CN109100406A - A kind of rear-earth-doped TiO2The method that optical electro-chemistry sensor quickly detects organophosphorus pesticide - Google Patents
A kind of rear-earth-doped TiO2The method that optical electro-chemistry sensor quickly detects organophosphorus pesticide Download PDFInfo
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Abstract
The invention discloses a kind of rear-earth-doped TiO2The method that optical electro-chemistry sensor reads detection organophosphorus pesticide fastly.The sensor combines rare earth doped TiO with CdSe2As light-sensitive material, under visible light illumination, using the inhibiting effect of electron donor caused by organophosphorous pesticides on acetylcholinesteraseand and its substrate acetylthiocholine, organophosphorus pesticide is detected.Detection range to chlorine pyrazothion is 1ng/mL-100ug/mL, and detection is limited to 0.1ng/mL.The advantages that this method inherits the quick, portable of optical electro-chemistry, cheap, while also there is excellent sensitivity and anti-interference.
Description
Technical field
The invention belongs to field of electrochemical detection, and in particular to a kind of rear-earth-doped TiO2The detection of optical electro-chemistry sensor has
The method of machine phosphorus insecticide.
Background technique
Organophosphorus pesticide (OPs) is a kind of extremely strong neurotoxin, is widely used in agricultural production process,
Convenience, high efficiency and wide applicability are received by people.In recent years, with mankind's development in science and technology progress, Ren Menfa
Existing machine phosphorus insecticide, can its substrate acetyl choline of the irreversible intracorporal acetylcholine ester enzymatic hydrolysis of inhibition people.Lead to people
Intracorporal acetylcholine accumulation, seriously can life threatening so as to cause being overexcited.
Following several method focused primarily upon for the detection of organophosphorus pesticide at present: chromatography, immunization, photometry and
Enzyme inhibition etc..General chromatography sensitivity is low, and poor accuracy often can only qualitative analysis.And some high-end chromatographies, instrument
The heavy complexity of device can not detect when participating in the cintest, and testing cost is high, is not suitable for regular detection.Photometry is that one kind is deposited in color developing agent
Under the conditions, oxidation, esterification, complexing etc. occur with certain functional groups in organophosphorus pesticide to react, so that color is generated, in
This is quantitatively or qualitatively tested and analyzed, but it is easy to interfere, and the case where false negative occurs.Immunization is using anti-
The principle of original antibody specific reaction is detected, so requiring the selection of its reagent often very high.
In the present invention, in conjunction with the rapidity of sensor, and the accuracy of reaction, establish one kind has for quickly detecting
The optical electro-chemistry sensor, method of machine phosphorus insecticide.It proposes to be based on rare earth doped TiO2And combine a step of CdSe unmarked
Sensor detects organophosphorus pesticide for quick and hypersensitization.
Summary of the invention
The purpose of the present invention is intended to construct one kind, and high sensitivity, anti-interference strong, detection time is short, low-cost photoelectricity
Chemical sensor, the detection for organophosphorus pesticide.
A kind of the technical solution adopted by the present invention are as follows: rear-earth-doped TiO2Optical electro-chemistry sensor detects organophosphorus pesticide
Method, steps are as follows:
Step 1, preparation Ho3+Yb3+Adulterate TiO2Quantum dot
Tetrabutyl titanate is dissolved in ethyl alcohol, dropwise addition contains Ho3+Yb3+The concentrated nitric acid solution of ion, after mixing
It is kept for 10 hours for 200 DEG C in a high pressure reaction kettle, collects sediment and washed rear drying.Specifically:
By Ho2O3Yb2O3It is dissolved in concentrated nitric acid respectively, generates Ho3+Yb3+, tetrabutyl titanate is dissolved in ethyl alcohol, magnetic force
It is gradually added dropwise under stirring and contains Ho3+Yb3+The solution of ion, then be sufficiently stirred, it is anti-that uniformly mixed suspension is transferred to high pressure
It answers in kettle, 200 DEG C are kept for 10 hours, are collected sediment and are washed respectively with distilled water and ethyl alcohol, dry under 80 DEG C of vacuum conditions
10 hours.
