CN109382079B - Sephadex integral adsorption extraction stirring rod and preparation method and application thereof - Google Patents
Sephadex integral adsorption extraction stirring rod and preparation method and application thereof Download PDFInfo
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- CN109382079B CN109382079B CN201710680482.3A CN201710680482A CN109382079B CN 109382079 B CN109382079 B CN 109382079B CN 201710680482 A CN201710680482 A CN 201710680482A CN 109382079 B CN109382079 B CN 109382079B
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Abstract
The invention relates to a sephadex whole adsorption extraction stirring rod, which comprises a homogeneous body of sulfhydryl sephadex and dextran modified magnetic powder, wherein the homogeneous body contains a cavity matched with a template molecule; the invention also relates to a preparation method of the sephadex whole adsorption extraction stirring rod, the whole adsorption extraction stirring rod prepared by the interaction of the magnetic material and the sephadex is a uniform body, the mechanical strength is high, the solvent resistance is strong, the preparation method is simple and easy to implement, the cost is low, and the enrichment of a target object can be quickly and efficiently realized.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to a sephadex integral adsorption extraction stirring rod and a preparation method and application thereof.
Background
The dextran gel is a polymer compound having a porous network structure formed by crosslinking straight-chain dextran molecules and a crosslinking agent. The size of the meshes in the gel particles can be controlled by adjusting the ratio of the glucan to the cross-linking agent, and the larger the cross-linking degree is, the tighter the mesh structure is; the smaller the degree of crosslinking, the looser the mesh structure, and the mesh size determines the molecular weight range within which the material to be separated can freely enter and exit the gel. The dextran gel contains hydrophilicity and is also rich in ligand, and is easy to carry out chemical modification, thus being an ideal polymer support. The first time, the WangQi et al in 1986 connects sulfydryl to the dextran gel to synthesize the sulfhydryl dextran gel for the separation and enrichment of metal ions. However, sephadex cannot separate targets with similar molecular volumes, and cannot specifically bind to molecules with similar structures.
The Stir Bar for adsorptive Extraction (SBSE) technique was proposed by Baltussen et al, a commercial plant introduced by Gerstel GmbH in 2000. SBSE is an important extension of Solid Phase Extraction (SPE), and self-stirring is completed during extraction, so that competitive adsorption of stirrers is avoided. The SBSE is prepared by fixedly carrying a high-molecular polymer coating on the outer layer of an end-capped glass capillary tube with a built-in magnetic core, wherein the coating is mainly a non-specific adsorption coating such as polydimethylsiloxane and the like, a heat-resistant engineering plastic such as polyether sulfone ketone PPESK and the like, the selectivity is low, and the coating thickness is limited and can fall off or be damaged. The stirring rod is coated on the outer part and provided with an iron core on the inner part, and sufficient magnetic force is difficult to provide when the weight of the stirring rod is larger.
Therefore, research and development of an integral adsorption extraction stirring rod, a preparation method thereof and application thereof in extraction and detection of a target object in a complex sample are urgently needed to overcome the problems of weak specificity, insufficient magnetic force of the adsorption extraction stirring rod and the like in the enrichment process of the existing SBSE extraction technology.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a sephadex whole adsorption extraction stirring rod, a preparation method and application thereof. The glucan integral adsorption extraction stirring rod provided by the invention is of a uniform integral structure, strong in mechanical stability, strong in magnetism, strong in solvent resistance, simple and easy to implement, low in cost and capable of quickly and efficiently realizing enrichment of a target substance.
Therefore, the invention provides a sephadex whole adsorption extraction stirring rod, which comprises a homogeneous body of mercaptodextran gel and dextran modified magnetic powder, wherein the homogeneous body contains a cavity matched with a template molecule.
In some preferred embodiments of the invention, the magnetic powder is a highly magnetic superparamagnetic powder. The magnetic powder is more preferably superparamagnetic neodymium iron boron magnetic powder.
According to the invention, the mercaptodextran gel used as a main adsorption material has the advantages of strong chemical stability and strong organic solvent resistance. Particularly, the glucan modified magnetic powder (preferably the superparamagnetic neodymium iron boron magnetic powder) and the sulfhydryl glucan gel have a certain synergistic effect when used together, so that the stirring rod has stronger organic solvent resistance, mechanical stability and better reproducibility and stability. Furthermore, the use of the above-mentioned structure in which the specific homogenate and the specific hole are combined further improves the analytical sensitivity.
