CN112666141A - Fluorescence ratio detection method for vozaphosphorine pesticide - Google Patents
Fluorescence ratio detection method for vozaphosphorine pesticide Download PDFInfo
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a nitrogen-doped fluorescent carbon quantum dot, which is synthesized by taking natural macromolecular saccharides as a carbon source, adding a nitrogen source and adopting a one-step hydrothermal method. Due to the double-excitation-single-emission fluorescence characteristic of the nitrogen-doped fluorescent carbon quantum dots, the single nitrogen-doped fluorescent carbon quantum dots are used as fluorophores, no additional fluorophores are needed, double-output signals can be realized, and the fluorescence ratio sensor is established. Thus, a fluorescence ratio detection method of the vozapyr pesticide is established. With the addition of the vozaphosphorus, the nitrogen-doped fluorescent carbon quantum dots can react within 1min, specifically, the excitation peak at 235nm is continuously quenched, while the fluorescence peak at 327nm is basically kept unchanged, and a standard curve is established by the quenching peak; and (4) detecting the vozapyr in the sample by taking the standard curve as a basis. In a word, the method does not need expensive large-scale instruments, is simple to operate, green and environment-friendly, is quick in response, and has potential application value in real-time detection of the vozapyr.
Description
Technical Field
The invention belongs to the technical field of pesticide analysis and detection, and particularly relates to a fluorescence ratio detection method of a vozapyr pesticide.
Background
The organophosphorus pesticide refers to organic compound pesticide containing phosphate or thiophosphate pesticide, and is mainly used for preventing and treating plant diseases and insect pests. Due to the advantages of relatively high environmental degradation speed, high efficiency, safety to plants, low price and the like, the organic chlorine pesticide has been widely replaced and is widely promoted to the world from the fifties and sixties of the 20 th century. Fusha is a broad-spectrum efficient organophosphorus insecticide and miticide, and is widely applied to pest control in grains, fruit trees, vegetables and cotton. Once inside the body, vozapine can bind and thus inhibit acetylcholinesterase activity, preventing the catalytic hydrolysis of thioacetylcholine, causing neurotoxicity. Therefore, it is a highly toxic neurotoxin, which can cause damage to human body function even at low concentrations, can cause people to enter toxic states, such as vomiting, cold sweating, mental disorders, and in severe cases can cause respiratory paralysis and even death. Residues of vozapine in crops and the environment also pose a significant hazard to mammals and the environment: it can pass through polluted water body, pass through food chain, enter from digestive tract and respiratory tract and harm human body.
At present, the chromatography is still the mainstream method for detecting the vozapyr, and comprises high performance liquid chromatography, gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry, ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry and the like. Although the chromatography or/and the combination technology can realize high-flux detection of the vozapyr and other organophosphorus pesticides, the equipment is expensive, the operation is complex, the analysis time is long, the requirement on operators is high, and the real-time detection of emergency events is not facilitated. Therefore, the development of a simple, rapid and cheap technology for detecting the vozapyr is of great significance.
The fluorescence detection technology can respond to a target detection object quickly and sensitively, is simple to operate and low in price, and has received attention of more and more scholars. However, most of the common analytical detection techniques focus on the detection of a single signal, and are easily interfered by background signals, instrument noise and the surrounding environment, and the accuracy of the detection techniques is reduced. In order to overcome the defects, a ratio type fluorescence sensor is produced, the ratio of two fluorescence signals is used as an output signal, namely, an internal standard is introduced into the sensor, so that the system error can be effectively eliminated, and the accuracy is improved. In order to obtain multiple fluorescence signals, a common strategy is to introduce different fluorophores, but the additional fluorophores not only increase the operation steps and the detection cost, but also may interfere with or repel the target detection object. Thus, fluorophores with multiple fluorescence signals would be more advantageous in the construction of ratiometric sensors. Although the construction of ratiometric sensors based on a single fluorophore with dual emission properties has been reported, the reported fluorescence sensors are mostly focused on the emission spectrum, and few fluorescence sensors based on the excitation spectrum, let alone ratiometric fluorescence sensors based on the excitation spectrum. For the innovative scientific research, a quicker and wider channel is provided for the material detection technology in the future life.
