CN112816639A - Construction method of photoelectrochemical aptamer sensor for sensitive detection of enrofloxacin - Google Patents
Construction method of photoelectrochemical aptamer sensor for sensitive detection of enrofloxacin Download PDFInfo
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- 229960000740 enrofloxacin Drugs 0.000 title claims abstract description 57
- 238000010276 construction Methods 0.000 title claims abstract description 8
- 108091023037 Aptamer Proteins 0.000 title claims description 30
- 238000011896 sensitive detection Methods 0.000 title claims description 6
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/15—Medicinal preparations ; Physical properties thereof, e.g. dissolubility
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention provides a construction method of a photoelectrochemical sensor for sensitively detecting Enrofloxacin (ENR), which comprises the following steps: step 1, preparing bismuth oxybromide (Bi)4O5Br2) Nanosheets; step 2, preparing aza-bismuth oxybromide (N-Bi)4O5Br2) A nanocomposite; and 3, constructing a photoelectrochemical sensor for sensitively detecting Enrofloxacin (ENR). Compared with the traditional detection method, the photoelectrochemical detection method of ENR provided by the invention has the characteristics of simpler and more flexible operation, simpler instruments and equipment, wide detection range, low detection limit, low detection cost and the like.
Description
Technical Field
The invention belongs to the field of electrochemical detection, and relates to a construction method and application of a photoelectrochemical aptamer sensor for detecting enrofloxacin in lake water.
Background
Enrofloxacin (enrofloxacin, ENR) is a fluoroquinolone antibiotic, is a special quinolone antibacterial drug for livestock, poultry and aquatic products, and is widely used for human activities. However, the increased levels of ENR found in aquatic environments can have serious consequences for the health of humans and livestock. The European Commission and the department of agriculture in China stipulate that ENR and its active metabolite ciprofloxacin at the maximum residual limit of animal muscle tissue (MRLs) is 100 μ g/kg, while the U.S. food and drug administration completely prohibits its use in poultry. Several antibiotic detection methods have been developed, including High Performance Liquid Chromatography (HPLC), liquid chromatography-electrospray ionization-tandem mass spectrometry, colorimetric, fluorescent, etc. Although these methods can meet the requirements of sensitivity and specificity detection, they have certain limitations in practical application. For example, chromatography can be used for qualitative and quantitative detection, and the detection result is relatively accurate, reliable, high in sensitivity and good in reproducibility, but the used instruments and equipment are expensive, the operation is complex, and professional technicians are required, so that the method is not suitable for processing and analyzing large-batch samples and performing rapid detection on the spot.
Photoelectrochemical (PEC) technology, an emerging electroanalytical technology, has received widespread attention in a number of fields, such as the biological field, environmental science, and the medical field. PEC sensing technology, a novel analytical technology, has many advantages that are not possible or difficult to implement on traditional electrochemical platforms. Since the PEC uses two different forms of excitation and detection signals, and the background signal is low, the PEC has higher sensitivity.
Based on aza-oxybromide bismuth (N-Bi)4O5Br2) The nano-composite is used as a photoelectric active material to establish a photoelectric chemical sensing platform, and is not reported yet for photoelectric chemical detection of enrofloxacin in lake water.
Disclosure of Invention
The invention aims to provide a photoelectrochemical aptamer sensor which integrates the advantages of high sensitivity, high selectivity, wide measurement range and the like. The sensor is simple in preparation process and low in cost, and the purpose of rapidly and quantitatively detecting ENR is achieved.
The adopted scheme is summarized as follows: to prepare N-Bi4O5Br2The nano-composite is used as a photoelectric active material to create an ultra-sensitive photoelectric chemical sensing platform. Using N-Bi4O5Br2The nano composite has the properties of larger absorption of visible light, quick response and the like, and plays a role in signal amplification for a detection system. When adding the target ENR, N-Bi4O5Br2The nano composite is excited by visible light, the generated hole pair oxidizes ENR, and the oxidation product of ENR can effectively prevent the generated ENRThe electron-hole pairs are recombined, so that the photocurrent response intensity of the electron-hole pairs is enhanced, and the relationship between the photocurrent response value and the ENR concentration is established, so that the aim of quickly, sensitively and selectively detecting the ENR content in the lake water is fulfilled.
