CN114460048B - Method for measuring mass content of polar substances in edible oil by perovskite quantum dot fluorescence quenching method - Google Patents

Method for measuring mass content of polar substances in edible oil by perovskite quantum dot fluorescence quenching method Download PDF

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CN114460048B
CN114460048B CN202011240807.4A CN202011240807A CN114460048B CN 114460048 B CN114460048 B CN 114460048B CN 202011240807 A CN202011240807 A CN 202011240807A CN 114460048 B CN114460048 B CN 114460048B
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CN114460048A (en
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冯亮
皇甫常欣
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Dalian Institute of Chemical Physics of CAS
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432Quenching

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Abstract

The application discloses a method for determining mass content of polar substances in edible oil by perovskite quantum dot fluorescence quenching method, which comprises the following steps: s1, obtaining an edible oil standard series group which comprises a plurality of standard edible oil samples, wherein the polar substances in different standard edible oil samples have different mass contents; s2, obtaining a solution containing perovskite quantum dots; s3, mixing the solution containing the perovskite quantum dots with a standard edible oil sample, measuring the fluorescence intensity of each mixed solution under preset conditions, and establishing a linear function relation between the mass content of polar substances in the standard edible oil sample and the fluorescence intensity; s4, mixing the edible oil sample to be detected with the solution containing the perovskite quantum dots, measuring the fluorescence intensity of the mixed solution under preset conditions, and measuring the content of polar substances in the edible oil to be detected by utilizing a linear function relation. The method has low cost, easy operation and high accuracy, and provides a new basis for the application of the perovskite quantum dots in the field of food safety.

Description

Method for measuring mass content of polar substances in edible oil by perovskite quantum dot fluorescence quenching method
Technical Field
The invention relates to the field of application of perovskite quantum dots, in particular to a method for measuring the mass content of polar substances in edible oil by using a perovskite quantum dot fluorescence quenching method.
Background
The edible oil can undergo a series of reactions such as oxidation, polymerization, cracking, hydrolysis and the like when continuously and repeatedly used at high temperature. In these processes, various compounds containing carbonyl groups, carboxyl groups, ketone groups, aldehyde groups, etc. are formed, and because these compounds are more polar than triglycerides, they are collectively called polar compounds, which are generated continuously during frying, especially edible oils. These compounds not only adversely affect the quality of the oils themselves, but also cause direct damage to human health, such as growth arrest, hepatomegaly, fertility and liver dysfunction, lymphocyte distortion, etc. Therefore, it is important to evaluate the quality of edible oil effectively. The indexes for evaluating the quality of the edible oil mainly comprise sense organ, light transmittance, acid value, peroxide value, carbonyl value, iodine value, free fatty acid, polymer, total polar compound content and the like. The measurement of the polar compound content has the characteristics of high accuracy, high reliability and the like, and is the most stable index, so that the measurement is also an evaluation index recommended to be used in various countries in the world, and the national standard of China prescribes that the polar compound content of frying oil must be not higher than 27% (by mass).
The column chromatography, especially the preparative rapid column chromatography, is a method for determining the polar components of edible oil in national food safety standards in China, but the method is time-consuming and laborious, needs to consume a large amount of organic solvent, and cannot realize rapid and real-time monitoring of the mass content of total polar substances.
In recent years, a plurality of methods for detecting the mass content of total polar substances in edible oil are presented, including an infrared spectrometry method, a nuclear magnetic resonance method, a dielectric constant method and the like.
The infrared spectrometry involves measuring the oil sample at 4000-10000 cm -1 Scanning is performed below. Because substances such as aldehyde, ketone, acid and the like are formed in the use process of the grease, in the infrared absorption spectrum obtained by oil samples with different polar substance contents, the intensity and the position of the characteristic peak of each group are different, and therefore, the content of the polar substance is judged through the intensity and the position of the characteristic peak of the infrared absorption spectrum. However, infrared spectrometers are expensive and require calibration modeling prior to use.
The detection principle of the nuclear magnetic resonance method is that the relaxation time of grease changes along with the change of the content of polar substances. The higher the polar substance content, the shorter the relaxation time, from which the polar substance content can be determined by establishing a mathematical relationship between the polar substance content and the relaxation time. However, the apparatus used in this method is expensive and requires a professional to operate, so that it is difficult to obtain a wide range of applications for a short time.