The second aspect of the present invention provides a method for preparing a sephadex monolithic adsorption extraction stir bar according to the first aspect of the present invention, comprising:
step A, pretreating magnetic powder to prepare glucan modified magnetic powder;
step B, mixing the mercaptodextran gel with the template molecules, uniformly stirring, and reacting to prepare a dextran imprinting solution;
step C, mixing and filling the dextran blotting solution and the dextran modified magnetic powder into a tube, performing ultrasonic treatment, and reacting to obtain a stirring rod precursor;
and D, taking out the stirring rod precursor, and eluting the template molecules to prepare the sephadex integral adsorption extraction stirring rod.
In a preferred embodiment of the invention, the tube is preferably a glass tube. Through research, compared with other materials (such as plastic pipes), the stirring rod is easier to take out of the glass pipe, and the preparation is simple.
In some preferred embodiments of the invention, in step a, the treatment comprises dextran modification of the magnetic particles.
According to the invention, the treatment also comprises the removal of impurities in the magnetic powder before the dextran modification of the magnetic powder.
According to the invention, the treatment also comprises the removal of organic matter on the surface of the magnetic powder before the dextran modification of the magnetic powder.
In some preferred embodiments of the invention, in step B, the mercaptodextran gel comprises the reaction product of tetrahydrofuran, dextran gel, thioglycolic acid and concentrated sulfuric acid.
According to the invention, the tetrahydrofuran accounts for 30-50 wt%, the glucan gel accounts for 15-35 wt%, the thioglycolic acid accounts for 25-40 wt%, and the concentrated sulfuric acid accounts for 0.1-0.3 wt%.
According to the invention, the reaction temperature is 40-50 ℃; and/or the reaction time is 40-60 h.
In some preferred embodiments of the present invention, in step B, the dextran blotting solution comprises an acrylate compound, azobisisobutyronitrile, mercaptodextran gel, a template molecule, and an organic solvent.
In some preferred embodiments of the present invention, the acrylate compound is 15 to 30wt%, the azobisisobutyronitrile is 0.3 to 1.5wt%, the mercaptodextran gel is 10 to 30wt%, the template molecule is 0.05 to 1.5wt%, and the organic solvent is 50 to 80 wt%.
In some preferred embodiments of the present invention, the acrylate compound is ethylene glycol dimethacrylate and/or trimethylolpropane trimethacrylate.
In some preferred embodiments of the present invention, the organic solvent is one or more of acetonitrile, methanol, and toluene.
In some preferred embodiments of the present invention, in step C, the dextran blotting solution and the dextran-modified magnetic powder are sequentially added to the tube, repeated several times, both ends of the tube are closed, sonicated, and the reaction is continued.
In some preferred embodiments of the present invention, the time of the ultrasonic treatment is 5 to 20 min; and/or the reaction temperature is 80-90 ℃; and/or the reaction time is 10-20 h.
According to the invention, the ultrasound time cannot be too short, otherwise the homogeneity is affected; but the temperature of the solution in the pipe is easy to rise due to long ultrasonic time; the two closed ends of the tube are easy to fall off after a long time. The research shows that the time of ultrasonic treatment is most suitable to be 5-20 min.
In some preferred embodiments of the invention, in step D, the stir bar is eluted in the eluent followed by methanol until no more template molecules flow out.
According to the invention, the stirring rod is stirred and eluted in the eluent under the action of magnetic stirring.
In a preferred embodiment of the invention, the eluent is a methanol/formic acid solution.
In some preferred embodiments of the present invention, the volume ratio of methanol to formic acid is (6-18): 1.
In some preferred embodiments of the present invention, in step D, before eluting the template molecule, the method further comprises cutting the removed stirring rod.
According to the invention, the cutting length is 1-3 cm. The length of the adsorption extraction stirring rod is selected to be 1-3 cm, the adsorption extraction stirring rod is easy to break when the length is too long, and the adsorption quantity is insufficient when the length is too short.
