CN105628758B - A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material - Google Patents

A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material Download PDF

Info

Publication number
CN105628758B
CN105628758B CN201610102027.0A CN201610102027A CN105628758B CN 105628758 B CN105628758 B CN 105628758B CN 201610102027 A CN201610102027 A CN 201610102027A CN 105628758 B CN105628758 B CN 105628758B
Authority
CN
China
Prior art keywords
electrode
parathion
chemistry
moo
tio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610102027.0A
Other languages
Chinese (zh)
Other versions
CN105628758A (en
Inventor
张勇
庞雪辉
李燕
王晓东
魏琴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN201610102027.0A priority Critical patent/CN105628758B/en
Publication of CN105628758A publication Critical patent/CN105628758A/en
Application granted granted Critical
Publication of CN105628758B publication Critical patent/CN105628758B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements

Abstract

The invention discloses a kind of preparation method of optical electro-chemistry parathion sensor.Belong to Nano-function thin films and biosensor technology field.The method comprises the steps of firstly, preparing a kind of New Two Dimensional nanometer light-sensitive material Mn MoO3/TiO2@g‑C3N4, good biocompatibility and big specific surface area using the material, parathion antibody in load, then alkaline phosphatase is fixed by the crosslinked action of glutaraldehyde, when being detected, because alkaline phosphatase can be catalyzed, the tricresyl phosphate sodium salt AAP of L ascorbic acid 2 is in situ to produce L ascorbic acid AA, and and then provide electron donor for Photoelectric Detection, antibody is recycled to be combined the influence to electron transport ability with the specific quantification of antigen, so that photo-current intensity accordingly reduces, it is low that cost finally has been made, high sensitivity, specificity is good, detection is quick, prepare the unmarked Photoelectrochemistrbiosensor biosensor of simple detection parathion.

