CN109030592A - A kind of optical electro-chemistry sensor and its preparation and application based on nitridation carbon signal amplification - Google Patents
A kind of optical electro-chemistry sensor and its preparation and application based on nitridation carbon signal amplification Download PDFInfo
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- CN109030592A CN109030592A CN201810840501.9A CN201810840501A CN109030592A CN 109030592 A CN109030592 A CN 109030592A CN 201810840501 A CN201810840501 A CN 201810840501A CN 109030592 A CN109030592 A CN 109030592A
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- 230000003287 optical effect Effects 0.000 title claims abstract description 31
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- 229960004475 chlortetracycline Drugs 0.000 description 3
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- 229960005091 chloramphenicol Drugs 0.000 description 2
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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Classifications
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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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Abstract
The invention belongs to electrochemical sensor fields, and in particular to a kind of optical electro-chemistry sensor and preparation method thereof based on nitridation carbon signal amplification.The present invention is with g-C3N4For light active material, using the aptamers of test substance as biological identification element, with Na2SO4Solution is electrolyte, using GaN as working electrode;By g-C3N4It is added in electrolyte with the aptamers of test substance, the optical electro-chemistry sensor based on nitridation carbon signal amplification is constituted together with three-electrode system.The sensor operations are simple, high sensitivity.
Description
Technical field
The invention belongs to electrochemical sensor fields, and in particular to a kind of optical electro-chemistry biography based on nitridation carbon signal amplification
Sensor and preparation method thereof.
Background technique
Tetracycline antibiotics are a kind of broad-spectrum antibiotics of discovery the 1940s.This kind of antibiotic are widely applied
The treatment of infection caused by bacterium, intracellular mycoplasma, Chlamydia etc. in animal is either raised in human body.But tetracycline
Abuse cause make it through and directly take drugs or accumulated in human body by indirect edible animal food, this will be generated
Serious risk such as increases microorganism fungus kind to the drug resistance of drug, to some sensitive peoples and generates allergy or toxic reaction,
And bone uptake can be inhibited.Moreover, it is early from 1956, just have been found that tetracycline is possible to influence the development and formation of tooth, no
But so that tooth is turned yellow, can also cause enamel depauperation or deformity teeth.Therefore, the detection with environmental monitoring of tetracycline have
Important social effect.
At present tetracycline detection method mainly include the following types:
(1) plasma resonance detection method: this method is relied in real time with aimed quality by monitoring refractive index (Ri) offer closely
Signal.The method higher cost, pre-processing are more complex.
(2) Electrochemiluminescince detects: method measurement accuracy is high, and detection range is wide, but in stability and specificity side
Face is to be improved.
(3) Liquid Chromatography/Mass Spectrometry detects: although this method may be implemented high sensitivity, highly selective detection, but complicated for operation,
And instrument cost is relatively expensive, detection time is longer.
(4) optical electro-chemistry sensor method: the high sensitivity of photoelectrochemical assay, and also background signal is low, and operation is convenient, sets
For simple, testing cost is low, but it is usually present the problem of selectivity deficiency.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of tetracycline based on nitridation carbon signal amplification
The preparation method of optical electro-chemistry sensor.The sensor simple structure, low in cost, selectivity is high.
To achieve the purpose of the present invention, it adopts the following technical scheme that
A kind of preparation method of the optical electro-chemistry sensor based on nitridation carbon signal amplification, with g-C3N4For light active material, with
The aptamers of test substance are biological identification element, using GaN as working electrode;By g-C3N4It is added with the aptamers of test substance
In electrolyte, the optical electro-chemistry sensor based on nitridation carbon signal amplification is constituted together with three-electrode system.
g-C3N4Concentration in the electrolytic solution is 0.66 ~ 19.8 mg/ml.
The concentration of the aptamers of test substance in the electrolytic solution is the nM of 40 nM ~ 120.
It is to electrode that the three-electrode system, which is with platinum electrode, and Ag/AgCl electrode is as reference electrode.
A kind of preparation method as described above optical electro-chemistry sensor obtained based on nitridation carbon signal amplification.
A kind of application of the optical electro-chemistry sensor as described above based on nitridation carbon signal amplification: for four in solution
The detection of ring element, signified solution can be the solution that food, drug etc. are configured to herein.
