CN112694564A - Preparation method and application of furfural molecularly imprinted polymer - Google Patents
Preparation method and application of furfural molecularly imprinted polymer Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a furfural molecularly imprinted polymer. The method takes furfurals as a template and vinyl functionalized silicon dioxide as a carrier to prepare the furfurals molecularly imprinted polymer by a surface precipitation method. Uniformly mixing template molecules, functional monomers, a cross-linking agent, a proper amount of an initiator and a solvent according to a certain molar ratio in a flat-bottomed flask, filling nitrogen to remove oxygen, and heating in a sealed water bath to obtain a furfural molecular imprinting polymer with the template molecules; and then carrying out centrifugal separation and collection, Soxhlet elution and vacuum drying on the obtained molecularly imprinted polymer to obtain the template-removed furfural molecularly imprinted polymer. The obtained furfural molecular imprinted polymer without the template is used as column chromatography filler for column packing, is applied to adsorbing furfural substances in honey, vinegar and coffee, and has the advantages of strong selectivity, large adsorption capacity and the like.
Description
Technical Field
The invention belongs to the technical field of solid-phase extraction, and relates to a preparation system for simultaneously adsorbing four furfural molecular imprinted polymers and application thereof, which are combined with a high performance liquid chromatography method for selectively separating, enriching and detecting the content of furfural substances in food.
Background
The heat treatment of food is considered to be one of the most effective means for preserving food, and not only can the shelf life of food be prolonged by heating the food, but also good quality assurance can be provided for the food. Wherein various heating means (baking, frying, braising, cooking, etc.) are accompanied by a number of necessary or unnecessary chemical reactions, mainly including maillard reactions, caramelization reactions and oxidation of fats and oils. These reactions enhance the flavor and taste characteristics of the food to some extent, and also enhance a series of characteristics of the food such as color, aroma, texture, etc., and even if the same raw material is subjected to different heat treatment methods, different effects can be produced. However, the mutagenicity, carcinogenicity and toxicity of some products generated during heating are important concerns, and heterocyclic amines, nitrosamines, polycyclic aromatic hydrocarbons and the like are well known. In recent years, the toxicity and pseudo-odor of furfural have been attracting attention. At present, no clear method for reducing the content of furfural substances in food is available, mainly because the precursor substances and the formation routes of the furfural substances are mainly Maillard reaction and caramelization reaction, which are the main formation routes for providing the color, the taste and the flavor of the food. The browning degree of the food and the content of the furfural substances have obvious linear relation, if the browning degree of the food is reduced, the content of the corresponding furfural substances is also reduced, but the means for reducing the furfural substances is obviously not a required result. Or changing the ordinary eating habits of people, and trying to use non-reducing sugar (cane sugar and starch) or polycyclic compounds instead of reducing sugar or fructose, the method seems to have certain effect, but when the heating temperature reaches 250 ℃, furfural substances still appear in the food. The furfural substances belong to medium-toxicity substances and have irritation to eyes, mucous membranes and skin, and after being absorbed by organisms, a certain dosage of furfural substances can have adverse effects on organs such as livers, kidneys, hearts and the like.
Disclosure of Invention
Aiming at the purification and enrichment of furfural substances in a complex food matrix, the invention provides a preparation method of a furfural molecular imprinted polymer. Aiming at furfural (2-Furaldehyde), 5-Methylfurfural (5-Methylfurfural), 5-Hydroxymethylfurfural (5-Hydroxymethylfurfural) and 2-acetylfuran (2-Acetyl furan), optimizing parameter conditions such as functional monomers, cross-linking agents, reaction temperature, reaction time and the like, preparing functional molecularly imprinted microspheres capable of specifically adsorbing furfural in a weak polar solvent, applying the microspheres to analysis and detection of trace furfural substances in complex matrix food, and having important significance for improving analysis technology of trace furfural substances in complex matrix food, controlling residual level of furfural substances in food, guaranteeing physical and psychological health of people and the like.
The invention also aims to provide the non-furfural molecularly imprinted polymer prepared by the method.
The invention also aims to provide application of the molecularly imprinted polymer.
The above object of the present invention is achieved by the following means.
