CN115728279A - Method for detecting cadmium content in rice based on enzyme inhibition and fluorescence inner filtering effect - Google Patents
Method for detecting cadmium content in rice based on enzyme inhibition and fluorescence inner filtering effect Download PDFInfo
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- CN115728279A CN115728279A CN202211563882.3A CN202211563882A CN115728279A CN 115728279 A CN115728279 A CN 115728279A CN 202211563882 A CN202211563882 A CN 202211563882A CN 115728279 A CN115728279 A CN 115728279A
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Abstract
The invention discloses a method for detecting cadmium content in rice based on enzyme inhibition and fluorescence inner filtering effect, belonging to the field of rapid detection of heavy metal in food. The invention discloses a method for detecting cadmium content in rice based on enzyme inhibition and fluorescence inner filtering effect, which comprises the following steps: constructing an ethanolamine phosphate modified up-conversion fluorescent material, carrying out fluorescence quenching by using a horseradish peroxidase enzymatic product, analyzing a quantitative relation model of fluorescence intensity and cadmium element concentration according to the inhibition of cadmium element on the horseradish peroxidase activity and the fluorescence inner filtering effect between the horseradish peroxidase enzymatic product and the up-conversion material, and calculating the cadmium content in the liquid to be detected according to the model. The method has stable quantitative detection range and detection limit, the detection range can be kept between 0.003 and 6mg/kg, the detection limit can reach 0.001mg/kg, the accuracy is high, and the content of cadmium element in the rice can be specifically detected.
Description
Technical Field
The invention relates to a method for detecting cadmium content in rice based on enzyme inhibition and fluorescence internal filtering effects, and belongs to the technical field of rapid detection of heavy metals in food.
Background
Eating a large amount of rice with excessive cadmium for a long time can cause irreversible damage to human bodies and directly cause the reduction of body functions such as liver and the like. The cadmium element in the rice is reported to generate biological toxicity when the content of the cadmium element in the rice is 210-308 ng/kg, and the cadmium element has the most obvious harm to organisms when the content of the cadmium element in the rice reaches 308 ng/kg.
The common detection methods such as graphite furnace atomic absorption spectroscopy, inductively coupled plasma emission spectroscopy, atomic absorption spectroscopy and other detection technologies have complex sample processing processes, expensive equipment and need to be operated by professional technicians.
In order to solve the problem of detection of cadmium in rice, chemical/biological sensors for detecting cadmium are increasingly applied, and the chemical/biological sensors mainly comprise novel rapid detection modes such as electrochemical-based sensors, colorimetric-based sensors and fluorescent-based sensors.
Disclosure of Invention
[ problem ] to
In the prior art, the detection accuracy is reduced due to the factors such as complex sample processing process, unstable fluorescence signal, photobleaching phenomenon and the like in the detection of cadmium element.
[ solution ]
In order to solve the technical problems in the prior art, the invention provides a method for detecting the cadmium content in rice based on enzyme inhibition and fluorescence inner filtering effect, which is used for carrying out specific rapid detection on cadmium element in rice based on the fluorescence inner filtering effect generated by an up-conversion nano material modified by horseradish peroxidase, 3', 5' -tetramethylbenzidine and ethanolamine phosphate, and in order to solve the application problems of the existing chemical/biological sensor, a reaction system of the up-conversion nano material horseradish peroxidase-3, 3', 5' -tetramethylbenzidine modified by ethanolamine phosphate is based on Cd 2+ The method has the advantages of short detection time, stronger specificity and higher detection sensitivity.
