CN117603380A - Cation exchange mode polymer separation medium and preparation method and application thereof - Google Patents
Cation exchange mode polymer separation medium and preparation method and application thereof Download PDFInfo
- Publication number
- CN117603380A CN117603380A CN202311585952.XA CN202311585952A CN117603380A CN 117603380 A CN117603380 A CN 117603380A CN 202311585952 A CN202311585952 A CN 202311585952A CN 117603380 A CN117603380 A CN 117603380A
- Authority
- CN
- China
- Prior art keywords
- cation exchange
- separation medium
- polymer
- polymer separation
- exchange mode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 238000005341 cation exchange Methods 0.000 title claims abstract description 41
- 238000000926 separation method Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004005 microsphere Substances 0.000 claims abstract description 33
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical group OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 13
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UCTWMZQNUQWSLP-VIFPVBQESA-N (R)-adrenaline Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 claims description 8
- 229930182837 (R)-adrenaline Natural products 0.000 claims description 8
- 229960005139 epinephrine Drugs 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229940103494 thiosalicylic acid Drugs 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000012528 membrane Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 7
- 235000015277 pork Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- 229940043376 ammonium acetate Drugs 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- 238000002552 multiple reaction monitoring Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- -1 acetonitrile saturated n-hexane Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
- B01D15/362—Cation-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a cation exchange mode polymer separation medium, a preparation method and application thereof, wherein the cation exchange mode polymer separation medium is novel in structure and consists of polymer microspheres and mercaptobenzoic acid bonded on the surfaces of the polymer microspheres, a mercaptobenzoic acid structure is introduced for the first time as a cation exchange group, and the existence of mercapto can promote additional polar action and promote interaction force with a target compound. The cation exchange mode polymer separation medium is prepared by oxidizing the polymer microspheres and then performing epoxy ring-opening reaction, the preparation process is simple and reliable, the reaction condition is mild, and the industrialization is facilitated. The cation exchange mode polymer separation medium has good yield for alkaline compounds in the pretreatment process of complex samples.
Description
Technical Field
The invention belongs to the technical field of separation materials, and particularly relates to a cation exchange mode polymer separation medium, and a preparation method and application thereof.
Background
Ion exchange materials are commonly used to enrich or remove ionizable components from fluids used in a variety of applications. Solid phase extraction is an indispensable link in a complex sample analysis flow, and can realize enrichment of target objects or removal of impurities, so that matrix effect is reduced, service life of a liquid chromatographic column is prolonged, and accuracy of detection results is improved, and the solid phase extraction method is widely applied to industries such as food safety, medicines, environment, forensics and the like. In solid phase extraction, the separation material is the basis and the cation exchange material is an important component. The surface of the cation exchange material contains a large number of negatively charged groups, such as sulfonic acid groups or carboxyl groups, and the like, and can reversibly adsorb and combine cations in the solution. At present, solid phase extraction materials of cationic polymers are available on the market, but the problems of poor recovery rate and poor reproducibility and stability of part of samples exist, so that development of new cation exchange solid phase extraction materials is needed.
Disclosure of Invention
In order to solve the problems existing in the prior art, the invention provides a cation exchange mode polymer separation medium and a preparation method thereof. The cation exchange mode polymer separation medium has novel structure, the mercaptobenzoic acid structure is introduced for the first time as a cation exchange group, and the existence of mercapto can promote the extra polar action and the interaction force with a target compound. The preparation process is simple and reliable, the reaction condition is mild, and the industrialization is realized. The polymer provided by the invention is used as a cation exchange mode separation medium, and has good yield on alkaline compounds in the pretreatment process of complex samples.
The technical scheme adopted by the invention is as follows:
the structure of the cation exchange mode polymer separation medium comprises polymer microspheres and a mercaptobenzoic acid structure bonded on the surfaces of the polymer microspheres, and the structure formula is as follows:
the polymer microsphere is a divinylbenzene-vinylbenzene copolymer microsphere or a divinylbenzene-N-vinylpyrrolidone copolymer microsphere.