Step 2, preparation water solubility TGA-CdSe quantum dot solution
Utilize Se powder and NaBH4It is reacted in ultrapure water, prepares precursor solution；
By CdCl2·2.5H2O is dissolved in distilled water, is added thioacetic acid (TGA), pH is adjusted with NaOH, before addition is above-mentioned
Liquid solution is driven, sufficiently obtains water solubility TGA-CdSe solution after reaction under a nitrogen atmosphere.Specifically:
It takes appropriate ultrapure water in 10mL test tube, is passed through high pure nitrogen 3 minutes, respectively by Se powder and NaBH4Successively pour into
In bottle, it is simultaneously stopped logical nitrogen, beyond the Great Wall rubber stopper, reaction a period of time to black Se powder is completely dissolved, to give birth to after reaction
Yellowly clear solution, successfully prepares precursor solution；
By CdCl2·2.5H2O is dissolved in distilled water, and thioacetic acid (TGA) is added under the conditions of magnetic agitation, generates precipitating
Solution adjusts pH with NaOH, is transferred in three-neck flask, sufficiently reacts under condition of nitrogen gas, above-mentioned precursor solution is added, sufficiently
Water solubility TGA-CdSe solution is obtained after reaction.
Step 3, building detection organophosphorus pesticide optical electro-chemistry working sensor electrode
By Ho prepared by step (1)3+Yb3+Adulterate TiO2Quantum dot (Ho3+/Yb3+-TiO2Nanoparticle) it is placed in water
It is uniformly mixed, pipettes 10ul and set on FTO glass, it is dry under condition of nitrogen gas, then 30-90 points are calcined in 400-600 DEG C of Muffle furnace
Clock, preferably are as follows: calcined 30 minutes in 450 DEG C of Muffle furnaces, be cooled to room temperature and water solubility prepared by 8ul step (2) is added dropwise
TGA-CdSe quantum dot solution, it is dry under nitrogen, 10ul enzyme is added dropwise on FTO after the drying and mixes liquid, 4 DEG C of dryings, working electrode
Successfully it is fabricated.
Step 4, detect organophosphorus pesticide optical electro-chemistry sensor application
It is working electrode, platinum filament electricity by detection organophosphorus pesticide optical electro-chemistry working sensor electrode prepared by step 3
Extremely to electrode, saturated calomel electrode is auxiliary electrode, is respectively placed in three electricity of building in the PBS buffer solution containing organophosphorus pesticide
Polar body system, is added 0.5mmol/L acetylthiocholine, and xenon source irradiation carries out electrochemical analysis.The organophosphorus pesticide is
Chlorine pyrazothion.Specific step is as follows:
The preparation of a standard solution: chlorine pyrazothion pesticide standard sample solution is prepared；
The prepared standard solution of step a is added drop-wise in PBS buffer solution by b, obtains the PBS buffering of the sulphur of pyrrole containing chlorine pesticide
Solution；
C will detect the optical electro-chemistry working sensor electrode of organophosphorus pesticide as working electrode, platinum prepared by step 3
Silk electrode is to electrode, and saturated calomel electrode is auxiliary electrode, and the PBS for being respectively placed in the sulphur pesticide of pyrrole containing chlorine of step b acquisition is slow
It rushes and constructs three-electrode system in solution, 0.5mmol/L acetylthiocholine is added, xenon source irradiation carries out electrochemical analysis,
I-T image is that (I-T image is the image that electric current changes over time to experimental basis, has not been added according to addition organophosphorus pesticide and
The difference of the curent change of machine phosphorus insecticide detects pesticide), it draws standard curve and is used to judge that its detection range (linearly becomes
The range of gesture).
According to technical solution above, in step 1, Ho3+The doping (doping concentration) of ion is 1%, Yb3+Ion
Doping (doping concentration) is 3-6%, such as 3%, 4%, 5%, 6%.
According to technical solution above, in step 2, Se, Cd ion populations ratio are 1:1, adjust pH to 9-11 with NaOH, such as
9,10,11, the reaction time 0.5-2h under condition of nitrogen gas.