In some preferred embodiments of the invention, the template molecule comprises one or more of sudan red i, sudan red ii, sudan red iii, sudan red iv, solvent yellow2, naphthalene, fluorene, phenanthrene, pyrene and fluoranthene.
According to the invention, the template molecule comprises one or more of Sudan I, Sudan II, Sudan III, Sudan IV and solvent yellow 2.
According to the invention, the template molecule comprises one or more of naphthalene, fluorene, phenanthrene, pyrene and fluoranthene.
In a third aspect, the invention provides a sephadex whole adsorption extraction stirring rod according to the first aspect of the invention or the sephadex whole adsorption extraction stirring rod prepared by the method according to the second aspect of the invention, and the application of the sephadex whole adsorption extraction stirring rod in extraction of a target object in sample detection is provided.
The glucan integral adsorption extraction stirring rod provided by the invention is of a uniform integral structure, does not have the problem that an extraction layer is easy to fall off, and is strong in mechanical stability; moreover, the stirring rod does not contain an iron core, so that the weight is greatly reduced, and the magnetic powder is filled in the stirring rod, so that the provided magnetic force is larger than SBSE; particularly, the dextran integral adsorption extraction stirring rod prepared by adopting the specific method of the combined action of sequentially mixing and filling high-magnetism super-paramagnetic powder and sulfhydryl dextran gel, ultrasonic treatment and constant temperature reaction greatly improves the magnetism and mechanical stability of the adsorption extraction stirring rod. The method has the advantages that the mercaptodextran gel, the treated magnetic powder and the molecular imprinting technology are combined to use a synergistic effect, so that the adsorption extraction stirring rod contains a large number of specific holes which are reasonably distributed and have specific recognition on a target object, the specificity is stronger in the enrichment process, the target object is better enriched, the target object enrichment is realized more quickly and efficiently, and the reutilization property and the stability are greatly improved. In addition, the method provided by the invention also has the advantages of simple preparation, easy control of conditions, low cost and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the attached drawings
FIG. 1 is a chromatogram of the extraction effect of the dextran monolith adsorption extraction stirring rod of example 1 of the present invention;
FIG. 2 is a chromatogram of the extraction effect of the dextran monolithic adsorption extraction stirring rod of example 2 of the present invention;
description of reference numerals: in fig. 1: 1-solvent yellow2, 2-Sudan red I, 3-Sudan red II, 4-Sudan red III and 5-Sudan red IV; a is a standard solution chromatogram before extraction; b is an eluent chromatogram after extraction; in fig. 2: 1-naphthalene, 2-fluorene, 3-phenanthrene, 4-pyrene, 5-fluoranthene; a is a standard solution chromatogram before extraction; and B is an eluent chromatogram after extraction.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
In the present invention, the term "solvent yellow 2", english name: solvent Yellow2, CAS number: 60-11-7; the chemical formula is as follows: C14H15N 3;
the term "sudan red i", english name: sudan I; CAS number: 842-07-9; the chemical formula is as follows: C16H12N 20;
the term "sudan red ii", english name: sudan II; CAS number: 3118-97-6; the chemical formula is as follows: C18H16N 2O;
the term "sudan red iii", english name: sudan III; CAS number: 85-86-9; the chemical formula is as follows: C22H16N 4O;
the term "sudan red iv", english name: sudan IV; CAS number: 85-83-6; the chemical formula is as follows: C24H20N 4O;
the term "naphthalene", english name: naphthalene; CAS number: 91-20-3; the chemical formula is as follows: C10H 8;
the term "fluorene", english name: fluoroene; CAS number: 86-73-7; the chemical formula is as follows: C13H 10;
the term "phenanthrene", english name: phenanthrene; CAS number: 85-01-8; the chemical formula is as follows: C14H 10;
the term "pyrene", english name: pyrene; CAS number: 129-00-0; the chemical formula is as follows: C16H 10;
the term "fluoranthene", english name: fluoranthene; CAS number: 206-44-0; the chemical formula is as follows: C16H 10;
the above reagents were purchased from carbofuran technologies, inc.
In addition, the first and second substrates are,
unless otherwise specified, all test methods used in the present invention are conventional in the art.
The apparatus used in the present invention is, unless otherwise specified, a conventional apparatus in the art.
The materials and reagents used in the present invention are commercially available unless otherwise specified.
