CN111089922A - Sample purification method for gel permeation chromatography detection - Google Patents
Sample purification method for gel permeation chromatography detection Download PDFInfo
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- CN111089922A CN111089922A CN201911408322.9A CN201911408322A CN111089922A CN 111089922 A CN111089922 A CN 111089922A CN 201911408322 A CN201911408322 A CN 201911408322A CN 111089922 A CN111089922 A CN 111089922A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/56—Packing methods or coating methods
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
- G01N2030/324—Control of physical parameters of the fluid carrier of pressure or speed speed, flow rate
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/56—Packing methods or coating methods
- G01N2030/562—Packing methods or coating methods packing
Abstract
The invention relates to the technical field of sample purification, and particularly provides a sample purification method for gel permeation chromatography detection, which is characterized by comprising the following steps of: (1) dissolving and concentrating a sample, and then adding the sample into a gel chromatographic column for purification to obtain a primary purification solution; the flow rate of solvent elution in the preparation process of the gel chromatographic column is 0.5-1 mL/s; (2) concentrating the primary purified liquid, and purifying with a chromatographic column to obtain eluate; (3) concentrating the eluate, and performing post-treatment purification.
Description
Technical Field
The invention relates to the technical field of sample purification, and particularly provides a sample purification method for gel permeation chromatography detection.
Background
Dioxin-like substances are a general term for a large class of substances, mainly including chlorodioxin (commonly referred to as dioxin), bromodioxin, polychlorinated biphenyl, polybrominated biphenyl and the like, and most of the substances have strong teratogenicity, carcinogenicity, mutagenicity and genetic toxicity, and also have environmental persistence, bioaccumulation and long-distance migration capability. Due to the fact that the dioxin-like compounds are more in variety, the dioxin-like compounds are low in content in the environment, existing matrixes of the dioxin-like compounds are complex, and meanwhile, an analysis instrument is required to have a lower detection limit.
In the detection and analysis process, various impurities are often contained in a detected sample, so that a chromatographic column and a detector of expensive instruments such as GC/MS, GC and HPLC are polluted in the detection process, and the service life, the detection efficiency and the detection sensitivity of the instruments are affected. Therefore, the sample is purified or pretreated, so that the instrument and equipment are protected, the equipment keeps high sensitivity for a long time, the sample processing speed is accelerated, the sensitivity is improved, and the minimum detection limit is reduced.
Disclosure of Invention
In order to solve the technical problem, the invention provides a sample purification method for gel permeation chromatography detection, which comprises the following steps:
(1) dissolving and concentrating a sample, and then adding the sample into a gel chromatographic column for purification to obtain a primary purification solution; the flow rate of solvent elution in the preparation process of the gel chromatographic column is 0.5-1 mL/s;
(2) concentrating the primary purified liquid, and purifying with a chromatographic column to obtain eluate;
(3) concentrating the eluate, and performing post-treatment purification.
As a preferred technical scheme of the invention, the chromatographic column in the step (2) comprises a composite silica gel column.
As a preferred technical scheme of the invention, the chromatographic column in the step (2) further comprises an alkaline alumina column or an activated carbon column.
As a preferred technical scheme of the invention, the composite silica gel column comprises silica gel, acidic silica gel, alkaline silica gel, silver nitrate silica gel and anhydrous sodium sulfate.
As a preferred technical scheme of the invention, the acidic silica gel is sulfuric acid silica gel.
As a preferred technical scheme of the invention, the sulfuric acid silica gel comprises 44 wt% sulfuric acid silica gel and 22 wt% sulfuric acid silica gel.
As a preferred technical scheme of the invention, the weight ratio of the 44 wt% sulfuric acid silica gel to the 22 wt% sulfuric acid silica gel is 1: (1-1.6).
As a preferred technical scheme of the invention, the alkaline silica gel is potassium hydroxide silica gel.
As a preferred technical scheme of the invention, the potassium hydroxide silica gel is 1-3 wt% of potassium hydroxide silica gel.
As a preferred technical scheme of the invention, the solvent used in the leaching process of the alkaline alumina column or the activated carbon column comprises dichloromethane and n-hexane.
Has the advantages that: the invention provides a purification method of a sample for gel permeation chromatography detection, which can improve the purification efficiency by preparing uniform and clean gel permeation chromatography; the concentrated sample solution can improve the detection accuracy of the sample, simultaneously avoid influencing detection equipment, weaken the sensitivity or improve the detection limit of an instrument.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
In order to solve the technical problem, the invention provides a sample purification method for gel permeation chromatography detection, which comprises the following steps:
(1) dissolving and concentrating a sample, and then adding the sample into a gel chromatographic column for purification to obtain a primary purification solution; the flow rate of solvent elution in the preparation process of the gel chromatographic column is 0.5-1 mL/s;
(2) concentrating the primary purified liquid, and purifying with a chromatographic column to obtain eluate;
(3) concentrating the eluate, and performing post-treatment purification.