Disclosure of Invention
The invention aims to provide a cheap, quick and green fluorescence ratio detection method for the vozaphosphoric pesticide.
In order to solve the technical problems, the invention adopts the following technical scheme:
the nitrogen-doped fluorescent carbon quantum dots are synthesized by taking natural macromolecular saccharides as a carbon source, adding a nitrogen source and adopting a one-step hydrothermal method; the nitrogen-doped fluorescent carbon quantum dot has a double-excitation-single-emission fluorescent characteristic, and when the fixed emission wavelength is 400-440 nm, the nitrogen-doped fluorescent carbon quantum dot has an excitation peak at about 235nm and 327 nm.
The natural polymer saccharide is one or more of cellulose, xylose and cellobiose; the nitrogen source is one or more of urea, ammonium bicarbonate, dicyanodiamine, ethylenediamine and ammonia water.
The preparation method of the nitrogen-doped fluorescent carbon quantum dot comprises the steps of taking natural macromolecular saccharides as a carbon source, adding a nitrogen source, adding deionized water into a hydrothermal reaction kettle, carrying out hydrothermal reaction in a high-temperature environment, and cooling to obtain a crude product of the nitrogen-doped fluorescent carbon quantum dot; and filtering the crude product by a filter membrane, and dialyzing by a dialysis bag to obtain a purified product of the nitrogen-doped fluorescent carbon quantum dot.
0.05-0.5 g of natural macromolecular saccharides, 0.2-2.0 g of nitrogen source and 10-50 mL of deionized water, performing hydrothermal reaction at 140-210 ℃ for 1-15 h, and dialyzing for 12-36 h by using a dialysis bag of 500-1000 Da.
0.2g of natural polymer saccharides, 0.75g of urea as a nitrogen source and 20mL of deionized water, carrying out hydrothermal reaction at 180 ℃ for 4h, dialyzing for 24h by adopting a 1000Da dialysis bag, and fixing the volume of the dialyzed solution to 50 mL.
The nitrogen-doped fluorescent carbon quantum dot is used for visual detection of vozapyr and preparation of a ratio type fluorescent sensor.
A fluorescence ratio detection method of the Vozaphosphorus pesticide comprises the steps of preparing a Vozaphosphorus solution with gradient concentration by using the nitrogen-doped fluorescent carbon quantum dots and the Vozaphosphorus standard substance, fixing the emission wavelength at 400-440 nm, scanning a fluorescence excitation spectrum by using a fluorescence spectrophotometer, and recording an excitation peak 235nm (I)1) And 327nm (I)2) The fluorescence intensity of (a) is expressed as the ratio I of the fluorescence excitation peak intensity2/I1Taking the concentration of the vozapyr as the ordinate and the concentration of the vozapyr as the abscissa, and establishing a standard curve; and (4) detecting the vozapyr in the sample by taking the standard curve as a basis.
The emission wavelength is fixed at 420-430 nm.
The phosphorus-removing solution with gradient concentration adopts a mixed solution of methanol and water as a solvent, and the ratio of the methanol to the water in the mixed solution of the methanol and the water is 1-4: 4-1.
The ratio of methanol to water in the mixed solution of methanol and water is 1:4, 2:3, 3:2 or 4: 1.
Aiming at the problem that effective targeted detection measures are lacked in the existing vodka, the inventor develops a nitrogen-doped fluorescent carbon quantum dot, takes natural macromolecular saccharides as a carbon source, adds a nitrogen source, and adopts a one-step hydrothermal method for synthesis; the nitrogen-doped fluorescent carbon quantum dot has a double-excitation-single-emission fluorescent characteristic, and when the fixed emission wavelength is 400-440 nm, the nitrogen-doped fluorescent carbon quantum dot has an excitation peak at each of 235nm and 327 nm. Due to the double-excitation-single-emission fluorescence characteristic of the nitrogen-doped fluorescent carbon quantum dots, the single nitrogen-doped fluorescent carbon quantum dots are used as fluorophores, no additional fluorophores are needed, double-output signals can be realized, and the fluorescence ratio sensor is established. Accordingly, the inventors have established a fluorescence ratio detection method for a vozapyr pesticide. With the addition of the vozaphosphorus, the nitrogen-doped fluorescent carbon quantum dots can react within 1min, specifically, the excitation peak at 235nm is continuously quenched, while the fluorescence peak at 327nm is basically kept unchanged, and a standard curve is established by the quenching peak; and (4) detecting the vozapyr in the sample by taking the standard curve as a basis. In a word, the method does not need expensive large-scale instruments, is simple to operate, green and environment-friendly, has quick response, and has potential application value in the real-time detection of the vozapyr.