The instrument and the characterization test method adopted by the invention are as follows: measurement was carried out by means of an ACQUIT UPLC ultra performance liquid chromatograph and an ACQUITY ultra performance phase chromatograph, both of which are available from waters.
Examples
Example 1
1. And (3) carrying out glucan modification pretreatment on the magnetic powder:
(1) pretreatment of magnetic powder: soaking the superparamagnetic neodymium-iron-boron magnetic powder in an acetone solution for 30min, washing with deionized water, soaking with 1mol/L sodium hydroxide solution at 80 ℃ for 20min to remove organic matters on the surface of the magnetic powder, washing with deionized water, and vacuum drying for later use;
(2) and (3) dextran modification pretreatment of magnetic powder: firstly, preparing a sodium hydroxide/diethylene glycol mixed solution, adding 100mmol of sodium hydroxide into 40mL of diethylene glycol, stirring and heating until the sodium hydroxide is completely dissolved, then preserving at 70 ℃, adding 2g of treated magnetic powder and 5g of sephadex into 200mL of diethylene glycol, fully stirring at 210 ℃, slowly adding 20mL of the sodium hydroxide/diethylene glycol mixed solution, reacting for 2 hours at 210 ℃, washing products with ethyl acetate, ethanol and deionized water respectively after cooling, and drying in vacuum for later use.
2. Preparation of mercaptodextran gel:
adding the following reactants into the reactor by mass percent: tetrahydrofuran 40%, sephadex 25%, thioglycollic acid 34.7% and concentrated sulfuric acid 0.3%, uniformly stirring the mixed solution, reacting for 50h at 50 ℃, cleaning the product by deionized water, and drying in vacuum for later use.
3. Preparing mixed solution of glucan sudan red print and glucan modified magnetic powder, mixing and filling the mixed solution and the glucan modified magnetic powder in a glass tube:
adding the following reactants into the reactor by mass percent: acetonitrile 60%, ethylene glycol dimethacrylate 20%, azodiisobutyronitrile 1%, mercaptodextran gel 18%, template molecules of Sudan red I, Sudan red II, Sudan red III, Sudan red IV and solvent yellow2 0.2% respectively, stirring the mixed solution uniformly, introducing inert gas for 10min, reacting for 6h at 50 ℃, heating to 85 ℃, reacting for 10h, and cooling to room temperature for later use. And taking 500 mu L of the dextran blotting mixed solution and 2.5g of dextran-modified magnetic powder, loading the mixture-magnetic powder-mixed solution-magnetic powder into a glass tube with the inner diameter of 0.4cm and the length of 8cm for 6 times, sealing two ends, and performing ultrasonic treatment for 10min to continue the reaction at 85 ℃ for 15 h.
4. Cutting the prepared integral adsorption extraction stirring rod:
and taking out the reacted glass tube, breaking the outer layer glass tube, and cutting the glass tube into an integral adsorption extraction stirring rod with the length of 2 cm.
5. And (3) eluting molecules of the integral adsorption extraction stirring rod template:
stirring and eluting in a methanol/formic acid (v/v is 9:1) solution by virtue of the self magnetic stirring action of an integral adsorption extraction stirring rod, and then eluting with methanol until the eluent is subjected to liquid chromatography until no Sudan I, Sudan II, Sudan III, Sudan IV or solvent yellow2 is detected.
The stirring rod prepared according to the steps is placed into 50mL of aqueous solution with the concentration of Sudan red I, Sudan red II, Sudan red III, Sudan red IV and solvent yellow2 of 5mg/L for extraction and stirring for 30min, the stirring rod is washed by 3 times by 6mL of methanol after extraction is finished, washing solutions are combined and concentrated to 1mL, the ultra-high performance liquid chromatography detection is carried out, a detection chromatogram is shown in figure 1, and the stirring rod has a good enrichment effect on a target object.