When the sensor is for tetracycline detection in solution, more specifically: be system to be measured is added to it is described
In the electrolyte of optical electro-chemistry sensor based on nitridation carbon signal amplification, it is combined ultraviolet lamp (wavelength is generally 350~400nm)
Electrolyte is irradiated, in having system existing for tetracycline, the optical electro-chemistry sensor of the nitridation carbon signal amplification
Photoelectric current enhancing can be generated, by drawing the known concentration of tetracycline and the standard curve of photoelectric current, by described based on nitridation
The photoelectric current that the optical electro-chemistry sensor of carbon signal amplification detects can determine the concentration of tetracycline in system to be measured.
When detecting for the tetracycline in solution, the sequence of aptamers used is 5 '-CGTAC GGAAT TCGCT
AGCCC CCCGG CAGGC CACGG CTTGG GTTGG TCCCA CTGCG CGTGG ATCCG AGCTC CACGT。
When detecting for the tetracycline in solution, detection range is 0.1-10 nmol/L, and the detection of tetracycline is limited to 0.03
nM。
When detecting for the tetracycline in solution, the bias-voltage of GaN working electrode is+0.2-+0.6V.
Further, when sensor of the invention is used for the detection of tetracycline, preparation method are as follows: with g-C3N4For light
Active material, using tetracycline aptamers as biological identification element, with Na2SO4Solution is electrolyte, using GaN as working electrode, with
Platinum electrode is to electrode, and Ag/AgCl electrode is assembled into tetracycline optical electro-chemistry sensor as reference electrode.
Further, preparation method specifically includes the following steps:
1. after tetracycline DNA aptamers are prepared with PBS buffer solution, in Na2SO4In solution be added tetracycline DNA aptamers and
g-C3N4, obtain mixed liquor;Using GaN as working electrode, platinum electrode is to electrode, and Ag/AgCl electrode is as reference electrode, with mixing
Liquid is electrolyte, and the photoelectric current under 365 nm irradiation, as background photo current are measured in three-electrode system;
2. the mixed liquor of step 1. is mixed with a series of tetracycline standard solution of isometric various concentrations respectively, it is incubated at room temperature
After 5-20 min, a series of test solutions are obtained;
3. platinum electrode is to electrode, 2. Ag/AgCl electrode is made with step respectively as reference electrode using GaN as working electrode
A series of test solutions be electrolyte, measured in three-electrode system 365 nm irradiation under photoelectric current;3. step is measured
Photoelectric current and the difference DELTA I of step 1. background photo current be used as y value, the concentration of tetracycline standard solution is x value, is obtained linearly
Regression equation;
4. tetracycline sample to be measured is added in the mixed liquor of step 1., after being incubated at room temperature 5-20min, photoelectricity is measured again
Stream, by it, 1. the difference DELTA I of background current is substituted into the equation of linear regression of step 3. with step, obtains Fourth Ring in sample to be tested
The content of element.
Preferably, for step 2. in the test solution, the concentration of tetracycline DNA aptamers is 60 nM;g-C3N4It is dense
Degree is 13.2 mg/ml;The concentration range of tetracycline standard solution is 0.1-10 nmol/L, and volume is 5 μ L;Three-electrode system
In, the bias-voltage on GaN electrode is 0.4 V.
The mechanism of action of inventive sensor detection tetracycline are as follows:
The present invention is using in water with the g-C of good dispersion3N4For light active material, it is in conjunction with tetracycline DNA aptamers
Biological identification element provides a kind of preparation side of novel photoelectric chemistry aptamer sensor for tetracycline specific detection
Method.Due to g-C3N4The band structure of both materials of/GaN has good matching, and photohole and electronics are in GaN and g-
C3N4Between, it can easily shift.Under light illumination, electronics is from g-C3N4Valence to its conduction band, be then transferred into
On the conduction band of GaN.In addition, in g-C3N4Valence band in can produce hole, and participate in the oxidation of TET, and significant inhibit light
Give birth to the compound of electron hole carrier.Therefore, photoelectric current significantly increases.
Similarly, when detecting other substances, the aptamers that can accordingly specifically bind the substance are chosen.
The present invention has the advantage that compared with the prior art
1) the present invention is based on g-C3N4The band structure of both materials of/GaN has good matching, photohole and electronics
In GaN and g-C3N4Between, it can easily shift;Under light illumination, electronics is from g-C3N4Valence to its conduction band,
It is then transferred on the conduction band of GaN;In addition, in g-C3N4Valence band in can produce hole, test substance is aoxidized, thus significantly
Inhibit the compound of photo-generate electron-hole carrier;Therefore when, there are when test substance, photoelectric current significantly increases in system to be measured,
The measurement for the test substance content that can be used in system;The sensor simple structure, low in cost, selectivity is high;
2) when sensor of the invention is detected for tetracycline, also have to tetracycline highly selective, and aureomycin, sulfuric acid are newly mould
Element, chloramphenicol, kanamycin sulfate and fortimicin etc. are substantially noiseless to detecting;Sound of the sensor of the invention to tetracycline
Should be linear within the scope of 0.1-10 nmol/L, detection limit (3S/N) is 0.03 nM;The sensor solves previous Fourth Ring
The problems such as plain detection method or device are expensive, process is complicated or selectivity is insufficient, provide a kind of simple structure, it is low in cost,
The high tetracycline sensor of selectivity can be applied to the medicine detection and environmental monitoring of tetracycline.
