CN102735735B - 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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CN102735735B
CN102735735B CN201210220104.4A CN201210220104A CN102735735B CN 102735735 B CN102735735 B CN 102735735B CN 201210220104 A CN201210220104 A CN 201210220104A CN 102735735 B CN102735735 B CN 102735735B
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ito
nfs
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CN102735735A (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 control of agricultural pest medicament, the neural paralysis agent in military affairs and in the attack of terrorism.Because organophosphorus pesticide has continuation, biogenic accumulation, a high toxicity in biosome and human body.For human health, environment, and food security, thereby organophosphorus pesticide receives great concern.Along with the pursuit of human health protection, and the control of environment is wanted, trace organophosphorus detects and has become increasingly important.
In more than ten years in the past, people have set up by gas phase, liquid phase or mass spectrographic 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 traditional several 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.Because its excitation source and the efficient of detection signal separate, the reduction of some impurity background signals, thereby make to detect and obtain high sensitivity.Due to its high sensitivity, intrinsic microminiaturization, portable, and simple combination, Optical Electro-Chemistry is detected becomes the very promising analytical technology of one.In Optical Electro-Chemistry bioanalysis, probing into of Optical Electro-Chemistry material becomes vital thing, and it is directly relevant with last identification performance with the stability of biological recognition element.Some metal-oxide semiconductor (MOS) nano particles, as ZrO 2,znO, TiO 2be used as main Optical Electro-Chemistry material.Wherein, TiO 2once be extensively studied the material as various Optical Electro-Chemistry application, because it has stronger oxidisability, nontoxicity, low cost, biological and chemical inertia.But by TiO 2forbidden band is wider, just works, thereby can kill biomolecule under the irradiation of ultraviolet light.In addition TiO under optical excitation, 2there is 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.For example TiO 2nanotube, the TiO of gold doping 2nanotube, CdS-TiO 2nanometer tube composite materials, CdSexTe 1-x/ TNs Multiple heterostructures, the TiO of porphyrin-multifunction 2the efficient excited by visible light material of the studied conduct such as nanotube, detects for Optical Electro-Chemistry sensor.Recently, the people such as Xu has reported based on living things catalysis precipitation CdS quanta dot modified electrode and has carried out immune Optical Electro-Chemistry detection.Detect although these achievements in research meet rapidly and efficiently, develop more high performance light active material, the critical value of change photoresponse is carried out the detection of Optical Electro-Chemistry sensor and is remained the very big challenge that this detection technique faces to visible region.
The present invention, by building the photoelectric sensing applicator platform of novel biological functional AChE-BiOI nanometer sheet, has effectively avoided the preparation process of titania nanotube complexity and the loaded down with trivial details integration of other unit thing, has greatly saved time and cost.Meanwhile, ultraviolet light and illumination TiO have been reduced to a great extent 2the damaging influence that the photohole exciting produces biomolecule.Technique of the present invention is simple, and cost is low, and environmental friendliness, is convenient to further expanding production.
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.The biology sensor of preparing by the inventive method 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 that is fixed with acetylcholinesterase) combination electrode.
The preparation method of functionalization bismuth oxyiodide sheet-like array Optical Electro-Chemistry organophosphorus pesticide biology sensor of the present invention, comprises the following steps:
1) substrate processing, successively puts into alcohol and redistilled water ultrasonic cleaning by ito glass sheet (the tin-oxide glass Indium Tin Oxides that fluorine mixes), and general each ultrasonic cleaning 5 minutes after cleaning up completely, dries up for subsequent use under nitrogen;
2) prepare BiOI and KI solution: take respectively 0.254 g Bi (NO 3) 35H 2o and 0.083 g KI solid, be made into 100 mL solution with redistilled water; Prepare two 25 mL beakers, pour respectively isopyknic BiOI and KI solution into, ready step 1) ito glass sheet is first immersed in to 10 s clocks in BiOI solution, then washing by soaking in the beaker that distilled water is housed, then be immersed into approximately 10 s in KI solution, be transferred to again washing by soaking in the beaker that distilled water is housed, so cycling just can obtain BiOI NFs/ITO electrode, after every 5 circulations of redistilled water, to change once, through 20 times with cocycle, preferably, after 30 circulations, the BiOI NFs/ITO electrode obtaining, is at room temperature dried;
3) by step 2) the BiOI NFs/ITO electrode for preparing, rinse well with redistilled water, then BiOI NFs/ITO electrode is immersed in to AChE(acetylcholinesterase biomolecules acetylcholinesterase) pH be in 7.0 phosphate buffer solutions, place the BiOI NFs/ITO combination electrode that is fixed acetylcholinesterase half an hour in room temperature, be designated as AChE-BiOI NFs/ITO, then AChE-BiOI NFs/ITO being immersed in to pH is in 7.0 phosphate buffer solutions, and be in 7.0 phosphate buffer solutions by the pH that electrode is kept at 5 mM, the refrigerator of 4 DEG C of left and right of juxtaposition is interior for using afterwards.