A preparation method of a furfural molecularly imprinted polymer sequentially comprises the following steps:
s1, with furanone as a template, adding the template, a functional monomer and a cross-linking agent into a flat-bottomed flask, magnetically stirring and uniformly mixing, ultrasonically degassing, then filling nitrogen to remove oxygen, and polymerizing for 18-24 hours in a constant-temperature water bath at 50-70 ℃ after sealing to obtain a molecularly imprinted polymer with template molecular furfural;
s2, centrifugally separating and vacuum drying the polymer obtained in the step S1 to obtain molecular imprinting polymer particles uniformly provided with template molecules, namely furfural, removing the template molecules through soxhlet elution of methanol and acetic acid, removing acetic acid through soxhlet elution of methanol to obtain neutral polymer particles with molecular imprinting holes, and drying under vacuum to obtain the template-removed furfural molecular imprinting polymer.
Wherein, the functional monomer in the step S1 is one or two of 4-vinylpyridine or methyl methacrylate; the cross-linking agent is one or two of ethylene glycol dimethacrylate or pentaerythritol triacrylate; the mole ratio of the template to the functional monomer to the cross-linking agent is 1: 2-10: 10-40.
The functional monomers and the cross-linking agents used by different substances are different, and the dosage ratio of the substances directly influences the property of the prepared molecularly imprinted polymer, thereby influencing the adsorption effect and the enrichment efficiency. The inventor conducts a great deal of research and research in the initial stage of experiments, screens out proper functional monomers and a cross-linking agent matched with the functional monomers, and finds that when the functional monomers adopt one or two of 4-vinylpyridine or methyl methacrylate, and the cross-linking agent adopts one or two of ethylene glycol dimethacrylate or pentaerythritol triacrylate, the obtained molecularly imprinted polymer can be used for adsorbing a plurality of furfural simultaneously; the prepared molecularly imprinted polymer microspheres have good adsorption effect and high enrichment efficiency on furfural substances.
Through a large number of experimental researches, the inventor finds that the property of the polymer prepared by selecting 4-vinylpyridine as the functional monomer is obviously superior to that of other functional monomers aiming at furfural. For example, for furfural, 4-vinylpyridine is preferred as the functional monomer, and the polymer prepared from the functional monomer such as methyl methacrylate has poor properties; for furanone, methyl methacrylate is preferred as the functional monomer, while 4-vinylpyridine functional monomers produce polymers with poor properties.
Preferably, the synthetic molecularly imprinted polymer of S2 is sieved by a sieve of 250-300 meshes.
Preferably, the initiator is azobisisobutyronitrile.
Preferably, the porogen is one or both of acetonitrile or toluene.
Preferably, the molar ratio of the template to the functional monomer to the cross-linking agent is 1: 2-10: 10-40.
Preferably, the molar ratio of the template to the functional monomer to the cross-linking agent is 1: 2-10: 10-40; the furfural molecular engram polymer is characterized in that the functional monomer is 4-vinylpyridine, and the cross-linking agent is pentaerythritol triacrylate. Researches show that when the functional monomer 4-vinylpyridine is matched with the cross-linking agent pentaerythritol triacrylate, and the ratio of the substances is in the range, the properties of the prepared polymer are obviously superior to those of other polymers.
Preferably, the molar ratio of the template to the functional monomer to the cross-linking agent is 1: 2-10: 10-40; the functional monomer is methyl methacrylate, and the cross-linking agent is ethylene glycol dimethacrylate. Researches show that when the functional monomer methyl methacrylate is matched with the cross-linking agent ethylene glycol dimethacrylate, and the ratio of each substance is in the range, the properties of the prepared polymer are obviously superior to those of the other substances.
Preferably, the drying of S2 is drying at 60 ℃ for 12 h.
Preferably, the elution of S2 is performed using a methanol-acetic acid mixed solution and methanol. More preferably, the ratio of methanol to acetic acid in the mixed solution of methanol: the ratio of acetic acid is 8-10: 1.