According to technical solution above, in step 3, Ho3+Yb3+Adulterate TiO2Quantum dot (Ho3+/Yb3+-TiO2Nanoparticle
Son) concentration be 5-20mg/ml, such as 5mg/ml, 10mg/ml, 15mg/ml, 20mg/ml, enzyme mixes liquid by acetylcholinesterase, shell
Glycan solution and bovine serum albumin(BSA) (BSA) composition, the volume ratio of acetylcholinesterase, chitosan solution and BSA are 5:3:2,
Become 5ul acetylcholinesterase, 3ul chitosan solution and 2ul BSA as 8ul enzyme mixes liquid group.
According to technical solution above, in step 4, PBS buffer solution pH is 6-9, such as 6,7,8,9, three electrode spacings
For 1cm.
According to technical solution above, in step 4, organophosphorus pesticide concentration in the PBS buffer solution containing organophosphorus pesticide
For 1ng/mL-100ug/mL.
Inventive sensor combines rare earth doped TiO with CdSe2As light-sensitive material, under visible light illumination, benefit
The electron donor caused by organophosphorous pesticides on acetylcholinesteraseand (AchE) and its substrate acetylthiocholine (ATch)
Inhibiting effect detects organophosphorus pesticide.
Beneficial effects of the present invention: the present invention is prepared for Ho3+/Yb3+-TiO2Material coats FTO as light-sensitive material, building
For optical electro-chemistry sensor for detecting organophosphorus pesticide, advantage and characteristic are as follows out:
(1) rare earth element Ho3+Yb3+Adulterate TiO2, the responding ability of photoelectric current is greatly improved, while optical electro-chemistry passes
The distinctive low background current characteristic of sensor itself, effectively reduces the interference of other factors.
(2)Ho3+/Yb3+-TiO2In conjunction with CdSe nanoparticle, the mutual doping of one side semiconductor improves carrier
Quantity, another aspect CdSe excellent electrochemical properties are exaggerated the responding ability to photoelectric current.
(3) organophosphorus pesticide is detected by acetylcholinesterase and the principle of the interaction of its substrate, greatly improved
The accuracy and anti-interference of experiment.
(4) this method detection organophosphorus pesticide detects organophosphorus pesticide compared with other methods, and detection time shortens, while cost
It is cheap, potential portability etc..
(6) the advantages that this method inherits the quick, portable of optical electro-chemistry, cheap, while also there is excellent sensitivity
And anti-interference.
It (7) is 1ng/mL-100ug/mL to chlorine pyrazothion linear detection range, detection is limited to 0.1ng/mL.
Detailed description of the invention
Fig. 1 is rear-earth-doped TiO2The building principle of optical electro-chemistry sensor；Such as figure: when radiation of visible light, TiO2With
Upper valence-band electrons (the e of CdSe-) can be excited by light radiation to conduction band and form photohole, after ATCh is added in detection architecture at this time
It can be reacted with AChE and generate thiocholine, thiocholine can capture this hole as electron donor, realize photohole and light
Raw electronics (e-) separation, to make light induced electron (e-) it is transferred to electrode surface, form photoelectric current.
Fig. 2 is rear-earth-doped TiO2XRD diagram picture, wherein a curve be Ho3+: Yb3+Ion ratio adulterates TiO when being 1:42, b
Curve is pure TiO2XRD diagram picture；As figure shows, the TiO after rear-earth-doped2Peak compared with standard TiO2It is higher narrower.
Fig. 3 is different Ho3+Yb3+The doping TiO of ratio2UV-Vis image；As figure shows, in Ho3+: Yb3+Ion ratio is
When 1:4, ultravioletvisible absorption situation is best.
Fig. 4 various concentration Yb3+The photoelectricity stream picture of the doping of ion, from left to right doping be respectively 3%, 4%,
5%, 6%, pure TiO2；Such as scheme known, the response for photoelectric current, Ho3+: Yb3+When ion ratio is 1:4, photocurrent response is most
It is high.
Fig. 5 be the corresponding photoelectricity stream picture of various concentration organophosphorus pesticide, wherein a to f be respectively 1ng/mL, 10ng/mL,
100ng/mL, 1ug/mL, 10ug/mL, 100ug/mL, as chlorine pyrazothion concentration increases, downward trend is presented in photoelectric current.
