CN110785228A

CN110785228A - Porous modified adsorbent for solid phase extraction, preparation method thereof and solid phase extraction device

Info

Publication number: CN110785228A
Application number: CN201880031822.2A
Authority: CN
Inventors: 陈高明; 胡玉梅; 王来玲; 张娟; 丁正华; 刘祺霞
Original assignee: SHENZHEN BIOCOMMA TECHNOLOGY Co Ltd
Current assignee: SHENZHEN BIOCOMMA TECHNOLOGY Co Ltd
Priority date: 2018-10-29
Filing date: 2018-10-29
Publication date: 2020-02-11
Also published as: WO2020087209A1

Abstract

A porous modified adsorbent for solid phase extraction is prepared from thermoplastic polymer resin (PE) and/or polypropylene (PP) and/or polyvinyl chloride (PVC) and/or Polystyrene (PS) and/or polyethylene terephthalate (PET) and/or nylon (PA) through sintering. The porous modified adsorbent has controllable pore size, high assembling efficiency and high product homogeneity, and is suitable for solid phase extraction of viscous and particle-containing samples.

Description

Porous modified adsorbent for solid phase extraction, preparation method thereof and solid phase extraction device

Technical Field

The invention relates to the technical field of solid-phase extraction, in particular to a porous modified adsorbent for solid-phase extraction, a preparation method thereof and a solid-phase extraction device.

Background

Solid Phase Extraction (SPE) is a sample pretreatment technology developed in recent years, and is developed by combining liquid-Solid Extraction and column liquid chromatography, and the SPE technology is based on the liquid chromatography separation principle of selective adsorption and selective elution. The more common method is to make the liquid sample solution pass through the adsorbent to retain the tested substance, then to select the solvent with proper strength to wash out the impurity, then to use a small amount of solution to quickly elute the tested substance, thus to achieve the purpose of quick separation, purification and concentration. Interference impurities can be selectively adsorbed, so that the measured substance flows out; or adsorbing impurities and the substance to be detected simultaneously, and then selectively eluting the substance to be detected by using a proper solvent. SPE is mainly used for separating, purifying and concentrating samples, and compared with a traditional liquid-liquid extraction method, the SPE can improve the recovery rate of analytes, more effectively separate the analytes from interfering components, reduce the sample pretreatment process, and is simple to operate, time-saving and labor-saving.

The classical syringe type SPE column is mostly an injection syringe type device taking medical polypropylene as a material, two sieve plates taking Polyethylene (PE) or polypropylene (PP) as a material are arranged in the device, and a certain amount of solid adsorbent is filled between the two sieve plates. SPE post upper end is opened, and the lower extreme is the liquid outlet, and liquid is discharged from the liquid outlet behind the solid adsorbent. At present, the SPE column is mostly assembled by manual operation, and the specific operation flow is as follows: a lower sieve plate is arranged in the needle cylinder type hollow column tube by a push rod, then a certain amount of adsorbent is filled, the lower sieve plate is arranged in an upper sieve plate by the push rod, and the filler between the upper sieve plate and the lower sieve plate is tightly filled by compaction. The automated SPE column assembler also assembles according to the lower sieve-adsorbent-upper sieve flow. However, when the classical syringe type SPE column faces a sample with high viscosity and containing particles, the pore channel is easy to block, the flow rate is low, and the effect is poor. Classical SPE plates, including 96/384/1536 wells, each well is two plates with a certain amount of solid adsorbent in between, the amount of adsorbent dispensed per well is as low as microgram, and the assembly difficulty is high.

Disclosure of Invention

The invention provides a porous modified adsorbent for solid phase extraction, a preparation method thereof and a solid phase extraction device. The porous modified adsorbent belongs to an improved solid phase extraction adsorbent, namely the solid phase extraction adsorbent obtained by sintering and modifying a common solid phase extraction adsorbent by using thermoplastic polymer resin, has controllable pore diameter, can realize specification miniaturization, does not need a sieve plate as a support during assembly, has high assembly efficiency, can realize the function of the corresponding solid phase extraction adsorbent, and is suitable for extracting viscous and particle-containing samples.

According to a first aspect, there is provided in one embodiment a porous modified adsorbent for solid phase extraction made by sintering a material comprising a thermoplastic polymer resin and a solid phase extraction adsorbent, wherein the thermoplastic polymer resin is Polyethylene (PE) and/or polypropylene (PP) and/or polyvinyl chloride (PVC) and/or Polystyrene (PS) and/or polyethylene terephthalate (PET) and/or nylon (PA).

In a preferred embodiment, the solid phase extraction adsorbent is selected from the group consisting of HLB, WAX, WCX, MAX, MCX, and,C18、C8、C4、C2、C1、Silica、Diol、CN、Carb-GCB、Florisil、ALA、ALN、ALB、SCX、SAX、NH ₂PSA, PRS and activated carbon.

In a preferred embodiment, the thermoplastic polymer resin and the solid phase extraction adsorbent are respectively as follows by weight percent: 15-95% of thermoplastic polymer resin and 5-85% of solid phase extraction adsorbent.

In a preferred embodiment, the thermoplastic polymer resin and the solid phase extraction adsorbent are respectively as follows by weight percent: 15-90% of thermoplastic polymer resin and 10-85% of solid phase extraction adsorbent.

In a preferred embodiment, the pore size of the above porous modified adsorbent is 1 to 200. mu.m, preferably 5 to 150. mu.m.

In a preferred embodiment, the Polyethylene (PE) is Ultra High Molecular Weight Polyethylene (UHMWPE) and/or High Density Polyethylene (HDPE).

In a preferred embodiment, the molecular weight of the ultra-high molecular weight polyethylene (UHMWPE) is 150 ten thousand or more.

In a preferred embodiment, the specific gravity of the above High Density Polyethylene (HDPE) is 0.941 to 0.960.

In a preferred embodiment, the particle size of the thermoplastic polymer resin is 50 to 800 mesh.

In a preferred embodiment, the polypropylene (PP) is a polypropylene having a molecular weight of 10 ten thousand or more.

In a preferred embodiment, the molecular weight of the polyvinyl chloride (PVC) is 5 to 11 ten thousand.

In a preferred embodiment, the Polystyrene (PS) is a polymer synthesized by radical addition polymerization of a styrene monomer.

In a preferred embodiment, the polyethylene terephthalate (PET) is prepared by exchanging dimethyl terephthalate with ethylene glycol and then performing polycondensation.

In a preferred embodiment, the nylon (PA) is preferably nylon 6.

In a preferred embodiment, the solid phase extraction adsorbent has an average particle size of 5 to 500. mu.m.

In a preferred embodiment, the porous modified adsorbent is made into a cylindrical shape, a disk shape or a sheet shape by sintering.

In a preferred embodiment, the cylindrical shape has a diameter of 0.1 to 500mm and a height of 0.2 to 30 mm.

In a preferred embodiment, the cylindrical shape has a diameter of 1 to 15mm and a height of 1 to 15 mm.

According to a second aspect, there is provided in one embodiment a method for preparing a porous modified adsorbent for solid phase extraction, the method comprising sintering a material comprising a thermoplastic polymer resin and a solid phase extraction adsorbent to form the porous modified adsorbent, wherein the thermoplastic polymer resin is Polyethylene (PE) and/or polypropylene (PP) and/or polyvinyl chloride (PVC) and/or Polystyrene (PS) and/or polyethylene terephthalate (PET) and/or nylon (PA).

In a preferred embodiment, the solid phase extraction adsorbent is selected from the group consisting of HLB, WAX, WCX, MAX, MCX, C18, C8, C4, C2, C1, Silica, Diol, CN, Carb-GCB, Florisil, ALA, ALN, ALB, SCX, SAX, NH, and mixtures thereof ₂PSA, PRS and activated carbon.

In a preferred embodiment, the nylon (PA) is preferably nylon 6.

In a preferred embodiment, the porous modified adsorbent is made into a cylindrical, disk-like or sheet-like shape by sintering.

In a preferred embodiment, the above sintering is performed at 120 ℃ to 250 ℃ for 1min to 120 min.

In a preferred embodiment, the preparation method comprises the following steps:

1) adding 15-95 wt% of thermoplastic polymer resin and 5-85 wt% of solid phase extraction adsorbent in a container, and mixing uniformly to obtain a standby raw material;

2) uniformly adding the standby raw materials into a mould by adopting the mould, and compressing and vibrating the raw materials to be flat;

3) sintering at 120-250 deg.c for 1-120 min, cooling and taking out to obtain the porous modified adsorbent.

According to a third aspect, there is provided in an embodiment a solid phase extraction apparatus comprising the porous modified adsorbent of the first aspect and a containment means, the porous modified adsorbent being disposed in the containment means.

In a preferred embodiment, the receiving means is a syringe-type empty column tube, a pipette tip or a multi-well plate.