Description

A kind of preparation of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material Method and application
Technical field
The present invention relates to a kind of preparation method of optical electro-chemistry parathion sensor.Belong to Nano-function thin films and life Thing sensor technical field.
Background technology
Parathion is a kind of broad spectrum activity high poison insecticide, have tag, stomach toxicity, fumigation action, and plant can be infiltrated through It is interior.Parathion is acted on insect quickly, available for fruit tree pest insects and wheat red mite etc. such as preventing and treating cotton, apple, citrus, pears, peaches. In soil, parathion can slightly be migrated by the eluviation of water to deep subsoil.Parathion in soil can pass through plant Thing root absorption and enter plant in.After people eat this kind of plant or plant containing its residue by mistake, parathion can pass through Alimentary canal, respiratory tract and complete skin and mucous membrane enter human body, it may appear that Nausea and vomiting, have a headache, have loose bowels, whole body weakness nothing The preliminary symptom of the poisonings such as power, long-term consumption or excessive eat can cause canceration.
At present, the method for detecting parathion mainly has chromatography, mass spectrography etc..Such method instrument is valuable, complex operation, Laboratory personnel could be detected after needing professional training.Therefore, R&D costs are low, detection is fast, high sensitivity, high specificity Parathion sensor is significant.
Optical electro-chemistry sensor due to high sensitivity, testing cost is low the features such as, in recent years by increasing researcher It is of interest.Optical electro-chemistry sensor is to cause electron-hole pair to be separated based on additional light source activation Electrophotosensitivmaterial material, Under suitable potential condition partially, quick transmission of the electronics on electrode, semiconductor and trim and analyte is realized, and form light Electric current.In optimal conditions, combined using biological immune, the change of analyte concentration can directly affect the size of photoelectric current, just The qualitative and quantitative analysis to analyte can be realized according to the change of photoelectric current.
Optical electro-chemistry sensor most critical technology is exactly the raising to performances such as the size of photoelectric current and stability.Titanium dioxide Titanium is a kind of photochemical catalyst and the light induced electron host material being most widely used, because sheet-like titanium dioxide nanomaterial can The more high miller index surfaces of exposure, have higher photocatalytic activity, and titanium dioxide nanoplate has than nano-particle preferably Application prospect, the research for titanium dioxide nanoplate also receive much concern.And the photoproduction electricity of single titanium dioxide nano material Son-hole is to easily compound, and so as to cause the decrease of photosignal, and titanium dioxide poorly conductive also limit by single dioxy It is universal not high to change the sensitivity of the optical electro-chemistry sensor of titanium nano material structure, is unfavorable for practical application.But in semiconductor Modification or compound special nano material in nano material, the valid density of photo-generated carrier pair can be effectively improved, improves light Photoelectric transformation efficiency, and greatly improve detection sensitivity.Therefore, design, prepare titanium dioxide nanoplate efficiently, stable and its repair Jewelry is the key technology for preparing optical electro-chemistry sensor.
The content of the invention
Prepare that simple, high sensitivity, detection be quick, optical electro-chemistry of high specificity it is an object of the invention to provide a kind of The preparation method of parathion sensor, prepared sensor, quick, Sensitive Detection available for parathion.Based on this purpose, The method comprises the steps of firstly, preparing a kind of New Two Dimensional nanometer light-sensitive material, i.e., molybdenum oxide/bis- of In-situ reaction additive Mn on carbonitride The two-dimensional nano composite Mn-MoO of TiOx nano piece3/TiO2@g-C3N4, utilize the good biocompatibility of the material With big specific surface area, parathion antibody in load, alkaline phosphatase is then fixed by the crosslinked action of glutaraldehyde, carried out During detection, because alkaline phosphatase can be catalyzed, L-AA -2- tricresyl phosphate sodium salts AAP is in situ to produce L-AA AA, And and then provide electron donor for Photoelectric Detection, recycle antibody to be combined with the specific quantification of antigen to electron transport ability Influence so that photo-current intensity accordingly reduces, and finally realizes the life using unmarked PhotoelectrochemicalMethod Method detection parathion The structure of thing sensor.
The technical solution adopted by the present invention is as follows:
1. a kind of preparation method of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material, described two Wiener rice light-sensitive material is the two-dimensional nano composite wood of molybdenum oxide/titanium dioxide nanoplate of In-situ reaction additive Mn on carbonitride Expect Mn-MoO3/TiO2@g-C3N4, described optical electro-chemistry parathion sensor is by working electrode, Mn-MoO3/TiO2@g-C3N4、 Parathion antibody, bovine serum albumin(BSA), glutaraldehyde, alkaline phosphatase composition;
Characterized in that, described preparation method includes following preparation process:
a. Mn-MoO3/TiO2@g-C3N4Preparation;
B. the preparation of optical electro-chemistry parathion sensor;
Wherein, step a prepares Mn-MoO3/TiO2@g-C3N4Concretely comprise the following steps:
First, take 0.6 ~ 1.0 mmol sodium molybdates and 0.8 ~ 1.2 mmol manganese salts to be added in 5 mL butyl titanates, stir During mixing, 0.5 ~ 0.8 mL hydrofluoric acid is slowly added to, reacts 18 ~ 24 hours, is cooled in a kettle at 160 ~ 200 DEG C After room temperature, with ultra-pure water and absolute ethyl alcohol centrifuge washing three times after, be dried in vacuo at 50 DEG C;Secondly, 150 ~ 250 mg are taken to dry Solid afterwards mixes with 400 mg melamines, and grind into powder;Then, the powder of grinding is put into Muffle furnace, heated up Speed is 1 ~ 3 DEG C/min, is calcined 0.5 ~ 5 hour at 480 ~ 560 DEG C;Finally, the powder after calcining is cooled to room temperature, i.e., Mn-MoO is made3/TiO2@g-C3N4