The particle diameter of the polymer microsphere is 50-70 mu m, and the specific surface area is 650-800 m 2 /g。
The preparation method of the cation exchange mode polymer separation medium comprises the following steps:
(1) Oxidizing the polymer microsphere: adding 0.1-2 g of oxidant and 1g of polymer microsphere into 5-20 mL of organic solvent, reacting under certain conditions, and sequentially filtering, washing and drying to obtain oxidized polymer microsphere;
(2) Epoxy ring opening reaction: adding 0.2-2 g of thiosalicylic acid, 0.1-2 g of alkaline catalyst and 1g of oxidized polymer microsphere into 10-40 mL of water, reacting under certain conditions, and then sequentially filtering, washing and drying to obtain the cation exchange mode polymer separation medium.
In the step (1), the organic solvent is one or a combination of several of dichloromethane, chloroform, n-heptane and isooctane.
In the step (1), the oxidant is one or a combination of a plurality of 3-chloroperoxybenzoic acid, tert-butyl hydroperoxide and potassium hydrogen persulfate.
In step (1), the reaction conditions are: reacting for 8-48h at 20-60 ℃;
the washing is as follows: sequentially washing with ethanol and dichloromethane;
the drying is as follows: vacuum drying at 20-80 deg.c for 8-24 hr.
In the step (2), the alkaline catalyst is one or a combination of a plurality of diisopropylethylamine, triethylamine, sodium hydroxide, sodium bicarbonate, potassium carbonate and pyridine.
In step (2), the reaction conditions are: reacting for 3-24 h at 30-100 ℃;
the washing is as follows: washing with water, 0.1M dilute hydrochloric acid, water and methanol in sequence;
the drying is as follows: vacuum drying at 40-80 deg.c for 8-24 hr.
The cation exchange mode polymer separation medium is used as a solid phase extraction filler for measuring the content of epinephrine in animal-derived foods.
The invention has the following advantages:
(1) The cation exchange mode polymer separation medium is novel in structure, consists of polymer microspheres and mercaptobenzoic acid bonded on the surfaces of the polymer microspheres, and is characterized in that the mercaptobenzoic acid structure is introduced for the first time as a cation exchange group, and the existence of mercapto can promote additional polar action and promote interaction force with a target compound.
(2) According to the preparation method of the cation exchange mode polymer separation medium, the polymer microspheres are oxidized firstly and then prepared through epoxy ring-opening reaction, the preparation process is simple and reliable, the reaction condition is mild, and industrialization is facilitated.
(3) The cation exchange mode polymer separation medium has good yield for alkaline compounds in the pretreatment process of complex samples.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a graph of epinephrine test spectra in pork matrix standards;
figure 2 shows a graph of epinephrine test spectra of real samples of pork.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the embodiments described are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Example 1
The embodiment provides a cation exchange mode polymer separation medium, the structure of which comprises divinylbenzene-N-vinylpyrrolidone copolymer microspheres and mercapto-benzoic acid bonded on the surfaces of the polymer microspheres. The cation exchange mode polymer separation medium has the structural formula:
the preparation method of the cation exchange mode polymer separation medium comprises the following specific operations:
(1) 1g of 3-chloroperoxybenzoic acid and 1g of divinylbenzene-N-vinylpyrrolidone copolymer microspheres (particle diameter 65 μm, specific surface area 780 m) were added to 10mL of methylene chloride 2 And/g), reacting at 30 ℃ for 24 hours, filtering, washing with ethanol and dichloromethane in sequence, and vacuum drying the obtained solid in a drying oven at 30 ℃ for 16 hours to obtain the oxidized divinylbenzene-N-vinylpyrrolidone copolymer microspheres.
(2) Epoxy ring opening reaction: 0.78g of thiosalicylic acid, 1.04g of diisopropylethylamine and 1g of oxidized divinylbenzene-N-vinylpyrrolidone copolymer microspheres are added into 20mL of water, the mixture is reacted for 24 hours at 90 ℃, the mixture is filtered, the filtered mixture is washed by water, 0.1M dilute hydrochloric acid, water and methanol in sequence, and the obtained solid is dried in vacuum for 16 hours at 60 ℃ in a drying box, so that the polymer filler is the cation exchange mode polymer separation medium.