In a preferred embodiment, the multi-well plate is a 96-well plate, or a 384-well plate, or a 1536-well plate.

The porous modified adsorbent is sintered by thermoplastic polymer resin and a solid-phase extraction adsorbent to prepare a sintered body, can be assembled in a containing device without a sieve plate as a support to form a solid-phase extraction device, replaces the traditional SPE column with a sieve plate-filler-sieve plate structure, and can realize the functions of the classical SPE column/plate/suction head as a sieve-plate-free porous modified adsorbent SPE column/plate/suction head. The porous modified adsorbent SPE column/plate/suction head is simple to assemble, the assembly efficiency can be effectively improved, and the product uniformity is ensured; meanwhile, the pore diameter of the porous modified adsorbent is controllable, the specification miniaturization can be realized, and a convenient solution is provided for the solid phase extraction of viscous and particle-containing samples.

Drawings

FIG. 1 is a schematic cross-sectional view of a porous modified adsorbent in an embodiment of the present invention;

FIG. 2 is a schematic diagram of a solid phase extraction column with a porous modified adsorbent according to an embodiment of the present invention;

FIG. 3 is a florfenicol assay chromatogram for an embodiment of the present invention;

FIG. 4 is a furazolidone detection chromatogram in an example of the invention;

FIG. 5 is a chromatogram for olaquindox detection in an embodiment of the present invention;

FIG. 6 is a chromatogram for chloramphenicol detection in the example of the present invention;

FIG. 7 is a chromatogram for the detection of hydrocortisone in an example of the present invention;

FIG. 8 is a malachite green detection chromatogram of an embodiment of the invention;

FIG. 9 is a chromatogram for detection of organic acid in an example of the present invention;

FIG. 10 is a chromatogram for the detection of hydroquinone in an example of the present invention;

figure 11 is a chromatogram for ibuprofen detection in the examples of the invention.

Detailed Description

The present invention will be described in further detail with reference to the following detailed description and accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, those skilled in the art will readily recognize that some of the features may be omitted or replaced with other elements, materials, methods in different instances.

Furthermore, the features, operations, or characteristics described in the specification may be combined in any suitable manner to form various embodiments. Also, the various steps or actions in the method descriptions may be transposed or transposed in order, as will be apparent to one of ordinary skill in the art. Thus, the various sequences in the specification and drawings are for the purpose of describing certain embodiments only and are not intended to imply a required sequence unless otherwise indicated where such sequence must be followed.

As shown in fig. 1, an embodiment of the present invention provides a porous modified adsorbent for solid phase extraction, which is made of a material comprising a thermoplastic polymer resin 1 and a solid phase extraction adsorbent (i.e., a solid adsorbent 2) by sintering, and contains a large number of pores inside the porous modified adsorbent to form a reagent flow channel 3. In the present invention, the terms "solid phase extraction adsorbent" and "solid adsorbent" are used interchangeably. The porous modified adsorbent belongs to an improved solid phase extraction adsorbent, namely the solid phase extraction adsorbent obtained by sintering and modifying a common solid phase extraction adsorbent by using thermoplastic polymer resin, has controllable pore diameter, can realize specification miniaturization, does not need a sieve plate as a support during assembly, has high assembly efficiency, and can realize the function of the corresponding solid phase extraction adsorbent.

In the embodiment of the present invention, the thermoplastic polymer resin is at least one selected from Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), Polystyrene (PS), polyethylene terephthalate (PET), and nylon (PA), and may be one of them, or a mixture of two, three, four, five, or six of them. Polyethylene (PE), a polymer formed by the polymerization of ethylene and having a linear structure, has outstanding performance stability. The Polyethylene (PE) is preferably Ultra High Molecular Weight Polyethylene (UHMWPE) and/or High Density Polyethylene (HDPE), either alone or as a mixture. The UHMWPE is particularly preferably UHMWPE having a molecular weight of more than 150 ten thousand, more preferably 200 to 500 ten thousand, for example the molecular weight of UHMWPE may be 150, 160, 170, 180, 190, 200, 220, 250, 280, 300, 320, 350, 400, 410, 420, 450, 480 or 500 ten thousand, etc. The particle diameter of the UHMWPE is preferably 50 mesh or more, more preferably 50 to 800 mesh, for example 50 mesh, 60 mesh, 80 mesh, 100 mesh, 120 mesh, 150 mesh, 200 mesh, 250 mesh, 300 mesh, 400 mesh, 500 mesh, 600 mesh, 650 mesh, 680 mesh, 700 mesh, 720 mesh, 750 mesh, 780 mesh, 800 mesh, and the like. HDPE is particularly preferably HDPE having a specific gravity of 0.941 to 0.960, for example HDPE may have a specific gravity of 0.941, 0.942, 0.943, 0.944, 0.945, 0.946, 0.947, 0.948, 0.949, 0.950, 0.951, 0.952, 0.953, 0.954, 0.955, 0.956, 0.957, 0.958, 0.959, 0.960, etc., preferably 0.945 to 0.956. The particle size of the HDPE is preferably 80-400 mesh, for example, 80 mesh, 100 mesh, 120 mesh, 150 mesh, 200 mesh, 250 mesh, 300 mesh, 320 mesh, 380 mesh, 400 mesh, etc. Polypropylene (PP), which is a polymer having a linear structure formed by polymerization of propylene, is very stable to water and has a good tensile strength. The polypropylene (PP) is preferably a polypropylene having a molecular weight of 10 ten thousand or more, for example, a polypropylene having a molecular weight of 10 ten thousand, 11 ten thousand, 12 ten thousand, 13 ten thousand, 14 ten thousand, 15 ten thousand, 18 ten thousand or 20 ten thousand, more preferably a polypropylene having a molecular weight of 10 ten thousand to 14 ten thousand. The molecular weight of the polyvinyl chloride (PVC) is preferably 5 to 11 ten thousand, for example 5 ten thousand, 6 ten thousand, 7 ten thousand, 8 ten thousand, 9 ten thousand, 10 ten thousand, 11 ten thousand, etc. Polystyrene (PS) is a polymer synthesized by the free radical addition polymerization of styrene monomer. Polyethylene terephthalate (PET) is made by the exchange of dimethyl terephthalate with ethylene glycol followed by a polycondensation reaction. The nylon (PA) is preferably nylon 6.

In embodiments of the invention, the solid adsorbent may be any solid adsorbent useful for solid phase extraction, such as HLB (hydrophilic lipophilic balance polymer), WAX (weak anion)(ii) a cation exchange polymer), WCX (weak cation exchange polymer), MAX (mixed anion exchange polymer), MCX (mixed cation exchange polymer), C18 (octadecyl Silica gel including end-capped C18, uncapped C18, hydrophilic C18), C8 (octyl Silica gel), C4 (butyl Silica gel), C2 (ethyl Silica gel), C1 (methyl Silica gel), Silica (unbound Silica gel), Diol (Diol-based Silica gel), CN (cyanopropyl Silica gel), Carb-GCB (graphitized carbon black), Florisil (Florisil), ALA (acidic alumina), ALN (neutral alumina), ALB (basic alumina), SCX (strong cation exchange Silica gel), SAX (strong anion exchange Silica gel), NH (NH) Silica gel ₂(aminopropyl silica gel), PSA (ethylenediamine-N-propyl silica gel), PRS (benzenesulfonyl silica gel), and activated carbon. The average particle size of these solid-phase extraction adsorbents is preferably 5 to 500. mu.m, for example, 5. mu.m, 10. mu.m, 15. mu.m, 20. mu.m, 30. mu.m, 40. mu.m, 50. mu.m, 60. mu.m, 80. mu.m, 100. mu.m, 120. mu.m, 130. mu.m, 150. mu.m, 180. mu.m, 200. mu.m, 220. mu.m, 225. mu.m, 230. mu.m, 245. mu.m, 250. mu.m, 280. mu.m, 300. mu.m, 320. mu.m, 350. mu.m, 380. mu.m, 400. mu.m, 420. mu.m, 440. mu.m, 470. The solid phase extraction adsorbent may be a pore-containing adsorbent or a non-pore-size adsorbent, wherein the average pore size of the pore-containing adsorbent is preferably 70 to 1000 angstroms For example

And the like. And non-porous adsorbents such as Carb-GCB, Florisil, etc.