Compared with the prior art, the invention has at least the following advantages:
(1) the nitrogen-doped fluorescent carbon quantum dot takes natural macromolecular saccharides as a carbon source, and has wide sources, low cost and easy obtainment.
(2) The nitrogen-doped fluorescent carbon quantum dot has the fluorescent characteristic of double excitation-single emission, and two fluorescent signals can be provided without adding other fluorophores; most of the existing fluorescence sensors are based on emission spectra, and the invention creatively utilizes the excitation spectra to construct the ratiometric fluorescence sensor for the vodkil, and identifies the ratiometric fluorescence sensor based on the response of the fluorescence excitation spectra to the vodkil, thereby providing a new idea for the construction of the ratiometric fluorescence sensor, and being green, environment-friendly and low in cost.
(3) The invention adopts the ratio type fluorescence sensor to carry out the vodka detection, and has the characteristics of high accuracy, good sensitivity, quick response and the like.
(4) The method has good application prospect and application value in the field of analysis and detection, and can be applied to detection of the vozapyr in environmental water samples and agricultural products.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) image of fluorescent carbon quantum dots.
Fig. 2 is a graph of excitation and emission spectra of fluorescent carbon quantum dots.
FIG. 3 is a graph of fluorescence response of different concentrations of Vozaphosphorus to fluorescence excitation spectra at 235nm and 327nm of fluorescent carbon quantum dots.
FIG. 4 is a standard graph for detecting Vozapyr.
FIG. 5 is a fluorescence diagram of nitrogen-doped fluorescent carbon quantum dots under 254nm ultraviolet light irradiation in the presence of different concentrations of vozaphos, wherein: 1-11 correspond to the concentration of vozapyr of 0.00,0.16,0.24,0.40,0.60,0.80,1.00,2.00,4.00,6.00, 10.00. mu.g/mL.
FIG. 6 is a graph showing the fluorescence ratio response of nitrogen-doped fluorescent carbon quantum dots to vodka and other interfering substances.
Detailed Description
Example 1 preparation of nitrogen-doped fluorescent carbon quantum dots
Adding 0.2g of cellobiose, 0.75g of urea and 20mL of deionized water into a hydrothermal reaction kettle, reacting for 4 hours at 180 ℃, and cooling to room temperature to obtain a nitrogen-doped fluorescent carbon quantum dot crude product; the crude product was passed through a 0.22 μm filter to remove large particulate matter and then dialyzed in a 1000Da dialysis bag for 24h to remove unreacted starting material and small particulate matter. And (5) fixing the volume of the dialyzed solution to 50mL to obtain a nitrogen-doped fluorescent carbon quantum dot solution, and storing in a dark place for later use.
As shown in figure 1, the nitrogen-doped fluorescent carbon quantum dot of the invention has good monodispersity and spherical shape, the size distribution range is 1.2-4.6 nm, and the particle size is 2.7nm calculated by counting the average particle size of 100 particles. The presence of graphitic carbon was confirmed by the clear observation of lattice striations of CQDs with a lattice spacing of 0.23nm using high resolution transmission electron microscopy, due to the (100) graphitic plane.
As shown in FIG. 2, the nitrogen-doped fluorescent carbon quantum dot of the present invention has a fluorescence excitation peak at about 235nm and 327nm, respectively corresponding to sp2Pi-pi transition of graphite carbon core and n-pi transition of functional group such as C-O, N-O. Interestingly, whether excited by 235nm or 327nm, the nitrogen-doped fluorescent carbon quantum dot is only observed at about 420nmA fluorescence emission peak, the new phenomenon probably due to n-pi-conjugated functional groups and sp2The graphitic carbon forms a hyperconjugated system. This dual excitation-single emission phenomenon provides a new strategy for the construction of fluorescence ratio sensors.
