CN102735735A - Functional bismuth oxyiodide nanoflake array photoelectric organophosphorus pesticide biosensor and preparation method thereof - Google Patents

Functional bismuth oxyiodide nanoflake array photoelectric organophosphorus pesticide biosensor and preparation method thereof Download PDF

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CN102735735A
CN102735735A CN2012102201044A CN201210220104A CN102735735A CN 102735735 A CN102735735 A CN 102735735A CN 2012102201044 A CN2012102201044 A CN 2012102201044A CN 201210220104 A CN201210220104 A CN 201210220104A CN 102735735 A CN102735735 A CN 102735735A
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bioi
ito
nfs
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CN102735735B (en
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龚静鸣
李雪
王小庆
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Huazhong Normal University
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Abstract

The invention discloses a functional bismuth oxyiodide nanoflake array photoelectric organophosphorus pesticide biosensor and a preparation method thereof. The biological sensor is an AChE-BiOINFs/ITO electrode which is prepared by using ITO as a substrate and using Bi(NO3)3.5H2O, KI and acetylcholinesterase as raw materials. Application of the method provided in the invention in constructing a photoelectric sensor platform for biological functional AChE-BiOI nanoflakes enables complicated preparation process for titania nano-tubes and cumbersome integration of other elemental elements to be effectively avoided, thereby greatly saving time and cost; meanwhile, destructive influence on biomolecules by photo-generated holes excited by irradiation of ultraviolet light and light on TiO2 is greatly reduced. The preparation method provided in the invention has the advantages of a simple process, low cost, environment friendliness, high yield and accordance with actual production needs.