The invention is realized by the following specific technical scheme:
a method for constructing a photoelectrochemical aptamer sensor for sensitive detection of Enrofloxacin (ENR), comprising the steps of:
step 1, preparing bismuth oxybromide (Bi) by solvothermal method4O5Br2) Nanosheet:
first, bismuth bromide (BiBr)3) Dissolving in glycol, adding NaOH solution drop by drop with stirring, and transferring into a polytetrafluoroethylene autoclave for solvothermal reaction. The solid product is recovered by filtration, washing and centrifugation and then dried to obtain Bi4O5Br2Nanosheets.
adding Bi4O5Br2The nano-sheets are respectively and uniformly mixed with urea with different mass, the mixture is heated in a muffle furnace, the obtained product is respectively washed and dried by dimethyl sulfoxide and distilled water, and N-Bi with different doping contents is obtained4O5Br2A composite material.
Step 3, constructing a photoelectrochemical aptamer sensor for sensitive detection of Enrofloxacin (ENR):
adding N-Bi4O5Br2Dispersing the composite material in N, N-dimethylformamide DMF to obtain N-Bi4O5Br2Dispersing liquid, namely dripping the dispersing liquid on an ITO electrode, dripping chitosan CS solution, drying, dripping glutaraldehyde GA solution on the surface of the electrode, placing the electrode at room temperature, reacting, and leaching with phosphoric acid buffer solution PBS; and dropwise adding the ENR aptamer on the electrode, reacting for a period of time, leaching with PBS, and then dropwise adding bovine serum albumin BSA solution to finally obtain the aptamer modified material electrode, namely the photoelectrochemical aptamer sensor for detecting enrofloxacin.
In step 1, the BiBr is3The dosage ratio of the NaOH solution to the NaOH solution is 1.33 g: 12.6mL, wherein the concentration of the NaOH solution is 2 mol/L; the hydrothermal reaction temperature is 140-160 ℃, and the reaction time is 10-12 h; the centrifugation speed is 8000-9000 rmp/s, and the centrifugation time is 6-8 min; the drying temperature is 50-60 ℃, and the drying time is 10-12 h.
In step 2, the N-Bi4O5Br2The mass percentage content of the medium nitrogen is 10-50 percent; the muffle furnace is set at 200-220 ℃ and the reaction time is 3-5 h.
In step 3, the N-Bi4O5Br2The dispersion is 2 mg/mL; the CS concentration is 0.1%; the GA concentration is 2.5%, the dosage of the CS solution is 10 mu L, the dosage of the GA solution is 20 mu L, and the reaction time of the CS and the GA is 0.5-1 h;
the ENR aptamer sequence is: 5' -NH2-CCC ATC AGG GGG CTA GGC TAA CAC GGT TCG GCT CTC TGA GCC CGG GTT ATT TCA GGG GGA-3'; the ENR aptamer concentration is 3 mu M, the dropping amount is 20 mu L, and the reaction time is 10 h; the BSA concentration is 3%; the concentration of the PBS is 0.1mol/L, the pH value is 7.4, and the dosage is 10-20 mL.
The photoelectrochemical aptamer sensor constructed by the invention is used for detecting enrofloxacin, ENR solutions with different concentrations are dropped on the photoelectrochemical aptamer sensor for detecting enrofloxacin, and are incubated for a period of time, an ITO electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and photoelectric analysis is sequentially carried out according to the concentrations under the irradiation of a xenon lamp light source through an electrochemical workstation three-electrode system.
Wherein the ENR concentration is 0.1-108ng/mL, 0.1ng/mL, 1ng/mL, 100ng/mL, 10 ng/mL, respectively3ng/mL，104ng/mL，105ng/mL，106ng/mL，107ng/mL and 108ng/mL, the dropping amount is 10-20 mu L; the incubation temperature was 37 ℃; the intensity of the xenon lamp light source is 25-100%.
The invention has the beneficial effects that:
the invention prepares N-Bi4O5Br2The nano composite is used as a photoelectric active material, a photoelectric chemical sensing platform is successfully established, and a photoelectric chemical detection method of enrofloxacin in lake water is established, and the characteristics and advantages of the method are expressed as follows:
(1) the invention prepares N-Bi4O5Br2The nano-composite is used as a photoelectric active material to construct a photoelectric chemical aptamer sensor, and a photocurrent response signal is amplified.