In a preferred embodiment, the purification method comprises the following steps:
(1) dissolving and concentrating a sample to 1-2 mL, and then adding the sample into a gel chromatographic column for purification to obtain an extracting solution; the flow rate of solvent elution in the preparation process of the gel chromatographic column is 0.5-1 mL/s;
(2) concentrating the primary purified liquid to 1-2 mL, and adding a composite silica gel column for purification to obtain an extracting solution;
(3) concentrating the extracting solution to 1-2 mL, and then adding an alkaline alumina column or an activated carbon column for purification to obtain an eluate;
(4) concentrating the eluate to 1-2 mL, and then carrying out post-treatment purification.
<Gel chromatography column purification>
The gel chromatographic column is obtained by self-making.
In one embodiment, the gel permeation chromatography column is prepared by:
(1) adding filler into a beaker, adding a solvent until the solvent is completely covered, and placing the beaker in a fume hood;
(2) after the filler is fully swelled, stirring the filler, gradually transferring the filler to a chromatographic column by using a suction pipe, opening a four-fluorine valve in the middle to remove redundant solvent, after the filler is completely transferred, adding a plug at the upper end, closing the valve at the bottom, turning the column upside down, opening the valve, and oscillating the column to gradually and uniformly invert the filler integrally. Closing the valve, slowly righting the column, opening the grinding plug at the upper end, and observing that the filler is uniformly settled until the filler is completely settled, wherein the column body has no fault, no bubble and no settlement decomposition layer;
(3) and (4) eluting the chromatographic column by using a solvent, closing the plug after elution and sealing to obtain the product.
In a preferred embodiment, the gel permeation chromatography column is prepared by the following steps:
(1) adding 30g of filler into a beaker, adding a solvent until the filler is completely covered, and placing the beaker in a fume hood for 12-24 hours;
(2) after the filler is fully swelled, stirring the filler, gradually transferring the filler to a chromatographic column by using a suction pipe, opening a four-fluorine valve in the middle to remove redundant solvent, after the filler is completely transferred, reserving 10cm of solvent on the upper part, adding a plug on the upper end, closing the valve at the bottom, turning the column upside down, opening a valve, oscillating the column body, and gradually and uniformly inverting the filler integrally. Closing the valve, slowly righting the column, opening the grinding plug at the upper end, and observing that the filler is uniformly settled until the filler is completely settled, wherein the column body has no fault, no bubble and no settlement decomposition layer;
(3) and (3) leaching the chromatographic column by using 500mL of solvent, closing the plug after leaching, sealing, and reserving the solvent with the length of more than 5cm on the upper layer to obtain the product.
In the preparation process of the gel permeation chromatographic column, a filler is swelled by using a solvent, the preparation method can realize uniform distribution of the chromatographic column, remove bubbles in gel, control a certain pressure, realize the solvent flow rate of 0.5-1 mL/s, wash a gel bed, further effectively remove residual monomers, powder and impurities in a system, balance a column phase, and simultaneously leave the solvent with the height of 5cm, which is beneficial to uniform dispersion of a concentrated solution of a detected sample in the gel column and uniform entry of the concentrated solution into the gel bed, thereby efficiently removing impurities and improving the purification efficiency.
In a more preferred embodiment, the packing material of the gel chromatography column is Bio Beads S-X3.
In a more preferred embodiment, the gel permeation chromatography column has a diameter to column length ratio of 1: (13-16); more preferably, the ratio of the diameter to the length of the gel permeation chromatography column is 1: 15.
in a more preferred embodiment, the gel permeation chromatography column is rinsed as the sample passes through it, either manually or automatically.
In a more preferred embodiment, the manual mode is: before use, 100mL of solvent is used for pre-leaching, a sample concentrated to 1.5mL is added into a gel permeation chromatographic column, 70mL of solvent is used for leaching to remove macromolecules, 70mL of solvent is added for eluting dioxin substances to obtain a primary purifying solution, and finally 100mL of solvent is used for leaching the gel permeation chromatographic column.
In a more preferred embodiment, the automatic mode is: placing a sample to be detected in a sample injector by using PrepLinc GPC equipment, sampling by using an automatic sampling needle, connecting a solvent bottle of a solvent pump, and determining whether a waste liquid bottle is empty; automatically filling 5000-15000 mu L of solvent; setting the pressure sensor to zero and balancing the column; after the use is finished, switching the gel chromatographic column to a bypass, increasing the flow rate of the solvent pump, and stopping the volume pump after 3-5 min; equilibrating the gel chromatography column again; and leaching the sample in the sample injection needle through a gel permeation chromatographic column to obtain a primary purifying solution.
In a more preferred embodiment, the solvent is selected from one or more of dichloromethane, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylformamide, carbon tetrachloride, cyclohexane.
In a more preferred embodiment, the solvent is dichloromethane.
In another preferred embodiment, the solvent comprises ethyl acetate and cyclohexane; more preferably, the weight ratio of ethyl acetate to cyclohexane is 1: (0.9 to 1.1); more preferably, the weight ratio of ethyl acetate to cyclohexane is 1: 1.
<purification with chromatographic column>
Composite silica gel column
In one embodiment, the composite silica gel column comprises silica gel, acidic silica gel, basic silica gel, silver nitrate silica gel, anhydrous sodium sulfate.
In a preferred embodiment, the acidic silica gel is a sulfuric acid silica gel.
In a more preferred embodiment, the silica gel sulfate comprises 44 wt% silica gel sulfate and 22 wt% silica gel sulfate.