Preparing a series of standard aqueous solutions with different concentrations, taking the concentration of the standard solution as a horizontal coordinate, taking the response peak area on the high performance liquid chromatography after extraction by a stirring rod as a vertical coordinate, drawing a linear range curve of 5 Sudan red target substances, and solving a linear regression equation. The results are shown in table 1 (linear equation, quantitative limit and detection limit of 5 methods for measuring Sudan red by using adsorption extraction stirring bar and liquid chromatography together). As can be seen from the table, the linear range of the adsorption extraction stirring rod during extraction is 0.05-4.0mg/L, the detection limit is 0.004mg/L, the quantification limit is 0.01mg/L, and the correlation coefficient is greater than 0.92, which indicates that the adsorption extraction stirring rod has higher sensitivity for analyzing 5 Sudan red target substances.
TABLE 1
The above extraction detection process was repeated 5 times for each concentration sample by adding 0.1mg/L and 1.0mg/L of the target to the water sample without the above 5 Sudan red targets, and the average recovery and relative standard deviation RSD of the target are shown in Table 2 (the recovery and relative standard deviation of the 5 Sudan red methods are determined by using an adsorption extraction stirring rod in combination with liquid chromatography). The results were satisfactory with target recovery > 80% at both concentrations and a relative standard deviation < 7.4%.
TABLE 2
Example 2
1. And (3) carrying out glucan modification pretreatment on the magnetic powder:
(1) pretreatment of magnetic powder: soaking the superparamagnetic neodymium-iron-boron magnetic powder in an acetone solution for 30min, washing with deionized water, soaking with 1mol/L sodium hydroxide solution at 80 ℃ for 20min to remove organic matters on the surface of the magnetic powder, washing with deionized water, and vacuum drying for later use;
(2) and (3) dextran modification pretreatment of magnetic powder: firstly, preparing a sodium hydroxide/diethylene glycol mixed solution, adding 80mmol of sodium hydroxide into 40mL of diethylene glycol, stirring and heating until the sodium hydroxide is completely dissolved, then preserving at 70 ℃, adding 3g of treated magnetic powder and 5g of sephadex into 200mL of diethylene glycol, fully stirring at 210 ℃, slowly adding 35mL of the sodium hydroxide/diethylene glycol mixed solution, reacting for 2 hours at 210 ℃, washing products with ethyl acetate, ethanol and deionized water respectively after cooling, and drying in vacuum for later use.
2. Preparation of mercaptodextran gel:
adding the following reactants into the reactor by mass percent: tetrahydrofuran 40%, dextran gel 30%, mercaptoacetic acid 29.8% and concentrated sulfuric acid 0.2%, stirring the mixed solution uniformly, reacting for 40h at 45 ℃, cleaning the product with deionized water, and drying in vacuum for later use.
3. Preparing polycyclic aromatic hydrocarbon dextran blotting mixed liquor and dextran modified magnetic powder, mixing and filling the mixed liquor and the dextran modified magnetic powder in a glass tube:
adding the following reactants into the reactor by mass percent: 60% of toluene, 15% of trimethylolpropane trimethacrylate, 0.5% of azodiisobutyronitrile, 23% of mercaptodextran gel, and 0.3% of each of naphthalene, fluorene, phenanthrene, pyrene and fluoranthene template molecules, uniformly stirring the mixed solution, introducing an inert gas for 20min, reacting for 8h at 50 ℃, heating to 85 ℃, reacting for 10h, and cooling to room temperature for later use. And taking 500 mu L of the dextran blotting mixed solution and 2.5g of dextran-modified magnetic powder, loading the mixture-magnetic powder-mixed solution-magnetic powder into a glass tube with the inner diameter of 0.4cm and the length of 8cm for 4 times, sealing two ends, and performing ultrasonic treatment for 10min to continuously react for 10h at 85 ℃.
4. Cutting the prepared integral adsorption extraction stirring rod:
and taking out the reacted glass tube, breaking the outer layer glass tube, and cutting the glass tube into an integral adsorption extraction stirring rod with the length of 3 cm.
5. And (3) eluting molecules of the integral adsorption extraction stirring rod template:
stirring and eluting in a methanol/formic acid (v/v is 6:1) solution by virtue of the self magnetic stirring action of an integral adsorption extraction stirring rod, and then eluting with methanol until no naphthalene, fluorene, phenanthrene, pyrene and fluoranthene template molecules flow out when eluent is subjected to liquid chromatography detection.