Described manganese salt is selected from one of following:Manganese sulfate, manganese chloride, manganese nitrate;
Step b prepares concretely comprising the following steps for optical electro-chemistry parathion sensor:
(1)Using ITO electro-conductive glass as working electrode, in the μ L of electrode surface drop coating 8 ~ 12 Mn-MoO3/TiO2@g-C3N4 Colloidal sol, dry at room temperature;
(2)By step(1)In obtained electrode cushioning liquid PBS, continue in the μ L of electrode surface drop coating 8 ~ 12 10 μ g/mL parathion antibody-solutions, preserve in 4 DEG C of refrigerators and dry;
(3)By step(2)In obtained electrode PBS, it is 100 to continue in the μ L concentration of electrode surface drop coating 8 ~ 12 μ g/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry;
(4)By step(3)In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 2 ~ 4 is molten Liquid, preserve in 4 DEG C of refrigerators and dry;
(5)By step(4)In obtained electrode PBS, it is 20 μ to continue in the μ L concentration of electrode surface drop coating 6 ~ 10 G/mL alkaline phosphatase enzyme solutions, preserve in 4 DEG C of refrigerators and dry;
(6)By step(5)In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, photoelectricity be made Chemical parathion sensor;
Described Mn-MoO3/TiO2@g-C3N4Colloidal sol is by 50 mg Mn-MoO3/TiO2@g-C3N4Powder is dissolved in 10 In mL ultra-pure waters, and the obtained hydrosol after 30 min of ultrasound;
Described PBS is 10mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4;
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
2. the application of the optical electro-chemistry parathion sensor prepared by preparation method of the present invention, it is characterised in that Including following applying step:
A. standard liquid is prepared:Prepare the parathion standard liquid of one group of various concentrations including blank standard specimen;
B. working electrode is modified:By the optical electro-chemistry parathion sensor prepared by preparation method as described in the present invention For working electrode, the parathion standard liquid for the various concentrations prepared in step a is distinguished into drop coating to working electrode surface, 4 DEG C Preserved in refrigerator;
C. working curve is drawn:Using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step The working electrode composition three-electrode system that rapid b has been modified, is connected on optical electro-chemistry detection device;Successively add in a cell Enter 15mL pH=5.4 Tris-HCl cushioning liquid and the mmol/L of 5 mL 10 L-AA -2- tricresyl phosphate sodium salts AAP it is molten Liquid;Using i-t means of testing, according to the relation between the photocurrent values of gained and parathion concentration of standard solution, drawing Curve;
D. the detection of parathion:The parathion standard liquid in step a is replaced with testing sample, according in step b and c Method detected, according to the photocurrent values and working curve of gained, obtain the content of parathion in testing sample.
The useful achievement of the present invention
(1)Optical electro-chemistry parathion sensor of the present invention is prepared simply, easy to operate, is realized to the fast of sample Fast, sensitive, high selectivity detection, and cost is low, can be applied to portable inspectiont, has market development prospect;
(2)The present invention is prepared for New Two Dimensional light-sensitive material Mn-MoO first3/TiO2@g-C3N4, due to manganese molybdenum oxide/ Growth in situ on titanium dioxide nanoplate and fully contacted with titanium dioxide nanoplate, utilize the metal surface plasma body of manganese The mutual promoting action of both effect and molybdenum oxide and titanium dioxide, effectively prevents the compound of photo-generate electron-hole pair, solves Although titanium dioxide nanoplate photocatalysis effect of having determined is good, photoelectric current produces less technical problem;Simultaneously because nitridation Carbon g-C3N4Good electric conductivity and molybdenum oxide/titanium dioxide nanoplate it is fully dispersed thereon, greatly increase oxidation The photocatalytic activity of molybdenum/titanium dioxide nanoplate and solve molybdenum oxide/titanium dioxide nanoplate poorly conductive and be unfavorable for making The technical problem of standby optical electro-chemistry sensor, therefore, effective preparation of the material, there is important scientific meaning and using valency Value;
(3)The present invention is first by Mn-MoO3/TiO2@g-C3N4Applied in the preparation of Photoelectrochemistrbiosensor biosensor, show The valid density for improving photo-generated carrier is write, substantially increases the detection sensitivity of optical electro-chemistry sensor so that photoelectrochemical Biosensors realize the application in real work;The application of the material, also it is associated biomolecule sensor, such as electroluminescentization Learn luminescence sensor, electrochemical sensor etc. and provide Technical Reference, there is extensive potential use value.
Embodiment
The Mn-MoO of embodiment 13/TiO2@g-C3N4Preparation
First, 0.6 mmol sodium molybdates and 0.8 mmol manganese salts is taken to be added in 5 mL butyl titanates, in whipping process, 0.5 mL hydrofluoric acid is slowly added to, is reacted in a kettle at 160 DEG C 24 hours, after being cooled to room temperature, with ultra-pure water and anhydrous Ethanol centrifuge washing three times after, be dried in vacuo at 50 DEG C;Secondly, the dried solids of 150 mg are taken to be mixed with 400 mg melamines Close, and grind into powder;Then, the powder of grinding is put into Muffle furnace, programming rate is 1 DEG C/min, at 480 DEG C Calcining 5 hours;Finally, the powder after calcining is cooled to room temperature, that is, Mn-MoO is made3/TiO2@g-C3N4
Described manganese salt is manganese sulfate.
The Mn-MoO of embodiment 23/TiO2@g-C3N4Preparation
First, 0.8 mmol sodium molybdates and 1.0 mmol manganese salts are taken to be added in 5 mL butyl titanates, in whipping process, 0.65 mL hydrofluoric acid is slowly added to, is reacted in a kettle at 180 DEG C 21 hours, after being cooled to room temperature, with ultra-pure water and nothing Water-ethanol centrifuge washing three times after, be dried in vacuo at 50 DEG C;Secondly, the dried solids of 200 mg and 400 mg melamines are taken Mixing, and grind into powder;Then, the powder of grinding is put into Muffle furnace, programming rate is 2 DEG C/min, at 520 DEG C Lower calcining 2 hours;Finally, the powder after calcining is cooled to room temperature, that is, Mn-MoO is made3/TiO2@g-C3N4