In a more preferred embodiment, the weight ratio of 44 wt% silica sulfate to 22 wt% silica sulfate is 1: (1-1.6); more preferably, the weight ratio of the 44 wt% sulfuric acid silica gel to the 22 wt% sulfuric acid silica gel is 1: 1.3.
in a more preferred embodiment, the basic silica gel is potassium hydroxide silica gel.
In a more preferred embodiment, the potassium hydroxide silica gel is 1 to 3 wt% of potassium hydroxide silica gel; more preferably, the potassium hydroxide silica gel is 2 wt% potassium hydroxide silica gel.
The purification steps of the composite silica gel column are as follows:
(1) filling a small group of quartz wool at the bottom of the filling column, and washing the inner wall by using n-hexane;
(2) silica gel, acidic silica gel, alkaline silica gel, silver nitrate silica gel and anhydrous sodium sulfate are filled into the silica gel column, and the silica gel column is leached by normal hexane;
(3) when the liquid level in the silica gel column is reduced to 0.4-0.6 cm away from the uppermost layer, closing the plunger, and replacing the receiving bottle at the lower end of the silica gel column;
(4) and transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid with n-hexane for three times, transferring all the primary purifying liquid to the silica gel column, leaching the primary purifying liquid with the n-hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.4-0.6 mL/s.
In a more preferred embodiment, the composite silica gel column purification step is:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) filling anhydrous sodium sulfate, silica gel, 2 wt% potassium hydroxide silica gel, 44 wt% sulfuric acid silica gel, 22 wt% sulfuric acid silica gel, silver nitrate silica gel and anhydrous sodium sulfate into the silica gel column in sequence, and leaching the silica gel column by using 100mL of normal hexane;
(3) when the liquid level in the silica gel column is reduced to 0.4-0.6 cm away from the uppermost layer of anhydrous sodium sulfate, closing the plunger, and replacing the receiving bottle at the lower end of the silica gel column;
(4) and transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid for three times by using n-hexane, transferring all the concentrated primary purifying liquid to the silica gel column, leaching the concentrated primary purifying liquid by using 200mL of n-hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.4-0.6 mL/s.
In a more preferred embodiment, the composite silica gel column purification step is:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) 4g of anhydrous sodium sulfate, 0.9g of silica gel, 3g of 2 wt% potassium hydroxide silica gel, 0.9g of silica gel, 4.5g of 44 wt% sulfuric acid silica gel, 6g of 22 wt% sulfuric acid silica gel, 0.9g of silica gel, 3g of 10 wt% silver nitrate silica gel and 6g of anhydrous sodium sulfate are sequentially filled in the silica gel column, and the silica gel column is leached by 100mL of n-hexane;
(3) when the liquid level in the silica gel column is reduced to 0.4-0.6 cm away from the uppermost layer of anhydrous sodium sulfate, closing the plunger, and replacing the receiving bottle at the lower end of the silica gel column;
(4) and transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid for three times by using n-hexane, transferring all the concentrated primary purifying liquid to the silica gel column, leaching the concentrated primary purifying liquid by using 200mL of n-hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.4-0.6 mL/s.
The applicant uses anhydrous sodium sulfate, silica gel, alkaline silica gel, acidic silica gel and silver nitrate silica gel to prepare the composite silica gel, and the composite silica gel is used for purifying a sample, and in the experimental process, the applicant finds that when the anhydrous sodium sulfate, the silica gel, the alkaline silica gel, the acidic silica gel, the silver nitrate silica gel and the anhydrous sodium sulfate are sequentially filled, a better purification effect is achieved on a sample concentrated solution, the detection accuracy of dioxin substances in the sample can be improved, the detection equipment can be protected, and the high sensitivity and the low detection line can be maintained for a long time. Firstly, when the anhydrous sodium sulfate treatment is carried out initially, the water content in the system can be effectively reduced, the reduction of the activity of various silica gel fillers is avoided, through the mutual filling of silica gel, alkaline silica gel, silica gel and acidic silica gel, promotes the circulation of macromolecules in the column body while realizing better adsorption of dioxin substances, meanwhile, the method promotes the impurity molecules such as part of pigments and the like to be removed and washed out along with macromolecules, improves the purification effect of the sample, particularly when 44 wt% sulfuric acid silica gel and 22 wt% sulfuric acid silica gel are used together, can promote the free state of acidic impurities in a system, avoids tailing and difficult separation, thereby further improving the precision measurement accuracy, leading dioxin substances with relatively high detection limit to be detected, and the silver nitrate silica gel is arranged on the lower layer, so that the problem of chromatographic column blockage is avoided while high-efficiency adsorption of dioxin substances is realized.
Alkaline alumina column
The purification steps of the alkaline alumina column of the invention are as follows:
(1) filling a small group of quartz wool at the bottom of the filling column, and washing the inner wall by using n-hexane;
(2) adding alumina and n-hexane into a beaker, slowly stirring by using a glass rod to remove bubbles, pouring into a packed column, allowing the n-hexane to flow out, refilling anhydrous sodium sulfate after an alumina layer is stabilized, washing sodium sulfate powder on the tube wall by using the n-hexane, and leaching the alumina column by using the n-hexane;
(3) concentrating the extracting solution, quantitatively transferring the extracting solution to an alumina column, and leaching the alumina column by using leacheate.