The invention aims to provide a method for detecting cadmium content in rice based on enzyme inhibition and fluorescence internal filtering effect, which comprises the following steps:
(1) Pretreatment of sample to be tested
Placing the crushed paddy sample powder into a polytetrafluoroethylene digestion tube, adding nitric acid and H 2 O 2 Sealing, placing in microwave for digestion, performing acid-dispelling treatment by using an acid-dispelling instrument after digestion is completed, cooling to room temperature, transferring ultrapure water, fixing volume, and passing through a water film to obtain a solution to be detected;
(2) Ethanolamine phosphate modified upconversion nano material
Dissolving ethanolamine phosphate and an up-conversion material in a mixed solution of ethanol, trichloromethane and water, adjusting the pH value to 2.5-3 by adopting hydrochloric acid, and stirring for reaction; after the reaction is finished, washing the reactant by using an ethanol water solution, and drying to obtain the catalyst;
(3) Detection of cadmium element in liquid to be detected
Preparing a series of rice matrix cadmium standard solutions with different concentrations, respectively taking the rice matrix cadmium standard solutions with different concentrations and the solution to be detected in the step (1), adjusting the pH value, adding the ethanolamine phosphate prepared in the step (2) to modify an up-conversion nano material, then adding horseradish peroxidase for reaction, and then adding 3,3', 5' -tetramethyl benzidine to form a reaction system; and (3) measuring the intensity of the fluorescence signal after the reaction is finished, constructing a quantitative relation model by taking the concentration of the cadmium element in the rice matrix cadmium standard solution with different concentrations as an abscissa and the corresponding intensity of the fluorescence signal as an ordinate, and calculating the content of the cadmium element in the liquid to be measured according to the quantitative relation model and the intensity of the fluorescence signal of the liquid to be measured.
In one embodiment, the mass fraction of the nitric acid in the step (1) is 65-70%; h 2 O 2 The mass fraction of (A) is 30%; nitric acid and H 2 O 2 The volume ratio of (A) to (B) is 5-8.
In one embodiment, the acid-removing treatment time in step (1) is 40-60 min.
In one embodiment, the mass ratio of the ethanolamine phosphate to the upconverting material in step (2) is 1: 25-1: 20.
in one embodiment, the volume ratio of ethanol, chloroform and water in the mixed solution of ethanol, chloroform and water in step (2) is 2.
In one embodiment, the concentration of the hydrochloric acid in the step (2) is 1mol/L.
In one embodiment, the ethanol aqueous solution in the step (2) is 40 to 60 percent of ethanol aqueous solution by mass fraction.
In one embodiment, the drying conditions of step (2) are: drying in an oven at 60-80 ℃ for 6-8 h.
In one embodiment, the upconverter material of step (2) is a lanthanide series upconverter nano-solid material.
In one embodiment, the lanthanide upconversion nanosolids material is specifically prepared as follows:
1) Dissolving ytterbium chloride hexahydrate, yttrium chloride hexahydrate, erbium chloride hexahydrate and gallium chloride hexahydrate in methanol, transferring to a three-neck flask, adding oleic acid and 1-octadecene, mixing, heating to 150-160 ℃, maintaining for 20-30 minutes, and magnetically stirring; then will contain NH 4 F and a methanol solution of NaOH are added into the three-neck flask drop by drop; after the dripping is finished, the mixture is heated for 40 to 60 minutes in water bath at a temperature of between 60 and 70 ℃, and thenThen quickly heating to 300-350 ℃, and continuously magnetically stirring for 1-2 hours to obtain a product;
2) Washing the product obtained in the step 1) by using an ethanol water solution, centrifuging, taking the precipitate, and drying to obtain the product.
In one embodiment, the pH adjustment in step (3) is performed by adjusting the pH of the solution to 7 with sodium hydroxide solution.
In one embodiment, 400. Mu.L of ethanolamine phosphate modified up-conversion nanomaterial with a concentration of 0.1mg/mL is added to 1mL of the solution to be tested, 10. Mu.L of horseradish peroxidase is added to react for 10-15 minutes, and 400. Mu.L of 3,3', 5' -tetramethylbenzidine is added to react for 10-13 minutes in the reaction system in step (3).
The invention also aims to provide an application of the method in the aspect of rapid detection of cadmium content.
[ advantageous effects ]
(1) The method for rapidly detecting the cadmium content in the rice has the advantages that the linear concentration detection range is 0.003-6 mg/kg, the linear detection range is wide, and the corresponding detection limit LOD is 0.001mg/kg. The lowest detection limit of graphite furnace atomic absorption spectrometry used in NY/T1100-2006 in the industry standard is 0.008mg/kg, and the quantification limit is 0.1mg/kg; the method can realize quick detection of cadmium content in the rice under the condition of keeping the same detection precision as the national standard method;
(2) The specificity detection system for the cadmium content in the rice shows high transferability of detection on the cadmium element in the rice, can eliminate interference of other heavy metal elements, eliminates the phenomenon of weak background fluorescence signals, overcomes the defects of the traditional detection method, realizes high specificity and high sensitivity detection on the cadmium content in the rice, has reasonable detection steps, is simple to operate, has a wider detection linear range and a lower detection limit, and has good practical value.