Fig. 6 is standard curve of the photoelectric current with concentration；It is P=-0.6369lgC+ according to fitting experimental data linear equation
5.8238 related coefficient R2=0.997.Wherein P is photo-current intensity, microampere；C is organophosphorus pesticide concentration, ng/mL.
Fig. 7 is the interference that common ion detects chlorine pyrazothion to this method；Known to such as scheming, the above common ion is to detection chlorine
Pyrazothion has not significant impact.
Specific embodiment
Following nonlimiting examples can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Embodiment 1 prepares Ho3+ Yb3+Adulterate TiO2Quantum dot
By 0.038g Ho2O3It is dissolved in 10ml concentrated nitric acid, generates Ho3+；Respectively by 0.118g, 0.158g, 0.197g,
0.236g Yb2O3It is dissolved in 10ml concentrated nitric acid, generates Yb3+；0.02mol tetrabutyl titanate is taken to be dissolved in 30ml ethyl alcohol, magnetic
It is gradually added dropwise prepared by whole under power stirring and contains Ho3+Yb3+The solution of ion, then be sufficiently stirred, it is suspended by what is be uniformly mixed
Liquid is transferred in autoclave, and 200 DEG C are kept for 10 hours；It collects sediment and washs 3 times respectively with distilled water and ethyl alcohol, 80
It is 10 hours dry under DEG C vacuum condition, it can be prepared by Ho3+Yb3+The TiO of doping2Quantum dot (Ho3+/Yb3+-TiO2Nanoparticle),
Wherein Ho3+: Yb3+Ion ratio is respectively 1:3,1:4,1:5,1:6.
Embodiment 2 prepares water-soluble TGA-CdSe quantum dot solution
It takes 3mL ultrapure water in 10mL test tube, is passed through high pure nitrogen 3 minutes, respectively by 0.04g Se powder and 0.12g
NaBH4It successively pours into bottle, is simultaneously stopped logical nitrogen, beyond the Great Wall rubber stopper, reaction a period of time to black Se powder is completely dissolved, to
Yellow clear solution is generated after reaction, successfully prepares precursor solution；
By 1.14g CdCl2·2.5H2O is dissolved in ultrapure water, and 120uL thioacetic acid is added under the conditions of magnetic agitation
(TGA), solution generates precipitating immediately, adjusts pH to 11 with 1M NaOH, is transferred in three-neck flask, and lower 30 DEG C of condition of nitrogen gas add
Heat 1 hour is rapidly added above-mentioned precursor solution, 30 DEG C of reaction temperature, sufficiently reaction 1 hour, i.e. acquisition water solubility TGA-
CdSe solution.
The building detection organophosphorus pesticide optical electro-chemistry working sensor electrode of embodiment 3
Weigh Ho prepared by embodiment 13+/Yb3+-TiO2Nanoparticle is placed in 10mL ultrapure water and is ultrasonically treated to suspended
Liquid is uniformly mixed, and is pipetted 10ul and is placed on FTO glass, dry under condition of nitrogen gas, then is calcined 30 minutes in 450 DEG C of Muffle furnaces,
It is cooled to room temperature and water-soluble TGA-CdSe quantum dot solution prepared by 8ul embodiment 2 is added dropwise, dry 30min, ultrapure under nitrogen
10ul enzyme is added dropwise on FTO after the drying and mixes liquid for water cleaning electrode surface, and 4 DEG C of refrigerators are placed, until dry, working electrode at
Function is fabricated, the specific steps are as follows:
(1) by wide 1cm long 2cmFTO glass, 15min is successively cleaned by ultrasonic in acetone, water and alcohol mixeding liquid, water, clearly
It is put in baking oven and dries after wash clean；
(2) Ho is taken3+: Yb3+Ion ratio is the Ho of 1:43+/Yb3+-TiO2Nanoparticle is in 10ml water, wherein Ho3+/Yb3 +-TiO2Nanoparticle is respectively 0.05g, 0.1g, 0.15g, 0.2g, makes Ho3+/Yb3+-TiO2The concentration of nanoparticle is respectively
5mg/ml, 10mg/ml, 15mg/ml, 20mg/ml pipette 10ul and set on FTO glass until suspension is uniformly mixed, nitrogen item
It is dry under part, then calcined 30 minutes in 450 DEG C of Muffle furnaces, it is cooled to room temperature；
(3) take 8ul TGA-CdSe quantum dot solution in above-mentioned Ho3+/Yb3+-TiO2Nanoparticle film surface is done under nitrogen
Dry 30 minutes, and with ultrapure water cleaning electrode surface；
(4) continue to be added dropwise on the FTO glass after dry 10ul enzyme mix liquid (enzyme, which mixes liquid group, becomes 5ul acetylcholinesterase,
3ul chitosan solution, 2ul BSA), 4 DEG C of refrigerators are placed, until dry, working electrode is successfully fabricated.