Detailed description of the invention
Fig. 1 is the working principle diagram of inventive sensor;TET-tetracycline;Aptamer-aptamers;
Fig. 2 is photocurrent response figure;(a) the photocurrent response figure of GaN electrode;(b) 13.2 mg/ ml g-C are added3N4Light
Current-responsive figure;(c) continue the photocurrent response figure for adding 5 nmol/L TET;Medium: 0.01 M Na2SO4;Bias (vs
SCE) :+0.4 V;Excitation wavelength: 365 nm;Aptamers: 40 nM;
Fig. 3 is the g-C of various concentration3N4In influence of the three-electrode system to the photocurrent response of TET;(a) 0.66, (b) 6.6,
(c) 13.2, (d) 16.5, (e) 19.8 mg/ ml;
Fig. 4 is influence of the aptamers of various concentration for the photocurrent response on TET :(a) 40 nM(b) 60 nM(c) 80 nM
(d) 100 nM(e) 120 nM;In 0.01 M Na2SO 4With 13.2 mg/ ml g-C3N4In, under the bias of+0.4 V
Record PEC measurement, poor stick=SD(n=5);
Influence of the Fig. 5 for the bias voltage for 40 nM aptamers on GaN electrode to photocurrent response :(a) 0.2, (b)
0.3, (c) 0.4, (d) 0.5, (e) 0.6 V;In 0.01 M Na2SO4With 13.2mg/ ml g-C3N4In, in the inclined of+0.4 V
PEC measurement, error bar=SD(n=5 are recorded under piezoelectric position);
Fig. 6 is that sensor of the invention uses 60 nM aptamers and 13.2 mg/ ml g-C3N4, to the PEC of various antibiotic
Response;In 0.01M Na2SO4With 13.2 mg/ ml g-C3N4In, under the bias of+0.4V record PEC measurement (n=
5);
Fig. 7 is using 60 nM aptamers and on the GaN electrode of various concentration towards the 13.2 mg/ml g-C of TET3N4Light
The calibration curve of current-responsive;PEC measurement result is recorded in 0.01 M Na2SO 4On, bias be+0.4 V, error bar=
SD(n=3).
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
The present invention is described in detail by taking the detection of tetracycline as an example.Other test substances referring to tetracycline detection into
Row.
With Na2SO4Solution (0.01 M) is electrolyte, and appropriate tetracycline (TET) aptamers are added, and (DNA aptamers are to use down
The sequence in face: 5 '-CGTAC GGAAT TCGCT AGCCC CCCGG CAGGC CACGG CTTGG GTTGG TCCCA CTGCG
CGTGG ATCCG AGCTC CACGT) and g-C3N4, with light of the three-electrode system as shown in Figure 1 measurement under 365 nm irradiation
Current signal, wherein GaN is working electrode, and platinum electrode is to electrode, and Ag/AgCl electrode is as reference electrode.Each photoelectric current
Signal testing is averaged in triplicate.As shown in Fig. 2, with the open and close of illumination, under photoelectric current sharply increases respectively and is quick
Drop illustrates that photocathode has quick photoresponse.It measures after the background photo current under 365 nm irradiation, by Fourth Ring to be measured
Plain sample is added in the solution, after being incubated at room temperature 5-20 min, measures photoelectric current again, the difference with background current is
The response of corresponding TCT concentration.
Increase g-C3N4Concentration, photoelectric current obviously increase (Fig. 3).It is separated based on Photoinduced Charge carrier, so that electronics is from g-
C3N4As electronics transfer to GaN electrode.Work as g-C3N4Concentration when being more than 13.2 mg/ ml, photoelectric current decline.This knot
Fruit may be due to excessive g-C3N4The transfer of light induced electron can be prevented, therefore manufactures PEC biography using 13.2 m g/ml
Sensor.