The permittivity method is to measure the polar substance according to the principle that the conductivity of the oil sample increases with the content of the polar substance, and the permittivity is proportional to the capacitance. The content of polar substances can thus be determined by measuring the capacitance. Portable edible oil quality detectors based on this principle are commercialized, but such instruments are still expensive to manufacture, require calibration before use, and are susceptible to electromagnetic fields, temperatures, etc. to cause inaccuracy in the measurement results.
Therefore, there is a need in the art to provide a method for determining the mass content of polar substances in edible oil with low cost, easy operation and high accuracy.
Disclosure of Invention
In order to provide an edible oil measuring method which is low in cost, easy to operate and high in accuracy. The inventors of the present application found that polar substances in edible oils can affect perovskite quantum dot stability. Since perovskite quantum dots belong to ionic crystals, they cannot exist stably when damaged by polar substances. Whereas, by utilizing the unique property of sensitivity to polar substances, the inventors of the present application used perovskite quantum dots for quantitative analysis of polar substances in edible oils.
The application provides a method for determining the mass content of polar substances in edible oil by using a perovskite quantum dot fluorescence quenching method, which comprises the following steps:
s1: obtaining an edible oil standard series group, wherein the edible oil standard series group comprises a plurality of standard edible oil samples, each standard edible oil sample comprises polar substances with known mass content, and the mass content of the polar substances in different standard edible oil samples is different;
s2: obtaining a solution containing perovskite quantum dots;
s3: mixing the solution containing the perovskite quantum dots with the plurality of standard edible oil samples respectively to obtain a plurality of mixed liquids, measuring the fluorescence intensity of each mixed liquid under preset conditions respectively, and establishing a linear function relation between the mass content of polar substances in the standard edible oil samples and the fluorescence intensity;
s4: and uniformly mixing the edible oil sample to be detected with the solution containing the perovskite quantum dots, measuring the fluorescence intensity of the mixed solution under the preset condition, and measuring the mass content of the polar substances in the edible oil to be detected by utilizing the linear function relation.
Specifically, the method for measuring the mass content of polar substances in edible oil by using the perovskite quantum dot fluorescence quenching method comprises the following steps: step (1), a series of edible oil samples with known polar substance mass contents are absorbed and added into a centrifuge tube filled with quantum dot solution, and the materials are fully mixed; and (2) sucking the mixed solution into a cuvette, and placing the cuvette into a fluorometer to measure the fluorescence intensity, wherein the measured fluorescence intensity is different due to different contents of polar substances and different quenching degrees of different oil samples on the fluorescence of the quantum dots. Recording fluorescence intensity after all oil samples and the solution containing perovskite quantum dots react; step (3), taking the content of polar substances in the oil sample as an independent variable x, taking the fluorescence intensity of the mixed solution as a dependent variable y, and establishing a linear equation between the mass content of the polar substances and the fluorescence intensity by regression analysis; and (4) measuring the fluorescence intensity of the oil sample with unknown polar substance mass content after the oil sample reacts with the solution containing the perovskite quantum dots according to the operation methods of the steps (1) and (2) and the linear equation obtained in the step (3), substituting the obtained fluorescence intensity into the obtained linear equation to obtain the mass content of the polar substance in the oil sample, and verifying the obtained polar substance content by adopting a column chromatography method.
Optionally, the preset condition includes: the fluorescence excitation wavelength λex ranges from 350 to 370nm, and the detected emission wavelength λem ranges from 512 to 515nm.
Alternatively, the fluorescence excitation wavelength λex is any value or a range value determined by any two values among 350nm, 365nm, 370 nm.
Optionally, in the step S1, the edible oil is added to the solution for a mixing reaction time of 1 to 10 minutes, wherein the volume of the edible oil is 0.1 to 1mL, the concentration of the perovskite quantum dots is 10 to 30mg/mL, and the volume of the perovskite quantum dot solution is 0.1 to 3 mL.
Alternatively, the concentration of perovskite quantum dots is any value of 10mg/mL, 14mg/mL, 25mg/mL, 30mg/mL, or a range of values determined by any two values.
Optionally, in the step S1, the edible oil is selected from one or more blend oils of soybean oil, corn oil, sunflower seed oil, olive oil, peanut oil, rice bran oil, and palm oil.
Alternatively, the perovskite quantum dots are selected from CH 3 NH 3 PbX 3 、CH(NH 2 ) 2 PbX 3 And CsPbX 3 Wherein X is selected from one or more of Cl, br and I.