Drawings
FIG. 1 is a schematic diagram of the rapid detection and detection of cadmium content in rice based on enzyme inhibition and fluorescence inner filtering effect according to the present invention;
FIG. 2 is a transmission electron microscope image of ethanolamine phosphate modified upconversion nanomaterial prepared in example 1 of the present invention;
FIG. 3 is a spectrum diagram of fluorescence signals of a specific detection system for cadmium standard solutions of different concentrations in example 1 of the present invention;
FIG. 4 is a graph showing the relationship between fluorescence and quantitation of cadmium standard solutions of different concentrations in example 1 of the present invention;
FIG. 5 is a graph showing the relationship between the fluorescence and the quantity of cadmium standard solution in comparative example 1;
FIG. 6 is a graph showing the intensity of fluorescence signals corresponding to different metal ions in example 1 and comparative example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly make reference to the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following description will explain embodiments of the present invention in further detail with reference to the accompanying drawings.
Example 1
A method for detecting cadmium content in rice based on enzyme inhibition and fluorescence inner filtering effect comprises the following steps:
s1, rice digestion treatment:
(1) Weighing 5g of paddy to be detected and blank paddy, putting the paddy and the blank paddy into a high-speed crusher, crushing for 1 minute at 6000 revolutions per minute, and sieving by a 40-mesh sieve; accurately weighing 0.2000g of sample powder in a polytetrafluoroethylene digestion tube, slowly adding 5.0mL of nitric acid with a mass fraction of 65%, 2.0mL of 30% 2 O 2 Then screwing up and sealing, and putting in microwave to clear up; raising the temperature from 80 ℃ to 200 ℃, keeping for 5 minutes, after digestion, carrying out acid-removing treatment for 45 minutes at 160 ℃ by using an acid-removing instrument, taking out, and cooling to room temperature;
(2) Transferring the cooled digestion solution for many times by using ultrapure water, fixing the volume to 10mL, filtering by using a 0.22-micron filter membrane, and collecting filtrate as the solution to be detected and the rice matrix solution.
S2, preparation of ethanolamine phosphate modified up-conversion nano solid material
(1) Respectively weighing 0.065g of ytterbium chloride hexahydrate, 0.117g of yttrium chloride hexahydrate, 0.006g of erbium chloride hexahydrate and 0.091g of gallium chloride hexahydrate, dissolving in 4mL of methanol (analytically pure), transferring to a three-neck flask, adding oleic acid and 1-octadecene, mixing, heating to 160 ℃, maintaining for 30 minutes, and magnetically stirring; then the solution containing 0.4446g of NH 4 F and 0.3g of NaOH in 20mL of methanol are added dropwise into the three-neck flask; after the dripping is finished, heating the mixture in water bath for 40 minutes at 70 ℃, then quickly heating the mixture to 300 ℃, and continuously stirring the mixture for 1 hour by magnetic force; obtaining reaction mixed liquid;
(2) Washing the reaction mixed solution obtained in the step (1) with 75mL of 80% ethanol aqueous solution for 3 times, then centrifuging at 6000 rpm for 10 minutes to remove unreacted precursors, drying in a vacuum drying oven at 60 ℃ for 24 hours, and collecting the upconversion nanoparticle solid powder;
(3) 20.8mg of ethanolamine phosphate and 200mg of the upconverting nano solid powder prepared in step (2) were weighed out separately and dissolved in 18mL of ethanol: trichloromethane: in the water mixed solution, the volume ratio of ethanol to chloroform to water is 2; then adding 1mol/L hydrochloric acid to adjust the pH value to 2.5, and violently stirring and reacting for 1 hour; finally, washing the mixture for three times by using 50% ethanol water solution, and drying the mixture for 6 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the ethanolamine phosphate modified up-conversion nano material;
s3, constructing standard curves of different cadmium concentrations
Preparing standard solutions (0, 0.5,1.0,2.0,3.0,4.0,5.0 and 6.0 mu mol/L) with different rice matrix configurations and cadmium concentrations, adjusting the pH to 7 by using a sodium hydroxide solution, adding 400 mu L of 0.1mg/mL ethanolamine phosphate to modify the up-conversion nanomaterial, and then adding 10 mu L of horseradish peroxidase to react for 15 minutes; then 400 mu L of 3,3', 5' -tetramethyl benzidine is added for mixed reaction for 13 minutes, a fluorescence signal determinator is adopted to carry out fluorescence signal intensity determination, and a quantitative relation model is constructed by taking the concentration of cadmium element as abscissa and the fluorescence signal intensity as ordinate.