Example 2
This example provides a cation exchange mode polymer separation media differing from example 1 only in: the polymer microsphere is a divinylbenzene-N-vinyl pyrrolidone copolymer microsphere.
Example 3
This example provides a cation exchange mode polymer separation media differing from example 1 only in: in the step (1), the organic solvent is chloroform, and the oxidant is tert-butyl hydroperoxide.
Experimental example
A150 mg/6mL solid phase extraction column was packed with the polymer packing obtained in example 1 for detecting epinephrine content in pork. The specific operation is as follows:
step 1: standard stock solution preparation: a certain amount of epinephrine is weighed respectively, and 0.1% methanolic formate is used for preparing 1mg/mL standard stock solution, and the standard stock solution is preserved at-18 ℃ in a dark place. Sample preparation: accurately weighing 5g (accurately to 0.01 g) of a sample into a 50mL centrifuge tube, adding 10mL of an extracting solution, swirling for 1min, adding 5mL of chloroform, swirling and uniformly mixing for 30s,10000r/min, centrifuging for 10min, taking a supernatant into another 50mL centrifuge tube, adding 5mL of acetonitrile saturated n-hexane, swirling and uniformly mixing for 30s,10000r/min, centrifuging for 3min, collecting a lower supernatant, fixing the volume to 25mL by using 100mM ammonium acetate, taking 12.5mL into a 15mL centrifuge tube, and purifying. Adding a standard sample (200 LOQ), accurately weighing 5g (accurate to 0.01 g) of the sample into a 50mL centrifuge tube, adding 10mL of an extracting solution, swirling for 1min, adding 5mL of chloroform, swirling and uniformly mixing for 30s,10000r/min, centrifuging for 10min, taking a supernatant into another 50mL centrifuge tube, adding 5mL of acetonitrile-saturated n-hexane, swirling and uniformly mixing for 30s,10000r/min, centrifuging for 3min, collecting a lower supernatant, fixing the volume to 25mL by using 100mM ammonium acetate, taking 12.5mL into 15mL centrifuge tubes, and adding 0.1mL of standard stock solution respectively.
Step 2: the solid phase extraction process is as follows, the flow rate is less than 1mL/min, and the preparation of the on-machine test solution is carried out: the sample loading residual liquid, the cleaning 1 and the cleaning 2 are directly detected by a machine, the volume of the sample is fixed to 5mL by eluting 1 and 2, the nitrogen of the substrate is blown to 4mL by adding the standard elution 1, the volume of the substrate is fixed to 5mL by using the eluent after the standard addition, the liquid chromatograph is used for measuring, the test spectrograms are shown in the figures 1 and 2, no impurity peak interference exists near the epinephrine peak position in the sample pork sample separated by the solid phase extraction column, and the impurity in the sample can be well removed; the target peak in the substrate standard substance and the separated pork sample has the same peak position and the peak response is close.
The specific operation and procedure of the solid phase extraction are shown in table 1.
TABLE 1 specific procedures and procedures for solid phase extraction
Step 3: detection conditions
1) Liquid phase conditions
Instrument: HPMS-TQ;
chromatographic column: alphasil VC-C18,2.1 x 100mm,2.5 μm; mobile phase: a:0.5M ammonium acetate, B:0.1% methanol formate;
TABLE 2 composition of mobile phases
| Time | A | B |
| 0 | 90 | 10 |
| 1.5 | 90 | 10 |
| 5.5 | 10 | 90 |
| 7 | 10 | 90 |
| 10 | 90 | 10 |
Flow rate: 0.25mL/min;
column temperature: 35 ℃;
sample injection amount: 10 mu L.