(2) The invention adopts the urea to Bi4O5Br2Further doping is carried out, on one hand, the doping of the semiconductor material can play a role in signal amplification, and the visible light absorption is widened; on the other hand, the stability is further improved and the transfer of electrons is facilitated by utilizing the specific recognition of the aptamer and the combination between the aptamer and the ENR molecules.
(3) The signal amplification method and the detection mode provided by the invention realize the ultra-sensitive detection of ENR, and the detection is between 0.1ng/mL and 106Logarithm of ENR concentration in the concentration interval of ng/mL (lg C)ENR) The linear relation with the photocurrent response value is good, and the detection limit can reach 0.033 ng/mL.
(4) Compared with the traditional detection method, the photoelectrochemical detection method of ENR provided by the invention has the characteristics of simpler and more flexible operation, simpler instruments and equipment, wide detection range, low detection limit, low detection cost and the like.
Drawings
FIG. 1 shows the prepared material Bi4O5Br2(a) And N-Bi4O5Br2(b) Photocurrent response of (A) and a proportion of 10% N-Bi of different components4O5Br2(a)，20％N-Bi4O5Br2(b)，30％N-Bi4O5Br2(c)，40％N-Bi4O5Br2(d) And 50% of N-Bi4O5Br2(e) Photocurrent response diagram (B);
fig. 2 is a graph (a) of the correspondence between ENR concentration and photocurrent response value and a graph (B) of the linear relationship.
Detailed Description
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
Example 1:
(1) solvothermal method for preparing bismuth oxybromide (Bi)4O5Br2) Nano-sheet
First, 1.33g of bismuth bromide (BiBr)3) Dissolved in 50mL of ethylene glycol, 2mol/L of NaHOH (12.6 mL) was added dropwise with stirring, followed by transferring to a polytetrafluoroethylene autoclave and reacting at 140 ℃ for 12 hours. After the reaction kettle cooled to room temperature, we washed the resulting sample 3 times with ethanol and deionized water and centrifuged at 9000rmp for 8min in the laboratory, which was finally dried in an oven at 60 ℃ for 12 h. According to the method, Bi is obtained4O5Br2Nanosheets.
(2) Preparation of N-Bi4O5Br2Nanocomposite
0.2g of Bi are weighed out4O5Br2And 0.02g of urea, and heated in a muffle furnace at 220 ℃ for 3 hours, and the resulting compound was washed with dimethyl sulfoxide and distilled water. Then dried at 60 ℃ for 12h to obtain 10% N-Bi4O5Br2。
Different amounts of N-Bi (0.04g, 0.06g, 0.08g and 0.1g) of urea were prepared in the same procedure to obtain different contents of N-Bi4O5Br2Composite material and its designation as 20% N-Bi4O5Br2、30％N-Bi4O5Br2、40％N-Bi4O5Br2And 50% of N-Bi4O5Br2。
FIG. 1(A) shows Bi obtained in this example4O5Br2(a) And N-Bi4O5Br2(b) The photocurrent response map shows that the photocurrent response value is enlarged by 18 times, and the current response signal is enhanced; FIG. 1(B) shows 10% N-Bi of different composition ratios obtained in example 14O5Br2(a)，20％N-Bi4O5Br2(b)，30％N-Bi4O5Br2(c)，40％N-Bi4O5Br2(d) And 50% of N-Bi4O5Br2(e) A photocurrent response diagram of (1), in which 30% N-Bi can be seen4O5Br2(c) The most intense photocurrent response of (2) was 0.37. mu.A, so we chose this ratio of N-Bi4O5Br2And constructing a subsequent sensing platform as a material.
(3) Construction of photoelectrochemical aptamer sensors
2mg of N-Bi was dissolved in 1mL of N, N-Dimethylformamide (DMF)4O5Br2Preparation of N-Bi composites4O5Br2Dispersing 20 μ L of N-Bi4O5Br2The dispersion liquid is modified on an ITO electrode, 10 mu L of Chitosan (CS) solution is dripped and dried under an infrared lamp. Then, 20. mu.L of Glutaraldehyde (GA) solution was dropped on the electrode surface and allowed to react at room temperature for 1 hour, and after completion of the reaction, the electrode surface was rinsed with 0.1mol/L Phosphate Buffer Solution (PBS) having a pH of 7.4 to remove excess GA on the electrode surface. And (2) preparing a 2 mu M ENR aptamer solution by using PBS as a solvent, dropwise adding the ENR aptamer on an electrode, after reacting for 12 hours, rinsing by using PBS to remove excessive unadsorbed aptamer, then dropwise adding 10 mu L of Bovine Serum Albumin (BSA) solution, and standing for 0.5 hour to block the nonspecific active site, thereby finally obtaining the aptamer modified material electrode.