DNA molecular has the phosphate group of negative electrical charge in sugar chain (phosphate backbone), and each base has in aqueous solution
One negative electrical charge.g-C3N4Nanometer sheet is positively charged, provides fabulous platform for fixed tetracycline aptamers.
Fig. 4 shows influence of the adaptation bulk concentration to photocurrent response.It observes and the PEC of TET is responded with aptamers
Concentration increases to 120 nM from 40 nM and dramatically increases.The result and it is fixed on g-C3N4On the aptamers of higher concentration can catch
The fact that obtain more TET molecules is consistent.However, PEC response reduces when aptamer concentrations are more than 60 nM.Excessive aptamers institute
The steric hindrance of generation may cause the obstruction of electron transmission.Therefore 60 nM aptamers of selection are for manufacturing sensor.
Light induced electron will be driven to counterelectrode by the bias potential of external circuit, therefore help to create high photoelectricity
Stream.Bias potential also shows apparent influence to the PEC of sensor response.As shown in figure 5, the photocurrent response of TET with
Bias potential increases to 0.6 V from 0.2 V and increases, this shows that biggish anodic bias potential can drive more light induced electrons
To on to electrode to more effectively inhibit the compound of hole-electron pair.However, when the potential of application is greater than 0.4 V, it is right
The response of TET does not show further enhancing, caused by this may be the photohole saturation consumed due to TET.Therefore,
0.4 V is the best potential for PEC sensing.
In order to study the selectivity of this PEC aptamer sensor, we are incubated in 0.01 M PBS solution contains 5 nM
After various antibiotic (including tetracycline, aureomycin, neomycinsulphate, chloramphenicol, kanamycin sulfate), aptamers/g- is recorded
C3N4In 0.01 M Na2SO4To the response of GaN electrode in solution.Different from TET, all these antibiotic are on GaN electrode
Aptamer/g-C3N4It does not all show significantly to respond (Fig. 6), this shows due to the specificity between aptamer and target TET molecule
Identification, the sensor proposed have highly selective.In addition, also having evaluated the reproducibility of PEC aptamer sensor.
With the increase of tetracycline concentration, photo-current intensity is gradually increased, song of the photo-current intensity relative to aimed concn
Line has good linear relationship for target within the scope of 0.1 to 10 nM.Equation of linear regression is expressed as A=1.53 Δ I/
e-4 + 2.45 e-4Lg [C/(nmol/L)], related coefficient 0.997, range is 0.1-10 nmol/L.It is calculated according to 3 δ
Tetracycline detection limit (LOD) be 0.03 nM.This in the past reported most methods for tetracycline analysis quite or
It is more sensitive.
These are the result shows that be based on g-C3N4Photoelectric current nano-probe can be used in homogeneous solution with high sensitivity quantitation
Analyte.5 nmol/L(n=5) tetracycline detection response relative standard deviation (RSD) be 5.3%.
The experimental results showed that the PEC sensing platform uses the g-C3N4 of 13.2 mg/ml, adaptation bulk concentration is 60 nM, partially
Pressure is 0.4 V, in the case where pH is 7.4 PBS buffer solution (0.01M) reaction condition, shows optimal photocurrent response.It is linear to return
Equation is returned to be expressed as Δ I/A=1.53e-4+ 2.45e-4Lg [C/(nmol/L)], related coefficient 0.997, range 0.1-
10 nmol/L.Detection limit (LOD) according to the 3 δ tetracycline calculated is 0.03 nM.With aureomycin, neomycinsulphate, chlorine is mould
As chaff interferent, which responses to which signal much smaller than it to tetracycline for element, kanamycin sulfate and fortimicin
Response signal.
Embodiment 1
A kind of preparation method of the tetracycline optical electro-chemistry sensor based on nitridation carbon signal amplification, comprising the following steps:
(1) foundation of standard curve:
1. after the PBS buffer solution of tetracycline DNA aptamers pH=7.4 is prepared, in 0.01M Na2SO4Fourth Ring is added in solution
Plain DNA aptamers and g-C3N4, obtain mixed liquor;Using GaN as working electrode, platinum electrode is to electrode, and Ag/AgCl electrode is as ginseng
Than electrode, using mixed liquor as electrolyte, the photoelectric current under 365 nm irradiation, as background photoelectricity are measured in three-electrode system
Stream;
2. the mixed liquor of step 1. is mixed with a series of tetracycline standard solution of isometric various concentrations respectively, it is incubated at room temperature
After 5-20 min, a series of test solutions are obtained;
3. platinum electrode is to electrode, 2. Ag/AgCl electrode is made with step respectively as reference electrode using GaN as working electrode
A series of test solutions be electrolyte, measured in three-electrode system 365 nm irradiation under photoelectric current;3. step is measured
Photoelectric current and the difference DELTA I of step 1. background photo current be used as y value, the concentration of tetracycline standard solution is x value, is obtained linearly
Regression equation are as follows: y(A)=1.53e-4+2.45e-4Lg [x/ (nmol/L)], related coefficient 0.997;
(2) detection of actual samples:
Milk sample to be measured is added in the mixed liquor of step 1., after being incubated at room temperature 5-20min, measures photoelectric current again,
By it, 1. the difference DELTA I of background current is substituted into the equation of linear regression of step 3. with step, obtains tetracycline in sample to be tested
Content.
