CN113933272B - Fluorescent probe detection method for phthalate plasticizer in food - Google Patents
Fluorescent probe detection method for phthalate plasticizer in food Download PDFInfo
- Publication number
- CN113933272B CN113933272B CN202111143655.0A CN202111143655A CN113933272B CN 113933272 B CN113933272 B CN 113933272B CN 202111143655 A CN202111143655 A CN 202111143655A CN 113933272 B CN113933272 B CN 113933272B
- Authority
- CN
- China
- Prior art keywords
- sample
- phthalate
- diluting
- solution
- plug
- 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
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Landscapes
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a fluorescent probe detection method of phthalate plasticizer in food, the invention adopts a pyrolysis method to prepare bimetallic atom catalyst Cu, Fe-N-C nanoenzyme, Cu, Fe-N-C show peroxidase activity, in the presence of hydrogen peroxide, Cu, Fe-N-C oxidize o-phenylenediamine (OPD) to generate 2, 3-Diaminophenazine (DAP) product with fluorescence, Phthalate Substances (PAEs) can inhibit the activity of Cu, Fe-N-C peroxidase, and the concentration change of the PAEs and the reduction of fluorescence intensity are in a linear relation, thereby establishing a new method for fluorescence detection of the phthalate substances, and the method quantitative limit is 0.5 mu g/kg; the method has the characteristics of high sensitivity, strong specificity, simple and rapid operation and the like.
Description
Technical Field
The invention relates to the technical field of chemical analysis and detection, in particular to a method for detecting phthalate fluorescent probe in food.
Background
The plasticizer is a material auxiliary agent which is widely applied to plastic products and used for enhancing flexibility. There are over 100 types of plasticizers available commercially, with Phthalic Acid Esters (PAEs) being the most common, exceeding 80% of the total plasticizer. The research proves that the PAEs are environmental hormone substances, and the PAEs are combined with polymers in plastic products in an unstable non-covalent bond form, so that the PAEs can easily migrate out of the plastic products to cause environmental pollution, particularly food pollution. At present, the PAEs in the food can be measured by a high performance liquid chromatography, a gas chromatography-mass spectrometry combined method, a fluorescence method, an electrochemical detection method and the like.
The nano enzyme is a mimic enzyme which not only has the unique performance of nano materials, but also has a catalytic function. As a novel mimic enzyme, the nano-enzyme has the advantages that many other traditional mimic enzymes cannot achieve, and people can research and utilize the nano-enzyme according to the characteristics of the nano-material mimic enzyme, so that the nano-enzyme has a larger application prospect. The monatomic nanoenzyme with high enzyme activity is designed, the unit activity of the nanoenzyme is greatly improved, the monatomic nanoenzyme becomes a hotspot of current research, and the nanoenzyme with double activity centers has great advantages in the aspects of improving the enzyme activity and selectivity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for detecting phthalate fluorescent probe in food, the invention adopts a pyrolysis method to prepare bimetallic atom catalyst Cu, Fe-N-C nanoenzyme, Cu, Fe-N-C show extremely high peroxidase mimetic (POD) activity, and Phthalate Substances (PAEs) can inhibit the activity of Cu, Fe-N-C peroxidase mimetic. In the presence of hydrogen peroxide, oxidizing o-phenylenediamine (OPD) by using Cu, Fe-N-C nano enzyme to generate a fluorescent 2, 3-Diaminophenazine (DAP) product, wherein the concentration change of PAEs and an enzyme inhibition reaction are in a linear relation; thus establishing a novel PAEs fluorescence detection method, the quantitative limit of the method of the invention reaches 0.5 mug/kg; the method has the characteristics of high sensitivity, strong specificity, simple and rapid operation and the like.