2) Mass spectrometry conditions
a) Ionization mode: electrospray ionization positive ion mode (esi+);
b) Mass spectrometry scanning mode: multiple Reaction Monitoring (MRM);
c) Resolution ratio: unit resolution;
d) Ion pair and conditions
TABLE 3 specific parameter settings for Mass Spectrometry
TABLE 4 determination of recovery and reproducibility
Experimental results: the polymer filler in example 1 has good recovery rate of epinephrine in pork, and has good reproducibility and stability.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The cation exchange mode polymer separation medium is characterized by comprising polymer microspheres and a mercaptobenzoic acid structure bonded on the surfaces of the polymer microspheres, wherein the cation exchange mode polymer separation medium has the structural formula:
2. the cation exchange pattern polymer separation medium of claim 1, wherein the polymer microspheres are divinylbenzene-vinylbenzene copolymer microspheres or divinylbenzene-N-vinylpyrrolidone copolymer microspheres.
3. The cation exchange pattern polymer separation medium according to claim 1 or 2, wherein the polymer microspheres have a particle size of 50 to 70 μm and a specific surface area of 650 to 800m 2 /g。
4. A process for the preparation of a cation exchange mode polymer separation medium according to any one of claims 1 to 3, comprising the steps of:
(1) Oxidizing the polymer microsphere: adding 0.1-2 g of oxidant and 1g of polymer microsphere into 5-20 mL of organic solvent, reacting under certain conditions, and sequentially filtering, washing and drying to obtain oxidized polymer microsphere;
(2) Epoxy ring opening reaction: adding 0.2-2 g of thiosalicylic acid, 0.1-2 g of alkaline catalyst and 1g of oxidized polymer microsphere into 10-40 mL of water, reacting under certain conditions, and then sequentially filtering, washing and drying to obtain the cation exchange mode polymer separation medium.
5. The method for producing a cation exchange membrane polymer separation medium according to claim 4, wherein in the step (1), the organic solvent is one or a combination of several of dichloromethane, chloroform, n-heptane and isooctane.
6. The cation exchange pattern polymer separation medium of claim 4, wherein in step (1), the oxidizing agent is one or a combination of several of 3-chloroperoxybenzoic acid, t-butyl hydroperoxide, and potassium hydrogen persulfate.
7. The cation exchange polymer separation media of claim 4 wherein in step (1), the reaction conditions are: reacting for 8-48h at 20-60 ℃;
the washing is as follows: sequentially washing with ethanol and dichloromethane;
the drying is as follows: vacuum drying at 20-80 deg.c for 8-24 hr.
8. The method for producing a cation exchange membrane polymer separation medium according to claim 4, wherein in the step (2), the basic catalyst is one or a combination of several of diisopropylethylamine, triethylamine, sodium hydroxide, sodium bicarbonate, potassium carbonate, and pyridine.
9. The method for producing a cation exchange pattern polymer separation medium according to claim 4, wherein in the step (2), the reaction conditions are: reacting for 3-24 h at 30-100 ℃;
the washing is as follows: washing with water, 0.1M dilute hydrochloric acid, water and methanol in sequence;
the drying is as follows: vacuum drying at 40-80 deg.c for 8-24 hr.
