curve 8d) is added drop-wise on electrode, there is apparent reduction in cathode signal.
The reason of these signals reduce is attributed to Dexp, BSA and Con A, these substances are non-electroactive materials, hinders electronics biography
It passs.When electrode surface is arrived in Dexp-ABEI-Au-Pt (curve 8e) modification, emission of cathode reduces, a new anode ECL transmitting
Signal appears in+0.6V, and anode signal is attributed to ABEI, shows the successful building of sensor.
The test method of specific cyclic voltammetry curve are as follows: in 5.0mmol/L [Fe (CN)6 4-]/[Fe(CN)6 3-] solution in
It is characterized with cyclic voltammetry, wherein scanning current potential is set as -1.7V to+0.6V.
As can be known from Fig. 9, it is observed that a pair of apparent redox peaks on bare electrode (curve 9a).When on electrode
When being modified with G-CdTe QDs (curve 9b), redox peak point current is obviously reduced.As Dexp (curve 9c) and BSA (curve
When 9d) in modification to electrode, redox peak point current successively declines.When determinand Con A (curve 9e) is incubated for onto electrode
When, peak point current further decreases.These redox peak point currents persistently reduced are because Dexp, BSA and Con A hinder
Electronics transfer.When electrode surface is arrived in Dexp-ABEI-Au-Pt (curve 9f) modification, there is apparent liter in peak point current
Height, because ABEI, Au and Pt promote the transfer of electronics.
Experimental example 3
For the operating condition for advanced optimizing the sensor, the pH of the PBS solution used when to test optimizes survey
Examination.
G-CdTe QDs and ABEI are respectively placed in the PBS solution that pH is 6.5,7.0,7.5,8.0 and 8.5, to respective
ECL response signal tested, test results are shown in figure 10, be G-CdTe QDs, ABEI ECL signal strength with pH
Variation diagram.
It can be seen that the ECL signal strength of G-CdTe QDs and ABEI pH be 6.5-8.5 in the range of, with
The increase of pH and increase, and the biochemical activity of determinand Con A of the present invention pH be 7.4 when it is best, thus optimize
PH is 7.4.
Experimental example 4
This experimental example tests ECL response curve of the sensor of the present invention under the concentration of different Con A,
The final quantitative detection realized to Con A.
Specifically, being incubated for the sensor using the solution of the standard Con A containing various concentration by taking embodiment 3 as an example
Afterwards, the luminous signal of cathodoluminescence body and anode light body is acquired, test result is as shown in figure 11, is biography of the present invention
ECL response curve of the sensor under the concentration of different Con A, it is 1.0 × 10 that a-f, which respectively corresponds concentration, in figure-4ng/mL、1.0×
10-3ng/mL、1.0×10-2The ECL letter of sensor after the Con A incubation of ng/mL, 0.1ng/mL, 1ng/mL and 10ng/mL
Number.It can be seen that the increase of the concentration with Con A, ECL transmitting of the G-CdTe QDs at cathode -1.7V is gradually decreased,
And the ECL transmitting of the ABEI at anode+1.6V gradually rises.
By the logarithm of the intensity rate of cathode and two kinds of ECL signals of anode and the solution concentration of the standard Con A into
Row linear fit obtains working curve, as shown in figure 12, shows good linear relationship；Detection range to Con A is
1.0×10-4Ng/mL to 10ng/mL, and its detection is limited down to 3.0 × 10-5Ng/mL, linear regression equations IG-CdTe QDs/
IABEI=-0.5189+0.6459logc (wherein IG-CdTe QDsRepresent the ECL signal of cathode G-CdTe QDs, IABEIRepresent ABEI-
The ECL signal of Au-Pt, c then represent the concentration of Con A), coefficient R 0.995.
In order to which compared with the method for other detections Con A, the following table 1 lists the detection of the method for other detections Con A
Energy.
The detection performance of the detection method of the different Con A of table 1
Remarks: bibliography:
[1]Zou,L.,Pang,H.L.,Chan,P.H.,Huang,Z.S.,Gu,L.Q.,Wong,K.Y.,
2008.Carbohydr.Res.343,2932-2938.
[2]Huang,C.F.,Yao,G.H.,Liang,R.P.,Qiu,J.D.,
2013.Biosens.Bioelectron.50,305-310.