Embodiment 4
Organophosphorus pesticide sensor prepared by embodiment 3 is used for the sensitivity detection of chlorine pyrazothion, steps are as follows:
(1) the chlorine pyrazothion standard solution of various concentration gradient is prepared；Concentration be respectively 20ng/mL, 200ng/mL,
2ug/mL,20ug/mL,200ug/mL,2mg/mL；
(2) the prepared standard solution 1mL of step (1) is taken to be added drop-wise in 19mL PBS buffer solution, 20 times of extension rate,
It obtains institute's detectable concentration and is respectively as follows: 1ng/mL, 10ng/mL, 100ng/mL, 1ug/mL, 10ug/mL, 100ug/mL；
(3) by electrode (Ho prepared by embodiment 33+/Yb3+-TiO2The concentration of nanoparticle is 5mg/ml) it is used as work
Electrode, platinum electrode are to electrode, and saturated calomel electrode is auxiliary electrode, are respectively placed in the sulphur agriculture of pyrrole containing chlorine of step (2) acquisition
Three-electrode system is constructed in the PBS buffer solution of medicine, 0.5mmol/L acetylthiocholine, xenon source irradiation is added in pH=7
Electrochemical analysis is carried out, i-t image is experimental basis (Fig. 5), is drawn standard curve (Fig. 6)；Organophosphorus pesticide (chlorine pyrazothion)
Linear detection range be 1ng/mL-100ug/mL, detection be limited to 0.1ng/mL.
Embodiment 5
Organophosphorus pesticide sensor prepared by embodiment 3 is used for the interference experiment of chlorine pyrazothion:
Three-electrode system, difference are as follows: respectively to electrolyte solution (in embodiment 4 are constructed according to method as described in example 4
Obtain the PBS buffer solution containing chlorine pyrazothion and 0.5mmol/L acetylthiocholine mixed solution) in add 0.1M
Ca2+、Mg2+、SO4 2-、NO3 -Ion detects influence of the various common ions to sensor detection chlorine pyrazothion, experimental result table
Bright: the above common ion has not significant impact (Fig. 7) to detection chlorine pyrazothion.
For any person skilled in the art, without departing from the scope of the technical proposal of the invention, all
Many possible changes and modifications are made to technical solution of the present invention using the technology contents of the disclosure above, or are revised as equivalent
The equivalent embodiment of variation.Therefore, anything that does not depart from the technical scheme of the invention, according to the technical essence of the invention to
Any simple modifications, equivalents, and modifications that upper embodiment is done should all still fall within the range of technical solution of the present invention protection
It is interior.