The solid adsorbent used in the present invention is mainly classified into a polymer matrix type, a silica gel matrix type and an adsorption type according to the type. Wherein, the polymer matrix adsorbent is a macroporous high-molecular adsorbent, the adsorption capacity and the sample loading capacity are far higher than those of a C18 bonded silica gel matrix adsorbent, the pH range can be tolerated by the polymer matrix adsorbent to be 1-14, and the polymer matrix adsorbent is compatible with most solvents. Polymeric matrix adsorbents are classified into polymeric reverse phase adsorbents and polymeric ion exchange adsorbents in principle. The polymer reverse phase adsorbent comprises HLB (hydrophile-lipophile balance), is widely applied to pretreatment of veterinary drug residues in food, such as the pretreatment of tetracycline, chloramphenicol, nitrofuran and quinolone veterinary drug residues in animal-derived food, and can be used for enriching and purifying small-molecule drugs in biological samples such as blood samples and urine samples and the pretreatment of environmental samples. Polymeric ion exchange adsorbents include, for example, WCX, WAX, MCX, MAX, and the like. The silica gel matrix adsorbent is monodisperse spherical silica gel filler, and comprises reversed phase, normal phase, ion exchange and other types. The silica gel matrix type reverse phase adsorbent comprises C18, namely octadecyl silica gel, can retain nonpolar compounds through hydrophobic interaction, can retain most organic matters, and is widely used in the fields of environment, food safety and the like. The Silica gel matrix type normal phase adsorbent includes Silica, Diol, CN, etc. The silica gel matrix adsorption type adsorbent comprises high-activity porous alumina, has three types of acidity (ALA), neutrality (ALN) and Alkalinity (ALB), and can be respectively matched with target compounds with different properties; Carb-GCB (graphitized carbon black) consists of non-porous sheet molecules that retain both non-polar compounds (such as organochlorine insecticides) and strongly polar compounds (such as surfactants); the residual Florisil is activated at 675 ℃, is a porous adsorbent with strong polarity and high activity, and can adsorb target compounds with low polarity and medium polarity, such as organic pesticides containing chlorine, nitrogen and phosphorus. The silica gel matrix ion exchange adsorbent includes SCX, SAX, NH ₂PSA, PRS, etc.

In the examples of the present invention, the contents of the thermoplastic polymer resin and the solid phase extraction adsorbent are, in terms of weight percent: 15-95% of thermoplastic polymer resin and 5-85% of solid phase extraction adsorbent. For example, the content of the thermoplastic polymer resin may be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, and the content of the solid phase extraction adsorbent may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%. Preferably, the thermoplastic polymer resin accounts for 15% -90%, and the solid phase extraction adsorbent accounts for 10% -85%.

In embodiments of the invention, the pore size of the porous modified adsorbent is from 1 to 200 μm, preferably from 5 to 150 μm, for example 2 μm, 4 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 40 μm, 50 μm, 80 μm, 100 μm, 120 μm, 125 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 185 μm, 190 μm, 195 μm, 200 μm and the like. In the embodiment of the invention, the pore size of the prepared porous modified adsorbent can be controlled by the specific selection and dosage of raw materials. In the embodiment of the invention, the porous modified adsorbent can be sintered into a cylinder, a disk or a sheet as required so as to adapt to solid phase extraction columns/plates/suction heads with different specifications. Wherein the diameter of the cylinder or disk may be 0.1 to 500mm, for example, 0.2mm, 0.5mm, 0.8mm, 2mm, 5mm, 10mm, 20mm, 50mm, 100mm, 150mm, 200mm, 300mm, 400mm, 450mm, 480mm, 490mm, etc., and the height may be 0.2 to 30mm, for example, 0.2mm, 0.5mm, 0.8mm, 2mm, 5mm, 10mm, 20mm, 22mm, 25mm, 28mm, etc. Preferably, the cylindrical shape has a diameter of 1-15mm and a height of 1-15 mm.

It should be noted that the raw material for preparing the porous modified adsorbent in the present invention may contain other suitable additives, such as a porogen, in addition to the thermoplastic polymer resin and the solid phase extraction adsorbent. Of course, the porous modified adsorbent of the present invention may be prepared by sintering only the thermoplastic polymer resin and the solid phase extraction adsorbent.

In a preferred embodiment, the sintering is performed at 120 ℃ to 250 ℃ for 1min to 120 min. For example, the sintering temperature may be 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 162 ℃, 165 ℃, 168 ℃, 170 ℃, 172 ℃, 175 ℃, 178 ℃, 180 ℃, 182 ℃, 185 ℃, 190 ℃, 191 ℃, 193 ℃, 195 ℃, 197 ℃, 199 ℃, 200 ℃, 210 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 248 ℃ or the like, and the sintering time may be 1min, 2min, 5min, 8min, 10min, 12min, 15min, 18min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min or the like. In general, the higher the sintering temperature, the correspondingly shorter the sintering time. Of course, the sintering temperature and time may vary from material to material and may be adjusted according to specific needs.

In a preferred embodiment, the method for preparing the porous modified adsorbent of the present invention comprises the steps of:

The present invention utilizes a sintering technique to sinter a thermoplastic polymer resin (such as PE, PP, or a mixture of PE and PP) and a solid adsorbent to form a porous modified adsorbent. The solid adsorbent is modified by utilizing the thermoplastic polymer resin, and under a semi-molten state, the solid adsorbent is embedded into a net structure formed by bridging the thermoplastic polymer resin, so that a flow channel of a reagent is prolonged, the contact area of a sample solution and the solid adsorbent is greatly increased, and the efficiency of sample pretreatment is improved. And the porous modified adsorbent has large pore diameter, the pore diameter structure is improved, pore channel blockage caused by sample viscosity or impurity particles is avoided, the compatibility of the sample is improved, and the variety and complexity of the applicable sample are increased. The pore modified adsorbent can effectively improve the purification speed and shorten the extraction time, and can be widely applied to analysis of pesticide residues, animal residues, drug residues, clinical detection, environmental detection and the like.

The embodiment of the invention also provides a solid phase extraction device, which comprises the porous modified adsorbent and a containing device, wherein the porous modified adsorbent is arranged in the containing device.

In a preferred embodiment, the containment device is a syringe-type empty column tube, a pipette tip or a multi-well plate, wherein the multi-well plate may be a 96-well plate or a 384-well plate or a 1536-well plate.

As shown in fig. 2, a solid phase extraction device comprises a syringe type hollow column tube 4, a thermoplastic polymer resin 5 and a solid adsorbent 6, wherein the thermoplastic polymer resin 5 and the solid adsorbent 6 are co-sintered to form a porous modified adsorbent, and the porous modified adsorbent is placed in the syringe type hollow column tube 4.

In the case where the accommodating means is a syringe-type hollow column tube, the solid phase extraction apparatus of the present invention is called a solid phase extraction column comprising a porous modified adsorbent prepared from a thermoplastic polymer resin and a solid adsorbent according to a method for preparing the porous modified adsorbent, i.e., a sintering method. The solid phase extraction column also comprises a syringe type hollow column tube, for example, a syringe type hollow column tube made of medical polypropylene, and the column tube is internally provided with the porous modified adsorbent. The upper end of the solid phase extraction column is open, the lower end of the solid phase extraction column is a liquid outlet, and liquid is discharged from the liquid outlet after passing through the porous modified adsorbent.

In the case where the holding means is a multi-well plate, for example, a 96-well plate or a 384-well plate or a 1536-well plate, the solid phase extraction device of the present invention is referred to as a solid phase extraction plate, and the solid phase extraction plate comprises a porous modified adsorbent prepared from a thermoplastic polymer resin and a solid adsorbent according to a method for preparing the porous modified adsorbent, that is, a sintering method. The solid phase extraction plate also comprises a 96-well plate, a 384-well plate or a 1536-well plate, for example, a 96-well plate, a 384-well plate or a 1536-well plate made of medical polypropylene, and each well of the plate is provided with a porous modified adsorbent. The upper end of the solid phase extraction plate is open, the lower end of the solid phase extraction plate is provided with a liquid outlet, and liquid is discharged from the liquid outlet after passing through the porous modified adsorbent.

In the case where the receiving device is a tip, the solid phase extraction device of the present invention is referred to as a solid phase extraction tip comprising a porous modified adsorbent prepared from a thermoplastic polymer resin and a solid adsorbent according to a method for preparing the porous modified adsorbent, i.e., a sintering method. The solid phase extraction tip comprises a tip, for example, a tip made of medical grade polypropylene, the tip of the column portion or the tip of the liquid outlet of the tip being equipped with a porous modified adsorbent. The solid phase extraction suction head can be used in combination with a manual or automatic liquid transfer device and also can be used in combination with an automatic liquid processing workstation.

The solid phase extraction device can be called a porous modified adsorbent SPE column/plate/suction head, adopts a manual assembly or automatic SPE column/plate/suction head assembly machine, simply and one-step installs the porous modified adsorbent into the bottom of a syringe type hollow column tube or other accommodating devices of solid phase extraction devices, such as a 96-hole plate, a 384-hole plate, a 1536-hole plate and a suction head, has simpler assembly, can effectively improve the assembly efficiency, and further reduces the cost of the SPE column/plate/suction head. The porous modified adsorbent is adopted, so that the adsorbent split charging loss in the SPE column/plate/suction head assembling process is avoided, and the problems of uneven split charging and cross contamination of the adsorbent can be avoided; in addition, the problem that the uniformity of the degree of tightness and density of adsorbent filling is low, which is easily caused by a classical SPE column/plate/sucker, can be avoided, the uniformity of a product is ensured, the problems that sedimentation or loss easily occurs in the practical use process of the SPE column/plate/sucker or part of target compounds possibly occurring in the sample loading process cannot be adsorbed to cause low recovery rate and poor repeatability are further solved, and the product quality of the SPE column/plate/sucker is improved.