Preferably, the preparation method of the furfural molecular imprinted polymer comprises the following steps:
s1, adding a furfural template molecule, a functional monomer, a cross-linking agent, an initiator and a solvent into a flat-bottomed flask according to the proportion of the substances, uniformly mixing, ultrasonically degassing for 10min, then filling nitrogen to remove oxygen for 10min, sealing, and polymerizing for 24 hours in a constant-temperature water bath at 60 ℃ to obtain a molecularly imprinted polymer with the template molecule furfural;
s2, grinding the polymer obtained in the step S1, sieving with a 250-300-mesh sieve to obtain molecular imprinting polymer particles with template molecule furfural, eluting with a methanol-acetic acid mixed solution and methanol in sequence, and drying at 70 ℃ for 12 hours in vacuum to obtain the template-removed furfural molecular imprinting polymer; wherein, the functional monomer in the step S1 is one or two of 4-vinylpyridine or methyl methacrylate; the cross-linking agent is one or two of ethylene glycol dimethacrylate or pentaerythritol triacrylate.
The template-removed furfural molecularly imprinted polymer prepared by the invention has imprinted sites matched with the volume, structure and polarity of furfural substances, and has high affinity and obvious selectivity on furfural.
The invention also provides application of the furfural molecular imprinted polymer in furfural extraction, separation and enrichment. The polymer prepared by the invention has specific adsorption and strong separation capacity, and effectively solves the problems of difficult separation and enrichment and the like caused by low content of complex furfural pollutants in a complex matrix food sample matrix.
Preferably, the obtained furfural molecular imprinted polymer is used as column chromatography packing and is filled into a column, then a sample extracting solution is used for loading the column, and the furfural substance solution is obtained by leaching, eluting and recovering an eluent.
The furfural molecular imprinted polymer prepared by the method is applied to the separation and extraction of furfural, and the application method comprises the following steps: loading the obtained furfural molecular imprinted polymer as column chromatography filler, loading the furfural molecular imprinted polymer as column chromatography filler, eluting with acetone aqueous solution, eluting the column chromatography with acetic acid aqueous solution, recovering the eluate, filtering with 0.22 μm filter membrane, and detecting with HPLC.
Compared with the prior art, the invention has the following beneficial effects:
(1) the inventor conducts a great deal of research and study in the initial stage of experiment, screens out proper functional monomers and cross-linking agents matched with the functional monomers, and the obtained molecularly imprinted polymer can be used for adsorbing a plurality of furfural substances simultaneously; and when the molar ratio of the template to the functional monomer to the cross-linking agent is within the range of 1: 4-10: 10-40, the prepared molecularly imprinted polymer microspheres have imprinted sites matched with the volume, structure and polarity of furfural substances, and have high affinity and obvious selectivity for the furfural substances.
(2) The invention synthesizes the molecular imprinting polymer suitable for the organic phase in the weak polar solution, has specific adsorption and stronger separation capability, effectively solves the problems of difficult separation and enrichment and the like caused by low content of complex furfural substances of complex matrix food samples, and is beneficial to the adsorption and enrichment of the furfural substances.
(3) The molecularly imprinted polymer for extracting furfural substances has strong selectivity, the recovery rate of furfural substances obtained by extracting furfural by using the material is high, the polymer is renewable, and the regeneration method is simple and easy to implement.
(4) The molecular imprinting polymer for extracting furfural substances has low production cost, small eluent consumption and cost saving.
Drawings
FIG. 1 is a flow chart of the preparation and application of the molecularly imprinted polymer of the invention
FIG. 2 is a Scanning Electron Microscope (SEM) image of furfural molecularly imprinted polymer in example 1 of the present invention
FIG. 3 is a Scanning Electron Microscope (SEM) image of 4 furfural molecularly imprinted polymers in example 2 of the present invention
FIG. 4 is a Scanning Electron Microscope (SEM) image of the furanone molecularly imprinted polymer in example 3 of the invention.
Detailed Description
The invention is described in further detail below with reference to the drawings and specific examples, but the examples are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
A preparation method of a furfural molecularly imprinted polymer sequentially comprises the following steps:
the molar ratio of the furfural template to the functional monomer to the cross-linking agent is 1: 2-10: 10-40, the dosage of the pore-foaming agent is 30-100 ml, and the dosage of the initiator is 50-120 mg; the functional monomer is 4-vinylpyridine, the cross-linking agent is ethylene glycol dimethacrylate, the initiator is azobisisobutyronitrile, and the pore-forming agent is one or two of acetonitrile or toluene.