Optionally, the solvent in the solution containing perovskite quantum dots is selected from one of n-hexane, cyclohexane and toluene.
Optionally, the linear function relationship is y= -ax+b, R 2 And the fluorescent intensity of the mixed solution of the edible oil and the solution containing the perovskite quantum dots is more than or equal to 0.993, wherein x is the mass content of polar substances in the edible oil, y is the fluorescent intensity of a mixed solution of the edible oil and the solution containing the perovskite quantum dots, a is between 3500 and 17000, and b is between 3000 and 11000.
Alternatively, a is any of 3590, 4542, and 16370, and b is any of 3239, 5774, and 10583.
Optionally, the edible oil is olive oil, and the linear function relation is y= -3590x+3239, R 2 =0.993, where x is the mass content of polar material in olive oil, y is the fluorescence intensity of the mixture of olive oil and the solution containing perovskite quantum dots, R 2 Is a linear correlation coefficient.
Optionally, the edible oil is soybean oil, and the linear function relation is y= -16370x+10583, R 2 =0.983, where x is the mass content of polar substances in soybean oil, and y is the fluorescence intensity of the mixed solution of soybean oil and the solution containing perovskite quantum dots.
Optionally, the edible oil is sunflower seed oil, the linear function relation is y= -4542x+5774, R 2 =0.980, where x is the mass content of polar substances in sunflower seed oil, and y is the fluorescence intensity of the mixture of sunflower seed oil and the solution containing perovskite quantum dots.
Optionally, a series of edible oils containing polar materials with different mass contents have at least 5 polar materials with different mass contents, i.e. the number of samples selected for determining each linear function relationship is more than or equal to 5.
Optionally, the mass content of polar material in the edible oil is any value or range of values determined by any two of 18.5%, 20.5%, 21.5%, 23%, 25%, 26%, 26.5%, 27.5%, 28%, 29%, 30%, 30.5%, 33%.
The beneficial effects that this application can produce include:
1) The novel edible oil detection method provided by the application is simple and convenient to operate, low in cost, rapid and efficient in real-time detection, greatly shortens the detection time, reduces the use amount of organic reagents, and is based on the fluorescence quenching principle of quantum dots, and has the advantages of high detection reaction sensitivity, good reproducibility, high accuracy of detection results and high precision.
2) The method provided by the application can realize the detection of the total polar substances of the edible oil at room temperature without heating, thereby avoiding the influence of temperature on the detection result.
3) The method provided by the application expands the application range of the perovskite quantum dot and provides a new basis for the application of the perovskite quantum dot in the field of food safety.
Drawings
FIG. 1 shows the olive oil polar substance content as a function of fluorescence intensity in a linear manner according to example 1 of the present invention.
FIG. 2 shows a linear dependence of the polar material content of soybean oil according to example 2 of the present invention on fluorescence intensity.
FIG. 3 shows a graph of the polar material content of sunflower seed oil as a function of fluorescence intensity according to example 3 of the present invention.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The endpoints and any values of the ranges disclosed in this application are not limited to the precise range or value, and such range or value is to be understood to include the proximity of such range or value. For numerical ranges, the endpoints of each of the ranges and the individual points are combinable with each other to provide one or more new numerical ranges, which should be considered as specifically disclosed herein.
Unless otherwise specified, the edible oil, the solvent, and the like in the examples of the present application are all purchased commercially, for example, by purchasing in a supermarket.
The perovskite quantum dots in the examples of the present application are all prepared by known methods, and specific reference is made to Song, J.Z.etc. room-temperature triple-ligand surface engineering synergistically boosts ink stability, recombination dynamics, and charge injection toward EQE-11.6%perovskite QLEDs.Adv.Mater.2018,30,1800764.
The fluorescence intensity in the examples of the present application was measured by a fluorescence spectrometer (FL 4600, hitachi, japan), and specific test conditions were: the fluorescence excitation wavelength λex ranges from 350 to 370nm, the detected emission wavelength λem ranges from 512 to 515nm, and the scanning speed is high: 1200nm/min, excitation wavelength slit: 10mn, emission wavelength slit: 10nm.
The column chromatography in the examples of the present application is a method commonly used in the art, for example, refer to national standard GB-5009.202-2016.
Example 1
This example shows a method for determining the mass content of polar materials in olive oil using perovskite quantum dot fluorescence quenching.