The purification operation of the porous modified adsorbent SPE column/plate/suction head comprises activation, sample loading, leaching, elution and drying, and is similar to the purification operation of a classical SPE column/plate/suction head. The porous modified adsorbent has controllable pore diameter, can realize specification miniaturization, and is more suitable for sample pretreatment with high viscosity. Meanwhile, the pore diameter of the porous modified adsorbent is large, the flow rate can be obviously improved, the extraction time is saved, the flow channel can be prolonged due to the porous structure, the contact area of a sample solution and the solid adsorbent is increased, and the efficiency of sample pretreatment is improved.

The technical solutions and effects of the present invention are described in detail by the following specific examples, which should be understood that the examples are only illustrative and should not be construed as limiting the scope of the present invention.

Example 1:

(1) preparing porous modified adsorbent HLB:

thermoplastic polymer resin: UHMWPE, molecular weight about 300 ten thousand, particle size 80-100 mesh.

Solid adsorbent: HLB, average particle size of 40 μm, and average pore diameter

1) Sequentially adding 80% of UHMWPE and 20% of HLB into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 9.1mm, the height of each hole is 7.1mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 190 deg.C for 20min, cooling, and taking out.

The obtained porous modified adsorbent has HLB, diameter of 9.1mm, height of 7.1mm, and pore diameter of 50-100 μm.

(2) Preparing a porous modified adsorbent HLB column:

and assembling the obtained porous modified adsorbent HLB into a syringe type hollow column tube with the capacity of 3mL to obtain a porous modified adsorbent HLB column.

(3) Solid phase extraction method for detecting florfenicol in milk sample

The HLB column of the porous modified adsorbent obtained by the method is utilized together with the conventional HLB column

The HLB column (specification 60mg/3mL) is used for sample pretreatment and purification of florfenicol detection in milk samples, and an HPLC method is used as a detection means.

Extracting a sample solution from a milk sample according to a method of GB/T20756 and 2006; then respectively passing the sample liquid through an activated porous modified adsorbent HLB column and

HLB column (specification 60mg/3mL), discarding filtrate; taking ammoniated methanol to elute components to be detected on the column, collecting eluent, and drying by nitrogen; finally, the test is carried out on a constant volume machine by using the mobile phase.

The results of the addition of florfenicol at an addition level of 1mg/kg milk are shown in Table 1, the flow rate vs. time in Table 2, and the florfenicol chromatogram in FIG. 3.

TABLE 1 comparison results of the addition recovery of florfenicol to milk at an addition level of 1mg/kg

TABLE 2 porous modified adsorbent HLB column vs. classical

Comparison of HLB column flow rates

In summary, the HLB column of the porous modified adsorbent of the embodiment can effectively enrich and purify florfenicol in milk samples, and achieve the classical purification

The purification effect of an HLB column (specification 60mg/3mL) and a flow rate of 2mL/min are significantly higher than that of The flow rate of the HLB column (specification 60mg/3mL) was 1mL/min, and the recovery was slightly the same.

The porous modified adsorbent has controllable HLB column pore diameter, and is suitable for purifying conventional sample, especially high viscosity sample containing particle, such as milk.

Example 2:

(1) preparation of porous modified adsorbent MCX:

thermoplastic polymer resin: UHMWPE with molecular weight of about 400 ten thousand and particle size of 200-300 meshes; HDPE, density 0.945, particle size 300 and 400 mesh.

Solid adsorbent: MCX with an average particle size of 40 μm and an average pore diameter of

1) Sequentially adding 40% of UHMWPE, 50% of HDPE and 10% of MCX into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 9.1mm, the height of each hole is 6.8mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 180 deg.C for 30min, cooling, and taking out.

The obtained porous modified adsorbent MCX has a diameter of 9.1mm, a height of 6.8mm and a pore diameter of 100-120 μm.

(2) Preparing a porous modified adsorbent MCX column:

and assembling the obtained porous modified adsorbent MCX into a syringe type hollow column tube with the capacity of 3mL to obtain the porous modified adsorbent MCX column.

(3) Solid phase extraction method of furazolidone in feed sample

The obtained porous modified adsorbent MCX column and the like are utilized

MCX column (specification 60mg/3mL) is used for sample pretreatment and purification of furazolidone detection in feed samples, and HPLC method is used as a detection means.

Extracting a feed sample by a method of standard No. 1486 bulletin-8-2010 of Ministry of agriculture; then respectively passing the sample liquid through an activated porous modified adsorbent MCX column and an activated porous modified adsorbent MCX column

MCX column (specification 60mg/3mL), discarding the filtrate; taking ammoniated methanol to elute components to be detected on the column, collecting eluent, and drying by nitrogen; finally, the test is carried out on a constant volume machine by using the mobile phase.

The results of the comparison of the recovery of furazolidone addition at an addition level of 1mg/kg feed sample are shown in Table 3, the flow rate vs. ratio in Table 4, and the furazolidone chromatogram in FIG. 4.

TABLE 3 comparative results of the recovery of furazolidone from feed samples at an add level of 1mg/kg

TABLE 4 porous modified adsorbent MCX column and classic

Comparison of flow rates in MCX column

In summary, the porous modified adsorbent MCX column of the embodiment can effectively enrich and purify furazolidone in a feed sample to achieve the classical effect

The purification effect of an MCX column (specification 60mg/3mL) is obviously higher than that of a flow rate of 2mL/min

The flow rate of the MCX column (specification 60mg/3mL) was 1mL/min, and the recovery was slightly the same.

The porous modified adsorbent MCX column of the embodiment has controllable pore diameter, and is not only suitable for the purification treatment of conventional samples, but also suitable for the purification treatment of complex substrates such as feed.

Example 3:

(1) preparation of porous modified adsorbent MAX:

thermoplastic polymer resin: UHMWPE with molecular weight of about 350 ten thousand and particle size of 300-400 meshes; PP, molecular weight about 10 ten thousand.

Solid adsorbent: MAX, average particle diameter of 40 μm, average pore diameter

1) Sequentially adding 30% of UHMWPE, 30% of PP and 40% of MAX into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 9.1mm, the height of each hole is 7.6mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 190 deg.C for 50min, cooling, and taking out.

The obtained porous modified adsorbent MAX has a diameter of 9.1mm, a height of 7.6mm, and a pore diameter of 20-50 μm.

(2) Preparing a porous modified adsorbent MAX column:

and (3) assembling the obtained porous modified adsorbent MAX into a syringe type hollow column tube with the capacity of 3mL to obtain the porous modified adsorbent MAX column.

(3) Solid phase extraction method of olaquindox in fish sample

The obtained porous modified adsorbent MAX column and the obtained porous modified adsorbent are utilized

MAX column (specification 60mg/3mL) is used for sample pretreatment purification of olaquindox detection in fish samples, and HPLC method is used as detection means.

Extracting a sample solution from a fish sample according to a method of the Standard SCT 3019-2004; then respectively passing the sample liquid through the activated porous modified adsorbent MAX column and the activated porous modified adsorbent MAX column

MAX column (specification 60mg/3mL), discarding filtrate; taking methanoic acid to elute the components to be detected on the column, collecting the eluent, and drying the eluent by nitrogen; finally, the test is carried out on a constant volume machine by using the mobile phase.

The results of addition and recovery comparison of olaquindox at an addition level of 1mg/kg of fish meat are shown in Table 5, and the olaquindox chromatogram is shown in FIG. 5.

TABLE 5 comparative results of addition recovery of olaquindox in fish meat at an addition level of 1mg/kg

In summary, the MAX column of the porous modified adsorbent of the embodiment can effectively enrich and purify olaquindox in a fresh meat sample, and achieves the purpose of the traditional method

MAX column (specification 60mg/3mL) purification effect, and the flow rate is fast, and the recovery rate is slightly the same as that of MAX column

Recovery on a MAX column (60 mg/3mL specification).

Example 4:

(1) preparation of porous modified adsorbent WAX:

thermoplastic polymer resin: PP, molecular weight about 10 ten thousand.

Solid adsorbent: WAX, average particle diameter of 40 μm, average pore diameter of

1) Sequentially adding 50% of PP and 50% of WAX into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 9.1mm, the height of each hole is 7.5mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 190 deg.C for 70min, cooling, and taking out.