The present invention 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 the inventive method obtains.There is the structure of 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, by the photoelectric sensing applicator platform of the biological functional AChE-BiOI nanometer sheet of structure, has effectively been avoided the preparation process of titania nanotube complexity and the loaded down with trivial details integration of other unit thing, has greatly saved time and cost.
Below in conjunction with drawings and Examples, further the present invention will be described.
Brief description of the 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 that the biological functional AChE-BiOI nanometer sheet of embodiment gained is for the Optical Electro-Chemistry response signal of the MP of detection variable concentrations
Fig. 5 is inhibition degree to AChE-BiOI NFs/ITO of the MP of biological functional AChE-BiOI nanometer sheet of embodiment gained 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 processing, ito glass sheet is successively put into alcohol and the each ultrasonic cleaning of redistilled water 5 minutes, clean up completely, under nitrogen, dry up for subsequent use;
2), take respectively 0.254 g Bi (NO 3) 35H 2o and 0.083 g KI solid, be made into 100 mL solution with redistilled water.At two 25 mL beakers, pour respectively isopyknic BiOI and KI solution into, ready step 1) ito glass sheet is first immersed in to approximately 10 s clocks in BiOI solution, then washing by soaking in the beaker that distilled water is housed, then be immersed into approximately 10 s in KI solution, be transferred to washing by soaking in the beaker that distilled water is housed, so cycling just can obtain BiOI NFs/ITO electrode again, after every 5 circulations of redistilled water, will change once.Finally, after certain cycle index, the BiOI NFs/ITO electrode obtaining is at room temperature dry;
3), by 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 to AChE is 6 mU mL -1the pH of 5 mM be approximately 6 h in 7.0 phosphate buffer solutions, place in room temperature the BiOI NFs/ITO combination electrode that half an hour is fixed acetylcholinesterase, be designated as AChE-BiOI NFs/ITO, then AChE-BiOI NFs/ITO being immersed in to pH is about 20min in 7.0 phosphate buffer solutions, to remove loose acetylcholinesterase, and be in 7.0 phosphate buffer solutions by the pH that electrode is kept at 5 mM, and be placed in the refrigerator of 4 DEG C of left and right for using afterwards.
The XRD diffractogram of prepared sample is as Fig. 1, and SEM schemes as 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 as Fig. 3.Process is to the BiOI nanometer sheet number of plies, concentration of substrate, pH value, after the optimization of inhibition time, in the time of optimal conditions respectively under variable concentrations, to the Optical Electro-Chemistry response signal of AChE-BiOI NFs/ITO electrode detection MP, as Fig. 4, under selected optimal condition, the linear relationship of the inhibition degree of MP to AChE-BiOI NFs/ITO and its concentration is as Fig. 5.

Claims (3)

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, and its preparation method comprises the following steps:
1) base treatment, successively puts into alcohol and redistilled water ultrasonic cleaning by ito glass sheet, after cleaning up completely, dries up for subsequent use under nitrogen;
2) prepare BiOI and KI solution: take respectively 0.254 g Bi (NO 3) 35H 2o and 0.083 g KI solid, be made into 100 mL solution with redistilled water; Prepare two 25 mL beakers, pour respectively isopyknic BiOI and KI solution into, ready step 1 ito glass sheet is first immersed in to 10 s clocks in BiOI solution, then washing by soaking in the beaker that distilled water is housed, then be immersed into approximately 10 s in KI solution, be transferred to again washing by soaking in the beaker that distilled water is housed, so cycling just can obtain BiOI NFs/ITO electrode, after every 5 circulations of redistilled water, to change once, through 20 times with after cocycle, the BiOI NFs/ITO electrode obtaining, at room temperature dry;
3) BiOI NFs/ITO electrode step 2 being prepared, rinse well with redistilled water, then the pH that BiOI NFs/ITO electrode is immersed in to AChE is in 7.0 phosphate buffer solutions, place the BiOI NFs/ITO combination electrode that is fixed acetylcholinesterase half an hour in room temperature, be designated as AChE-BiOI NFs/ITO, then AChE-BiOI NFs/ITO being immersed in to pH is in 7.0 phosphate buffer solutions, and be in 7.0 phosphate buffer solutions by the pH that electrode is kept at 5 mM, in the refrigerator of 4 DEG C of left and right of juxtaposition for using afterwards.
2. the preparation method of functionalization bismuth oxyiodide sheet-like array Optical Electro-Chemistry organophosphorus pesticide biology sensor as claimed in claim 1, is characterized in that: in step 1), ito glass sheet is successively put into alcohol and redistilled water ultrasonic cleaning 5 minutes.
3. the preparation method of functionalization bismuth oxyiodide sheet-like array Optical Electro-Chemistry organophosphorus pesticide biology sensor as claimed in claim 1, is characterized in that: step 2) in through 30 times with after cocycle, the BiOI NFs/ITO electrode obtaining.
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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