Specifically, 1mL of olive oil sample with polar substances of 18.5%, 20.5%, 21.5%, 25%, 26.5% and 30% by mass is respectively absorbed, and added with 2mLCsPbBr 3 Fully mixing the quantum dots (the concentration is 10 mg/mL) in a centrifuge tube of toluene solution at room temperature; after 3 minutes of reaction, 1mL of the mixed solution is absorbed in a quartz cuvette, the fluorescence intensity of the mixed solution is measured by a fluorescence spectrometer, the excitation wavelength λex=365 nm, the emission wavelength λem=512 nm, and each group is measured for 3 times in parallel; establishing a linear equation between the fluorescence intensity and the mass content of the olive oil polar substance, gradually weakening the fluorescence intensity of the mixed solution along with the increase of the mass content of the polar substance, wherein the obtained linear equation is y= -3590x+3239, R 2 =0.993, x is the mass content of polar substances in the olive oil (i.e. TPM in fig. 1), and y is the fluorescence intensity of the mixture of the olive oil and the solution containing perovskite quantum dots, as shown in fig. 1.
According to the method, the mass content of the polar substance is unknownThe fluorescence intensity of olive oil sample was 2257, and the content of polar substance was 27.4% as determined by substituting the above equation. The oil sample was verified by column chromatography, and the result was 27.5%. Thereby explaining the use of CsPbBr 3 The quantum dot fluorescence quenching method can accurately and quantitatively measure the mass content of the olive oil polar substance.
Example 2
This example shows a method for determining the mass content of polar materials in soybean oil using perovskite quantum dot fluorescence quenching.
Specifically, 0.5mL of soybean oil sample containing 25%, 26%, 27.5%, 28%, 29%, 30%, 30.5% of polar substance by mass was aspirated, and 1mLCsPbBr was added 3 Fully mixing the quantum dots (the concentration is 14 mg/mL) in a centrifuge tube of toluene solution at room temperature; after 1 minute of reaction, 1mL of the mixed solution is absorbed in a quartz cuvette, the fluorescence intensity of the mixed solution is measured by a fluorescence spectrometer, the excitation wavelength λex=365 nm, the emission wavelength λem=512 nm, and each group is measured for 3 times in parallel; a linear equation between the fluorescence intensity and the mass content of the soybean oil polar substance is established, and the fluorescence intensity of the mixed solution gradually weakens along with the increase of the mass content of the polar substance, and the obtained linear equation is y= -16370x+10583, R 2 =0.983, x (i.e. TPM in fig. 2) is the mass content of polar substances in soybean oil, y is the fluorescence intensity of the mixture of soybean oil and the solution containing perovskite quantum dots, as shown in fig. 2.
According to the method, the fluorescence intensity of the soybean oil sample with unknown mass content of the polar substance is measured to obtain the fluorescence intensity of 5637, and the fluorescence intensity is substituted into the equation to obtain the content of the polar substance of 30.2%. The oil sample was verified by column chromatography, and the result was 30.5%. Thereby explaining the use of CsPbBr 3 The quantum dot fluorescence quenching method can accurately and quantitatively measure the mass content of the soybean oil polar substance.
Example 3
This example shows a method for determining the mass content of polar materials in sunflower seed oil using perovskite quantum dot fluorescence quenching.
Absorbing the mass content of polar substances0.9mL of soybean oil samples of 23%, 26.5%, 27.5%, 29%, 30.5%, 33%, respectively, were charged with 1mLCsPbBr 3 Fully mixing the quantum dots (the concentration is 25 mg/mL) in a centrifuge tube of toluene solution at room temperature; after 2 minutes of reaction, 1mL of the mixed solution is absorbed in a quartz cuvette, the fluorescence intensity of the mixed solution is measured by a fluorescence spectrometer, the excitation wavelength λex=365 nm, the emission wavelength λem=512 nm, and each group is measured for 3 times in parallel; establishing a linear equation between the fluorescence intensity and the mass content of the sunflower seed oil polar substance, gradually weakening the fluorescence intensity of the mixed solution along with the increase of the mass content of the polar substance, wherein the obtained linear equation is y= -4542x+5774, R 2 =0.980, x (i.e. TPM in fig. 3) is the mass content of polar substances in sunflower seed oil, and y is the fluorescence intensity of the mixture of sunflower seed oil and the solution containing perovskite quantum dots, as shown in fig. 3.
According to the method, the fluorescence intensity of the sunflower seed oil sample with unknown mass content of the polar substance is measured to be 4504, and the obtained fluorescent intensity is substituted into an equation to obtain the content of the polar substance to be 27.96%. The oil sample was verified by column chromatography, and the result was 28%. Thereby explaining the use of CsPbBr 3 The quantum dot fluorescence quenching method can accurately and quantitatively measure the mass content of the sunflower seed oil polar substance.
Although the present application only exemplifies the above embodiments, the oil samples in the above embodiments may be replaced by other kinds of oils, such as any one of corn oil, sunflower seed oil, olive oil, peanut oil, rice bran oil, palm oil or blend oil of several of soybean oil, corn oil, sunflower seed oil, olive oil, peanut oil, rice bran oil, palm oil, and the corresponding linear function relationship may be obtained. Also although the above embodiment uses only CsPbBr 3 Quantum dots quench edible oil, but CsPbBr can be used 3 The quantum dots being replaced by other perovskite quantum dots, e.g. CH 3 NH 3 PbX 3 、CH(NH 2 ) 2 PbX 3 And CsPbX 3 X is selected from one or more of Cl, br and I.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (8)

1. The method for determining the mass content of polar substances in edible oil by using perovskite quantum dot fluorescence quenching method is characterized by comprising the following steps:
s1: obtaining an edible oil standard series group, wherein the edible oil standard series group comprises a plurality of standard edible oil samples, each standard edible oil sample comprises polar substances with known mass content, and the mass content of the polar substances in different standard edible oil samples is different;
s2: obtaining a solution containing perovskite quantum dots;
s3: mixing the solution containing the perovskite quantum dots with the plurality of standard edible oil samples respectively to obtain a plurality of mixed liquids, measuring the fluorescence intensity of each mixed liquid under preset conditions respectively, and establishing a linear function relation between the mass content of polar substances in the standard edible oil samples and the fluorescence intensity;
s4: uniformly mixing an edible oil sample to be detected with the solution containing the perovskite quantum dots, measuring the fluorescence intensity of the mixed solution under the preset condition, and measuring the mass content of polar substances in the edible oil sample to be detected by utilizing the linear function relation;
the preset conditions include: the fluorescence excitation wavelength λex ranges from 350nm to 370nm, and the detected emission wavelength λem ranges from 512nm to 515nm;
the linear function relation is y= -ax+b, R 2 And the fluorescent intensity of the mixed solution of the edible oil and the solution containing the perovskite quantum dots is more than or equal to 0.980, wherein x is the mass content of polar substances in the edible oil, y is the fluorescent intensity of a mixed solution of the edible oil and the solution containing the perovskite quantum dots, a is in the range of 3500-17000, and b is in the range of 3000-11000.
2. The method according to claim 1, wherein in step S1, the edible oil is added in a volume of 0.1 to 1mL, the concentration of the perovskite quantum dots is 10 to 30mg/mL, the volume of the perovskite quantum dot solution is 0.1 to 3mL, and the mixing reaction time is 1 to 10 minutes.
3. The method according to claim 1, wherein in the step S1, the edible oil is selected from one or more of soybean oil, corn oil, sunflower oil, olive oil, peanut oil, rice bran oil, and palm oil.
4. The method according to claim 1, wherein the perovskite quantum dots are selected from CH 3 NH 3 PbX 3 、CH(NH 2 ) 2 PbX 3 And CsPbX 3 Wherein X is selected from one or more of Cl, br and I.
5. The method according to claim 1, wherein the solvent in the solution containing perovskite quantum dots is selected from one of n-hexane, cyclohexane, toluene.
6. The method according to claim 1, wherein the edible oil is olive oil and the linear function relationship is y= -3590x+3239, r 2 =0.993, where x is the mass content of polar substances in the olive oil, and y is the fluorescence intensity of the mixture of olive oil and the solution containing perovskite quantum dots.
7. The method of claim 1, wherein the edible oil is soybean oil and the linear function relationship is y= -16370x+10583, r 2 =0.983, where x is the mass content of polar substances in soybean oil, and y is the fluorescence intensity of the mixed solution of soybean oil and the solution containing perovskite quantum dots.
8. The method according to claim 1, which comprisesCharacterized in that the edible oil is sunflower seed oil, the linear function relation is y= -4542x+5774, R 2 =0.980, where x is the mass content of polar substances in sunflower seed oil, and y is the fluorescence intensity of the mixture of sunflower seed oil and the solution containing perovskite quantum dots.
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