S1, taking 1mmol of template furfural, 4mmol of functional monomer 4-vinylpyridine, 20mmol of crosslinking agent ethylene glycol dimethacrylate, 50mg of initiator azobisisobutyronitrile and 80ml of solvent toluene, adding into a flat-bottomed flask, mixing, ultrasonically degassing for 10min, then filling nitrogen to remove oxygen for 15min, sealing, and polymerizing in a constant-temperature water bath at 60 ℃ for 24 hours to obtain the molecularly imprinted polymer with template molecular furfural.
S2, centrifugally separating and collecting the polymer obtained in the step S1 to obtain molecular imprinting polymer particles uniformly carrying template molecule furfural, sequentially eluting the molecular imprinting polymer particles by adopting a methanol-acetic acid mixed solution and methanol to obtain the polymer particles with the molecular imprinting holes, and drying the polymer particles at 60 ℃ for 12 hours under vacuum to obtain the template-removed furfural molecular imprinting polymer; methanol in the mixed solution of methanol and acetic acid: acetic acid is 9: 1, the prepared molecularly imprinted polymer is a nano-sized microsphere with the specific surface area of 356.650m2(iv)/g, total pore volume 0.388cm3(ii) in terms of/g. As shown in fig. 2.
S3, weighing 20g of molecularly imprinted polymer prepared by S2, loading the molecularly imprinted polymer into a column, weighing 1.0g of honey sample into a 10mL plastic centrifuge tube with a plug, adding 5mL of deionized water, carrying out vortex oscillation for 5min, carrying out ultrasonic extraction for 3min, carrying out centrifugal separation, and taking supernatant; 3mL of deionized water was added to the residue, the above procedure was repeated, and the residue was discarded. Combining the two supernatants, adding 1mL of 300g/L potassium ferrocyanide solution, uniformly mixing, adding 1mL of 150g/L zinc acetate solution, fully and uniformly mixing, standing for 30min, centrifuging for 10min, taking the supernatant into a 10mL volumetric flask, fixing the volume by using deionized water, loading the filtrate onto a column, after the solution on the column flows out, leaching by using 300mL of aqueous solution with the volume fraction of 5% of acetone, eluting by using aqueous solution with the volume fraction of 10% of acetic acid, collecting the eluent, passing the eluent through a 0.22 mu m filter membrane, and then carrying out high performance liquid chromatography detection.
S4, directly detecting furfural substances in honey by using a commercial HLB solid phase extraction column and high performance liquid chromatography.
Example 2
A preparation method of a four-template molecularly imprinted polymer taking furfural, 5-methylfurfural, 5-hydroxymethylfurfural and 2-acetylfuran as template molecules comprises the following steps in sequence:
s1, the molar ratio of the p-furfural to the 5-methylfurfural to the 5-hydroxymethylfurfural to the 2-acetylfuran template to the functional monomer to the cross-linking agent is 1: 2-6: 10-30, and the amount of the pore-forming agent is 30-100 ml of the initiator and is 50-120 mg; the functional monomer is 4-vinylpyridine, the cross-linking agent is pentaerythritol triacrylate, the initiator is azobisisobutyronitrile, and the pore-forming agent is one or two of acetonitrile or toluene.
S1, taking 0.5mmol of template furfural, 5-methylfurfural, 5-hydroxymethylfurfural and 2-acetylfuran respectively, 4mmol of functional monomer 4-vinylpyridine, 20mmol of cross-linking agent pentaerythritol triacrylate, 50mg of initiator azobisisobutyronitrile and 80ml of solvent acetonitrile, adding into a flat-bottomed flask, mixing, ultrasonically degassing for 10min, then filling nitrogen, deoxidizing for 15min, and polymerizing for 12 hours in a 70 ℃ constant-temperature water bath after sealing to obtain the molecularly imprinted polymer with template molecules.
S2, centrifugally separating and collecting the polymer obtained in the step S1, drying in vacuum, sieving with a 300-mesh sieve to obtain molecular imprinting polymer particles uniformly provided with template molecules and four furfural substances, sequentially carrying out Soxhlet elution by using a methanol-acetic acid mixed solution and methanol in a volume ratio of 10:90 to obtain polymer particles with molecular imprinting holes, drying at 60 ℃ for 12 hours in vacuum to obtain the template-removed furfural molecular imprinting polymer, wherein the prepared molecular imprinting polymer is nano-sized microspheres with a specific surface area of 114.310m2(ii)/g, total pore volume 0.105cm3In terms of/g, as shown in FIG. 3.