Described manganese salt is manganese chloride.
The Mn-MoO of embodiment 33/TiO2@g-C3N4Preparation
First, 1.0 mmol sodium molybdates and 1.2 mmol manganese salts are taken to be added in 5 mL butyl titanates, in whipping process, 0.8 mL hydrofluoric acid is slowly added to, is reacted in a kettle at 200 DEG C 18 hours, after being cooled to room temperature, with ultra-pure water and nothing Water-ethanol centrifuge washing three times after, be dried in vacuo at 50 DEG C;Secondly, the dried solids of 250 mg and 400 mg melamines are taken Mixing, and grind into powder;Then, the powder of grinding is put into Muffle furnace, programming rate is 3 DEG C/min, at 560 DEG C Calcining 0.5 hour;Finally, the powder after calcining is cooled to room temperature, that is, Mn-MoO is made3/TiO2@g-C3N4
Described manganese salt is manganese nitrate.
The preparation method of the optical electro-chemistry parathion sensor of embodiment 4
(1)Using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, the μ L's of electrode surface drop coating 8 Mn-MoO3/TiO2@g-C3N4Colloidal sol, dry at room temperature;
(2)By step(1)In obtained electrode cushioning liquid PBS, continue in the μ of 8 μ L of electrode surface drop coating 10 G/mL parathion antibody-solutions, preserve in 4 DEG C of refrigerators and dry;
(3)By step(2)In obtained electrode PBS, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 8 G/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry;
(4)By step(3)In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 2 is molten Liquid, preserve in 4 DEG C of refrigerators and dry;
(5)By step(4)In obtained electrode PBS, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 6 ML alkaline phosphatase enzyme solutions, preserve in 4 DEG C of refrigerators and dry;
(6)By step(5)In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, photoelectricity be made Chemical parathion sensor;
Described Mn-MoO3/TiO2@g-C3N4Colloidal sol is by 50 mg Mn-MoO3/TiO2@g-C3N4Powder is dissolved in 10 In mL ultra-pure waters, and the obtained hydrosol after 30 min of ultrasound;
Described PBS is 10mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4;
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
The preparation method of the optical electro-chemistry parathion sensor of embodiment 5
(1)Using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, the μ L's of electrode surface drop coating 10 Mn-MoO3/TiO2@g-C3N4Colloidal sol, dry at room temperature;
(2)By step(1)In obtained electrode cushioning liquid PBS, continue in the μ L 10 of electrode surface drop coating 10 μ g/mL parathion antibody-solutions, preserve in 4 DEG C of refrigerators and dry;
(3)By step(2)In obtained electrode PBS, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 10 G/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry;
(4)By step(3)In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 3 is molten Liquid, preserve in 4 DEG C of refrigerators and dry;
(5)By step(4)In obtained electrode PBS, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 8 ML alkaline phosphatase enzyme solutions, preserve in 4 DEG C of refrigerators and dry;
(6)By step(5)In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, photoelectricity be made Chemical parathion sensor;
Described Mn-MoO3/TiO2@g-C3N4Colloidal sol is by 50 mg Mn-MoO3/TiO2@g-C3N4Powder is dissolved in 10 In mL ultra-pure waters, and the obtained hydrosol after 30 min of ultrasound;
Described PBS is 10 mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4;
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
The preparation method of the optical electro-chemistry parathion sensor of embodiment 6
(1)Using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, the μ L's of electrode surface drop coating 12 Mn-MoO3/TiO2@g-C3N4Colloidal sol, dry at room temperature;
(2)By step(1)In obtained electrode cushioning liquid PBS, continue in the μ L 10 of electrode surface drop coating 12 μ g/mL parathion antibody-solutions, preserve in 4 DEG C of refrigerators and dry;
(3)By step(2)In obtained electrode PBS, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 12 G/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry;
(4)By step(3)In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 4 is molten Liquid, preserve in 4 DEG C of refrigerators and dry;
(5)By step(4)In obtained electrode PBS, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 10 ML alkaline phosphatase enzyme solutions, preserve in 4 DEG C of refrigerators and dry;
(6)By step(5)In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, photoelectricity be made Chemical parathion sensor;
Described Mn-MoO3/TiO2@g-C3N4Colloidal sol is by 50 mg Mn-MoO3/TiO2@g-C3N4Powder is dissolved in 10 In mL ultra-pure waters, and the obtained hydrosol after 30 min of ultrasound;
Described PBS is 10 mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4;
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
Optical electro-chemistry parathion sensor prepared by the embodiment 1 ~ 6 of embodiment 7, applied to the detection of parathion, step is such as Under:
(1)Standard liquid is prepared:Prepare the parathion standard liquid of one group of various concentrations including blank standard specimen;
(2)Working electrode is modified:By the optical electro-chemistry parathion sensor prepared by preparation method as described in the present invention For working electrode, by step(1)The parathion standard liquids of the various concentrations of middle preparation distinguishes drop coating to working electrode surface, and 4 Preserved in DEG C refrigerator;
(3)Working curve is drawn:Using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step Suddenly(2)The working electrode composition three-electrode system modified, is connected on optical electro-chemistry detection device;In a cell successively Add the Tris-HCl cushioning liquid of 15mL pH=5.4 and the mmol/L of 5 mL 10 L-AA -2- tricresyl phosphate sodium salts AAP Solution;Using i-t means of testing, according to the relation between the photocurrent values of gained and parathion concentration of standard solution, work is drawn Make curve;The linear detection range of parathion is:0.003 ~ 200 ng/mL, detection are limited to:1.0 pg/mL;
(4)Actual sample detects:Step is replaced with testing sample(1)In parathion standard liquid, according to step(2)With (3)In method detected, according to the photocurrent values and working curve of gained, obtain the content of parathion in testing sample.