In a preferred embodiment, the basic alumina column purification step is:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) adding 10g of alumina and 10mL of normal hexane into a beaker, slowly stirring by using a glass rod to remove bubbles, pouring into a packed column, allowing the normal hexane to flow out, refilling anhydrous sodium sulfate with the thickness of 9-11 mm after an alumina layer is stabilized, washing sodium sulfate powder on the tube wall by using the normal hexane, and leaching the alumina column by using 50mL of normal hexane;
(3) concentrating the extracting solution, quantitatively transferring the extracting solution to an alumina column, and leaching the alumina column by using leacheate.
In a more preferred embodiment, the step of rinsing the alumina column with the rinse solution is:
(1) firstly, leaching with 100mL of 1-3 wt% dichloromethane-n-hexane mixed solution, and adjusting the leaching flow rate to be 0.4-0.6 mL/s;
(2) and then eluting the alumina column by using 150mL of 45-55 wt% dichloromethane-n-hexane mixed solution to obtain an eluate.
Active carbon column
The purification steps of the activated carbon column of the invention are as follows:
(1) filling a small quartz wool at the bottom of the filling column, washing the inner wall with n-hexane, and filling anhydrous sodium sulfate and activated carbon silica gel by a dry method;
(2) injecting normal hexane into the activated carbon column, knocking the packed column to remove bubbles, refilling anhydrous sodium sulfate, washing sodium sulfate powder on the tube wall by the normal hexane, and leaching the silica gel column by the normal hexane;
(3) concentrating the extract, quantitatively transferring to an activated carbon column, and eluting the activated carbon column with eluent.
In a preferred embodiment, the activated carbon column purification step is:
(1) filling a small quartz wool at the bottom of the filling column, washing the inner wall with 10mL of n-hexane, and filling anhydrous sodium sulfate with the thickness of 9-11 mm and 1.0g of activated carbon silica gel by a dry method;
(2) injecting 10mL of normal hexane into the activated carbon column, knocking the packed column to remove bubbles, filling anhydrous sodium sulfate with the thickness of 9-11 mm, washing sodium sulfate powder on the tube wall with the normal hexane, and leaching the silica gel column with 20mL of normal hexane;
(3) concentrating the extract, quantitatively transferring to an activated carbon column, and eluting the activated carbon column with eluent.
In a more preferred embodiment, the step of eluting the activated carbon column with the eluent is:
(1) firstly, leaching with 200mL of 20-30 wt% dichloromethane-n-hexane mixed solution, and adjusting the leaching flow rate to be 0.4-0.6 mL/s;
(2) the activated carbon column was rinsed with 200mL of toluene to obtain an eluate.
The applicant finds that when the composite silica gel column is adopted for purification and then an alkaline alumina column or an activated carbon column is used for further purification, the purification efficiency can be improved, the sample solution is concentrated, and the detection accuracy of the sample is improved; meanwhile, the influence on detection equipment is avoided, the sensitivity is weakened or the detection limit of an instrument is improved, especially when solvents used in the leaching process are mixed liquor of dichloromethane and n-hexane and toluene, the applicant speculates that the ionization of alkaline substances is possibly inhibited in the alkaline alumina process, so that the alkaline impurities are in a free state, the alkaline impurities are well eluted, and meanwhile, the sample containing dioxin has a good adsorption effect, the alkaline impurities and part of macromolecular impurities can be eluted under the action of the dichloromethane and the n-hexane, and then the dioxin is leached by the toluene, and is eluted from a column layer under the action of desorption.
<Post-treatment purification>
The post-treatment purification method comprises the following steps:
(1) concentrating the eluate, transferring into a concentration tube, washing the flask with n-hexane for three times, and transferring into the concentration tube;
(2) and (3) placing the concentration tube on a nitrogen blower for nitrogen blowing concentration, taking out the concentration tube when the liquid level is lowered to the position of 0.8-1.2 cm at the lower end of the concentration tube, transferring the solution obtained after the eluate is concentrated to a sample injection vial, continuously cleaning the concentration tube with n-hexane for three times by using the nitrogen blowing tube, transferring the solution to the sample injection vial, and blowing the nitrogen to 20 mu L.
Examples
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Test method
Determining the content and the lowest detection limit of dioxin in the purified tenebrio molitor oil samples by using a high-resolution gas chromatography-high-resolution mass spectrometer; wherein, the sampling amount is 10.48g, and the recommended conditions of the high-resolution gas chromatography are set as follows:
and (3) sample introduction mode: injecting 1 mu L of sample without shunting;
sample inlet temperature: 270 ℃;
carrier gas flow: 1.0 mL/min;
interface temperature of color quality: 270 ℃;
a chromatographic column: the stationary phase is 5 percent of phenyl 95 percent of polymethylsiloxane, the length of the column is 60m, the inner diameter is 0.25mm, and the film thickness is 0.25 mu m;
temperature programming: the initial temperature is 140 ℃, the temperature is raised to 200 ℃ at the speed of 20/min after the temperature is maintained for 1min, the temperature is raised to 220 ℃ at the speed of 5/min after the temperature is maintained for 1min, the temperature is raised to 235 ℃ at the speed of 5/min after the temperature is maintained for 16min, the temperature is maintained for 7min, and the temperature is raised to 310 ℃ at the speed of 5/min and the temperature is maintained for 10 min.