Example 2 construction of ratiometric fluorescent sensor for vozaphosphorine
mu.L of the fluorescent carbon quantum dots prepared in example 1 and 4. mu.L, 8. mu.L, 10. mu.L, 12. mu.L, 20. mu.L, 30. mu.L, 40. mu.L, 60. mu.L, 100. mu.L, 140. mu.L, 200. mu.L, 300. mu.L, 400. mu.L, 600. mu.L and 700. mu.L of a vozapyr standard (100. mu.g/mL) are added into a series of colorimetric tubes, and a 2:3 methanol-water solution (pH 11) is used to fix the volume to 5mL and shake up. Fixing the emission wavelength at 400-440 nm, scanning fluorescence excitation spectrum with LS55 type fluorescence spectrophotometer, and recording excitation peak 235nm (I)1) And 327nm (I)2) Left and right fluorescence intensity. With I2/I1And taking the concentration of the vozapyr as the ordinate and the concentration of the vozapyr as the abscissa, establishing a standard curve, and obtaining a regression equation and a linear correlation coefficient. Meanwhile, fluorescent pictures of the fluorescent carbon quantum dots in the presence of different concentrations of the vozaphosphorine are observed under an ultraviolet lamp of 254 nm.
As shown in FIG. 3, with the continuous addition of the vozaphosphor, the nitrogen-doped fluorescent carbon quantum dots can respond to the vozaphosphor within 1min (can be stabilized for more than 1 h), and the specific expression is that the fluorescence excitation peak at 235nm is continuously quenched, accompanied by the blue shift of the excitation wavelength from 235nm to 220nm, and the excitation peak at 327nm is almost unchanged. Thus, it will be possible to use at 235nm (I)1) The signal at (E) is used as a response signal at 327nm (I)2) The signal is used as a reference signal to construct a ratiometric fluorescent sensor for vozapyr.
As shown in FIG. 4, the ratio I of the excitation signals2/I1Shows good linear relation with the concentration of the fosfestide within the ranges of 0.08-4.00 mu g/mL and 4.00-14.00 mu g/mL, and the linear regression equations are I2/I1＝0.18c+0.60，I2/I10.09c +0.89 (where c represents the concentration of vozapyr), correlation coefficients (r) were 0.9986 and 0.9990, respectively, with a detection limit of 26.67 ng/mL.
As shown in FIG. 5, with the continuous addition of the vozaphosphorus, continuous quenching of carbon quantum dots can be observed under a 254nm ultraviolet lamp, which indicates that the ratiometric fluorescent sensor constructed by the invention has potential application value in the visual detection of the vozaphosphorus.
Example 3 Selective examination of ratiometric fluorescent sensors for Vozaphosphorine
Selectivity is an important indicator for evaluating sensor performance. The selectivity of ratio sensors based on excitation spectra was investigated by detecting the ratio signals of coexisting materials and other pesticides.
200 μ L of the nitrogen-doped fluorescent carbon quantum dots obtained in example 1 and 4.00 μ g/mL of phorate, acetochlor, alachlor, chlorfenvinphos, pyridaben, clothianidin, phosphorus dibromide, systemic phosphate, hexachlorobenzene, phoxim, cypermethrin, NO, were added to a series of 5mL colorimetric tubes2-，S-，Cl-，F-，SO4 2-，Na+，Al3+，Cr6+，Mn2+，NH4 +，Ca2+And (4) metering the volume to a scale mark by using a methanol-water solution with the volume ratio of 2:3, and respectively marking the volume as A to V. Fixing the emission wavelength to 420nm, scanning the fluorescence excitation spectrum of the nitrogen-doped fluorescent carbon quantum dot, and simultaneously recording the fluorescence excitation peak I1And I2And calculating the ratio of the single nitrogen-doped fluorescent carbon quantum dots to obtain the value (I)2/I1)0The ratio of the amount of the thiobenate to the amount of the other interfering substances is I2/I1Fluorescence ratio change value (I)2/I1)0-(I2/I1)。
As shown in FIG. 6, the difference in fluorescence change (I) in the presence of vozaphosphorus at 4.00. mu.g/mL2/I1)0-(I2/I1) The fluorescence change difference value is between-0.03 and 0.182 when other interfering substances of 4.00 mu g/mL exist, which shows that the double excitation ratio sensor constructed by the invention has good selectivity on the vozapyr.