For step 2. in the test solution, the concentration of tetracycline DNA aptamers is 60 nM;g-C3N4Concentration be 13.2
mg/ml;The concentration range of tetracycline standard solution is 0.1-10 nmol/L, and volume is 5 μ L.
Table 1: the rate of recovery experimental result of tetracycline in measurement milk sample
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with repair
Decorations, are all covered by the present invention.
Sequence table
<110>University of Fuzhou
<120>a kind of optical electro-chemistry sensor and its preparation and application based on nitridation carbon signal amplification
<130> 1
<160> 1
<170> SIPOSequenceListing 1.0
<210> 1
<211> 75
<212> DNA
<213> Abedus herberti
<400> 1
cgtacggaat tcgctagccc cccggcaggc cacggcttgg gttggtccca ctgcgcgtgg 60
atccgagctc cacgt 75
Claims (10)
1. a kind of preparation method of the optical electro-chemistry sensor based on nitridation carbon signal amplification, it is characterised in that: with g-C3N4For light
Active material, using the aptamers of test substance as biological identification element, using GaN as working electrode;By g-C3N4With test substance
Aptamers are added in electrolyte, and the optical electro-chemistry sensor based on nitridation carbon signal amplification is constituted together with three-electrode system.
2. the preparation method of the optical electro-chemistry sensor according to claim 1 based on nitridation carbon signal amplification, feature
It is: g-C3N4Concentration in the electrolytic solution is 0.66 ~ 19.8 mg/ml.
3. the preparation method of the optical electro-chemistry sensor according to claim 1 based on nitridation carbon signal amplification, feature
Be: the concentration of the aptamers of test substance in the electrolytic solution is the nM of 40 nM ~ 120.
4. the preparation method of the optical electro-chemistry sensor according to claim 1 based on nitridation carbon signal amplification, feature
Be: it is to electrode that the three-electrode system, which is with platinum electrode, and Ag/AgCl electrode is as reference electrode.
5. a kind of preparation method according to any one of claims 1-4 optical electro-chemistry obtained based on nitridation carbon signal amplification
Sensor.
6. a kind of application of the optical electro-chemistry sensor as claimed in claim 5 based on nitridation carbon signal amplification, feature exist
In: for the tetracycline detection in solution.
7. the application of the optical electro-chemistry sensor according to claim 6 based on nitridation carbon signal amplification, it is characterised in that:
It is to be added to system to be measured described to amplify based on nitridation carbon signal when the sensor is for tetracycline detection in solution
In the electrolyte of optical electro-chemistry sensor, combination ultraviolet lamp irradiates electrolyte, in having system existing for tetracycline, institute
The optical electro-chemistry sensor for the nitridation carbon signal amplification stated can generate photoelectric current enhancing, by draw known tetracycline concentration and
The standard curve of photoelectric current, the photoelectric current detected by the optical electro-chemistry sensor based on nitridation carbon signal amplification
Determine the concentration of tetracycline in system to be measured.
8. the application of the optical electro-chemistry sensor according to claim 6 based on nitridation carbon signal amplification, it is characterised in that:
When detecting for the tetracycline in solution, the sequence of aptamers used is 5 '-CGTAC GGAAT TCGCT AGCCC CCCGG
CAGGC CACGG CTTGG GTTGG TCCCA CTGCG CGTGG ATCCG AGCTC CACGT。
9. the application of the optical electro-chemistry sensor according to claim 6 based on nitridation carbon signal amplification, it is characterised in that:
When detecting for the tetracycline in solution, detection range is 0.1-10 nmol/L, and the detection of tetracycline is limited to 0.03 nM.
10. the application of the optical electro-chemistry sensor according to claim 6 based on nitridation carbon signal amplification, feature exist
In: when detecting for the tetracycline in solution, the bias-voltage of GaN working electrode is+0.2-+0.6V.
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