The obtained adsorbent WAX complex has a diameter of 9.1mm, a height of 7.5mm, and a pore size of 80-120 μm.

(2) Preparing a porous modified adsorbent WAX column:

and assembling the obtained porous modified adsorbent WAX into a syringe type empty column tube with the capacity of 3mL to obtain the porous modified adsorbent WAX column.

Example 5:

(1) preparation of porous modified adsorbent C18:

thermoplastic polymer resin: UHMWPE, molecular weight is about 350 ten thousand, particle size 80-120 mesh.

Solid adsorbent: c18, average particle diameter of 40-60 μm, average pore diameter

1) Sequentially adding 30% of UHMWPE and 1870% of C into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 13.0mm, the height of each hole is 11.0mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 185 deg.C for 90min, cooling, and taking out.

The obtained porous modified adsorbent C18 has diameter of 13.0mm, height of 11.0mm, and pore diameter of 40-80 μm.

(2) Preparation of porous modified adsorbent C18 column:

the porous modified adsorbent C18 obtained above was packed in a syringe-type empty column tube having a capacity of 6mL to obtain a porous modified adsorbent C18 column.

(3) Solid phase extraction method of chloramphenicol in pork sample

The porous modified adsorbent C18 column obtained by the method is utilized with the classical method

A C18 column (specification 500mg/6mL) is used for sample pretreatment and purification of chloramphenicol detection in pork samples, and an HPLC method is used as a detection means.

Extracting a sample solution from a pork sample according to a method of the standard GB/T22338 and 2008; then the sample liquid passes through the activated porous modified adsorbent C18 column and the classical one respectively

C18 column (specification 500mg/6mL), discarding the filtrate; taking ethyl acetate to elute the components to be detected on the column, collecting eluent, and drying by nitrogen; finally, the test is carried out on a constant volume machine by using the mobile phase.

The results of comparison of the addition and recovery of chloramphenicol at an addition level of 1mg/kg pork are shown in Table 6, and the chloramphenicol chromatogram is shown in FIG. 6.

TABLE 6 comparison results of chloramphenicol addition/recovery from pork at an addition level of 1mg/kg

In conclusion, the porous modified adsorbent C18 column of the embodiment can effectively enrich and purify chloramphenicol in pork samples to achieve the classical purpose

The purification effect of the C18 column (specification 500mg/6mL) is high, the flow rate is high, and the recovery rate is slightly the same as that of the C18 columnIn that

Recovery of C18 column (specification 500mg/6 mL).

Example 6:

(1) preparing a porous modified adsorbent Silica:

thermoplastic polymer resin: UHMWPE with molecular weight of about 400 ten thousand and particle size of 400-600 meshes; HDPE, density 0.945, particle size 300 and 400 mesh.

Solid adsorbent: silica having an average particle diameter of 40 to 75 μm and an average pore diameter of

1) Sequentially adding 10% of UHMWPE, 5% of HDPE and 85% of Silica into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 13.0mm, the height of each hole is 10.8mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 190 deg.C for 110min, cooling, and taking out.

The diameter of the obtained porous modified adsorbent Silica is 13.0mm, the height is 10.8mm, and the pore diameter is 60-80 μm.

(2) Preparing a porous modified adsorbent Silica column:

the porous modified adsorbent Silica obtained above was assembled into a syringe-type hollow column tube having a capacity of 6mL to obtain a porous modified adsorbent Silica column.

(3) Solid phase extraction method of hydrocortisone in milk sample

The porous modified adsorbent Silica column obtained by the method is utilized with the classical method

The Silica column (specification 500mg/6mL) is used for sample pretreatment and purification of hydrocortisone in milk samples, and an HPLC method is used as a detection means.

Extracting a sample solution from a milk sample according to a method of the standard NY/T914-reservoir 2004; then respectively passing the sample liquid through activated porous modified adsorbent Silica column and activated porous modified adsorbent Silica column Silica column (specification 500mg/6mL), discarding the filtrate; eluting the component to be detected on the column by using a normal hexane-acetone mixed solution, collecting the eluent, and drying by using nitrogen; finally, the test is carried out on a constant volume machine by using the mobile phase.

Comparative results of the addition recovery of hydrocortisone at an addition level of 1mg/kg milk are shown in Table 7, and a hydrocortisone chromatogram is shown in FIG. 7.

TABLE 7 comparative results on the recovery of hydrocortisone addition from milk at an addition level of 1mg/kg

In summary, the porous modified adsorbent Silica column of the embodiment can effectively enrich and purify hydrocortisone in milk samples to achieve the classical purification

The purification effect of the Silica column (specification is 500mg/6mL), the flow rate is high, and the recovery rate is slightly the same as that of the Silica column

Recovery on Silica column (specification 500mg/6 mL).

Example 7:

(1) preparation of a porous modified adsorbent Carb-GCB:

thermoplastic polymer resin: UHMWPE, molecular weight is about 400 ten thousand, particle size 150 and 300 mesh.

Solid adsorbent: Carb-GCB, average particle size 100-300 mesh.

1) Sequentially adding 20 percent of UHMWPE and 80 percent of Carb-GCB into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 13.0mm, the height of each hole is 11.2mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 200 deg.C for 60min, cooling, and taking out.

The obtained porous modified adsorbent Carb-GCB has a diameter of 13.0mm, a height of 11.2mm and a pore diameter of 120-150 μm.

(2) Preparing a porous modified adsorbent Carb-GCB column:

assembling the obtained porous modified adsorbent Carb-GCB into a syringe type hollow column tube with the capacity of 6mL to obtain the porous modified adsorbent Carb-GCB column.

Example 8:

(1) preparation of porous modified adsorbent Florisil:

thermoplastic polymer resin: UHMWPE, molecular weight about 350 ten thousand, particle size 50-100 mesh.

Solid adsorbent: florisil, average particle size 150-250 μm.

1) Sequentially adding 50% of UHMWPE and 50% of Florisil into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 13.0mm, the height of each hole is 10.2mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 130 deg.C for 120min, cooling, and taking out.

The obtained adsorbent Florisil complex had a diameter of 13.0mm, a height of 10.2mm and a pore size of 10 to 20 μm.

(2) Preparation of a porous modified adsorbent Florisil column:

the porous modified adsorbent Florisil obtained above was assembled into a syringe-type empty column tube having a capacity of 6mL to obtain a porous modified adsorbent Florisil column.

(3) Solid phase extraction method for methomyl residue in leek sample

The obtained porous modified adsorbent Florisil column and the classical ones are utilized A Florisil column (specification 500mg/6mL) is used for sample pretreatment and purification of the detection of methomyl residue in a Chinese chive sample, and an HPLC method is used as a detection means.

Extracting a sample solution of the leek sample according to a method of the standard NY/T761-2008; then respectively leading the sample liquid to pass through an activated porous modified adsorbent Florisil column and

florisil column (specification 500mg/6mL), discarding filtrate; eluting the component to be detected on the column by using a normal hexane-acetone mixed solution, collecting the eluent, and drying by using nitrogen; finally, the test is carried out on a constant volume machine by using the mobile phase.

Comparative results of the addition recovery of methomyl residue in leek samples at an addition level of 0.5mg/kg are shown in table 8.

TABLE 8 comparison results of the recovery of methomyl residue from leek samples at an add level of 0.5mg/kg

In summary, the Florisil column of the porous modified adsorbent of the embodiment can effectively enrich and purify methomyl in the leek sample, and achieve the classical

The purification effect of the Florisil column (specification 500mg/6mL) is high, the flow rate is high, and the recovery rate is slightly the same as that of the Florisil column

Recovery on a Florisil column (specification 500mg/6 mL).

Example 9:

(1) preparing a porous modified adsorbent ALA:

thermoplastic polymer resin: UHMWPE, molecular weight is about 400 ten thousand, particle size 100-.

Solid adsorbent: ALA.

1) Sequentially adding 40% of UHMWPE and 60% of ALA into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 9.1mm, the height of each hole is 8.2mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 220 deg.C for 60min, cooling, and taking out.

The obtained porous modified adsorbent ALA has a diameter of 9.1mm, a height of 8.2mm and a pore diameter of 20-40 μm.

(2) Preparing a porous modified adsorbent ALA column:

and (3) assembling the obtained porous modified adsorbent ALA into a syringe type empty column tube with the capacity of 3mL to obtain a porous modified adsorbent ALA column.

(3) Solid phase extraction method of malachite green in fish sample

The porous modified adsorbent ALA column obtained by the method is utilized together with the porous modified adsorbent

An ALA column (specification 500mg/3mL) is used for sample pretreatment and purification of malachite green detection in a fish sample, and an HPLC method is used as a detection means.