Example 4 detection of Vozaphosphorus content in lake Water
Lake water is collected from university campus of Guangxi and calmLeft overnight to precipitate a large suspension, which is then passed through a 0.22 filter. And taking 200 mu L of the nitrogen-doped fluorescent carbon quantum dots obtained in the example 1 and 200 mu L of the lake water sample, metering to a scale with a methanol-water solution with the volume ratio of 2:3, and shaking up. The emission wavelength was fixed at 420nm, the fluorescence excitation spectrum was scanned by a LS55 type fluorescence spectrophotometer, and the excitation peak was recorded at about 235nm (I)1) And 327nm (I)2) The fluorescence intensity of (2). The standard addition recovery experiment was also performed at standard addition levels of 0.2, 0.4, 0.8. mu.g/mL. Each set of samples was assayed in duplicate 6 times. The recovery rate and relative standard deviation RSD were calculated.
The results showed that vozapine was not detected in lake water on campus of university in Guangxi, with recovery rates at three spiked levels of 90.64%, 110.17%, 104.78%, and corresponding RSDs of 5.33%, 7.93%, 4.02%, respectively. As can be seen, the fluorescence ratio sensor of the invention has good accuracy and precision in the detection of lake water samples.
Example 5 detection of Fugu content in river Water
River water was taken from the central polder of nanning, and left overnight to precipitate large suspended matter, which was then filtered through a 0.22 filter. Detection was performed with reference to example 4.
The results showed that vozapine was not detected in the river water of the central polder of naning, with recovery rates at the three spiked levels of 98.51%, 101.08%, 95.73% and corresponding RSDs of 5.07%, 5.87%, 7.22% respectively. As can be seen, the fluorescence ratio sensor of the invention has good accuracy and precision in river water sample detection.
Example 6 detection of Fugu phosphorus content in strawberry
A strawberry sample is obtained from a local market, homogenization treatment is carried out firstly, then 0.5-2 g of the sample is taken to be added into a 10mL centrifuge tube, 4mL methanol-water solution (2:3) is added, water bath extraction is carried out for 30min in a shaking table, centrifugation is carried out, supernatant liquid is taken, and the supernatant liquid is filtered through a 0.22 mu m filter membrane to be detected. Detection was performed with reference to example 4.
The results showed that vozapine was not detected in the strawberry samples, and the results of the spiked recovery experiments showed that the recovery at the three spiked levels was 112.74%, 111.98%, 98.22%, with corresponding RSD of 5.30%, 13.21%, 9.10%, respectively. It can be seen that the fluocinonide fluorescence ratio sensor of the invention has good accuracy and precision in strawberry sample detection.
In addition, the inventor also uses cellulose and xylose as carbon sources and NH4HCO3And dicyanodiamine, ammonia water and ethylenediamine are used as nitrogen sources, and the nitrogen-doped fluorescent carbon quantum dots are synthesized by the method. Research shows that the obtained nitrogen-doped fluorescent carbon quantum dots have similar structures and properties, and also have double-excitation-single-emission fluorescence properties and similar responses. Nevertheless, the reaction time required by the nitrogen-doped fluorescent carbon quantum dots synthesized by taking cellobiose as a carbon source and urea as a nitrogen source is shortest, the reaction temperature is mild, and the fluorescence property is strongest.
Claims (10)
1. A nitrogen-doped fluorescent carbon quantum dot is characterized in that natural polymer saccharides are used as a carbon source, a nitrogen source is added, and the nitrogen-doped fluorescent carbon quantum dot is synthesized by a one-step hydrothermal method; the nitrogen-doped fluorescent carbon quantum dot has a double-excitation-single-emission fluorescent characteristic, and when the fixed emission wavelength is 400-440 nm, the nitrogen-doped fluorescent carbon quantum dot has an excitation peak at each of 235nm and 327 nm.
2. The nitrogen-doped fluorescent carbon quantum dot of claim 1, wherein: the natural polymer saccharides are one or more of cellulose, xylose and cellobiose; the nitrogen source is one or more of urea, ammonium bicarbonate, dicyanodiamine, ethylenediamine and ammonia water.