Description

Functionalization bismuth oxyiodide nano-sheet array photoelectricity organophosphorus pesticide biology sensor and preparation
Technical field
The present invention relates to Optical Electro-Chemistry organophosphorus pesticide biology sensor and the preparation of a kind of biological functional bismuth oxyiodide nano-sheet array under excited by visible light.
Background technology
Organophosphorus insecticide is widely used as and is the control of agricultural pest medicament, reaches the neural paralysis agent in the attack of terrorism in the military affairs.Because organophosphorus pesticide has continuation, biogenic accumulation property, a high toxicity in biosome and human body.For human health, environment, and food security, thereby organophosphorus pesticide receives great concern.Desire along with the pursuit of human health protection with to the control of environment, the trace organophosphorus detects and has become increasingly important.
In more than ten years in the past, people have set up with gas phase, liquid phase or mass spectral method and have carried out the detection of organophosphorus pesticide, and these methods often require complicated pre-treatment step, a large amount of professional and technical personnel, and be unfavorable for field quick detection.Relatively pass by several kinds of traditional detection methods, the Optical Electro-Chemistry of new development detect because of it fast, and the biologic array of high throughput and seem very interesting.Since the high efficiency separation of its excitation source and detection signal, the reduction of some impurity background signals, thereby make detection obtain high sensitivity.Since its high sensitivity, intrinsic microminiaturization, portable, and simple the combination, Optical Electro-Chemistry is detected becomes a kind of very promising analytical technology.In the Optical Electro-Chemistry bioanalysis, probing into of Optical Electro-Chemistry material becomes vital thing, and it is directly with the stability of biological recognition element and last existing the closing of Identification Lists.Some metal-oxide semiconductor (MOS) nano particles are like ZrO 2,ZnO, TiO 2Be used as main Optical Electro-Chemistry material.Wherein, TiO 2Once studied the material of using as various Optical Electro-Chemistry widely, because it has stronger oxidisability, avirulence, low cost, biological and chemical inertia.But by TiO 2The forbidden band broad just works under the irradiation of ultraviolet light, thereby can kill biomolecule.In addition, TiO under the optical excitation 2Have strong oxidizing property, also can damage biomolecule.So, to TiO 2It is necessary that Optical Electro-Chemistry detection application is carried out in further modification.TiO for example 2Nanotube, the TiO that gold mixes 2Nanotube, CdS-TiO 2Nanometer tube composite materials, CdSexTe 1-xThe many heterojunction of/TNs, the TiO of porphyrin-multifunction 2Nanotubes etc. have been studied conduct excited by visible light material efficiently, are used for the Optical Electro-Chemistry sensor.Recently, people such as Xu has reported that carrying out immune Optical Electro-Chemistry based on living things catalysis deposition preparation CdS quanta dot modified electrode detects.Detect although these achievements in research satisfy rapidly and efficiently, develop more high performance light active material, critical value to the visible region that changes photoresponse carries out the Optical Electro-Chemistry sensor and remains the very big challenge that this detection technique faces.
The present invention has effectively avoided the loaded down with trivial details integration of the complicated preparation process of titania nanotube and other unit thing through making up the photoelectric sensing applicator platform of novel biological functional AChE-BiOI nanometer sheet, has greatly saved time and cost.Simultaneously, ultraviolet light and illumination TiO have been reduced to a great extent 2The damaging influence that the photohole that excites produces biomolecule.Technology of the present invention is simple, and cost is low, and environmental friendliness, is convenient to further enlarge produce.
Summary of the invention
The object of the present invention is to provide a kind of bismuth oxyiodide sheet-like array BiOI nanoflake arrays (BiOINFs) photoelectricity organophosphorus pesticide biology sensor and preparation of biological functional.Biology sensor with the inventive method preparation can be realized high-sensitivity detection to machine phosphorus insecticide in visible-range.
A kind of functionalization bismuth oxyiodide sheet-like array Optical Electro-Chemistry organophosphorus pesticide biology sensor of the present invention; It is characterized in that this sensor is BiOI NFs/ITO (BiOI nanoflake arrays and the Indium Tin Oxides) combination electrode that is fixed with acetylcholinesterase.
The preparation method of functionalization bismuth oxyiodide sheet-like array Optical Electro-Chemistry organophosphorus pesticide biology sensor of the present invention may further comprise the steps:
1) substrate is handled, and ito glass sheet (the tin-oxide glass Indium Tin Oxides that fluorine mixes) is successively put into alcohol and redistilled water ultrasonic cleaning, and generally each ultrasonic cleaning is 5 minutes, after cleaning up fully, under nitrogen, dries up subsequent use;