Extracting a sample solution from a fish sample according to a method of GB/T19857-2005; then respectively passing the sample liquid through activated porous modified adsorbent ALA column and activated porous modified adsorbent ALA column

ALA column (specification 500mg/3mL), discarding filtrate; taking acetonitrile to elute a component to be detected on the column, collecting eluent, and drying the eluent by nitrogen; finally, acetonitrile is used for dissolving, and a constant volume is carried out on a machine for testing.

The results of comparison of the addition and recovery of malachite green at an addition level of 1mg/kg of fish meat are shown in Table 9, and the chromatogram of malachite green is shown in FIG. 8.

TABLE 9 comparison results of the addition recovery of malachite green in fish at an addition level of 1mg/kg

In conclusion, the porous modified adsorbent ALA column can effectively enrich and purify malachite green in a fish sample to achieve the classical effect The purification effect of an ALA column (specification is 500mg/3mL) is high, the flow rate is high, and the recovery rate is slightly the same as that of an ALA column

Recovery of ALA column (500 mg/3mL specification).

Example 10:

(1) preparing a porous modified adsorbent ALN:

thermoplastic polymer resin: UHMWPE with molecular weight of about 400 ten thousand and particle size of 100-200 meshes; HDPE, density 0.945, particle size 80-150 mesh.

Solid adsorbent: ALN.

1) Sequentially adding 40% of UHMWPE, 20% of HDPE and 40% of ALN into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 9.1mm, the height of each hole is 8.5mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 200 deg.C for 80min, cooling, and taking out.

The obtained porous modified adsorbent ALN has a diameter of 9.1mm, a height of 8.5mm and a pore diameter of 5-40 μm.

(2) Preparing a porous modified adsorbent ALN column:

and (3) assembling the obtained porous modified adsorbent ALN into a syringe type hollow column tube with the capacity of 3mL to obtain a porous modified adsorbent ALN column.

(3) Solid phase extraction method of malachite green in fish sample

The porous modified adsorbent ALN column obtained by the method and the classical method are utilized An ALN column (specification 500mg/3mL) is used for sample pretreatment and purification of malachite green detection in a fish sample, and an HPLC method is used as a detection means.

Extracting a sample solution from a fish sample according to a method of GB/T19857-2005; then respectively passing the sample liquid through activated porous modified adsorbent ALN column and

ALN column (specification 500mg/3mL), discarding filtrate; taking acetonitrile to elute a component to be detected on the column, collecting eluent, and drying the eluent by nitrogen; finally, acetonitrile is used for dissolving, and a constant volume is carried out on a machine for testing.

The results of comparison of the addition and recovery of malachite green at an addition level of 1mg/kg of the fish meat sample are shown in Table 10, and the chromatogram of malachite green is shown in FIG. 8.

TABLE 10 comparison results of the addition recovery of malachite green in fish samples at an addition level of 1mg/kg

In conclusion, the porous modified adsorbent ALN column can effectively enrich and purify malachite green in a fresh meat sample to achieve the classical effect

The ALN column (specification 500mg/3mL) has the advantages of high purification effect, high flow rate and recovery rate which are similar to those of the ALN column Recovery of ALN column (500 mg/3mL specification).

Example 11:

(1) preparing a porous modified adsorbent ALB:

thermoplastic polymer resin: HDPE, density 0.945, particle size 300-; PP, molecular weight about 10 ten thousand.

Solid adsorbent: ALB.

1) Sequentially adding 65% of HDPE, 15% of PP and 20% of ALB into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 13.0mm, the height of each hole is 12.6mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 190 deg.C for 90min, cooling, and taking out.

The obtained porous modified adsorbent ALB has a diameter of 13.0mm, a height of 12.6mm and a pore diameter of 10-40 μm.

(2) Preparing a porous modified adsorbent ALB column:

and (3) assembling the obtained porous modified adsorbent ALB into a syringe type hollow column tube with the capacity of 6mL to obtain a porous modified adsorbent ALB column.

Example 12:

(1) preparing a porous modified adsorbent SAX:

thermoplastic polymer resin: HDPE, density 0.945, particle size 200 and 300 meshes.

Solid adsorbent: SAX, average particle size 40-75 μm.

1) Sequentially adding 30% of HDPE and 70% of SAX into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 13.0mm, the height of each hole is 10.6mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 160 deg.C for 30min, cooling, and taking out.

The obtained porous modified adsorbent SAX has a diameter of 13.0mm, a height of 10.6mm, and a pore diameter of 20-40 μm.

(2) Preparing a porous modified adsorbent SAX column:

and assembling the obtained porous modified adsorbent SAX into a syringe type hollow column tube with the capacity of 6mL to obtain the porous modified adsorbent SAX column.

(3) Solid phase extraction method for organic acid in yoghourt sample

The obtained porous modified adsorbent SAX column and the conventional column are utilized SAX column (specification 500mg/6mL) is used for sample pretreatment purification of organic acid detection in yoghourt sample, and HPLC method is used as detection means.

Extracting a sample solution from a yoghourt sample according to a method of GB/T5009.157-2016; then respectively passing the sample liquid through the activated porous modified adsorbent SAX column and

SAX column (specification 500mg/6mL), discarding filtrate; taking hydrochloric acid to elute the component to be detected on the column, collecting eluent, and drying by nitrogen; finally, the test is carried out on a constant volume machine by using the mobile phase.

The comparative results of the addition and recovery of organic acid at an addition level of 10mg/kg of yogurt are shown in Table 11, and the chromatogram of the organic acid is shown in FIG. 9.

TABLE 11 comparative results of addition recovery of organic acids at addition level of 10mg/kg yogurt

In conclusion, the porous modified adsorbent SAX column can effectively enrich and purify organic acid in a yoghourt sample to achieve the classical effect

The purification effect of the SAX column (specification 500mg/6mL) is high, the flow rate is high, and the recovery rate is slightly the same as that of the SAX column

Recovery of SAX column (specification 500mg/6 mL).

Example 13:

(1) porous modified adsorbent NH ₂Preparation:

Solid adsorbent: NH (NH) ₂The average particle size is 40-75 μm.

1) Sequentially adding 40% of UHMWPE and NH into a container ₂60 percent, and uniformly mixing to obtain standby raw materials;

3) sintering at 190 deg.C for 50min, cooling, and taking out.

The obtained porous modified adsorbent NH ₂Diameter of 13.0mm, height of 11.2mm, and pore diameter of 20-50 μm.

(2) Porous modified adsorbent NH ₂Column preparation:

the obtained porous modified adsorbent NH ₂The column is assembled into a syringe type hollow column tube with the capacity of 6mL to obtain the porous modified adsorbent NH ₂And (3) a column.

(3) Solid phase extraction method of carbendazim in ginger sample

Using the porous modified adsorbent NH obtained above ₂Column and classic

NH ₂The column (specification 500mg/6mL) is used for sample pretreatment and purification of carbendazim detection in ginger samples, and an HPLC method is used as a detection means.

Extracting a sample solution from a ginger sample according to a method of the Standard SN/T2441-2010; then respectively passing the sample liquid through an activated porous modified adsorbent NH ₂Column and

NH ₂column (specification 500mg/6mL), discard filtrate; eluting the components to be detected on the column by using a methanol-dichloromethane solution, collecting the eluent, and drying by using nitrogen; finally, the test is carried out on a constant volume machine by using the mobile phase.

Comparative results of carbendazim addition recovery at an addition level of 10 μ g/kg ginger samples are shown in table 12.

TABLE 12 comparative results of carbendazim addition recovery in ginger samples at an addition level of 10. mu.g/kg

In summary, the porous modified adsorbent NH of the present example ₂The column can effectively enrich and purify the carbendazim in the ginger sample to achieve the classical

NH ₂The purification effect of the column (specification 500mg/6mL) is high, the flow rate is high, and the recovery rate is slightly the same as that of the column

NH ₂Recovery of column (specification 500mg/6 mL).

Example 14:

(1) preparation of porous modified adsorbent PSA:

thermoplastic polymer resin: UHMWPE with molecular weight of about 400 ten thousand and particle size of 200-400 meshes; HDPE, density 0.945, particle size 300 and 400 meshes.

Solid adsorbent: PSA, average particle size 50-75 μm.

1) Sequentially adding 20% of UHMWPE, 30% of HDPE and 50% of PSA into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 13.0mm, the height of each hole is 12.8mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 180 deg.C for 60min, cooling, and taking out.

The obtained porous modified adsorbent PSA complex has a diameter of 13.0mm, a height of 12.8mm and a pore diameter of 40-60 μm.

(2) Preparing a porous modified adsorbent PSA column:

and assembling the obtained porous modified adsorbent PSA into a syringe type hollow column tube with the capacity of 6mL to obtain the porous modified adsorbent PSA column.

(3) Solid phase extraction method of hydroquinone in face cream sample

By using the obtained porous modified adsorbent PSA column and the conventional adsorbent

The PSA column (specification 500mg/6mL) is used for sample pretreatment purification of hydroquinone detection in a cream sample, and an HPLC method is used as a detection means.