3. The method for preparing the nitrogen-doped fluorescent carbon quantum dot as claimed in claim 1, wherein the method comprises the following steps: taking natural macromolecular saccharides as a carbon source, adding a nitrogen source, adding deionized water into a hydrothermal reaction kettle, carrying out hydrothermal reaction in a high-temperature environment, and cooling to obtain a nitrogen-doped fluorescent carbon quantum dot crude product; and filtering the crude product by a filter membrane, and dialyzing by a dialysis bag to obtain a purified product of the nitrogen-doped fluorescent carbon quantum dot.
4. The method for preparing nitrogen-doped fluorescent carbon quantum dots according to claim 2, wherein the method comprises the following steps: the natural macromolecular saccharides are 0.05-0.5 g, the nitrogen source is 0.2-2.0 g, and the deionized water is 10-50 mL, the hydrothermal reaction is carried out at 140-210 ℃ for 1-15 h, and the dialysis is carried out for 12-36 h by adopting a dialysis bag with the temperature of 500-1000 Da.
5. The method for preparing nitrogen-doped fluorescent carbon quantum dots according to claim 4, wherein the method comprises the following steps: the natural polymer saccharide is 0.2g of cellobiose, the nitrogen source is 0.75g of urea and 20mL of deionized water, the hydrothermal reaction is carried out for 4h at 180 ℃, dialysis is carried out for 24h by adopting a 1000Da dialysis bag, and the volume of the solution after dialysis is fixed to 50 mL.
6. The nitrogen-doped fluorescent carbon quantum dot of claim 1 is used for visual detection of vozapyr and preparation of a ratiometric fluorescent sensor thereof.
7. A fluorescence ratio detection method for a vozaphosphoric pesticide, which is characterized by comprising the following steps: preparing a phosphorus-vodkil solution with gradient concentration by using the nitrogen-doped fluorescent carbon quantum dots and the phosphorus-vodkil standard substance according to claim 1, fixing the emission wavelength at 400-440 nm, scanning a fluorescence excitation spectrum by using a fluorescence spectrophotometer, and recording an excitation peak 235nm (I)1) And 327nm (I)2) The fluorescence intensity of (a) is expressed as the ratio I of the fluorescence excitation peak intensity2/I1Taking the concentration of the vozapyr as the ordinate and the concentration of the vozapyr as the abscissa, and establishing a standard curve; and (4) detecting the vozapyr in the sample by taking the standard curve as a basis.
8. The fluorescence ratio detection method of a vozaphosphoric pesticide according to claim 7, wherein: the emission wavelength is fixed at 420-430 nm.
9. The fluorescence ratio detection method of a vozaphosphoric pesticide according to claim 8, wherein: the phosphorus-removing solution with gradient concentration adopts a mixed solution of methanol and water as a solvent, and the ratio of the methanol to the water in the mixed solution of the methanol and the water is 1-4: 4-1.