Example 1
Embodiment 1 of the present invention provides a method for purifying a sample for gel permeation chromatography detection, comprising the steps of:
(1) concentrating the sample to 1mL, and purifying with gel chromatographic column to obtain extractive solution; the flow rate of solvent elution in the preparation process of the gel chromatographic column is 0.5 mL/s;
(2) concentrating the primary purified liquid to 1mL, and adding a composite silica gel column for purification to obtain an extracting solution;
(3) concentrating the extracting solution to 1mL, and then adding an alkaline alumina column for purification to obtain an eluate;
(4) the eluate was concentrated to 1mL and purified by post-treatment.
The preparation method of the gel permeation chromatographic column comprises the following steps:
(1) adding 30g of filler into a beaker, adding a solvent until the filler is completely covered, and placing the beaker in a fume hood for 18 hours;
(2) after the filler is fully swelled, stirring the filler, gradually transferring the filler to a chromatographic column by using a suction pipe, opening a four-fluorine valve in the middle to remove redundant solvent, after the filler is completely transferred, reserving 10cm of solvent on the upper part, adding a plug on the upper end, closing the valve at the bottom, turning the column upside down, opening a valve, oscillating the column body, and gradually and uniformly inverting the filler integrally. Closing the valve, slowly righting the column, opening the grinding plug at the upper end, and observing that the filler is uniformly settled until the filler is completely settled, wherein the column body has no fault, no bubble and no settlement decomposition layer;
(3) and (3) leaching the chromatographic column by using 500mL of solvent, closing the plug after leaching, sealing, and reserving the solvent with the length of more than 5cm on the upper layer to obtain the product.
The packing of the gel chromatographic column is Bio Beads S-X3.
The ratio of the diameter to the length of the gel permeation chromatography column is 1: 15.
the elution mode of the gel permeation chromatographic column for eluting when the sample passes through is a manual mode; the manual mode is as follows: before use, 100mL of solvent is used for pre-leaching, a sample concentrated to 1.5mL is added into a gel permeation chromatographic column, 70mL of solvent is used for leaching to remove macromolecules, 70mL of solvent is added for eluting dioxin substances to obtain a primary purifying solution, and finally 100mL of solvent is used for leaching the gel permeation chromatographic column.
The solvent is dichloromethane.
The purification steps of the composite silica gel column are as follows:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) 4g of anhydrous sodium sulfate, 0.9g of silica gel, 3g of 2 wt% potassium hydroxide silica gel, 0.9g of silica gel, 5.2g of 44 wt% sulfuric acid silica gel, 5.2g of 22 wt% sulfuric acid silica gel, 0.9g of silica gel, 3g of 10 wt% silver nitrate silica gel and 6g of anhydrous sodium sulfate are sequentially filled in the silica gel column, and the silica gel column is leached by 100mL of n-hexane;
(3) when the liquid level in the silica gel column is reduced to 0.5cm away from the uppermost layer of anhydrous sodium sulfate, the plunger is closed, and the receiving bottle is replaced at the lower end of the silica gel column;
(4) transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid for three times by using normal hexane, transferring all the concentrated primary purifying liquid to the silica gel column, leaching the concentrated primary purifying liquid by using 200mL of normal hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.5 mL/s.
The purification steps of the alkaline alumina column are as follows:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) adding 10g of alumina and 10mL of normal hexane into a beaker, slowly stirring by using a glass rod to remove bubbles, pouring into a packed column, allowing the normal hexane to flow out, refilling anhydrous sodium sulfate with the thickness of 10mm after an alumina layer is stabilized, washing sodium sulfate powder on the tube wall by using the normal hexane, and leaching the alumina column by using 50mL of normal hexane;
(3) concentrating the extracting solution, quantitatively transferring the extracting solution to an alumina column, and leaching the alumina column by using leacheate.
The step of leaching the alumina column by the leacheate comprises the following steps:
(1) firstly, leaching with 100mL of 1 wt% dichloromethane-n-hexane mixed solution, and adjusting the leaching flow rate to be 0.5 mL/s;
(2) and then eluting the alumina column with 150mL of 45 wt% dichloromethane-n-hexane mixed solution to obtain an eluate.
The post-treatment purification comprises the following steps:
(1) concentrating the eluate, transferring into a concentration tube, washing the flask with n-hexane for three times, and transferring into the concentration tube;
(2) and (3) placing the concentration tube on a nitrogen blower for nitrogen blowing concentration, taking out the concentration tube when the liquid level is lowered to the position 1cm below the concentration tube, transferring the solution obtained after the eluate is concentrated to a sample injection vial, continuously blowing the concentration tube with n-hexane for three times, transferring the solution to the sample injection vial, and blowing the solution to 20 mu L by nitrogen.