S3, taking 20g of the molecularly imprinted polymer prepared by S2 for column packing; diluting a certain proportion of vinegar sample with pure water, centrifuging the mixed solution at 4 ℃ for 15min at 8000r/min, taking 1mL of supernatant, loading the filtrate into a column, eluting with 300mL of aqueous solution with the acetone volume fraction of 5% after the solution on the column flows out, eluting the chromatographic column with aqueous solution with the acetic acid volume fraction of 10%, collecting the eluent, filtering the eluent with a 0.22 mu m filter membrane, and then detecting by high performance liquid chromatography.
S4, directly adopting a commercialized HLB solid-phase extraction column and combining high performance liquid chromatography to detect furfural substances in vinegar.
Example 3
A preparation method of molecularly imprinted polymer taking furanone as a substitute template and taking vinyl functionalized silica microspheres as a carrier sequentially comprises the following steps:
s1, preparing silicon dioxide microspheres with vinyl functionalized surfaces uniformly by adopting a vinyltriethoxysilane hydrolysis method. The molar ratio of the furanone as the substitute template to the functional monomer to the cross-linking agent is 1: 4-10: 10-30, and the amount of the pore-forming agent is 30-100 ml of the initiator and is 50-120 mg; the functional monomer is methyl methacrylate, the cross-linking agent is ethylene glycol dimethacrylate, the initiator is azobisisobutyronitrile, and the pore-forming agent is one or two of acetonitrile or toluene.
S1, taking 1mmol of substituted template furanone, 4mmol of functional monomer methyl methacrylate and cross-linking agent B
20mmol of glycol-based dimethacrylate, 50mg of initiator and 80ml of solvent toluene are added into a flat-bottomed flask to be mixed, ultrasonic degassing is carried out for 10min, then nitrogen filling and oxygen removing are carried out for 15min, and polymerization is carried out for 12h in a constant-temperature water bath at 60 ℃ after sealing, thus obtaining the molecularly imprinted polymer with template molecule furanone.
S2, centrifugally separating and collecting the polymer obtained in the step S1, drying in vacuum, sieving by a 250-mesh sieve to obtain molecularly imprinted polymer particles uniformly provided with template molecular furanone, sequentially carrying out Soxhlet elution by adopting a methanol-acetic acid mixed solution and methanol to obtain polymer particles with the remaining molecularly imprinted holes, and drying for 12 hours at 60 ℃ in vacuum to obtain the molecularly imprinted polymer without the template; methanol in the mixed solution of methanol and acetic acid: acetic acid is 10:1, and the molecularly imprinted polymer microspheres are prepared.
S3, taking 20g of the molecularly imprinted polymer prepared by S2 for column packing; weighing 1.0g of coffee in a 10mL plastic centrifuge tube with a plug, adding 5mL of deionized water, carrying out vortex oscillation for 5min, carrying out ultrasonic extraction for 3min, carrying out centrifugal separation, and taking supernatant; 3mL of deionized water was added to the residue, the above procedure was repeated, and the residue was discarded. Mixing the two supernatants, adding 1mL of 300g/L potassium ferrocyanide solution, mixing, adding 1mL of 150g/L zinc acetate solution, mixing, standing for 30min, centrifuging for 10min, collecting supernatant, adding into 10mL volumetric flask, and diluting with deionized water to desired volume. And (3) loading 3mL of coffee sample treatment solution to a column, eluting with 300mL of aqueous solution with the volume fraction of 5% acetone after the solution on the column completely flows out, eluting the chromatographic column with 10% aqueous solution with the volume fraction of acetic acid, collecting eluent, filtering the eluent with a 0.22-micrometer filter membrane, and then carrying out high performance liquid chromatography detection.
S4, directly adopting a commercial HLB solid-phase extraction column and combining high performance liquid chromatography to detect furfural substances in coffee.
Comparative example 1
Comparative example 1 the method for preparing a molecularly imprinted polymer is substantially the same as in example except for the presence or absence of the template molecule.
Comparative example 2
Comparative example 2 is a commercial HLB solid phase extraction column
The prepared molecularly imprinted polymer nano-sized microsphere has the specific surface area of 352.370m2(ii)/g, total pore volume 0.346cm3In terms of/g, as shown in FIG. 4.