Claims (2)

1. a kind of preparation method of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material, described two-dimensional nano Light-sensitive material is the two-dimensional nano composite Mn- of molybdenum oxide/titanium dioxide nanoplate of In-situ reaction additive Mn on carbonitride MoO3/TiO2@g-C3N4, described optical electro-chemistry parathion sensor is by working electrode, Mn-MoO3/TiO2@g-C3N4, parathion Antibody, bovine serum albumin(BSA), glutaraldehyde, alkaline phosphatase composition;
Characterized in that, described preparation method includes following preparation process:
a. Mn-MoO3/TiO2@g-C3N4Preparation;
B. the preparation of optical electro-chemistry parathion sensor;
Wherein, step a prepares Mn-MoO3/TiO2@g-C3N4Concretely comprise the following steps:
First, 0.6 ~ 1.0 mmol sodium molybdates and 0.8 ~ 1.2 mmol manganese salts is taken to be added in 5 mL butyl titanates, it is stirred Cheng Zhong, 0.5 ~ 0.8 mL hydrofluoric acid is slowly added to, is reacted in a kettle at 160 ~ 200 DEG C 18 ~ 24 hours, is cooled to room temperature Afterwards, with ultra-pure water and absolute ethyl alcohol centrifuge washing three times after, be dried in vacuo at 50 DEG C;Secondly, take 150 ~ 250 mg dried Solid mixes with 400 mg melamines, and grind into powder;Then, the powder of grinding is put into Muffle furnace, programming rate For 1 ~ 3 DEG C/min, calcined 0.5 ~ 5 hour at 480 ~ 560 DEG C;Finally, the powder after calcining is cooled to room temperature, that is, be made Mn-MoO3/TiO2@g-C3N4
Described manganese salt is selected from one of following:Manganese sulfate, manganese chloride, manganese nitrate;
Step b prepares concretely comprising the following steps for optical electro-chemistry parathion sensor:
(1)Using ITO electro-conductive glass as working electrode, in the μ L of electrode surface drop coating 8 ~ 12 Mn-MoO3/TiO2@g-C3N4Colloidal sol, Dry at room temperature;
(2)By step(1)In obtained electrode cushioning liquid PBS, continue in the μ of 8 ~ 12 μ L of electrode surface drop coating 10 G/mL parathion antibody-solutions, preserve in 4 DEG C of refrigerators and dry;
(3)By step(2)In obtained electrode PBS, it is 100 μ g/ to continue in the μ L concentration of electrode surface drop coating 8 ~ 12 ML bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry;
(4)By step(3)In obtained electrode PBS, continue the glutaraldehyde solution in the μ L of electrode surface drop coating 2 ~ 4,4 Preserve and dry in DEG C refrigerator;
(5)By step(4)In obtained electrode PBS, it is 20 μ g/mL to continue in the μ L concentration of electrode surface drop coating 6 ~ 10 Alkaline phosphatase enzyme solutions, preserve in 4 DEG C of refrigerators and dry;
(6)By step(5)In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, optical electro-chemistry be made Parathion sensor;
Described Mn-MoO3/TiO2@g-C3N4Colloidal sol is by 50 mg Mn-MoO3/TiO2@g-C3N4Powder is dissolved in 10 mL and surpassed In pure water, and the obtained hydrosol after 30 min of ultrasound;
Described PBS is 10mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4;
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
2. the application of the optical electro-chemistry parathion sensor prepared by preparation method as claimed in claim 1, it is characterised in that Including following applying step:
A. standard liquid is prepared:Prepare the parathion standard liquid of one group of various concentrations including blank standard specimen;
B. working electrode is modified:It is by the optical electro-chemistry parathion sensor prepared by preparation method as claimed in claim 1 Working electrode, the parathion standard liquids of the various concentrations prepared in step a is distinguished into drop coating to working electrode surface, 4 DEG C Preserved in refrigerator;
C. working curve is drawn:Using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step b institutes The working electrode composition three-electrode system modified, is connected on optical electro-chemistry detection device;Successively add in a cell Tris-HCl the cushioning liquid of 15mL pH=5.4 and the mmol/L of 5 mL 10 L-AA -2- tricresyl phosphate sodium salts AAP are molten Liquid;Using i-t means of testing, according to the relation between the photocurrent values of gained and parathion concentration of standard solution, drawing Curve;
D. the detection of parathion:The parathion standard liquid in step a is replaced with testing sample, according to the side in step b and c Method is detected, and according to the photocurrent values and working curve of gained, obtains the content of parathion in testing sample.
CN201610102027.0A 2016-02-25 2016-02-25 A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material Active CN105628758B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610102027.0A CN105628758B (en) 2016-02-25 2016-02-25 A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610102027.0A CN105628758B (en) 2016-02-25 2016-02-25 A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material