The invention discloses a method for detecting phthalate fluorescent probe in food, comprising the following steps:
(1) preparation of working curve of dimethyl phthalate (DMP)
0.1mg/mL Cu, 50-100 muL Fe-N-C nano enzyme, 0.2mL 5mmol/L o-phenylenediamine (OPD) and 20mmol/L H are added into a 10mL colorimetric tube with a plug 2 O 2 Diluting 0.2mL of dimethyl phthalate standard solution to 5mL by using a phosphoric acid-phosphate buffer solution with the pH value of 7.0, wherein the concentration range of dimethyl phthalate in a color comparison tube with a plug is 0.5-45 mu g/kg, shaking up, standing for 5-10 min, measuring the fluorescence intensity at the emission wavelength of 560nm under the excitation wavelength of 360nm, and drawing a standard curve by taking the concentration of dimethyl phthalate as a horizontal coordinate and the fluorescence intensity as a vertical coordinate to obtain a regression equation;
(2) sample processing
② edible oil sample: taking 5-10 mL of liquid to be measured, adding 1-2 mL of absolute ethyl alcohol and 1-2 mL of acetonitrile into a clean separating funnel, shaking, standing for layering, taking out supernate, extracting for 2-3 times, combining the supernate, transferring to a 25mL volumetric flask, diluting to a scale with purified water, and preparing a sample measuring solution;
(3) and (3) sample determination: adding 0.1mg/mL Cu, Fe-N-C nanoenzyme 50-100 mu L, 5mmol/L o-phenylenediamine 0.2mL and 20mmol/L H into 10mL colorimetric tube with plug 2 O 2 And (3) 0.2mL, adding the sample determination solution prepared in the step (2), diluting to 5mL by using a phosphate-phosphate buffer solution with the pH value of 7.0, shaking up, standing for 5-10 min, determining the fluorescence intensity at the emission wavelength of 560nm, substituting into the regression equation in the step (1), and calculating the content of the phthalate plasticizer in the sample.
The Cu, Fe-N-C nanoenzyme is prepared by mixing 10-15 mL of CuCl 2-3 g 2 The methanol solution of (1) and 20-30 mL of a mixture of (4-6 g) meso-tetra (4-carboxyphenyl) porphine and (2-3 g) FeCl 3 After being uniformly mixed, the methanol solution is dried and aged for 2 to 3 hours at the temperature of between 75 and 85 ℃ to obtain dark green dry powder, and the dry powder is dried at the temperature of between 700 and 800 ℃ and N 2 Calcining for 2h under protection.
The phthalate plasticizer comprises dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP) and dinonyl phthalate (DINP), the five phthalates have the peroxidase-like activity on Cu, Fe-N-C nanoenzymes, the fluorescence inhibition effects generated by oxidizing OPD are consistent, DMP is used as a model during the preparation of a working curve, and the content of one or more of the five phthalate substances is measured by a sample.
The invention has the advantages that:
1. the prepared Cu and Fe-N-C nano enzyme serving as the bimetallic atom catalyst has the activity of a pseudo peroxidase, Phthalate Substances (PAEs) can inhibit the activity of the Cu and Fe-N-C pseudo peroxidase, in the presence of hydrogen peroxide, Cu and Fe-N-C oxidize o-phenylenediamine (OPD) to generate a 2, 3-Diaminophenazine (DAP) product with fluorescence, the concentration change of the PAEs and the fluorescence intensity of enzyme inhibition reaction are in a linear relation, and the method has the quantitative limit of 0.5 mu g/kg due to the establishment of a novel PAEs fluorescence detection method;
2. the method for detecting the content of the PAEs has the characteristics of high sensitivity, strong specificity, simplicity in operation, rapidness and the like.
Drawings
FIG. 1 is a linear relationship of the inhibition of the oxidation of OPD by Cu, Fe-N-C pseudooxidase by DMP in example 1;
FIG. 2 shows the effect of coexisting ions on the detection system in example 1, with no added substance as blank;
FIG. 3 shows the results of the effect of the coexisting materials on the detection system in example 1, and the blank is no added materials.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.
Example 1: determination of PAEs in food packaging Plastic bags
1. Preparing Cu, Fe-N-C nanoenzyme: 10mL of a solution containing 2.636g of CuCl 2 With 20mL of a solution containing 5g of meso-tetra (4-carboxyphenyl) porphine and 2.376g of FeCl 3 After being uniformly mixed, the methanol solution is dried and aged for 3 hours in an oven at the temperature of 80 ℃; the obtained dark green dry powder was weighed 5g into a quartz boat, and then placed in a tube furnace at 750 ℃ and N 2 Calcining for 2h under protection to obtain the catalyst;
2. preparation of a dimethyl phthalate (DMP) working curve: having a plug at 10mL0.1mg/mL Cu, 100 mu L Fe-N-C nano enzyme, 0.2mL 5mmol/L o-phenylenediamine (OPD) and 20mmol/L H are added into a colorimetric tube 2 O 2 Diluting a 0.2mL DMP standard solution to 5mL by using a phosphate-phosphate buffer solution with the pH value of 7.0, wherein the concentration range of DMP in a color comparison tube with a plug is 0.5-45 mu g/kg, shaking up, standing for 8min, measuring the fluorescence intensity at the emission wavelength of 560nm under the excitation wavelength of 360nm, drawing a standard curve by taking the concentration of DMP as a horizontal coordinate and the fluorescence intensity as a vertical coordinate, and obtaining a regression equation, wherein the correlation coefficient, the relative standard deviation, the linear range and the like are shown in Table 1;
TABLE 1 Linear equation, correlation coefficient, relative standard deviation, Linear Range
3. Method specificity investigation: the possible interfering substance with the concentration of 100 mug/kg is used for verifying the specificity of the detection system of the invention by replacing 10 mug/kg of DMP with the possible interfering substance with coexisting ions (Na) + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ 、Zn 2+ 、Fe 2+ 、Cl - 、SO 4 2- 、NO 2 - 、NO 3 - ) And substances (glucose, maltose, sucrose, ethanol); the results in FIGS. 2 and 3 show that only DMP has significant quenching effect, other substances have little quenching effect, and the method has good selection specificity.