The liquid phase detection conditions of the detection solutions obtained in examples 1 to 3 were as follows: a chromatographic column: SunAireC 18(250 mm. times.4.6 mm, 5 μm); mobile phase: 0.1% phosphoric acid water-acetonitrile; acetonitrile is 30% in 0-3min and 50% in 3-15 min; flow rate: 1 mL. min-1(ii) a Detection wavelength: 278 nm; column temperature: 25 ℃; sample introduction amount: 10 μ L. The results of the liquid chromatography analysis are shown in Table 1 below.
Table 1 shows the results of liquid chromatography analysis of each example
The results of comparing the adsorption effect of the furfural molecular imprinting solid-phase extraction column provided by the embodiment 1-3 with that of the commercialized HLB solid-phase extraction column on furfural substances show that the furfural molecular imprinting solid-phase extraction column provided by the invention has an obvious enrichment effect on furfural substances, mainly because the molecular imprinting selectively adsorbs template molecules and structural analogues, and most of binding sites of surface molecular imprinting are distributed on the surface of a carrier matrix material and in a hollow cavity, the adsorption efficiency is improved, and in addition, the furfural molecular imprinting can realize reversible adsorption and dissociation on furfural substances. The three effects act together, so that the MIPs solid-phase extraction column synthesized by the method has an obvious adsorption effect.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of protection is not limited thereto. The equivalents and modifications of the present invention which may occur to those skilled in the art are within the scope of the present invention as defined by the appended claims.
Claims (8)
1. The preparation method of the furfural molecularly imprinted polymer is characterized by sequentially comprising the following steps of:
s1, taking furfural substances as a template, adding template molecules, functional monomers and a solvent into a flat-bottomed flask, magnetically stirring for 30min, adding a cross-linking agent and an initiator, ultrasonically degassing for 10min, then filling nitrogen to remove oxygen, sealing, and polymerizing for 18-24 hours in a constant-temperature water bath at 50-70 ℃ to obtain a molecularly imprinted polymer with the template molecules and the furfural substances;
s2, performing centrifugal separation on the polymer obtained in the step S1 to obtain molecular imprinting polymer particles which are uniformly provided with template molecular furfural substances, performing Soxhlet elution until the furfural substances cannot be detected by using a high performance liquid chromatograph to obtain polymer particles with molecular imprinting holes, and drying under vacuum to obtain the template-removed furfural molecular imprinting polymer; wherein, the functional monomer in the step S1 is one or two of 4-vinylpyridine or acrylamide; the cross-linking agent is one or two of ethylene glycol dimethacrylate or pentaerythritol triacrylate; the mole ratio of the template to the functional monomer to the cross-linking agent is 1: 2-10: 10-40.
2. The preparation method according to claim 1, wherein the functional monomer is one or two of 2-vinylpyridine and methyl methacrylate, and the cross-linking agent is one or two of ethylene glycol dimethacrylate and pentaerythritol triacrylate.
3. The preparation method according to claim 1, wherein the initiator is azobisisobutyronitrile, and the solvent is one or both of acetonitrile and toluene; wherein the dosage of the initiator is 1mmol of the template: 4mmol 150-120 mg, solvent dosage is template 1 mmol: 30-100 ml of solvent; s2 the polymer is sieved by a sieve of 250-300 meshes.
4. The method according to claim 1, wherein the drying at S2 is drying at 60 ℃ for 12 h.
5. The preparation method according to claim 1, wherein the elution of S2 is performed by Soxhlet elution to remove template molecules and methanol to remove residual acetic acid by using a mixed solution of methanol and acetic acid in a volume ratio of 8-10: 1.
6. The furfural molecular imprinted polymer prepared by the preparation method of any one of claims 1 to 5, wherein the template-removed furfural molecular imprinted polymer has imprinted sites matching with the volume, structure and polarity of furfural molecules.
7. The application of the furfural molecular imprinted polymer as claimed in claim 6 in the extraction, separation and enrichment of furfural substances.
8. The application of claim 7, wherein the obtained furfural molecular imprinted polymer is used as column chromatography packing to be filled into a column, then a sample extracting solution is used for loading the column, and the furfural substances are obtained by leaching, eluting and recovering an eluent, filtered by 0.22 μm and subjected to HPLC detection.
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