S4, detecting concentration content of cadmium in rice
Measuring 1mL of the prepared rice digestion solution, adjusting the pH to 7 by using sodium hydroxide, adding 400 mu L of 0.1mg/mL ethanolamine phosphate to modify an up-conversion nano material, and then adding 10 mu L of horseradish peroxidase to react for 15 minutes; then 400 mu L of 3,3', 5' -tetramethyl benzidine is added for mixed reaction for 13 minutes, and the fluorescence signal intensity is measured; and calculating the cadmium concentration in the rice digestion solution according to the constructed quantitative relation model.
And (4) determining the result:
FIG. 2 is a transmission electron microscope image of ethanolamine phosphate modified upconversion nanomaterials; fig. 3 is the fluorescence intensity of the standard solution with different cadmium concentrations determined in this example, fig. 4 is a quantitative relationship model of a standard curve chart constructed by the fluorescence intensity with different cadmium concentrations and the cadmium concentrations, and the standard curve equation is: y =173.95X-85.254; r is 2 Is 0.9815; the linear concentration detection range is 0.003-6 mg/kg, the linear concentration detection range is wider, and the corresponding detection limit LOD is 0.001mg/kg.
Example 2 additive recovery test
A series of Cd with different concentrations 2+ The solution was added to a digestion vessel containing 0.4g of a rice sample, 2mL of deionized water and 10mL of concentrated nitric acid, and digestion treatment and measurement were carried out by the treatment method of example 1, with the results shown in table 1;
from the table 1, the standard adding recovery rate of the rice can reach 97.3-108.2%, and compared with the ICP-MS detection method, the two detection results are similar, which shows that the detection method provided by the invention has good accuracy.
TABLE 1 recovery rate of cadmium ion in rice
Comparative example 1
The only difference from embodiment 1 is that (3) in S2 is replaced by: weighing 10mg of upconversion particles, adding the upconversion particles into a 100mL conical flask containing 6mL of ethanol solution, performing ultrasonic treatment for 20min, transferring the mixture into a 35-DEG C water bath kettle, adding 2mL of deionized water and 0.25mL of 25% ammonia water solution, and reacting the mixture under magnetic stirring for 5-10 ℃; then, 0.006mL tetraethyl orthosilicate is added dropwise at 65 ℃ to react for 8 hours, and 0.01mL 3-aminopropyltriethoxysilane is added after the reaction is finished to react for 3 hours; after completion, the product was washed with 50% aqueous ethanol and dried in a vacuum oven to obtain amino-modified upconverting particles.
S3, constructing standard curves for detecting different cadmium concentrations
Preparing standard solutions (0, 0.5,1.0,2.0,3.0,4.0,5.0 and 6.0 mu mol/L) with different cadmium concentrations, adjusting the pH to 7 by using a sodium hydroxide solution, respectively adding 400 mu L of 0.1mg/mL amino-modified up-conversion nanomaterial and unmodified up-conversion nanomaterial, and then adding 10 mu L of horseradish peroxidase for reacting for 15 minutes; then, 400. Mu.L of 3,3', 5' -tetramethylbenzidine was added thereto and mixed to react for 13 minutes, and the intensity of the fluorescence signal was measured.
As a result, it was found that the fluorescence intensity changes of different concentrations of cadmium element are not linear, as shown in FIG. 5.
Comparative example 2
Respectively measuring 1mL of 5 mu mol/L sodium, magnesium, lead, mercury, palladium, iron, calcium and zinc solution and blank aqueous solution, adjusting the pH to 7 by adopting sodium hydroxide, adding 400 mu L of 0.1mg/mL ethanolamine phosphate to modify an up-conversion nano material, and then adding 10 mu L of horseradish peroxidase to react for 15 minutes; then, 400. Mu.L of 3,3', 5' -tetramethylbenzidine was added thereto and mixed for reaction for 13 minutes to measure the intensity of the fluorescence signal.