2) preparation BiOI and KI solution: take by weighing 0.254 g Bi (NO respectively 3) 35H 2O and 0.083 g KI solid are made into 100 mL solution with redistilled water; Prepare two 25 mL beakers, pour isopyknic BiOI and KI solution respectively into, the ready ito glass sheet of step 1) is immersed in 10 s clocks in the BiOI solution earlier; Washing by soaking in the beaker of distilled water is housed then is immersed into about 10 s in the KI solution then, is transferred to washing by soaking in the beaker that distilled water is housed again; So cycling just can obtain BiOI NFs/ITO electrode; Redistilled water per 5 times the circulation after to change once, through 20 times with cocycle, preferably through 30 times the circulation after; The BiOI NFs/ITO electrode that obtains, at room temperature dry;
3) with step 2) the BiOI NFs/ITO electrode for preparing; Rinse well with redistilled water; The pH that then BiOI NFs/ITO electrode is immersed in AChE (acetylcholinesterase biomolecules acetylcholinesterase) is in 7.0 phosphate buffer solutions; Place the BiOI NFs/ITO combination electrode that promptly obtains being fixed with acetylcholinesterase half an hour in room temperature, be designated as AChE-BiOI NFs/ITO, then AChE-BiOI NFs/ITO being immersed in pH is in 7.0 phosphate buffer solutions; And be in 7.0 phosphate buffer solutions, and put in the refrigerator about 4 ℃ for using afterwards with the pH that electrode is kept at 5 mM.
The present invention the preparation BiOI experimental implementation in reference to Wang ( Electrochem. Commun. 2010, 12,1764 -1767) method of successive ionic layer adsorption and reaction (SILAR).
Effect of the present invention and advantage:
1. the bismuth oxyiodide sheet enzyme biologic sensor that obtains of the inventive method.Structure with nanometer sheet porous, and reproducibility is good, reusable.
2. whole invention process is simple and easy to control, and power consumption is few, and cost is low, corresponds to actual needs.
3. this method has effectively been avoided the loaded down with trivial details integration of the complicated preparation process of titania nanotube and other unit thing through the photoelectric sensing applicator platform of the biological functional AChE-BiOI nanometer sheet of structure, has greatly saved time and cost.
Further the present invention will be described below in conjunction with accompanying drawing and embodiment.
Description of drawings
Fig. 1 is the XRD diffractogram of the prepared biological functional AChE-BiOI nanometer sheet sample of embodiment
Fig. 2 is the prepared biological functional AChE-BiOI nanometer sheet sample SEM figure of embodiment
Fig. 3 is the biological functional AChE-BiOI nanometer sheet sample ac impedance spectroscopy of embodiment gained
Fig. 4 is the Optical Electro-Chemistry response signal of the biological functional AChE-BiOI nanometer sheet of embodiment gained for the MP that detects variable concentrations
Fig. 5 is that the MP of biological functional AChE-BiOI nanometer sheet of embodiment gained is to the inhibition degree of AChE-BiOI NFs/ITO and the linear relationship of its concentration.
Embodiment
Embodiment 1
The preparation of functionalization bismuth oxyiodide nano-sheet array photoelectricity organophosphorus pesticide biology sensor, its step comprises:
1), substrate handles, and the ito glass sheet was successively put into alcohol and each ultrasonic cleaning of redistilled water 5 minutes, cleans up fully, under nitrogen, dries up subsequent use;
2), take by weighing 0.254 g Bi (NO respectively 3) 35H 2O and 0.083 g KI solid are made into 100 mL solution with redistilled water.At two 25 mL beakers; Pour isopyknic BiOI and KI solution respectively into, the ready ito glass sheet of step 1) is immersed in about 10 s clocks, washing by soaking in the beaker of distilled water is housed then in the BiOI solution earlier; Then be immersed into about 10 s in the KI solution; Be transferred to washing by soaking in the beaker that distilled water is housed again, so cycling just can obtain BiOI NFs/ITO electrode, will change once after per 5 circulations of redistilled water.At last, through after certain cycle index, that the BiOI NFs/ITO electrode that obtains is at room temperature dry;
3), with step 2) the BiOI NFs/ITO electrode for preparing, rinse well with redistilled water, the concentration that then BiOI NFs/ITO electrode is immersed in AChE is 6 mU mL -1The pH of 5 mM be about 6 h in 7.0 phosphate buffer solutions; Place the BiOI NFs/ITO combination electrode that half an hour promptly obtains being fixed with acetylcholinesterase in room temperature; Be designated as AChE-BiOI NFs/ITO, then AChE-BiOI NFs/ITO being immersed in pH is about 20min in 7.0 phosphate buffer solutions, to remove loose acetylcholinesterase; And be in 7.0 phosphate buffer solutions, and place in the refrigerator about 4 ℃ for using afterwards with the pH that electrode is kept at 5 mM.
XRD diffractogram such as Fig. 1 of prepared sample, SEM scheme like Fig. 2, and ac impedance spectroscopy [contains Fe (CN) at 0.1 M KCl 6 4/3-Oxidation-reduction pair (0.225 V vs Ag/AgCl) applying frequency is 0.1 hertz to 100 hertz] in measure like Fig. 3.Process is to the BiOI nanometer sheet number of plies; Concentration of substrate, the pH value is after the optimization of inhibition time; When optimal conditions respectively under variable concentrations; To Optical Electro-Chemistry response signal such as Fig. 4 of AChE-BiOI NFs/ITO electrode detection MP, under selected optimal condition, MP is to the inhibition degree of AChE-BiOI NFs/ITO and linear relationship such as Fig. 5 of its concentration.