Publications (2)

Publication Number Publication Date
CN105628758A CN105628758A (en) 2016-06-01
CN105628758B true CN105628758B (en) 2017-12-01

Family

ID=56043893

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610102027.0A Active CN105628758B (en) 2016-02-25 2016-02-25 A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material

Country Status (1)

Country Link
CN (1) CN105628758B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106248753B (en) * 2016-07-05 2019-03-12 济南大学 A kind of preparation method of the optical electro-chemistry Spanon sensor based on load type double-metal codope photosensitizer
CN106198668B (en) * 2016-07-05 2019-03-12 济南大学 A kind of preparation method of the optical electro-chemistry demeton sensor based on cobalt doped two-dimensional nano photoelectric material
CN106124590B (en) * 2016-07-05 2019-03-12 济南大学 A kind of preparation method of electrochemistry malathion sensor
CN106290528B (en) * 2016-07-27 2018-08-17 福建师范大学 One kind being based on TiO2It is situated between and sees the trypsase optical electro-chemistry detection method of crystal
CN106290514B (en) * 2016-10-16 2018-11-13 福建师范大学 A kind of TiO based on silicon phthalocyanine functionalization2It is situated between and sees the aflatoxin optical electro-chemistry detection method of crystal
CN106383156B (en) * 2016-10-16 2018-08-24 福建师范大学 One kind being based on TiO2It is situated between and sees the zearalenone optical electro-chemistry detection method of crystal
CN107255658B (en) * 2017-07-10 2019-08-27 山东利源康赛环境咨询有限责任公司 A kind of optical electro-chemistry diethylstilbestrol biosensor and its preparation and application based on the building of boron doping multi-element metal oxide
CN108872353B (en) * 2018-07-13 2020-04-14 广西壮族自治区农业科学院农产品质量安全与检测技术研究所 Electrochemical method for detecting parathion pesticide