As shown in FIG. 6, it is clear from the results that the fluorescence signal intensity of each detection system is equivalent to that of the blank, and there is no strong fluorescence response value; the system does not respond to metal ions of sodium, magnesium, lead, mercury, palladium, iron, calcium and zinc, and the detection method has specific response to cadmium.
Claims (10)
1. A method for detecting cadmium content in rice based on enzyme inhibition and fluorescence internal filtering effect is characterized by comprising the following steps:
(1) Pretreatment of sample to be tested
Placing the crushed rice sample powder into a polytetrafluoroethylene digestion tube, and adding nitric acid and H 2 O 2 Sealing, digesting, performing acid dispelling treatment by using an acid dispelling instrument after digestion is completed, cooling to room temperature, transferring, fixing the volume, and passing through a membrane to obtain a solution to be detected;
(2) Ethanolamine phosphate modified up-conversion nano material
Dissolving ethanolamine phosphate and an up-conversion material in a mixed solution of ethanol, chloroform and water, adjusting the pH value to 2.5-3 by adopting hydrochloric acid, and stirring for reaction; then washing the reactant with an ethanol water solution, and drying to obtain the catalyst;
(3) Detection of cadmium element in liquid to be detected
Preparing a series of rice matrix cadmium standard solutions with different concentrations, respectively taking the rice matrix cadmium standard solutions with different concentrations and the solution to be detected in the step (1), adjusting the pH value to be neutral, adding the ethanolamine phosphate prepared in the step (2) to modify an up-conversion nano material, then adding horseradish peroxidase for reaction, and then adding 3,3', 5' -tetramethyl benzidine to form a reaction system; and (3) measuring the intensity of the fluorescence signal after the reaction is finished, constructing a quantitative relation model by taking the concentration of the cadmium element in the rice matrix cadmium standard solution with different concentrations as an abscissa and the corresponding intensity of the fluorescence signal as an ordinate, and calculating the content of the cadmium element in the liquid to be measured according to the quantitative relation model and the intensity of the fluorescence signal of the liquid to be measured.
2. The method of claim 1, wherein the mass ratio of the ethanolamine phosphate to the upconverting material in step (2) is 1: 25-1: 20.
3. the method according to claim 1, wherein the volume ratio of ethanol, chloroform and water in the mixed solution of ethanol, chloroform and water in the step (2) is 2.
4. The method according to claim 1, wherein the ethanol aqueous solution in the step (2) is 40-60% ethanol aqueous solution in mass fraction.
5. The method according to claim 1, wherein the drying conditions of step (2) are: drying in an oven at 60-80 ℃ for 6-8 h.
6. The method of claim 1, wherein the upconverting material of step (2) is a lanthanide series upconverting nano-solid material.
7. The method as claimed in claim 6, wherein the preparation process of the lanthanide upconversion nanosolid material is as follows:
1) Dissolving ytterbium chloride hexahydrate, yttrium chloride hexahydrate, erbium chloride hexahydrate and gallium chloride hexahydrate in methanol, transferring to a three-neck flask, adding oleic acid and 1-octadecene, mixing, heating to 150-160 ℃, maintaining for 20-30 minutes, and magnetically stirring; then will contain NH 4 F and a methanol solution of NaOH are added into a three-neck flask drop by drop; after the dripping is finished, heating the mixture in water bath for 40 to 60 minutes at a temperature of between 60 and 70 ℃, then quickly heating the mixture to between 300 and 350 ℃, and continuously stirring the mixture for 1 to 2 hours by magnetic force to obtain a product;
2) Washing the product obtained in the step 1) by using an ethanol water solution, centrifuging, taking the precipitate, and drying to obtain the product.
8. The method according to claim 1, characterized in that the mass fraction of the nitric acid in the step (1) is 65-70%; h 2 O 2 The mass fraction of (A) is 30%; nitric acid and H 2 O 2 The volume ratio of (A) to (B) is 5-8.
9. The method according to claim 1, wherein the reaction system in step (3) comprises adding 400 μ L of 0.1mg/mL ethanolamine phosphate modified up-conversion nanomaterial into 1mL of the solution to be tested, reacting 10 μ L of horseradish peroxidase for 10-15 min, and adding 400 μ L of 3,3', 5' -tetramethylbenzidine for 10-13 min.
10. Use of the method of any one of claims 1 to 9 for rapid detection of cadmium content.
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