4. Determination of PAEs Total amount in food packaging Plastic bag
(1) Sample treatment: cutting a food packaging plastic bag into pieces, weighing 10.00g of sample from the processed sample, placing the sample in a conical flask with a plug, adding 10mL of acetone and 20mL of absolute ethyl alcohol, shaking for 30min, filtering, transferring the filtrate to a 50mL volumetric flask, diluting the filtrate to a scale with purified water, and preparing a sample determination solution;
(2) and (3) sample determination: 0.1mg/mL Cu, 100 mu L Fe-N-C nano enzyme, 0.2mL 5mmol/L o-phenylenediamine (OPD) and 20mmol/L H are added into a 10mL colorimetric tube with a plug 2 O 2 0.2mL, adding the sample determination solution prepared in the step (1), diluting to 5mL by using a phosphate-phosphate buffer solution with the pH value of 7.0, shaking up, standing for 10min, determining the fluorescence intensity at the emission wavelength of 560nm, substituting into the regression equation in the step 2, and calculating the content of phthalate in the sample to be 45.0 mu g/kg;
(3) recovery and precision experiments: respectively adding 3 DMP standard solutions with different concentrations into a food packaging plastic bag sample; each concentration is measured in parallel for 3 times, the standard recovery rate is calculated, and the relative standard deviation RSD is calculated, and the result is shown in a table 2; the measured standard recovery rate of the DMP is 97.2-102.4%, the RSD is 1.21-2.31%, and the method has good accuracy and precision;
TABLE 2 sample recovery with addition of standard and RSD (n = 3)
Example 2: determination of PAEs in Plastic bag-packaged pickled cucumber samples
1. Preparing Cu, Fe-N-C nanoenzyme: the Cu, Fe-N-C nano enzyme is prepared by mixing 15mL of CuCl with 2g 2 With 30mL of a solution containing 4g of meso-tetra (4-carboxyphenyl) porphine and 3g of FeCl 3 Mixing the above methanol solution, drying and aging at 85 deg.C for 2 hr to obtain dark green dry powder, drying at 800 deg.C and N 2 Calcining for 2h under protection to obtain the catalyst;
2. preparation of a dimethyl phthalate (DMP) working curve: the same as example 1;
3. determination of PAEs in Plastic bag-packaged pickled cucumber samples
(1) Sample treatment: homogenizing pickled cucumber, weighing 10.00g of sample from the treated sample, placing the sample in a conical flask with a plug, adding 12mL of acetone and 20mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 25min, filtering, transferring the filtrate to a 50mL volumetric flask, and diluting the filtrate to a scale with purified water to obtain a sample determination solution;
(2) and (3) sample determination: as in example 1, the phthalate content was 8.2. mu.g/kg.
Example 3: determination of PAEs in edible oil samples
1. Preparing Cu, Fe-N-C nanoenzyme: 10-1512 mL of Cu, Fe-N-C nanoenzyme containing 2.636g of CuCl 2 With 25mL of a solution containing 6g of meso-tetra (4-carboxyphenyl) porphine and 2.376g of FeCl 3 Mixing the above methanol solution, drying and aging at 75 deg.C for 3 hr to obtain dark green dry powder, and drying at 700 deg.C under N 2 Calcining for 2h under protection to obtain the catalyst;
2. preparation of a dimethyl phthalate (DMP) working curve: the same as example 1;
3. determination of PAEs in edible oil
(1) Sample treatment: taking 10mL of edible oil, adding 2mL of absolute ethyl alcohol and 2mL of acetonitrile into a clean separating funnel, shaking, standing for layering, taking out supernatant, extracting twice, combining the supernatants, transferring to a 25mL volumetric flask, diluting with purified water to a scale, and preparing a sample measuring solution;
(2) and (3) sample determination: the phthalate content was 14.1. mu.g/kg as in example 1.