Example 2
Embodiment 2 of the present invention provides a method for purifying a sample for gel permeation chromatography detection, comprising the steps of:
(1) concentrating the sample to 2mL, and purifying with gel chromatographic column to obtain extractive solution; the flow rate of solvent elution in the preparation process of the gel chromatographic column is 1 mL/s;
(2) concentrating the primary purified liquid to 2mL, and adding a composite silica gel column for purification to obtain an extracting solution;
(3) concentrating the extracting solution to 2mL, and then adding an alkaline alumina column for purification to obtain an eluate;
(4) the eluate was concentrated to 2mL and purified by post-treatment.
The preparation method of the gel permeation chromatographic column is the same as that of the example 1.
The packing of the gel chromatographic column is Bio Beads S-X3.
The ratio of the diameter to the length of the gel permeation chromatography column is 1: 15.
the elution mode of the gel permeation chromatographic column for eluting when the sample passes through is a manual mode; the manual procedure was the same as in example 1.
The solvent is dichloromethane.
The purification steps of the composite silica gel column are as follows:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) 4g of anhydrous sodium sulfate, 0.9g of silica gel, 3g of 2 wt% potassium hydroxide silica gel, 0.9g of silica gel, 4g of 44 wt% sulfuric acid silica gel, 6.5g of 22 wt% sulfuric acid silica gel, 0.9g of silica gel, 3g of 10 wt% silver nitrate silica gel and 6g of anhydrous sodium sulfate are sequentially filled in the silica gel column, and the silica gel column is leached by 100mL of normal hexane;
(3) when the liquid level in the silica gel column is reduced to 0.5cm away from the uppermost layer of anhydrous sodium sulfate, the plunger is closed, and the receiving bottle is replaced at the lower end of the silica gel column;
(4) transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid for three times by using normal hexane, transferring all the concentrated primary purifying liquid to the silica gel column, leaching the concentrated primary purifying liquid by using 200mL of normal hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.5 mL/s.
The purification steps of the alkaline alumina column are as follows:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) adding 10g of alumina and 10mL of normal hexane into a beaker, slowly stirring by using a glass rod to remove bubbles, pouring into a packed column, allowing the normal hexane to flow out, refilling anhydrous sodium sulfate with the thickness of 10mm after an alumina layer is stabilized, washing sodium sulfate powder on the tube wall by using the normal hexane, and leaching the alumina column by using 50mL of normal hexane;
(3) concentrating the extracting solution, quantitatively transferring the extracting solution to an alumina column, and leaching the alumina column by using leacheate.
The step of leaching the alumina column by the leacheate comprises the following steps:
(1) firstly, leaching with 100mL of 3 wt% dichloromethane-n-hexane mixed solution, and adjusting the leaching flow rate to be 0.5 mL/s;
(2) and then eluting the alumina column with 150mL of 55 wt% dichloromethane-n-hexane mixed solution to obtain an eluate.
The procedure for the work-up purification was the same as in example 1.
Example 3
Embodiment 3 of the present invention provides a method for purifying a sample for gel permeation chromatography detection, comprising the steps of:
(1) concentrating the sample to 1.5mL, and purifying with gel chromatographic column to obtain extractive solution; the flow rate of solvent elution in the preparation process of the gel chromatographic column is 0.7 mL/s;
(2) concentrating the primary purified liquid to 1.5mL, and adding a composite silica gel column for purification to obtain an extracting solution;
(3) concentrating the extracting solution to 1.5mL, and then adding an alkaline alumina column for purification to obtain an eluate;
(4) the eluate was concentrated to 1.5mL and purified by workup.
The preparation method of the gel permeation chromatographic column is the same as that of the example 1.
The packing of the gel chromatographic column is Bio Beads S-X3.
The ratio of the diameter to the length of the gel permeation chromatography column is 1: 15.
the elution mode of the gel permeation chromatographic column for eluting when the sample passes through is a manual mode; the manual procedure was the same as in example 1.
The solvent is dichloromethane.
The purification steps of the composite silica gel column are as follows:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) 4g of anhydrous sodium sulfate, 0.9g of silica gel, 3g of 2 wt% potassium hydroxide silica gel, 0.9g of silica gel, 4.5g of 44 wt% sulfuric acid silica gel, 6g of 22 wt% sulfuric acid silica gel, 0.9g of silica gel, 3g of 10 wt% silver nitrate silica gel and 6g of anhydrous sodium sulfate are sequentially filled in the silica gel column, and the silica gel column is leached by 100mL of n-hexane;
(3) when the liquid level in the silica gel column is reduced to 0.5cm away from the uppermost layer of anhydrous sodium sulfate, the plunger is closed, and the receiving bottle is replaced at the lower end of the silica gel column;
(4) transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid for three times by using normal hexane, transferring all the concentrated primary purifying liquid to the silica gel column, leaching the concentrated primary purifying liquid by using 200mL of normal hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.5 mL/s.
The purification steps of the alkaline alumina column are as follows:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) adding 10g of alumina and 10mL of normal hexane into a beaker, slowly stirring by using a glass rod to remove bubbles, pouring into a packed column, allowing the normal hexane to flow out, refilling anhydrous sodium sulfate with the thickness of 10mm after an alumina layer is stabilized, washing sodium sulfate powder on the tube wall by using the normal hexane, and leaching the alumina column by using 50mL of normal hexane;
(3) concentrating the extracting solution, quantitatively transferring the extracting solution to an alumina column, and leaching the alumina column by using leacheate.