Thereafter, different concentrations of ENR solutions were dropped onto the aptamer-modified material electrode and incubated for a period of time at 37 ℃ atmosphere. And performing photoelectric analysis on the ITO electrode serving as a working electrode, the saturated calomel electrode serving as a reference electrode and the platinum wire serving as a counter electrode sequentially according to the concentration under the irradiation of a xenon lamp light source through a three-electrode system of an electrochemical workstation.
FIG. 2(A) is the ENR concentration (a → j:0.1 → 10) obtained in the present example8ng/mL) and photocurrent response value, and FIG. 2(B) is a linear graph showing that, as the ENR concentration increases, N-Bi4O5Br2The photocurrent response of the sensor is gradually increased, and a good linear relation (R) is shown between the photocurrent magnitude and the ENR concentration20.991), linear equation is I0.01391 +0.00456lg [ C ═ CENR(ng mL–1)]. As shown in FIG. 2(B), at 0.1 ng/mL-106Log of ENR concentration (lg C) in the concentration interval of ng/mLENR) The linear relation with the photocurrent response value is good, and the detection limit can reach 0.033 ng/mL.
Example 2:
(1) solvothermal method for preparing bismuth oxybromide (Bi)4O5Br2) Nano-sheet
First, 2.66g of bismuth bromide (BiBr)3) Dissolved in 50mL of ethylene glycol, 2mol/L of NaHOH 25.2mL was added dropwise with stirring, followed by transferring to a polytetrafluoroethylene autoclave and reacting at 140 ℃ for 12 hours. After the reaction kettle cooled to room temperature, we washed the resulting sample 3 times with ethanol and deionized water and centrifuged at 9000rmp for 8min in the laboratory, which was finally dried in an oven at 60 ℃ for 12 h. According to the method, Bi is obtained4O5Br2Nanosheets.
(2) Preparation of N-Bi4O5Br2Nanocomposite
0.4g of Bi is weighed4O5Br2And 0.04g of urea, and heated in a muffle furnace at 220 ℃ for 3 hours, and the resulting compound was washed with dimethyl sulfoxide and distilled water. Then dried at 60 ℃ for 12h to obtain 10% N-Bi4O5Br2。
Different amounts of N-Bi (0.08g, 0.12g, 0.16g and 0.2g) of urea were prepared in the same procedure to obtain different contents of N-Bi4O5Br2Composite material and its designation as 20% N-Bi4O5Br2、30％N-Bi4O5Br2、40％N-Bi4O5Br2And 50% of N-Bi4O5Br2。
Step (3) is the same as step (3) of example 1.
Example 3:
(1) solvothermal method for preparing bismuth oxybromide (Bi)4O5Br2) Nano-sheet
First, 1.33g of bismuth bromide (BiBr)3) Dissolving in 50mL of ethylene glycol, dropwise adding 2mol/L of NaHOH 12.6mL under stirring,then transferred to a polytetrafluoroethylene autoclave and reacted at 160 ℃ for 10 h. After the reaction kettle cooled to room temperature, we washed the resulting sample 3 times with ethanol and deionized water and centrifuged at 9000rmp for 8min in the laboratory, which was finally dried in an oven at 60 ℃ for 12 h. According to the method, Bi is obtained4O5Br2Nanosheets.
(2) Preparation of N-Bi4O5Br2Nanocomposite
0.2g of Bi are weighed out4O5Br2And 0.02g of urea, and heated in a muffle furnace at 200 ℃ for 5 hours, and the resulting compound was washed with dimethyl sulfoxide and distilled water. Then dried at 60 ℃ for 12h to obtain 10% N-Bi4O5Br2. Different amounts of N-Bi (0.04g, 0.06g, 0.08g and 0.1g) of urea were prepared in the same procedure to obtain different contents of N-Bi4O5Br2Composite material and its designation as 10% N-Bi4O5Br2、20％N-Bi4O5Br2、30％N-Bi4O5Br2、40％N-Bi4O5Br2And 50% of N-Bi4O5Br2。
Step (3) is the same as step (3) of example 1.