Example 4: determination of white spirit sample PAEs bottled by glass
1. Preparing Cu, Fe-N-C nanoenzyme: the same as example 1;
2. preparation of a dimethyl phthalate (DMP) working curve: the same as example 1;
3. determination of PAEs in white spirit samples bottled by glass
(1) Sample treatment: taking 10mL of a white spirit sample in a clean 25mL volumetric flask, and diluting the white spirit sample to a scale with purified water to prepare a sample determination solution;
(2) and (3) sample determination: as in example 1, the phthalate content was 38.0. mu.g/kg;
the results of comparison of the methods of examples 1 to 4 with the method for measuring phthalate esters in food which is the national standard for food safety, GB 5009.271-2016, are shown in Table 3, and it can be seen from the results that the results of the two methods are consistent.
TABLE 3 comparative experimental results (μ g/kg)
The histamine determination method established by the invention has the advantages of few processing steps, short used time, low processing cost, simple and convenient operation, no need of large-scale instruments and equipment and stronger advantage in actual detection.
Claims (2)
1. A fluorescent probe detection method for phthalate plasticizers in food is characterized by comprising the following steps:
(1) preparation of working curve of dimethyl phthalate
Adding 0.1mg/mL Cu, 50-100 mu L Fe-N-C nano enzyme, 0.2mL 5mmol/L o-phenylenediamine and 20mmol/L H into a 10mL colorimetric tube with a plug 2 O 2 Diluting 0.2mL of dimethyl phthalate standard solution to 5mL by using a phosphoric acid-phosphate buffer solution with the pH value of 7.0, wherein the concentration range of dimethyl phthalate in a color comparison tube with a plug is 0.5-45 mu g/kg, shaking up, standing for 5-10 min, measuring the fluorescence intensity at the emission wavelength of 560nm under the excitation wavelength of 360nm, and drawing a standard curve by taking the concentration of dimethyl phthalate as a horizontal coordinate and the fluorescence intensity as a vertical coordinate to obtain a regression equation;
(2) sample processing
② edible oil sample: taking 5-10 mL of edible oil, adding 1-2 mL of absolute ethyl alcohol and 1-2 mL of acetonitrile into a clean separating funnel, shaking, standing for layering, taking out supernatant, extracting for 2-3 times, combining the supernatants, transferring to a 25mL volumetric flask, diluting to a scale by using purified water, and thus obtaining a sample determination solution;
directly diluting the water-soluble sample with purified water to a constant volume;
(3) and (3) sample determination: adding 0.1mg/mL Cu, 50-100 mu L Fe-N-C nano enzyme, 0.2mL 5mmol/L o-phenylenediamine and 20mmol/L H into a 10mL colorimetric tube with a plug 2 O 2 0.2mL, adding the sample determination solution prepared in the step (2), diluting to 5mL by using a phosphate-phosphate buffer solution with the pH value of 7.0, shaking up, standing for 5-10 min, determining the fluorescence intensity at the emission wavelength of 560nm, substituting into the regression equation in the step (1), and calculating the content of the phthalate plasticizer in the sample;
the Cu, Fe-N-C nanoenzyme is prepared by mixing 10-15 mL of CuCl 2-3 g 2 The methanol solution of (1) and 20-30 mL of a mixture of (4-6 g) meso-tetra (4-carboxyphenyl) porphine and (2-3 g) FeCl 3 After being uniformly mixed, the methanol solution is dried and aged for 2-3 hours at the temperature of 75-85 ℃ to obtain dark green dry powder, and the dry powder is dried at the temperature of 700-800 ℃ and N 2 Calcining for 2h under protection.