The step of leaching the alumina column by the leacheate comprises the following steps:
(1) firstly, leaching with 100mL of 2 wt% dichloromethane-n-hexane mixed solution, and adjusting the leaching flow rate to be 0.5 mL/s;
(2) and then eluting the alumina column with 150mL of 50 wt% dichloromethane-n-hexane mixed solution to obtain an eluate.
The procedure for the work-up purification was the same as in example 1.
Example 4
Embodiment 4 of the present invention provides a method for purifying a sample for gel permeation chromatography detection, comprising the steps of:
(1) concentrating the sample to 1.5mL, and purifying with gel chromatographic column to obtain extractive solution; the flow rate of solvent elution in the preparation process of the gel chromatographic column is 0.7 mL/s;
(2) concentrating the primary purified liquid to 1.5mL, and adding a composite silica gel column for purification to obtain an extracting solution;
(3) concentrating the extracting solution to 1.5mL, and then adding an activated carbon column for purification to obtain an eluate;
(4) the eluate was concentrated to 1.5mL and purified by workup.
The preparation method of the gel permeation chromatographic column is the same as that of the example 1.
The packing of the gel chromatographic column is Bio Beads S-X3.
The ratio of the diameter to the length of the gel permeation chromatography column is 1: 15.
the elution mode of the gel permeation chromatographic column for eluting when the sample passes through is a manual mode; the manual procedure was the same as in example 1.
The solvent is dichloromethane.
The purification steps of the composite silica gel column are as follows:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) 4g of anhydrous sodium sulfate, 0.9g of silica gel, 3g of 2 wt% potassium hydroxide silica gel, 0.9g of silica gel, 4.5g of 44 wt% sulfuric acid silica gel, 6g of 22 wt% sulfuric acid silica gel, 0.9g of silica gel, 3g of 10 wt% silver nitrate silica gel and 6g of anhydrous sodium sulfate are sequentially filled in the silica gel column, and the silica gel column is leached by 100mL of n-hexane;
(3) when the liquid level in the silica gel column is reduced to 0.5cm away from the uppermost layer of anhydrous sodium sulfate, the plunger is closed, and the receiving bottle is replaced at the lower end of the silica gel column;
(4) transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid for three times by using normal hexane, transferring all the concentrated primary purifying liquid to the silica gel column, leaching the concentrated primary purifying liquid by using 200mL of normal hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.5 mL/s.
The purification steps of the activated carbon column are as follows:
(1) filling a small quartz wool at the bottom of the filling column, washing the inner wall by using 10mL of normal hexane, and filling anhydrous sodium sulfate with the thickness of 10mm and 1.0g of activated carbon silica gel by a dry method;
(2) injecting 10mL of normal hexane into the activated carbon column, knocking the packed column to remove bubbles, filling anhydrous sodium sulfate with the thickness of 10mm, washing sodium sulfate powder on the tube wall by the normal hexane, and leaching the silica gel column by 20mL of normal hexane;
(3) concentrating the extract, quantitatively transferring to an activated carbon column, and eluting the activated carbon column with eluent.
The step of leaching the activated carbon column by the leacheate comprises the following steps:
(1) firstly, leaching with 200mL of 25 wt% dichloromethane-n-hexane mixed solution, and adjusting the leaching flow rate to be 0.4-0.6 mL/s;
(2) the activated carbon column was rinsed with 200mL of toluene to obtain an eluate.
The procedure for the work-up purification was the same as in example 1.
The test results were as follows:
comparative example 1
The embodiment of comparative example 1 is the same as example 4, except that the purifying step of the composite silica gel column comprises:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) 4g of anhydrous sodium sulfate, 0.9g of silica gel, 3g of 2 wt% potassium hydroxide silica gel, 0.9g of silica gel, 2.6g of 44 wt% sulfuric acid silica gel, 7.9g of 22 wt% sulfuric acid silica gel, 0.9g of silica gel, 3g of 10 wt% silver nitrate silica gel and 6g of anhydrous sodium sulfate are sequentially filled in the silica gel column, and the silica gel column is leached by 100mL of n-hexane;
(3) when the liquid level in the silica gel column is reduced to 0.5cm away from the uppermost layer of anhydrous sodium sulfate, the plunger is closed, and the receiving bottle is replaced at the lower end of the silica gel column;
(4) transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid for three times by using normal hexane, transferring all the concentrated primary purifying liquid to the silica gel column, leaching the concentrated primary purifying liquid by using 200mL of normal hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.5 mL/s.
The test results showed that PCB-169 could not be detected.
Comparative example 2
The embodiment of comparative example 2 is the same as example 4, except that the purifying step of the composite silica gel column comprises:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) 4g of anhydrous sodium sulfate, 0.9g of silica gel, 3g of 2 wt% potassium hydroxide silica gel, 0.9g of silica gel, 10.5g of 44 wt% sulfuric acid silica gel, 0.9g of silica gel, 3g of 10 wt% silver nitrate silica gel and 6g of anhydrous sodium sulfate are sequentially filled in the silica gel column, and the silica gel column is leached by 100mL of normal hexane;
(3) when the liquid level in the silica gel column is reduced to 0.5cm away from the uppermost layer of anhydrous sodium sulfate, the plunger is closed, and the receiving bottle is replaced at the lower end of the silica gel column;
(4) transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid for three times by using normal hexane, transferring all the concentrated primary purifying liquid to the silica gel column, leaching the concentrated primary purifying liquid by using 200mL of normal hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.5 mL/s.