Claims (4)

1. a functionalization bismuth oxyiodide sheet-like array Optical Electro-Chemistry organophosphorus pesticide biology sensor is characterized in that this sensor is the BiOI NFs/ITO combination electrode that is fixed with acetylcholinesterase.
2. the preparation method of a functionalization bismuth oxyiodide sheet-like array Optical Electro-Chemistry organophosphorus pesticide biology sensor is characterized in that may further comprise the steps:
1) base treatment is successively put into alcohol and redistilled water ultrasonic cleaning with the ito glass sheet, after cleaning up fully, under nitrogen, dries up subsequent use;
2) preparation BiOI and KI solution: take by weighing 0.254 g Bi (NO respectively 3) 35H 2O and 0.083 g KI solid are made into 100 mL solution with redistilled water; Prepare two 25 mL beakers, pour isopyknic BiOI and KI solution respectively into, the ready ito glass sheet of step 1 is immersed in 10 s clocks in the BiOI solution earlier; Washing by soaking in the beaker of distilled water is housed then; Then be immersed into about 10 s in the KI solution, be transferred to washing by soaking in the beaker that distilled water is housed again, so cycling just can obtain BiOI NFs/ITO electrode; To change once after per 5 circulations of redistilled water; Through 20 times with after the cocycle, the BiOI NFs/ITO electrode that obtains, at room temperature dry;
3) the BiOI NFs/ITO electrode that step 2 is prepared; Rinse well with redistilled water; The pH that then BiOI NFs/ITO electrode is immersed in AChE is in 7.0 phosphate buffer solutions; Place the BiOI NFs/ITO combination electrode that promptly obtains being fixed with acetylcholinesterase half an hour in room temperature, be designated as AChE-BiOI NFs/ITO, then AChE-BiOI NFs/ITO being immersed in pH is in 7.0 phosphate buffer solutions; And be in 7.0 phosphate buffer solutions, and put in the refrigerator about 4 ℃ for using afterwards with the pH that electrode is kept at 5 mM.
3. the preparation method of functionalization bismuth oxyiodide sheet-like array Optical Electro-Chemistry organophosphorus pesticide biology sensor as claimed in claim 2 is characterized in that: the ito glass sheet was successively put into alcohol and redistilled water ultrasonic cleaning 5 minutes in the step 1).
4. the preparation method of functionalization bismuth oxyiodide sheet-like array Optical Electro-Chemistry organophosphorus pesticide biology sensor as claimed in claim 2 is characterized in that: step 2) in through 30 times with after the cocycle, the BiOI NFs/ITO electrode that obtains.
CN201210220104.4A 2012-06-29 2012-06-29 Functional bismuth oxyiodide nanoflake array photoelectric organophosphorus pesticide biosensor and preparation method thereof Expired - Fee Related CN102735735B (en)

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CN104880495A (en) * 2015-06-09 2015-09-02 华中师范大学 Development and application of novel steric-hindrance-adjustable-and-controllable visible light photoelectric chemical detection PFOA (perfluorooctanoic acid) sensor
CN106938340A (en) * 2016-08-30 2017-07-11 江苏大学 A kind of preparation method and its usage of the halogenation oxygen bismuth of bismuth metal auto-dope
CN110632139A (en) * 2019-11-12 2019-12-31 江南大学 Method for cathode photoelectrochemical detection of zearalenone
CN110865103A (en) * 2019-11-19 2020-03-06 山西大学 Photoelectrochemical analysis method for selectively detecting pesticide atrazine

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104880495A (en) * 2015-06-09 2015-09-02 华中师范大学 Development and application of novel steric-hindrance-adjustable-and-controllable visible light photoelectric chemical detection PFOA (perfluorooctanoic acid) sensor
CN104880495B (en) * 2015-06-09 2017-08-25 华中师范大学 New spatial steric hindrance regulation type visible ray optical electro-chemistry detects PFOA sensor designs and its application
CN106938340A (en) * 2016-08-30 2017-07-11 江苏大学 A kind of preparation method and its usage of the halogenation oxygen bismuth of bismuth metal auto-dope
CN110632139A (en) * 2019-11-12 2019-12-31 江南大学 Method for cathode photoelectrochemical detection of zearalenone
CN110632139B (en) * 2019-11-12 2021-06-15 江南大学 Method for cathode photoelectrochemical detection of zearalenone
CN110865103A (en) * 2019-11-19 2020-03-06 山西大学 Photoelectrochemical analysis method for selectively detecting pesticide atrazine

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