Claims (8)
1. A construction method of a photoelectrochemical aptamer sensor for sensitive detection of enrofloxacin is characterized by comprising the following steps:
step 1, preparing bismuth oxybromide Bi by solvothermal method4O5Br2Nanosheet:
first, bismuth bromide BiBr3Dissolving in glycol, adding NaOH solution drop by drop while stirring, transferring into a polytetrafluoroethylene autoclave for solvothermal reaction, filtering, washing, centrifuging, recovering a solid product, and drying to obtain Bi4O5Br2Nanosheets;
step 2, calcining method for preparing N-Bi of aza-bismuth oxybromide4O5Br2Nano-composite:
firstly, the methodBi prepared in the step 14O5Br2The nano-sheets are respectively and uniformly mixed with urea with different mass, the mixture is heated in a muffle furnace, the obtained product is respectively washed and dried by dimethyl sulfoxide and distilled water, and N-Bi with different doping contents is obtained4O5Br2A composite material;
step 3, constructing a photoelectrochemical aptamer sensor for sensitively detecting Enrofloxacin (ENR):
the N-Bi prepared in the step 24O5Br2Dispersing the composite material in N, N-dimethylformamide DMF to obtain N-Bi4O5Br2Dispersing liquid, namely dripping the dispersing liquid on an ITO electrode, dripping chitosan CS solution, drying, dripping glutaraldehyde GA solution on the surface of the electrode, placing the electrode at room temperature, reacting, and leaching with phosphoric acid buffer solution PBS; and dropwise adding the ENR aptamer on the electrode, reacting for a period of time, leaching with PBS, and then dropwise adding bovine serum albumin BSA solution to finally obtain the aptamer modified material electrode, namely the photoelectrochemical aptamer sensor for detecting enrofloxacin.
2. The method of claim 1, wherein in step 1, the BiBr is3The dosage ratio of the NaOH solution to the NaOH solution is 1.33 g: 12.6mL, wherein the concentration of the NaOH solution is 2 mol/L; the hydrothermal reaction temperature is 140-160 ℃, and the reaction time is 10-12 h; the centrifugation speed is 8000-9000 rmp/s, and the centrifugation time is 6-8 min; the drying temperature is 50-60 ℃, and the drying time is 10-12 h.
3. The method according to claim 1, wherein in step 2, the N-Bi4O5Br2The mass percentage content of the medium nitrogen is 10-50 percent; the muffle furnace is set at 200-220 ℃ and the reaction time is 3-5 h.
4. The method according to claim 1, wherein in step 3, the N-Bi4O5Br2The dispersion is 2 mg/mL; the CS concentration is 0.1%; GA concentrationThe degree is 2.5%, the dosage of the CS solution is 10 mu L, the dosage of the GA solution is 20 mu L, and the reaction time of the CS and the GA is 0.5-1 h.
5. The construction method according to claim 1, wherein in step 3, the ENR aptamer sequence is: 5' -NH2-CCC ATC AGG GGG CTA GGC TAA CAC GGT TCG GCT CTC TGA GCC CGG GTT ATT TCA GGG GGA-3'; the ENR aptamer concentration is 3 mu M, the dropping amount is 20 mu L, and the reaction time is 10 h; the BSA concentration is 3%; the concentration of the PBS is 0.1mol/L, the pH value is 7.4, and the dosage is 10-20 mL.
6. Use of the photoelectrochemical aptamer sensor constructed by the construction method according to any one of claims 1 to 5 for detecting enrofloxacin.
7. The use according to claim 6, characterized in that ENR solutions with different concentrations are dropped on a photoelectrochemical aptamer sensor for enrofloxacin detection and incubated for a period of time, an ITO electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and photoelectric analysis is sequentially carried out according to the concentrations under the irradiation of a xenon light source through an electrochemical workstation three-electrode system.
8. The use according to claim 7, wherein the ENR concentration is 0.1 to 108ng/mL, the dropping amount is 10-20 mu L; the incubation temperature was 37 ℃; the intensity of the xenon lamp light source is 25-100%.
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