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104777201A (en) * 2015-04-16 2015-07-15 湖北民族学院 Method for preparing electrochemical sensor for detecting parathion

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07100603B2 (en) * 1987-08-17 1995-11-01 住友電気工業株式会社 Composite carbonitride manufacturing method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104777201A (en) * 2015-04-16 2015-07-15 湖北民族学院 Method for preparing electrochemical sensor for detecting parathion

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
g-C3N4/TiO2复合纳米材料的制备及其光催化性能分析;傅遍红 等;《功能材料》;20140630;第45卷(第12期);12138-12144 *
Visible-light-induced blue MoO3–C3N4 composite with enhanced photocatalytic activity;Yeping Li,et al.;《Materials Research Bulletin》;20150512;第70卷;500-505 *
负载金属对MoO3-TiO2光催化剂结构与催化性能的影响;梅长松 等;《燃料化学学报》;20050425;第33卷(第2期);229-234 *

Also Published As

Publication number Publication date
CN105628758A (en) 2016-06-01

Similar Documents

Publication Publication Date Title
CN105628758B (en) A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material
CN105572197B (en) A kind of preparation method and application of the optical electro-chemistry estradiol sensor based on magnetic Nano light-sensitive material
CN105572108B (en) A kind of preparation method and application of electrogenerated chemiluminescence demeton sensor
CN106018514B (en) A kind of preparation method of the optical electro-chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material
CN105717181B (en) A kind of preparation method and application of the electrochemistry malathion biology sensor based on bimetallic In-situ reaction two-dimension nano materials
CN105738437B (en) A kind of preparation method and application of the electrochemistry parathion sensor based on metal and metal oxide co-doped nano composite
CN105717180B (en) A kind of preparation method and application of the optical electro-chemistry aflatoxin biology sensor based on two-dimensional nano composite
CN105572193A (en) Preparation method and application of electrochemical chlordimeform sensor based on composite cerium-doped porous nanocomposite
CN104089999A (en) Carbon quantum dot-nanowire array-based cardiomyocyte signal molecule sensor and preparation method thereof
CN106198501B (en) A kind of preparation method for the Electrochemiluminescsensor sensor detecting aflatoxin
CN105717178A (en) Preparation method and application of electrochemical diethylstilbestrol sensor based on titanium-dioxide-based two-dimensional composite nanomaterial
CN105738353B (en) A kind of preparation method and application of optical electro-chemistry decis sensor
CN106198683B (en) A kind of preparation method of the optical electro-chemistry chloramphenicol biosensor based on two-dimensional nano photoelectric material
CN105675685A (en) Preparation method and application of electrochemical chlordimeform sensor based on manganese-doped two-dimensional nano composite material
CN105738350B (en) A kind of preparation method and application of the electrogenerated chemiluminescence carbamate sensor based on cobalt doped two-dimensional nano composite
CN105717099B (en) A kind of preparation method and application of electrogenerated chemiluminescence furazolidone biology sensor
CN106198668B (en) A kind of preparation method of the optical electro-chemistry demeton sensor based on cobalt doped two-dimensional nano photoelectric material
CN105738352B (en) A kind of preparation method and application of the optical electro-chemistry Ractopamine sensor based on bimetallic codope two-dimension nano materials
CN106053442B (en) A kind of preparation method of the electrogenerated chemiluminescence decis sensor based on iron cobalt codope two-dimension nano materials
CN105717179B (en) A kind of preparation method and application of optical electro-chemistry organo-chlorine pesticide biology sensor
CN106198657B (en) A kind of preparation method of the parathion sensor based on two-dimension nano materials building
CN106053572B (en) A kind of preparation method of electrochemistry bisphenol-A sensor
CN105699646B (en) A kind of preparation method and application of the electrogenerated chemiluminescence nonyl phenol sensor based on titanium dioxide nanoplate composite
CN106198682B (en) A kind of preparation method of the optical electro-chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent
CN106248753B (en) A kind of preparation method of the optical electro-chemistry Spanon sensor based on load type double-metal codope photosensitizer

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
GR01 Patent grant