[3]Guo,C.X.,Boullanger,P.,Jiang,L.,Liu,T.,
2007.Biosens.Bioelectron.22,1830-1834.
[4]Zhang,H.,Lu,Q.Y.,Zuo,F.M.,Yuan,R.,Chen,S.H.,2017.Sens.Actuator B:
Chem.241,887-894.
Experimental example 5
Stability is most important for sensor, and good stability is usually as one of the standard for judging ECL performance.It will
It is incubated for 1.0 × 10-3The sensor of the Con A of ng/mL, in the PBS solution that 0.1mol/L, pH of the saturation of the air are 7.4, continuously
Scan round 8 times, as shown in figure 13, it can be seen that ECL signal does not occur apparent difference, relative standard deviation
(RSD) it is 2.1%, within an acceptable range, illustrates that sensor of the present invention is with good stability.
In order to test the selectivity of sensor of the present invention, the bovine serum albumin(BSA) for being 1% by mass fraction
(BSA), the cancer antigen of the alpha-fetoprotein (PHA) of 50ng/mL, prostate-specific antigen (CA) and 0.1U/mL of 50ng/mL
(AFP) be used as interfering substance, be added into the Con A of 0.1ng/mL, compare sensor of the present invention with and without
ECL response signal in the presence of interfering substance, as shown in figure 14, it can be seen that above-mentioned interfering substance to the detection of Con A not
There can be interference, illustrate that sensor of the present invention has good selectivity Con A.
In order to further test the reproducibility of sensor of the present invention, with reference to the embodiment of the present invention in identical experiment item
5 identical sensors are prepared under part, and ECL response signal is tested, the relative standard of the ECL response of 5 sensors
Deviation (RSD) is 3.4% (cathode) and 4.7% (anode), shows that sensor of the present invention has good reproducibility.
Experimental example 6
The practicability of sensor of the present invention is tested using mark-on reclaims method.Firstly, before test, by human body
Serum sample dilutes 20 times with the PBS solution that 0.10mol/L, pH are 7.4.The Con A of various concentration is added to diluted people
In body serum sample, its rate of recovery is measured, test result is as shown in table 2, and the rate of recovery range of Con A is 95.3% to 106%
Between, show that this method can be used for practical biological sample analysis detection, there is preferable practical application potential.
The rate of recovery test result of Con A in 2 human serum of table
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (23)
1. a kind of for detecting the sensor of concanavalin A, which is characterized in that including cathodoluminescence body, anode light body and be total to
Reaction reagent, the cathodoluminescence body include the cadmium telluride quantum dot of graphene oxide modification, and the anode light body includes receiving
N- (aminobutyl)-N- (ethyl different luminol) of meter Jin and Platinum Nanoparticles modification；
The coreaction reagent is dissolved oxygen；
The sensor further includes modifying respectively in the recognition unit of cathodoluminescence body and anode light body, and the recognition unit is used
In identification concanavalin A；
The recognition unit is phenoxylation glucan.
2. according to claim 1 for detecting the sensor of concanavalin A, which is characterized in that
By cathodoluminescence body and the modification of anode light body in glassy carbon electrode surface.
3. of any of claims 1 or 2 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that including such as
Lower step:
Cadmium telluride quantum dot and the recognition unit of graphene oxide modification by pi-pi accumulation in conjunction with, and modification is in pretreated electricity
Pole surface；The anode light body for being combined with recognition unit is modified again, and incubation obtains the sensor.
4. according to claim 3 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that by institute
The cadmium telluride quantum dot for stating graphene oxide modification is dispersed in water, dispersion concentration 0.5-2.0mg/mL.
5. according to claim 4 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that described
The concentration of phenoxylation glucan is 5-30mg/mL.
6. according to claim 5 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that described
The volume ratio of the solution of the dispersion liquid and phenoxylation glucan of the cadmium telluride quantum dot of graphene oxide modification is 1 ﹕
(0.8-1.2)。
7. according to claim 3 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that described
The preparation method of anode light body includes: by HAuCl4, N- (aminobutyl)-N- (ethyl different luminol) and H2PtCl6Mixing is anti-
It answers, stirs to get the anode light body.