Claims (8)
1. a kind of rear-earth-doped TiO2The method of optical electro-chemistry sensor detection organophosphorus pesticide, which is characterized in that steps are as follows:
Step 1, preparation Ho3+Yb3+Adulterate TiO2Quantum dot
Tetrabutyl titanate is dissolved in ethyl alcohol, is gradually added dropwise and contains Ho3+Yb3+Concentrated nitric acid solution, after mixing in height
It presses in reaction kettle and is kept for 10 hours for 200 DEG C, collect sediment and washed rear drying；
Step 2, preparation water solubility TGA-CdSe quantum dot solution
Utilize Se powder and NaBH4It is reacted in ultrapure water, prepares precursor solution；
By CdCl2·2.5H2O is dissolved in distilled water, and TGA is added, and is adjusted pH with NaOH, above-mentioned precursor solution is added, in nitrogen
Under the conditions of sufficiently react after i.e. obtain water solubility TGA-CdSe solution；
Step 3, building detection organophosphorus pesticide optical electro-chemistry working sensor electrode
By Ho prepared by step (1)3+Yb3+Adulterate TiO2Quantum dot is placed in water uniformly mixed, pipettes 10ul and sets FTO glass
On, it is dry under condition of nitrogen gas, then calcined 30-90 minutes in 400-600 DEG C of Muffle furnace, it is cooled to room temperature and 8ul step is added dropwise
(2) the TGA-CdSe quantum dot solution prepared by, it is dry under nitrogen, 10ul enzyme is added dropwise on FTO after the drying and mixes liquid, 4 DEG C are dry
It is dry；
Step 4, detect organophosphorus pesticide optical electro-chemistry sensor application
It is working electrode by detection organophosphorus pesticide optical electro-chemistry working sensor electrode prepared by step 3, platinum electrode is
To electrode, saturated calomel electrode is auxiliary electrode, is respectively placed in the PBS buffer solution containing organophosphorus pesticide and constructs three electrode bodies
System, is added 0.5mmol/L acetylthiocholine, and xenon source irradiation carries out electrochemical analysis.
2. rear-earth-doped TiO according to claim 12The method that optical electro-chemistry sensor detects organophosphorus pesticide, step 1
In, Ho3+The doping concentration of ion is 1%, Yb3+The doping concentration of ion is 3-6%.
3. rear-earth-doped TiO according to claim 12The method that optical electro-chemistry sensor detects organophosphorus pesticide, feature
It is, in step 2, Se, Cd ion populations ratio are 1:1, adjust pH to 9-11 with NaOH, and the reaction time under condition of nitrogen gas is
0.5-2h。
4. rear-earth-doped TiO according to claim 12The method that optical electro-chemistry sensor detects organophosphorus pesticide, feature
It is, in step 3, Ho3+Yb3+Adulterate TiO2The concentration of quantum dot is 5-20mg/ml.
5. rear-earth-doped TiO according to claim 12The method that optical electro-chemistry sensor detects organophosphorus pesticide, feature
It is, in step 3, enzyme mixes liquid and is made of acetylcholinesterase, chitosan solution and BSA, acetylcholinesterase, chitosan solution
Volume ratio with BSA is 5:3:2.
6. rear-earth-doped TiO according to claim 12The method that optical electro-chemistry sensor detects organophosphorus pesticide, feature
It is, in step 4, the pH of PBS buffer solution is 6-9.
7. rear-earth-doped TiO according to claim 12The method that optical electro-chemistry sensor detects organophosphorus pesticide, feature
It is, organophosphorus pesticide is chlorine pyrazothion.
8. rear-earth-doped TiO according to claim 1 or claim 72The method that optical electro-chemistry sensor detects organophosphorus pesticide,
It is characterized in that, in step 4, organophosphorus pesticide concentration is 1ng/mL-100ug/mL in the PBS buffer solution containing organophosphorus pesticide.
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| CN109781817A (en) * | 2019-02-19 | 2019-05-21 | 大连工业大学 | A kind of Photoelectrochemistrbiosensor biosensor and preparation method thereof detecting vibrio parahemolyticus |
| CN109959684A (en) * | 2019-03-25 | 2019-07-02 | 扬州工业职业技术学院 | Preparation, the remaining method of the detection dead tick of vegetable poisoning and the detection device of double identification type chlopyrifos sensors |
| CN109959684B (en) * | 2019-03-25 | 2021-07-13 | 扬州工业职业技术学院 | Preparation of double-identification type chlorpyrifos sensor, method for detecting chlorpyrifos residues in vegetables and detection device |
| CN110068570A (en) * | 2019-04-03 | 2019-07-30 | 济南大学 | A kind of preparation of the electrochemical sensor shown with instant visualization colorimetric |
| CN110068570B (en) * | 2019-04-03 | 2021-05-25 | 济南大学 | Preparation of electrochemical sensor with instant visual colorimetric display |
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