2. The method for detecting the fluorescent probe of the phthalate plasticizer in the food according to claim 1, wherein the method comprises the following steps: phthalate plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dinonyl phthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111143655.0A CN113933272B (en) | 2021-09-28 | 2021-09-28 | Fluorescent probe detection method for phthalate plasticizer in food |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111143655.0A CN113933272B (en) | 2021-09-28 | 2021-09-28 | Fluorescent probe detection method for phthalate plasticizer in food |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113933272A CN113933272A (en) | 2022-01-14 |
| CN113933272B true CN113933272B (en) | 2022-08-09 |
Family
ID=79277242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111143655.0A Active CN113933272B (en) | 2021-09-28 | 2021-09-28 | Fluorescent probe detection method for phthalate plasticizer in food |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113933272B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102646810B1 (en) * | 2022-12-12 | 2024-03-14 | 한국재료연구원 | Highly sensitive and rapid detection kit of phthalates and method for detecting phthalates using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230007A (en) * | 2011-06-10 | 2011-11-02 | 东华大学 | Method for detecting phthalic acid esters (PAEs) with molecular beacon fluorescence quantitative PCR |
| CN113030079A (en) * | 2021-04-23 | 2021-06-25 | 中南民族大学 | Method for detecting pesticide carbaryl based on nanogold etching |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479241B (en) * | 2019-08-02 | 2021-09-28 | 电子科技大学 | Treatment method for improving peroxidase-like activity of nano-enzyme and product |
| CN110687172B (en) * | 2019-10-17 | 2021-12-03 | 山东师范大学 | Electrochemical luminescence biosensor, preparation method and application thereof in detection of base excision repair enzyme |
| CN112964706A (en) * | 2021-02-09 | 2021-06-15 | 贵阳海关综合技术中心(贵州国际旅行卫生保健中心、贵阳海关口岸门诊部) | Porous Co3O4Rapid colorimetric detection method of peroxidase applied to glyphosate |
| CN113155768B (en) * | 2021-04-09 | 2023-12-19 | 昆明理工大学 | Method for detecting propyl gallate and formaldehyde |
| CN113406068B (en) * | 2021-07-08 | 2024-07-23 | 云南伦扬科技有限公司 | Method for rapidly detecting glyphosate based on smart phone |
-
2021
- 2021-09-28 CN CN202111143655.0A patent/CN113933272B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230007A (en) * | 2011-06-10 | 2011-11-02 | 东华大学 | Method for detecting phthalic acid esters (PAEs) with molecular beacon fluorescence quantitative PCR |
| CN113030079A (en) * | 2021-04-23 | 2021-06-25 | 中南民族大学 | Method for detecting pesticide carbaryl based on nanogold etching |
Non-Patent Citations (1)
| Title |
|---|
| Highly active bimetallic CuFe–N–C electrocatalysts for oxygen reduction reaction in alkaline media;Yun Sik Kanga 等;《Journal of Industrial and Engineering Chemistry》;20181123;第71卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113933272A (en) | 2022-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112326579B (en) | Method for simultaneously detecting nitrite and ascorbic acid in food | |
| CN112326578B (en) | Method for rapidly detecting histamine in food | |
| CN110987843B (en) | Phosphate radical colorimetric detection method based on bimetallic MOF nano-oxidase | |
| CN112345475B (en) | Method for rapidly detecting nitrite in food | |
| CN113933272B (en) | Fluorescent probe detection method for phthalate plasticizer in food | |
| CN111795964B (en) | Method for quantitatively detecting caprylyl hydroximic acid in cosmetics based on spectrophotometry | |
| CN113155768B (en) | Method for detecting propyl gallate and formaldehyde | |
| CN111398393B (en) | Preparation method of electrochemical aptamer rate sensor for patulin detection | |
| CN109187470B (en) | Aptamer-mediated silver-doped carbon dot catalysis H2O2Method for measuring lead by reaction with TMB (tetramethylbenzidine) through fluorescence spectrum | |
| CN107746406B (en) | Preparation and application of ultrasensitive high-selectivity hypochlorous acid fluorescent probe | |
| CN115728262A (en) | Method for rapidly detecting glyphosate based on infrared light enhanced defect nanoenzyme | |
| CN113984726A (en) | Method for detecting mercury ions by amino phenylboronic acid functionalized magnetic beads/glyoxal modified DNA | |
| Guillemot et al. | Facile and fast detection of bacteria via the detection of exogenous volatile metabolites released by enzymatic hydrolysis | |
| CN112082978A (en) | Be used for detecting Hg2+Carbon nitride fluorescent sensor and preparation method and application thereof | |
| CN115490700B (en) | Fluorescent probe for rapidly detecting nitrite ions and application thereof | |
| CN112748164A (en) | Method for constructing photoelectrochemical aptamer sensor for sensitive detection of sulfadimethoxine | |
| CN102253019B (en) | Method for detecting benzoyl peroxide content of flour simply, conveniently and quickly | |
| CN113433101B (en) | Method for detecting ascorbic acid and sodium hypochlorite | |
| CN115656072A (en) | Method for rapidly detecting nitrite in food based on simulated laccase nanoenzyme | |
| CN113758908B (en) | Method for rapidly detecting chromium content by fluorescence | |
| CN109187465B (en) | Method for measuring SO 32-by using carbon dots to catalyze H2O2-TMB reaction product through fluorescence | |
| RU2779479C1 (en) | Method for luminescent determination of yttrium (iii) | |
| US9447008B2 (en) | Acetone production using silicon nanoparticles and catalyst compositions | |
| CN113281429B (en) | Gas chromatography-tandem mass spectrometry detection method for penicillic acid residue in grains | |
| CN103398968A (en) | Method for detecting 2-methylisoborneol in water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |