CN114460197A - Method for quantitatively detecting content of organic selenium in agricultural products - Google Patents
Method for quantitatively detecting content of organic selenium in agricultural products Download PDFInfo
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- CN114460197A CN114460197A CN202210110878.5A CN202210110878A CN114460197A CN 114460197 A CN114460197 A CN 114460197A CN 202210110878 A CN202210110878 A CN 202210110878A CN 114460197 A CN114460197 A CN 114460197A
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Abstract
The invention discloses a method for quantitatively detecting the content of organic selenium in agricultural products, which comprises the following steps: (1) measuring the total selenium content of the agricultural product to be measured; (2) measuring a standard selenium form solution and an inorganic selenium concentrated extract of the agricultural product by using an HPLC-ICP-MS combined system formed by combining a high performance liquid chromatography and an inductively coupled plasma mass spectrometer and taking methanol and a diammonium citrate buffer solution as mobile phases: (3) adopting external standard method to treat selenious acid (SeO) in sample3 2‑) And selenate (SeO)4 2‑) Carrying out quantitative analysis, and adding to obtain the inorganic selenium content in the sample; (4) and obtaining the organic selenium content in the sample by adopting a subtraction method. The method for detecting the selenium form of the plant has the advantages of complete form separation, convenient preparation of the mobile phase, simple experimental operation, accurate and reliable result obtained by quantitative analysis and rapid detection.
Description
Technical Field
The invention relates to a method for quantitatively detecting the content of organic selenium in agricultural products, belonging to the field of analysis and test.
Background
At present, methods for detecting inorganic selenium content include Hangzhou landmark atomic fluorescence spectrometry for detecting organic selenium and inorganic selenium content in rice (DB 3301/T117) 2007 and Hubei landmark Hubei province food safety local standard rich organic selenium food selenium content requirement (DBS 42/002-2014).
The method of Hubei landmark includes cyclohexane extraction of selenium in water phase to eliminate partial organic selenium and digesting the water soluble selenium to obtain inorganic selenium. The content of the organic selenium is obtained by subtracting the content of the inorganic selenium from the total selenium, belonging to a water extraction differential subtraction method.
Disclosure of Invention
In view of this, the main objective of the present invention is to provide a method for quantitatively detecting the content of organic selenium in agricultural products, which optimizes the quantitative method, eliminates experimental interference, and improves detection efficiency and accuracy.
In order to achieve the purpose, the invention provides a method for quantitatively detecting the content of organic selenium in agricultural products, which comprises the following steps:
(1) measuring the total selenium content in the agricultural product to be measured;
(2) analytical instrument system configuration: combining a high performance liquid chromatography and an inductively coupled plasma mass spectrometer into an HPLC-ICP-MS combined system;
the mobile phase in the high performance liquid chromatography is methanol and diammonium citrate buffer solution;
(3) sample treatment: adding ultrapure water and methanol into a sample to be detected, uniformly mixing, performing ultrasonic extraction in a water bath, absorbing supernate, concentrating until the supernate is dried, and redissolving for detection;
(4) measuring the standard selenium form solution and the selenium form enzymolysis solution of the sample, and adopting an external standard method to measure selenious acid (SeO) in the sample3 2-) And selenate (SeO)4 2-) Carrying out quantitative analysis;
(5) and subtracting the inorganic selenium content obtained by chromatography from the total selenium content of the sample to obtain the organic selenium content in the sample.
Preferably, in the step (1), the total selenium detection method refers to microwave digestion-inductively coupled plasma mass spectrometry in national food safety standard determination of selenium in food GB 5009.93-2017.
Preferably, in the step (3), the amount of the ultrapure water is 10-20ml, and the amount of the methanol is 5-15ml, preferably 15ml of ultrapure water and 10ml of methanol.
Preferably, in step (3), the purity of the methanol is chromatographic purity.
Preferably, in step (3), the ultrasonic extraction time is 30-60 min.
Preferably, in the step (3), the filtration membrane used for filtration is Sep-Pak C18 disposable column.
Preferably, in step (3), the extract is concentrated by using a refrigerated centrifugal vacuum concentrator.
Preferably, in step (3), the apparatus is in a vacuum environment at-25 ℃ during concentration.
Preferably, in step (4), the standard selenium form solution comprises two selenium form standard sample stock solutions of selenite and selenate, wherein the concentration of each selenium form standard sample stock solution is 0, 10, 20, 50, 100 and 150 μ g/L (calculated as selenium).
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts water extraction chromatography, and uses HPLC-ICP-MS combined technology to carry out quantitative analysis on the sample by using an external standard method, so that selenious acid (SeO) in agricultural products can be detected3 2-) And selenate (SeO)4 2-) The organic selenium content in the agricultural product to be detected is calculated. The extraction method is simple and rapid, the mobile phase is simple and convenient to prepare, and the analysis result is accurate and reliable. Compared with the prior water extraction differential subtraction method and the like, the method has better selectivity and stronger stability to the element form,the data is more accurate.
Drawings
FIG. 1 is a chromatogram of an inorganic selenium extract of green vegetable sample 1 according to an embodiment of the present invention.
Fig. 2 is a chromatogram of an inorganic selenium extract of an wogonian sample 2 according to an embodiment of the present invention.
Fig. 3 is a chromatogram of inorganic selenium extract of navel orange sample 3 in accordance with an embodiment of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description will be given to the specific implementation, structure, characteristics and effects of the method for quantitatively detecting the organic selenium content in agricultural products according to the present invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
All components referred to are commercially available products well known to those skilled in the art unless otherwise specified, and all methods referred to are conventional unless otherwise specified.
The embodiment of the invention provides a method for quantitatively detecting the content of organic selenium in agricultural products, which comprises the following steps:
(1) measuring the total selenium content in the agricultural product to be measured; the agricultural products may be edible vegetables, fruits and other agricultural products, and are not particularly limited herein.
(2) Analytical instrument system configuration: combining a high performance liquid chromatography and an inductively coupled plasma mass spectrometer into an HPLC-ICP-MS combined system;
the mobile phase in the high performance liquid chromatography is methanol (2% (v/v)) and diammonium citrate buffer (6 mmol/L);
(3) sample treatment: adding 15ml of ultrapure water and 10ml of methanol into a sample to be detected, uniformly mixing, extracting in a water bath ultrasonic mode, sucking a supernatant, concentrating until the supernatant is dried, and redissolving for detection;
(4) selenium form for standard selenium form solution and the sampleMeasuring the state enzymolysis solution, and measuring selenious acid (SeO) in the sample by external standard method3 2-) And selenate (SeO)4 2-) Carrying out quantitative analysis;
(5) and subtracting the inorganic selenium content obtained by chromatography from the total selenium content of the sample to obtain the organic selenium content in the sample.
In some embodiments, optionally, in step (1), the total selenium detection method is by reference to microwave digestion-inductively coupled plasma mass spectrometry in national food safety standard determination of selenium in food GB 5009.93-2017.
In some embodiments, optionally, in step (3), the methanol is chromatographically pure, which may maximize instrument protection. If the analytical grade and the goodness grade are selected, the noise of the instrument becomes large, and the result can be inaccurate.
In some embodiments, optionally, in step (3), the ultrasonic extraction time is 30-60min, preferably 40-45min, so that the time cost can be reduced to the maximum extent on the premise of ensuring the extraction effect. If the time is less than 30min, incomplete extraction may be caused; higher than 60min results in increased costs.
In some embodiments, optionally, in step (3), the filtration membrane used for filtration is a Sep-Pak C18 solid phase extraction disposable cartridge. The solid phase extraction combines the processes of selective retention, selective elution and the like, and can ensure high recovery rate and repeatability of elution.
In some embodiments, optionally, in step (3), the extract is concentrated using a refrigerated centrifuge vacuum concentrator, such that centrifugation prevents cross-contamination between samples.
In some embodiments, optionally, in step (3), when the cold well temperature reaches-105 ℃, the temperature of the concentrator is adjusted to-4 ℃, so that the solvent can be sublimated to meet the drying requirement of the sample.
In some embodiments, optionally, in step (4), the standard selenium form solution comprises two selenium form standard sample stocks of selenite and selenate, wherein the concentration of each selenium form standard sample stock is 0, 10, 20, 50, 100, 150 μ g/L (in terms of selenium). 0-150ppb was chosen because most of the produce's aqueous extract had total selenium in this range; the 6 points were chosen to better plot the standard curve.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
Example 1
The embodiment provides a method for quantitatively detecting the content of organic selenium in agricultural products, which comprises the following steps:
(1) determination of total selenium in a sample to be tested
The total selenium detection method refers to microwave digestion-inductively coupled plasma mass spectrometry in national food safety standard GB 5009.93-2017 for determination of selenium in food. The agricultural product is green vegetables, Or Citrus aurantium or navel orange.
(2) Analytical instrument system configuration
The high performance liquid chromatography and the inductively coupled plasma mass spectrometer are combined into a HPLC-ICP-MS combined system.
Subjecting selenious acid (SeO) to high performance liquid chromatography3 2-) And selenate (SeO)4 2-) Completely separating the selenium forms; chromatograms were generated on an inductively coupled plasma mass spectrometer, see fig. 1-3. From fig. 1, only the chromatographic peak of selenomethionine can be seen, and it can be seen that sample 1 does not contain inorganic selenium, and the organic selenium content is the total selenium content; from fig. 2-3, the chromatographic peaks of selenocysteine and selenite can be seen, so the organic selenium content of samples 2 and 3 is the total selenium content minus the selenite content.
(3) Instrumental analysis method
Weighing 1.13g of diammonium citrate, adding 850ml of ultrapure water for pre-dissolving, and uniformly stirring by using a glass rod; adding 20ml of refrigerated (-20 ℃) chromatographic pure methanol, adjusting the pH value to 5.7 by using 10 wt% of dilute hydrochloric acid, and then fixing the volume to 1L; filtering the mobile phase with 0.22 μm filter membrane, and ultrasonic degassing the prepared mobile phase for 15min (to remove air in the mobile phase) to obtain mobile phase;
(4) configuration of mixed standards
Weighing sodium selenite, adding water to constant volume, and storing at 4 deg.C in dark place. Making into sodium selenite (SeO) with concentration of 1mg/ml3 2-) And (4) standard solution.
Weighing sodium selenate, adding water to constant volume, and storing at 4 deg.C in dark place. Making sodium selenate (SeO) with concentration of 1mg/ml4 2-) And (4) standard solution.
Diluting the standard solution by 1000 times to 1mg/L, respectively sucking 0, 0.1, 0.2, 0.5, 1.0 and 1.5ml, diluting to 10ml with ultrapure water to prepare a mixed standard solution, wherein the concentrations of standard sample stock solutions in each selenium form are 0, 10, 20, 50, 100 and 150 mug/L (calculated as selenium), and filtering with a 0.22 mu m water phase filter membrane for use.
(5) Sample processing
Weighing 1.0g (accurate to 0.0001g) of a sample to be detected in a glass bottle, sequentially adding 15mL of ultrapure water and 10mL of methanol for uniformly mixing, performing ultrasonic extraction in a water bath at 37 ℃ for 45min, passing through a Sep-Pak C18 disposable column, transferring to a 50mL conical polypropylene tube, concentrating the supernatant by using a refrigerated centrifugal vacuum concentrator until the supernatant is completely dried or frozen (specifically, when the temperature of a cold well reaches-105 ℃, adjusting the temperature of a concentrator to-4 ℃ for concentration until the supernatant is completely dried or frozen, namely in a liquid-free state), adding 2mL of ultrapure water to redissolve the sample, transferring to a microcentrifuge tube, centrifuging at 4 ℃ and 10000r/min for 20min, and transferring the supernatant in the tube to a sample bottle special for HPLC by using a liquid transfer gun.
(6) Determination of organic selenium content
Adopting external standard method to treat selenious acid (SeO) in sample3 2-) And selenate (SeO)4 2-) Carrying out quantitative analysis to obtain the content of inorganic selenium; the external standard method comprises the following steps: firstly, a working curve is drawn by using a standard sample of a component to be measured, the peak height of each peak or the sample concentration corresponding to the peak area is measured, and a standard curve is drawn. In actual application, the sample concentration can be obtained by measuring the peak height or the peak area corresponding to the standard curve. The organic selenium content in the sample is calculated by subtracting the inorganic selenium from the total selenium. And existing methods (e.g. usingHangzhou landmarks mentioned in the background section) the default aqueous extract solution is all inorganic selenium, but the total selenium of the aqueous extract solution is simply subtracted from the total selenium of the sample to obtain organic selenium; in this embodiment, a step is added, that is, the water extract is detected by chromatography to obtain an accurate inorganic selenium content in the water extract, and finally the inorganic selenium content in the water extract is subtracted from the total selenium content of the sample to obtain the organic selenium content.
Samples 1-3 were detected by HPLC-ICP-MS (high performance liquid chromatography (HPLC, Shimadzu LC-20A, Japan), X series2 type ICP-MS (ThermoFisher) as an on-line monitoring device for HPLC, and a HPLC-ICP-MS combined detection system was set up), and the inorganic selenium content in the samples was measured by an external standard method, as shown in Table 1.
The total selenium of the sample 1-3 and the total selenium of the inorganic selenium supernatant extracted from the sample 1-3 by water are detected according to a microwave digestion-inductively coupled plasma mass spectrometry process (GB 5009.93-2017), and are shown in Table 2.
TABLE 1 chromatographic determination of inorganic selenium content in sample water extract supernatant
Note: SeO3 2-、SeO4 2-Selenite ion and selenate ion, respectively, and N.D. indicates no detection.
TABLE 2 sample Total selenium in hydroextraction supernatant and sample Total selenium
The organic selenium content of sample 1 was obtained by the differential subtraction of the existing water extraction, and the organic selenium content of sample 1 was obtained by the water extraction chromatography method of the present invention, and the specific data are shown in table 3.
TABLE 3 organic selenium content of samples under different detection methods
As can be seen from the results in Table 3, the organic selenium content obtained by the water extraction differential subtraction method is only obtained by subtracting the total selenium in the supernatant of the water extraction from the total selenium in the sample, and the method defaults that the supernatant of the water extraction only contains inorganic selenium and has imbalance; the water extraction chromatography rule adopted by the invention is to definitely obtain the inorganic selenium content in the supernatant liquid of water extraction, such as sample 1 in example 1, the inorganic selenium content in the extracting solution is 0 (see table 1), which indicates that the selenium in the sample is all in an organic form, and the organic selenium content is the total selenium content.
The above-mentioned embodiments are merely examples provided to fully illustrate the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A method for quantitatively detecting the content of organic selenium in agricultural products is characterized in that a high performance liquid chromatography and an inductively coupled plasma mass spectrometer are combined to determine a standard selenium form solution and an inorganic selenium concentrated extracting solution of a sample, an external standard method is adopted to quantitatively analyze selenite and selenate in the sample, and the difference subtraction method is adopted to obtain the content of the organic selenium in the sample.
2. The method for quantitatively detecting the content of organic selenium in agricultural products according to claim 1, characterized in that the method comprises the steps of:
1) measuring the total selenium content in the agricultural product to be measured;
2) analytical instrument system configuration: combining a high performance liquid chromatography and an inductively coupled plasma mass spectrometer into an HPLC-ICP-MS combined system;
the mobile phase in the high performance liquid chromatography is methanol and diammonium citrate buffer solution;
3) sample treatment: weighing a sample to be detected in a glass bottle with a cover, adding ultrapure water and methanol, uniformly mixing, performing ultrasonic extraction in a water bath, filtering to obtain an inorganic selenium extracting solution, concentrating the extracting solution until the extracting solution is completely dried, and redissolving the extracting solution to be detected;
4) measuring the standard selenium form solution and the inorganic selenium extract of the sample, and externally labeling to obtain selenious acid (SeO) in the sample3 2-) And selenate (SeO)4 2-) Carrying out quantitative analysis;
5) and calculating the content of the organic selenium in the sample by adopting a subtraction method.
3. The method for quantitatively detecting the content of the organic selenium in the agricultural products as claimed in claim 2, wherein in the step 1), the total selenium detection method refers to a microwave digestion-inductively coupled plasma mass spectrometry method in national food safety standard GB 5009.93-2017 for determination of selenium in food.
4. The method for quantitatively detecting the content of organic selenium in agricultural products as claimed in claim 2, wherein in the step 3), the sample to be detected is weighed in an amount of 0.8 to 1.2 g.
5. The method for quantitatively detecting the content of organic selenium in agricultural products as claimed in claim 2, wherein in the step 3), the amount of the ultrapure water is 10 to 20ml, and the amount of the methanol is 5 to 15 ml.
6. The method for quantitatively determining the content of organic selenium in agricultural products as claimed in claim 2, wherein in the step 3), the purity of methanol is chromatographic purity; the water bath ultrasonic extraction time is 30-60 min.
7. The method for quantitatively detecting the content of organic selenium in agricultural products as claimed in claim 2, wherein in the step 3), Sep-Pak C18 solid phase extraction disposable cartridge is used for filtration.
8. The method for quantitatively determining the content of organic selenium in agricultural products as claimed in claim 2, wherein in the step 3), the remaining extract is concentrated using a refrigerated centrifugal vacuum concentrator.
9. The method for quantitatively determining the content of organic selenium in agricultural products as claimed in claim 2, wherein in the step 3), the apparatus is in a vacuum environment of-4 ℃ to 0 ℃ during concentration.
10. The method for quantitatively determining the content of organic selenium in agricultural products as claimed in claim 2, wherein in the step 4), the standard selenium form solution comprises two selenium form standard sample stock solutions of selenite and selenate, wherein the concentration of each selenium form standard sample stock solution in selenium is 0, 10, 20, 50, 100 and 150 μ g/L respectively.
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