Extracting a sample solution from the face cream sample according to a method of the Standard SN/T2441-2010; then respectively passing the sample liquid through the activated porous modified adsorbent PSA column and

PSA column (specification 500mg/6mL), discarding the filtrate; taking methanol to elute components to be detected on the column, collecting eluent, and drying by nitrogen; and finally, dissolving the mixture by using methanol, fixing the volume and testing on a machine.

The results of comparison of hydroquinone addition recovery at 10mg/kg cream are shown in Table 13, and the hydroquinone chromatogram is shown in FIG. 10.

TABLE 13 comparative results on hydroquinone addition recovery from a 10mg/kg cream add level

In conclusion, the porous modified adsorbent PSA column of the embodiment can effectively enrich and purify hydroquinone in a facial cream sample to achieve the classical effect

The purification effect of the PSA column (specification 500mg/6mL) is high, the flow rate is high, and the recovery rate is slightly the same as that of the PSA column

Recovery of PSA column (specification 500mg/6 mL).

Example 15:

(1) preparation of porous modified adsorbent PRS:

thermoplastic polymer resin: UHMWPE, molecular weight about 200 ten thousand, particle size 300 and 400 mesh.

Solid adsorbent: PRS, average particle size 40-75 μm.

1) Sequentially adding 50% of UHMWPE and 50% of PRS into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 9.1mm, the height of each hole is 13.8mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 200 deg.C for 90min, cooling, and taking out.

The obtained porous modified adsorbent PRS has a diameter of 9.1mm, a height of 13.8mm and a pore diameter of 80-100 μm.

(2) Porous modified adsorbent PRS column:

and assembling the obtained porous modified adsorbent PRS into a syringe type hollow column tube with the capacity of 3mL to obtain the porous modified adsorbent PRS column.

(3) Solid phase extraction method of malachite green in fish sample

PRS (PRS) column and classical column by using porous modified adsorbent obtained by the method

PRS column (specification 500mg/3mL) for fish meat sampleAnd (3) sample pretreatment and purification for detecting the malachite green in the product, and taking an HPLC method as a detection means.

Extracting a sample solution from a fish sample according to a method of GB/T19857-2005; then respectively passing the sample liquid through activated PRS column and activated porous modified adsorbent

A PRS column (specification 500mg/3mL) and the filtrate is discarded; taking acetonitrile to elute a component to be detected on the column, collecting eluent, and drying the eluent by nitrogen; finally, acetonitrile is used for dissolving, and a constant volume is carried out on a machine for testing.

The results of comparison of the addition and recovery of malachite green at an addition level of 1mg/kg of fish meat are shown in Table 14, and the chromatogram of malachite green is shown in FIG. 8.

TABLE 14 comparison of the results of the addition recovery of malachite green in fish at an addition level of 1mg/kg

In summary, the PRS column with the porous modified adsorbent can effectively enrich and purify malachite green in a fish sample to achieve the classical purpose

The purification effect of the PRS column (specification 500mg/3mL) is high, the flow rate is high, and the recovery rate is slightly the same as that of the PRS column

Recovery on PRS column (specification 500mg/3 mL).

Example 16:

(1) porous modified adsorbent Carb-GCB/NH ₂Preparation:

(1-1) preparation of upper porous modified adsorbent Carb-GCB:

thermoplastic polymer resin: the molecular weight of the UHMWPE is 300 ten thousand, and the particle size is 200-300 meshes.

Solid adsorbent: Carb-GCB, average particle size 100-300 mesh.

1) Sequentially adding 30% of UHMWPE and 70% of Carb-GCB into a container, and uniformly mixing to obtain a standby raw material;

3) sintering at 200 deg.C for 50min, cooling, and taking out to obtain upper layer porous modified adsorbent Carb-GCB with diameter of 13.0mm, height of 11.2mm, and pore diameter of 20-40 μm.

(1-2) lower layer porous modified adsorbent NH ₂Preparation:

thermoplastic polymer resin: the molecular weight of the UHMWPE is 400 ten thousand, and the particle size is 600-800 meshes.

Solid adsorbent: NH (NH) ₂The average particle size is 40-75 μm.

1) Sequentially adding 40% of UHMWPE and 60% of PRS into a container, and uniformly mixing to obtain a standby raw material;

3) sintering at 200 deg.C for 50min, cooling, and taking out to obtain lower layer porous modified adsorbent NH ₂Diameter of 13.0mm, height of 11.0mm, and pore diameter of 20-40 μm.

The obtained upper and lower layer porous modified adsorbents are bonded to obtain a double-layer porous modified adsorbent Carb-GCB/NH ₂Diameter of 13.0mm, height of 22.2mm, and pore diameter of 20-40 μm.

(2) Porous modified adsorbent Carb-GCB/NH ₂Column preparation:

the obtained porous modified adsorbent Carb-GCB/NH ₂Assembling the mixture into a syringe type hollow column tube with the capacity of 6mL to obtain the porous modified adsorbent Carb-GCB/NH ₂And (3) a column.

(3) Solid phase extraction method of carbofuran in Pu' er sample

The obtained porous modified adsorbent Carb-GCB/NH is utilized ₂Column and classic

Carb-GCB/NH ₂Column (specification 500mg/500mg/3mL) for measuring gram hundred in Pu' er sampleThe sample pretreatment for detection was purified, and HPLC method was used as the detection means.

Extracting a sample solution from a Pu' er sample according to a method of GB/T19857-2005; then respectively passing the sample liquid through activated porous modified adsorbent Carb-GCB/NH ₂Column and

Carb-GCB/NH ₂column (specification 500mg/500mg/3mL), discard filtrate; taking acetonitrile-toluene to elute the component to be detected on the column, collecting the eluent, and drying by nitrogen; finally, acetonitrile is used for dissolving, and a constant volume is carried out on a machine for testing.

The comparative results of the addition and recovery of carbofuran in Pu' er tea at the addition level of 0.25mg/kg are shown in Table 15.

TABLE 15 comparative results of the recovery of carbofuran residue in Puer at an add level of 0.25mg/kg

In conclusion, the porous modified adsorbent of this example, Carb-GCB/NH ₂The column can effectively enrich and purify carbofuran in a Pu' er sample to achieve the classical

Carb-GCB/NH ₂The purification effect of the column (specification 500mg/500mg/3mL) is high, the flow rate is high, and the recovery rate is slightly the same as that of the column

Carb-GCB/NH ₂Recovery of column (specification 500mg/500mg/3 mL).

Example 17:

(1) preparation of porous modified adsorbent C18:

1) Sequentially adding 50% of UHMWPE and 1850% of C into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 4.0mm, the height of each hole is 5.0mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 185 deg.C for 70min, cooling, and taking out.

The obtained porous modified adsorbent C18 has diameter of 4.0mm, height of 5.0mm, and pore diameter of 60-100 μm.

(2) Preparation of porous modified adsorbent C18 suction head:

the porous modified adsorbent C18 obtained above was assembled into a tip having a capacity of 1mL to obtain a porous modified adsorbent C18 tip. According to practical application, 1mL, 200. mu.L, 10. mu.L and 1. mu.L of the porous modified adsorbent C18 tip can be selected for desalting biological samples such as oligonucleotides or polypeptides.

Example 18:

(1) preparation of porous modified adsorbent WCX:

thermoplastic polymer resin: HDPE, density 0.945, particle size 200 and 250 meshes; PP, molecular weight about 10 ten thousand.

Solid adsorbent: WCX, average particle size of 40 μm, average pore diameter

1) Sequentially adding 10% of HDPE, 30% of PP and 60% of WCX into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 2.5mm, the height of each hole is 2.0mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 200 deg.C for 80min, cooling, and taking out.

The obtained porous modified adsorbent WCX has a diameter of 2.5mm, a height of 2.0mm and a pore diameter of 10-60 μm.

(2) Preparing a porous modified adsorbent WCX 384 orifice plate:

the porous modified adsorbent WCX obtained above was assembled into a 384-well plate having a capacity of 150. mu.L, to obtain a porous modified adsorbent WCX 384-well plate. The WCX 384-pore plate of the porous modified adsorbent can be selected for new drug development according to actual requirements.

Example 19:

(1) preparing porous modified adsorbent HLB:

thermoplastic polymer resin: UHMWPE, molecular weight about 500 ten thousand, particle size 100 and 200 mesh.

1) Sequentially adding 40% of UHMWPE and 60% of HLB into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum mould with a plurality of holes, wherein the length of the edge of each hole is 3.5mm, the height of each hole is 1.0mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 200 deg.C for 60min, cooling, and taking out.

The obtained porous modified adsorbent has HLB, pore edge length of 3.5mm, height of 1.0mm, and pore diameter of 10-60 μm.