And (3) putting the stirring rod prepared according to the steps into 100mL of aqueous solution with the concentration of 3mg/L of naphthalene, fluorene, phenanthrene, pyrene and fluoranthene, extracting and stirring for 40min, washing the stirring rod for 3 times by using 6mL of chloroform after extraction is finished, combining washing liquids, concentrating to 1mL, carrying out ultra-high performance combined chromatography detection, and finding that the stirring rod has a good enrichment effect on a target object according to a detection chromatogram shown in FIG. 2.
Preparing a series of standard aqueous solutions with different concentrations, taking the concentration of the standard solution as an abscissa, taking a response peak area on the ultra-high performance synthesis chromatography after extraction by a stirring rod as an ordinate, drawing a linear range curve of naphthalene, fluorene, phenanthrene, pyrene and fluoranthene, and solving a linear regression equation. The results are shown in table 3 (linear equation, quantitative limit and detection limit for 5 sudan red determination methods using adsorption extraction stirring bar and liquid chromatography). As can be seen from Table 3, the linear range of the stirring rod for adsorption extraction during extraction is 0.1-10.0mg/L, the detection limit is 0.02mg/L, the quantification limit is 0.05mg/L, and the correlation coefficient is greater than 0.98, which indicates that the stirring rod for adsorption extraction has higher sensitivity for analyzing naphthalene, fluorene, phenanthrene, pyrene and fluoranthene.
TABLE 3
Example 3
The same preparation method and conditions as in example 1 were used except that tetrahydrofuran (30 wt%), dextran gel (15 wt%), thioglycolic acid (25 wt%), concentrated sulfuric acid (0.1 wt%), reaction temperature (40 deg.C) in step B, and reaction time (60 h); 30wt% of ethylene glycol dimethacrylate, 0.3wt% of azobisisobutyronitrile, 10 wt% of mercaptodextran gel and 50wt% of organic solvent; the ultrasonic time is 5min, the reaction temperature in the step C is 80 ℃, and the detection same as that in the example 1 shows that the stirring rod prepared in the example 3 has a good enrichment effect on the target object and has high analysis sensitivity.
Example 4
The same preparation method and conditions as in example 2 were used except that tetrahydrofuran was 50wt%, sephadex was 35wt%, thioglycolic acid was 40wt%, azobisisobutyronitrile was 1.5wt%, mercaptosephadex was 30wt%, organic solvent was 80wt%, the reaction temperature in step C was 90 ℃ and the reaction time was 20 hours; the methanol/formic acid (v/v ═ 18:1) solution template molecules were sudan red i and naphthalene, 0.025 wt% each. The same detection as that in example 2 shows that the stirring rod prepared in example 4 has a good enrichment effect on the target substance, and the analysis has high sensitivity.
Example 5
And (3) testing the reusability and stability of the adsorption extraction stirring rod:
carrying out adsorption-elution experiment on the Sudan I solution with the concentration of 0.5mg/L by using the adsorption extraction stirring rod prepared in the example 4 according to the conditions in the example 1, and detecting the eluent by using a liquid chromatograph; an adsorption-elution experiment was performed on a naphthalene solution having a concentration of 1.0mg/L under the conditions in example 2, and the eluate was subjected to a phase chromatograph for detection, and the relative error of the response value of the target substance to be detected was calculated to examine the reusability and stability of the adsorption extraction stir bar. The stirring rod is used for 5 times a day and repeatedly used for 30 times, and the relative error is less than 9.2 percent, which indicates that the stirring rod has good reproducibility and stability and long service life.
The stirring rod is placed in methanol, water and 0.1mol/L formic acid solution and is continuously stirred for 10 hours at the rotating speed of 500rpm, then the stirring rod is taken out for carrying out an adsorption-elution experiment, the error of the result is less than 7.5 percent, the stirring rod is not obviously abraded or fallen, and stronger solvent resistance and mechanical stability are shown.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (21)
1. A sephadex integral adsorption extraction stirring rod comprises a homogeneous body of mercaptosephadex and dextran-modified magnetic powder, wherein the homogeneous body contains a cavity matched with a template molecule.