8. according to claim 7 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that described
The preparation method of anode light body includes:
By HAuCl4Solution be added N- (aminobutyl)-N- (ethyl different luminol) solution in, be stirred at room temperature reaction 1-3h；
H is added2PtCl6Solution, 1-3h is stirred at room temperature, obtains mixed solution, solid is collected by centrifugation.
9. according to claim 7 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that anode
Illuminator is mixed with the solution of phenoxylation glucan, and anode light body is made to be combined with phenoxylation glucan.
10. according to claim 7 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that described
HAuCl4Solution mass concentration be 0.5-2%；
The H2PtCl6Solution mass concentration be 0.5-2%；
The concentration of the solution of N- (the aminobutyl)-N- (ethyl different luminol) is 5-15mmol/L；
The HAuCl4Solution, the H2PtCl6Solution, the N- (aminobutyl)-N- (ethyl different luminol) solution
Volume ratio be 1 ﹕ (0.8-1.2) ﹕ (1-3).
11. according to claim 3 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that described
The preparation method of sensor, includes the following steps:
It is dry in the cadmium telluride quantum dot of electrode surface drop coating graphene oxide modification, recognition unit is added dropwise and forms pi-pi accumulation.
12. according to claim 11 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that shape
After pi-pi accumulation, in the solution of electrode surface drop coating bovine serum albumin(BSA).
13. according to claim 12 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that institute
The mass fraction for stating the solution of bovine serum albumin(BSA) is 0.5-1.5%.
14. according to claim 12 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that institute
The volume ratio for stating the dispersion liquid of the solution of bovine serum albumin(BSA) and the cadmium telluride quantum dot of graphene oxide modification is 1 ﹕ (1-
1.5)。
15. 1-14 is described in any item for detecting the preparation method of the sensor of concanavalin A according to claim 1, special
Sign is, after the solution of drop coating bovine serum albumin(BSA), the prepare liquid containing concanavalin A is added dropwise and is incubated for；
The anode light body that modification after the prepare liquid containing concanavalin A is incubated for is combined with recognition unit is added dropwise.
16. according to claim 15 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that institute
The method for stating the anode light body that modification is combined with recognition unit includes: the electrode table by anode light body drop coating after incubation
Face is incubated for 1-3h under the conditions of 0-10 DEG C.
17. according to claim 15 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that institute
It states in prepare liquid, concentration >=3.0 × 10 of concanavalin A-5ng/mL。
18. according to claim 17 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that institute
It states in prepare liquid, the concentration of concanavalin A is 3.0 × 10-5-10ng/mL。
19. according to claim 3 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that described
The preparation method of the cadmium telluride quantum dot of graphene oxide modification includes: mixing CdCl2Solution and graphene oxide, be added
Na2TeO3、C6H5Na3O7, mercaptopropionic acid and NaBH4, in 120-140 DEG C of back flow reaction 8-12h, it is centrifuged using ethyl alcohol and water washing
Solid is collected, is dispersed in water, the cadmium telluride quantum dot of the graphene oxide modification is obtained.
20. according to claim 3 for detecting the preparation method of the sensor of concanavalin A, which is characterized in that electrode
The preprocess method on surface includes: to polish glass-carbon electrode through 0.25-0.35 μm and 0.45-0.55 μm of alumina powder respectively,
It is cleaned in water and ethyl alcohol, it is dry.
21. the application of sensor in detection concanavalin A of any of claims 1 or 2 for detecting concanavalin A,
It is characterized in that, the method for detecting concanavalin A includes the following steps:
(1) after being incubated for the sensor using the solution of the standard concanavalin A containing various concentration, acquisition cathodoluminescence body and
The luminous signal of anode light body, by the solution concentration of the intensity rate of two kinds of luminous signals and the standard concanavalin A
Logarithm carries out linear fit, obtains working curve；
(2) sensor is incubated for using prepare liquid, acquires the luminous signal of cathodoluminescence body and anode light body, passes through work
The concentration of concanavalin A in the prepare liquid is calculated in curve.
22. the application of sensor in detection concanavalin A according to claim 21 for detecting concanavalin A,
It is characterized in that, in the environment of acquisition luminous signal, pH 6.5-8.5.
23. the application of sensor in detection concanavalin A according to claim 22 for detecting concanavalin A,
It is characterized in that, in the environment of acquisition luminous signal, pH 7.4.
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