10. The fluorescence ratio detection method of a vozaphosphoric pesticide according to claim 9, wherein: the ratio of methanol to water in the mixed solution of methanol and water is 1:4, 2:3, 3:2 or 4: 1.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008036061A2 (en) * | 2005-04-06 | 2008-03-27 | Verenium Corporation | Enzymes and formulations for broad-specificity decontamination of chemical and biological warfare agents |
| CN103411935A (en) * | 2013-07-19 | 2013-11-27 | 中国科学院合肥物质科学研究院 | Method for visualized detection of organophosphorus pesticide residue by doped quantum dot ratio fluorescence technique |
| CN104267120A (en) * | 2014-01-20 | 2015-01-07 | 广西大学 | Ultra-high performance liquid chromatography-tandem mass spectrometry method (UPLC-MS/MS) for detecting endogenous hormone in tubers of Chinese yams |
| WO2016001125A1 (en) * | 2014-07-01 | 2016-01-07 | Bayer Cropscience Aktiengesellschaft | Active compound combinations and methods to protect the propagation material of plants |
| CN106477610A (en) * | 2016-09-21 | 2017-03-08 | 广西大学 | A kind of preparation method of technical grade cryolite with high molecular ratio |
| CN107490565A (en) * | 2017-06-27 | 2017-12-19 | 昆明理工大学 | A kind of method of nitrogen-doped carbon quantum dot fluorescence enhanced sensitivity detection Ciprofloxacin |
| CN107515206A (en) * | 2017-06-27 | 2017-12-26 | 昆明理工大学 | A kind of method of sulfur doping carbon quantum dot fluorescence sensitivity detection Norfloxacin |
| CN109061167A (en) * | 2018-08-29 | 2018-12-21 | 郑州工程技术学院 | A kind of immune chromatography test paper detecting pyrethroid |
| CN110108679A (en) * | 2019-04-26 | 2019-08-09 | 青岛农业大学 | A kind of organophosphorus pesticide based on Copper-cladding Aluminum Bar carbon nano dot is without enzyme ratio fluorescent new detecting method |
| CA3098986A1 (en) * | 2018-05-25 | 2019-11-28 | BASF Agricultural Solutions Seed US LLC | Plants containing elite event ee-gm4 and methods and kits for identifying such event in biological samples, and treatment thereof |
-
2020
- 2020-12-14 CN CN202011474829.7A patent/CN112666141B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008036061A2 (en) * | 2005-04-06 | 2008-03-27 | Verenium Corporation | Enzymes and formulations for broad-specificity decontamination of chemical and biological warfare agents |
| CN103411935A (en) * | 2013-07-19 | 2013-11-27 | 中国科学院合肥物质科学研究院 | Method for visualized detection of organophosphorus pesticide residue by doped quantum dot ratio fluorescence technique |
| CN104267120A (en) * | 2014-01-20 | 2015-01-07 | 广西大学 | Ultra-high performance liquid chromatography-tandem mass spectrometry method (UPLC-MS/MS) for detecting endogenous hormone in tubers of Chinese yams |
| WO2016001125A1 (en) * | 2014-07-01 | 2016-01-07 | Bayer Cropscience Aktiengesellschaft | Active compound combinations and methods to protect the propagation material of plants |
| CN106477610A (en) * | 2016-09-21 | 2017-03-08 | 广西大学 | A kind of preparation method of technical grade cryolite with high molecular ratio |
| CN107490565A (en) * | 2017-06-27 | 2017-12-19 | 昆明理工大学 | A kind of method of nitrogen-doped carbon quantum dot fluorescence enhanced sensitivity detection Ciprofloxacin |
| CN107515206A (en) * | 2017-06-27 | 2017-12-26 | 昆明理工大学 | A kind of method of sulfur doping carbon quantum dot fluorescence sensitivity detection Norfloxacin |
| CA3098986A1 (en) * | 2018-05-25 | 2019-11-28 | BASF Agricultural Solutions Seed US LLC | Plants containing elite event ee-gm4 and methods and kits for identifying such event in biological samples, and treatment thereof |
| CN109061167A (en) * | 2018-08-29 | 2018-12-21 | 郑州工程技术学院 | A kind of immune chromatography test paper detecting pyrethroid |
| CN110108679A (en) * | 2019-04-26 | 2019-08-09 | 青岛农业大学 | A kind of organophosphorus pesticide based on Copper-cladding Aluminum Bar carbon nano dot is without enzyme ratio fluorescent new detecting method |
Non-Patent Citations (5)
| Title |
|---|
| QINGYI WEI ETAL.: "Determination of acrylamide in food products based on the fluorescence enhancement induced by distance increase between functionalized carbon quantum dots", 《TALANTA》 * |
| S.A. NSIBANDE ETAL.: "Fluorescence detection of pesticides using quantum dot materials – A review", 《ANALYTICA CHIMICA ACTA》, pages 9 - 22 * |
| XIUFEN LIAO ETAL.: "Comparison of N-doped carbon dots synthesized from the main components of plants including cellulose, lignin, and xylose: Characterized, fluorescence mechanism, and potential applications", 《DYES AND PIGMENTS》, pages 1 - 10 * |
| 吕春秋等: "基于双荧光中心碳量子点的比率型荧光探针快速检测乐果", 《光谱学与光谱分析》, pages 468 - 474 * |
| 陈文森等: "农药伏杀磷气相色谱分析", 《浙江化工》, pages 27 - 29 * |
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