2. The stirring rod of claim 1, wherein the magnetic powder is a highly magnetic super-paramagnetic powder.
3. The stirring rod of claim 1, wherein the magnetic powder is superparamagnetic neodymium iron boron magnetic powder.
4. A method for preparing a sephadex monolith sorption extraction stir bar according to any of claims 1-3, comprising:
step A, pretreating magnetic powder to prepare glucan modified magnetic powder;
step B, mixing the mercaptodextran gel with the template molecules, uniformly stirring, and reacting to prepare a dextran imprinting solution;
step C, mixing and filling the dextran blotting solution and the dextran modified magnetic powder into a tube, performing ultrasonic treatment, and reacting to obtain a stirring rod precursor;
and D, taking out the stirring rod precursor, and eluting the template molecules to prepare the sephadex integral adsorption extraction stirring rod.
5. The method of claim 4, wherein in step A, the treatment comprises dextran modification of magnetic particles.
6. The method of claim 5, wherein in step A, the treatment further comprises removal of impurities from the magnetic particles prior to the dextran modification of the magnetic particles.
7. The method according to claim 6, wherein the removing of impurities in the magnetic powder is removing of organic matter on the surface of the magnetic powder.
8. The method of claim 4, wherein in step B, the mercaptodextran gel comprises the reaction product of tetrahydrofuran, dextran gel, thioglycolic acid, and concentrated sulfuric acid;
wherein the temperature of the reaction for forming the mercaptodextran gel is 40-50 ℃; and/or the time of the reaction for forming the mercaptodextran gel is 40-60 h.
9. The method of claim 8, wherein the reactants for forming the mercaptodextran gel comprise about 30 to about 50wt% tetrahydrofuran, about 15 to about 35wt% dextran gel, about 25 to about 40wt% thioglycolic acid, and about 0.1 to about 0.3wt% concentrated sulfuric acid.
10. The method of claim 4, wherein in step B, the dextran blotting solution comprises an acrylate compound, azobisisobutyronitrile, mercaptodextran gel, a template molecule, and an organic solvent;
wherein the acrylate compound is ethylene glycol dimethacrylate and/or trimethylolpropane trimethacrylate; the organic solvent is one or more of acetonitrile, methanol and toluene.
11. The method according to claim 10, wherein in the dextran blotting solution in step B, the acrylate compound is 15-30 wt%, the azobisisobutyronitrile is 0.3-1.5 wt%, the mercaptodextran gel is 10-30 wt%, the template molecule is 0.05-1.5 wt%, the organic solvent is 50-80 wt%, and the sum of the components is 100%.
12. The method according to any one of claims 4 to 10, wherein in step C, the dextran blotting solution and the dextran-modified magnetic powder are sequentially added to the tube, repeated a plurality of times, the both ends of the tube are closed, sonicated, and the reaction is continued.
13. The method according to claim 12, wherein in the step C, the ultrasonic treatment time is 5-20 min; and/or the reaction temperature of the dextran blotting solution and dextran-modified magnetic powder is 80-90 ℃; and/or the reaction time of the dextran blotting solution and dextran-modified magnetic powder is 10-20 h.
14. The method according to any one of claims 4 to 10, wherein in step D, the stir bar is eluted in the eluent and then eluted with methanol until no more template molecules flow out; wherein, the stirring rod is stirred and eluted in the eluent under the action of magnetic stirring.
15. The method of claim 14, wherein the eluent is a methanol/formic acid solution.
16. The method according to claim 15, wherein the volume ratio of methanol to formic acid in the eluent is (6-18): 1.
17. The method according to any one of claims 4 to 10, wherein in step D, before eluting the template molecule, the method further comprises cutting the removed stir bar.
18. The method of claim 17, wherein the cutting length is 1-3 cm.
19. The method of any one of claims 4 to 10, wherein the template molecule comprises one or more of Sudan Red I, Sudan Red II, Sudan Red III, Sudan Red IV, solvent yellow2, naphthalene, fluorene, phenanthrene, pyrene and fluoranthene.
20. The method of claim 19, wherein the template molecule comprises one or more of sudan red I, sudan red II, sudan red III, sudan red IV, and solvent yellow2 or one or more of naphthalene, fluorene, phenanthrene, pyrene, and fluoranthene.
21. Use of the sephadex bulk adsorption extraction stir bar according to any one of claims 1 to 3 or the sephadex bulk adsorption extraction stir bar prepared according to any one of claims 4 to 20 for extraction of a target in sample detection.
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