The test results showed that PCB-169 could not be detected.
Comparative example 3
The embodiment of comparative example 3 is the same as example 4 except that the purifying step of the composite silica gel column comprises:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) 4g of anhydrous sodium sulfate, 0.9g of silica gel, 3g of 2 wt% potassium hydroxide silica gel, 0.9g of silica gel, 10.5g of 22 wt% sulfuric acid silica gel, 0.9g of silica gel, 3g of 10 wt% silver nitrate silica gel and 6g of anhydrous sodium sulfate are sequentially filled in the silica gel column, and the silica gel column is leached by 100mL of normal hexane;
(3) when the liquid level in the silica gel column is reduced to 0.5cm away from the uppermost layer of anhydrous sodium sulfate, the plunger is closed, and the receiving bottle is replaced at the lower end of the silica gel column;
(4) transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid for three times by using normal hexane, transferring all the concentrated primary purifying liquid to the silica gel column, leaching the concentrated primary purifying liquid by using 200mL of normal hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.5 mL/s.
The test results showed that PCB-169 could not be detected.
Comparative example 4
The embodiment of comparative example 4 is the same as example 4 except that the purifying step of the composite silica gel column comprises:
(1) filling a small quartz wool at the bottom of the filling column, and washing the inner wall by using 10mL of n-hexane;
(2) 4g of anhydrous sodium sulfate, 0.9g of silica gel, 3g of 2 wt% potassium hydroxide silica gel, 0.9g of silica gel, 3g of 10 wt% silver nitrate silica gel, 0.9g of silica gel, 4.5g of 44 wt% sulfuric acid silica gel and 6g of 22 wt% sulfuric acid silica gel are sequentially filled in the silica gel column, and the silica gel column is leached by 100mL of n-hexane;
(3) when the liquid level in the silica gel column is reduced to 0.5cm away from the uppermost layer of anhydrous sodium sulfate, the plunger is closed, and the receiving bottle is replaced at the lower end of the silica gel column;
(4) transferring the concentrated primary purifying liquid into a silica gel column, washing the primary purifying liquid for three times by using normal hexane, transferring all the concentrated primary purifying liquid to the silica gel column, leaching the concentrated primary purifying liquid by using 200mL of normal hexane after the transfer is finished, and adjusting the leaching flow rate to be 0.5 mL/s.
The test results show that PCB-126 is not detectable.
Comparative example 5
The embodiment of comparative example 5 is the same as example 4 except that the step of eluting the activated carbon column with the eluent is:
(1) firstly, leaching with 200mL of 2 wt% dichloromethane-n-hexane mixed solution, and adjusting the leaching flow rate to be 0.4-0.6 mL/s;
(2) the activated carbon column was rinsed with 200mL of toluene to obtain an eluate.
The test results showed that PCB-169 could not be detected.
Comparative example 6
The embodiment of comparative example 6 is the same as example 4 except that the step of eluting the activated carbon column with the eluent is:
(1) firstly, leaching with 200mL of 25 wt% dichloromethane-n-hexane mixed solution, and adjusting the leaching flow rate to be 0.4-0.6 mL/s;
(2) and then leaching the activated carbon column with 200mL of 25 wt% dichloromethane-n-hexane to obtain an eluate.
The test results showed that PCB-169 could not be detected.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A method for purifying a sample for gel permeation chromatography detection, comprising the steps of:
(1) dissolving and concentrating a sample, and then adding the sample into a gel chromatographic column for purification to obtain a primary purification solution; the flow rate of solvent elution in the preparation process of the gel chromatographic column is 0.5-1 mL/s;
(2) concentrating the primary purified liquid, and purifying with a chromatographic column to obtain eluate;
(3) concentrating the eluate, and performing post-treatment purification.
2. The purification method according to claim 1, wherein the chromatography column in the step (2) comprises a composite silica gel column.
3. The purification method according to claim 2, wherein the chromatography column in step (2) further comprises an alkaline alumina column or an activated carbon column.
4. The purification method according to claim 2, wherein the composite silica gel column comprises silica gel, acidic silica gel, basic silica gel, silver nitrate silica gel, and anhydrous sodium sulfate.
5. The purification method according to claim 4, wherein the acidic silica gel is a sulfuric acid silica gel.
6. The purification method according to claim 5, wherein the sulfuric acid silica gel comprises 44 wt% sulfuric acid silica gel and 22 wt% sulfuric acid silica gel.
7. The purification method according to claim 6, wherein the weight ratio of 44 wt% sulfuric acid silica gel to 22 wt% sulfuric acid silica gel is 1: (1-1.6).
8. The purification method according to claim 4, wherein the basic silica gel is potassium hydroxide silica gel.
9. The purification method according to claim 8, wherein the potassium hydroxide silica gel is 1 to 3 wt% potassium hydroxide silica gel.
10. The purification method according to claim 3, wherein the solvent used in the elution process of the basic alumina column or the activated carbon column comprises dichloromethane and n-hexane.
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