(2) Preparing a porous modified adsorbent HLB 384 orifice plate:

the porous modified adsorbent HLB obtained above was assembled into 384-well plates having a capacity of 180 μ L to obtain porous modified adsorbent HLB 384-well plates.

(3) Solid phase extraction method of ibuprofen in serum sample

The obtained HLB 384-pore plate of the porous modified adsorbent is used for sample pretreatment and purification of ibuprofen detection in a serum sample, and LC-MS-MS is used as a detection means.

Serum samples were diluted 1+1 in 1% formic acid solution; then respectively enabling the sample liquid to pass through an activated porous modified adsorbent HLB 384-pore plate, and discarding filtrate; taking methanol to elute components to be detected on the column, collecting eluent, and drying by nitrogen; and finally, using a 60: and testing on a 40 water/methanol dissolution constant volume machine.

The results of the recovery of ibuprofen added at 25. mu.g/mL serum samples are shown in Table 16, and the ibuprofen chromatogram is shown in FIG. 11.

TABLE 16 results of recovery from the addition of ibuprofen to serum at an addition level of 25. mu.g/mL

Example 20:

(1) preparation of porous modified adsorbent C18:

thermoplastic polymer resin: UHMWPE, molecular weight is about 400 ten thousand, particle size 80-200 mesh.

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 7.0mm, the height of each hole is 3.6mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 200 deg.C for 90min, cooling, and taking out.

The obtained porous modified adsorbent C18 has a pore diameter of 7.0mm, a height of 3.6mm, and a pore diameter of 20-80 μm.

(2) Preparation of porous modified adsorbent C1896 pore plate:

the porous modified adsorbent C18 obtained above was packed in a 96-well plate having a capacity of 1.0mL to obtain a porous modified adsorbent C1896-well plate. The porous modified adsorbent C1896 pore plate can be selected according to practical application for desalting and purifying biological samples such as oligonucleotide or polypeptide.

Example 21:

(1) preparation of porous modified adsorbent C18:

thermoplastic polymer resin: UHMWPE, molecular weight about 500 ten thousand, particle size 120 and 200 mesh.

1) Sequentially adding 60% of UHMWPE and 1840% of C into a container, and uniformly mixing to obtain a standby raw material;

2) adopting an aluminum die with a plurality of holes, wherein the diameter of each hole is 0.5mm, the height of each hole is 0.5mm, uniformly adding the standby raw materials into the holes, and compressing and vibrating the standby raw materials to be flat;

3) sintering at 130 deg.C for 20min, cooling, and taking out.

The obtained porous modified adsorbent C18 has a pore diameter of 0.5mm, a height of 0.5mm, and a pore diameter of 20-40 μm.

(2) Preparation of porous modified adsorbent C181536 well plate:

the porous modified adsorbent C18 obtained above was packed into 1536 well plates having a capacity of 12. mu.L to obtain porous modified adsorbent C181536 well plates.

The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.

Claims

1. A porous modified adsorbent for solid phase extraction, characterized in that it is made by sintering a material comprising a thermoplastic polymer resin and a solid phase extraction adsorbent, wherein the thermoplastic polymer resin is Polyethylene (PE) and/or polypropylene (PP) and/or polyvinyl chloride (PVC) and/or Polystyrene (PS) and/or polyethylene terephthalate (PET) and/or nylon (PA).

2. The porous modified adsorbent of claim 1, wherein the solid phase extraction adsorbent is selected from the group consisting of HLB, WAX, WCX, MAX, MCX, C18, C8, C4, C2, C1, Silica, Diol, CN, Carb-GCB, Florisil, ALA, ALN, ALB, SCX, SAX, NH ₂PSA, PRS and activated carbon.

3. The porous modified adsorbent of claim 1, wherein the thermoplastic polymer resin and the solid phase extraction adsorbent are, in weight percent: 15% -95% of thermoplastic polymer resin and 5% -85% of solid phase extraction adsorbent;

preferably, the thermoplastic polymer resin and the solid phase extraction adsorbent respectively comprise the following components in percentage by weight: 15-90% of thermoplastic polymer resin and 10-85% of solid phase extraction adsorbent.

4. The porous modified adsorbent of claim 1, wherein the pore size of the porous modified adsorbent is 1 to 200 μm, preferably 5 to 150 μm.

5. The porous modified adsorbent of claim 1, wherein the Polyethylene (PE) is Ultra High Molecular Weight Polyethylene (UHMWPE) and/or High Density Polyethylene (HDPE);

preferably, the Ultra High Molecular Weight Polyethylene (UHMWPE) has a molecular weight of more than 150 ten thousand; preferably, the High Density Polyethylene (HDPE) has a specific gravity of 0.941 to 0.960.

6. The porous modified adsorbent of claim 1, wherein the particle size of the thermoplastic polymer resin is 50-800 mesh.

7. The porous modified adsorbent of claim 1, wherein the polypropylene (PP) is a polypropylene having a molecular weight of 10 ten thousand or more.

8. The porous modified adsorbent of claim 1, wherein the polyvinyl chloride (PVC) has a molecular weight of 5-11 ten thousand; the Polystyrene (PS) is a polymer synthesized by styrene monomer through free radical addition polymerization; the polyethylene terephthalate (PET) is prepared by exchanging dimethyl terephthalate and ethylene glycol ester and then carrying out polycondensation reaction; the nylon (PA) is nylon 6.

9. The porous modified adsorbent of claim 1, wherein the solid phase extraction adsorbent has an average particle size of 5-500 μm.

10. The porous modified adsorbent of claim 1, wherein the porous modified adsorbent is made into a cylindrical shape, a disk shape or a sheet shape by sintering.

11. The porous modified adsorbent of claim 10, wherein the cylindrical shape has a diameter of 0.1 to 500mm and a height of 0.2 to 30 mm; preferably, the diameter is 1-15mm and the height is 1-15 mm.

12. A preparation method of a porous modified adsorbent for solid phase extraction is characterized by comprising the step of sintering a material comprising a thermoplastic polymer resin and a solid phase extraction adsorbent to prepare the porous modified adsorbent, wherein the thermoplastic polymer resin is Polyethylene (PE) and/or polypropylene (PP) and/or polyvinyl chloride (PVC) and/or Polystyrene (PS) and/or polyethylene terephthalate (PET) and/or nylon (PA).

13. The method of claim 12, wherein the solid phase extraction adsorbent is selected from the group consisting of HLB, WAX, WCX, MAX, MCX, C18, C8, C4, C2, C1, Silica, Diol, CN, Carb-GCB, Florisil, ALA, ALN, ALB, SCX, SAX, NH, and mixtures thereof ₂PSA, PRS and activated carbon.

14. The method according to claim 12, wherein the thermoplastic polymer resin and the solid phase extraction adsorbent are, in weight percent: 15% -95% of thermoplastic polymer resin and 5% -85% of solid phase extraction adsorbent;

15. The method of claim 12, wherein the pore size of the porous modified adsorbent is 1 to 200 μm, preferably 5 to 150 μm.

16. The production method according to claim 12, characterized in that the Polyethylene (PE) is an ultra-high molecular weight polyethylene (UHMWPE) and/or a High Density Polyethylene (HDPE);

17. The production method according to claim 12, wherein the particle size of the thermoplastic polymer resin is 50 to 800 mesh.

18. The production method according to claim 12, wherein the polypropylene (PP) is a polypropylene having a molecular weight of 10 ten thousand or more.

19. The method of claim 12, wherein the polyvinyl chloride (PVC) has a molecular weight of 5 to 11 ten thousand; the Polystyrene (PS) is a polymer synthesized by styrene monomer through free radical addition polymerization; the polyethylene terephthalate (PET) is prepared by exchanging dimethyl terephthalate and ethylene glycol ester and then carrying out polycondensation reaction; the nylon (PA) is nylon 6.

20. The method according to claim 12, wherein the solid phase extraction adsorbent has an average particle diameter of 5 to 500 μm.

21. The method of claim 12, wherein the porous modified adsorbent is prepared in a cylindrical, disk-like or sheet-like shape by sintering;

preferably, the diameter of the cylinder is 0.1-500mm, and the height is 0.2-30 mm; more preferably, the diameter is 1-15mm and the height is 1-15 mm.

22. The method of claim 12, wherein the sintering is performed at 120 ℃ to 250 ℃ for 1min to 120 min.

23. The method of manufacturing according to claim 12, comprising the steps of:

3) sintering at 120-250 ℃ for 1-120 min, cooling, and taking out to obtain the porous modified adsorbent.

24. A solid phase extraction device comprising the porous modified adsorbent of any one of claims 1 to 11 and a containment device, the porous modified adsorbent being disposed in the containment device.

25. The solid phase extraction apparatus of claim 24, wherein the containment device is a syringe-type hollow column, a pipette tip, or a multi-well plate; preferably, the multi-well plate is a 96-well plate or a 384-well plate or a 1536-well plate.