10. Use of a cation exchange pattern polymer separation medium according to any one of claims 1-3 or prepared by a method according to any one of claims 4-9 as a solid phase extraction packing for determining the content of epinephrine in animal derived food.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311585952.XA CN117603380B (en) | 2023-11-27 | 2023-11-27 | Cation exchange mode polymer separation medium and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311585952.XA CN117603380B (en) | 2023-11-27 | 2023-11-27 | Cation exchange mode polymer separation medium and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117603380A true CN117603380A (en) | 2024-02-27 |
| CN117603380B CN117603380B (en) | 2024-07-23 |
Family
ID=89943723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311585952.XA Active CN117603380B (en) | 2023-11-27 | 2023-11-27 | Cation exchange mode polymer separation medium and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117603380B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5652348A (en) * | 1994-09-23 | 1997-07-29 | Massey University | Chromatographic resins and methods for using same |
| CN101743471A (en) * | 2007-07-13 | 2010-06-16 | 帝斯曼知识产权资产管理有限公司 | Analysis of doping compounds |
| CN102612511A (en) * | 2009-09-28 | 2012-07-25 | 肯塔基大学研究基金会 | Thiol-containing compounds for the removal of elements from contaminated milieu and methods of use |
| CN104525151A (en) * | 2014-12-02 | 2015-04-22 | 佛山市博新生物科技有限公司 | Endotoxin adsorbent used in hemoperfusion, and preparation method thereof |
| CN107200804A (en) * | 2017-06-21 | 2017-09-26 | 广州康盛生物科技有限公司 | A kind of inflammatory factor macroporous adsorbent and preparation method thereof |
| CN109575345A (en) * | 2018-12-12 | 2019-04-05 | 怀化学院 | Sulfonated divinylbenzene polymer microballoon, preparation method and applications |
| CN110041453A (en) * | 2019-04-17 | 2019-07-23 | 河海大学 | A kind of modified Amberlite XAD-4 resin and its preparation method and application |
-
2023
- 2023-11-27 CN CN202311585952.XA patent/CN117603380B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5652348A (en) * | 1994-09-23 | 1997-07-29 | Massey University | Chromatographic resins and methods for using same |
| CN101743471A (en) * | 2007-07-13 | 2010-06-16 | 帝斯曼知识产权资产管理有限公司 | Analysis of doping compounds |
| CN102612511A (en) * | 2009-09-28 | 2012-07-25 | 肯塔基大学研究基金会 | Thiol-containing compounds for the removal of elements from contaminated milieu and methods of use |
| CN104525151A (en) * | 2014-12-02 | 2015-04-22 | 佛山市博新生物科技有限公司 | Endotoxin adsorbent used in hemoperfusion, and preparation method thereof |
| CN107200804A (en) * | 2017-06-21 | 2017-09-26 | 广州康盛生物科技有限公司 | A kind of inflammatory factor macroporous adsorbent and preparation method thereof |
| CN109575345A (en) * | 2018-12-12 | 2019-04-05 | 怀化学院 | Sulfonated divinylbenzene polymer microballoon, preparation method and applications |
| CN110041453A (en) * | 2019-04-17 | 2019-07-23 | 河海大学 | A kind of modified Amberlite XAD-4 resin and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| WEIHUA TAO, ET AL.: "Adsorption of 5-sodiosulfoisophthalic acids from aqueous solution onto poly(2-vinylpyridine) resin", 《JOURNAL OF HAZARDOUS MATERIALS》, vol. 175, 2 October 2009 (2009-10-02), pages 111 - 116, XP026809699, DOI: 10.1016/j.jhazmat.2009.09.135 * |
| 刘小红 等: "环境雌激素SERS检测的研究进展", 《光谱学与光谱分析》, vol. 40, no. 10, 31 October 2020 (2020-10-31), pages 3038 - 3047 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117603380B (en) | 2024-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rodgers et al. | Combating selective ionization in the high resolution mass spectral characterization of complex mixtures | |
| WO2019196233A1 (en) | Method for measuring contents of various endocrine disruptors in estuary sediment | |
| CN105498694A (en) | Temperature-sensitive polymer-coated metal organic framework magnetic material and application thereof | |
| CN105597713B (en) | Magnetic solid-phase extraction material and preparation method and application thereof | |
| CN105536746A (en) | Solid-phase micro-extraction capsule and application of same in detection of phenol environmental estrogen in beverage | |
| Chipuk et al. | The influence of material and mesh characteristics on transmission mode desorption electrospray ionization | |
| CN114324639B (en) | Mixed-mode weak cation solid phase extraction material and preparation method and application thereof | |
| CN117603380B (en) | Cation exchange mode polymer separation medium and preparation method and application thereof | |
| Minamisawa et al. | Fragmentations of isomeric sulfated monosaccharides using electrospray ion trap mass spectrometry | |
| CN108414637B (en) | Method for detecting volatile disinfection byproducts in water by utilizing solid phase microextraction-gas chromatography-mass spectrometry combined technology | |
| CN104502486B (en) | A kind of apply the method for methyl vanillin and ethyl vanillin in Headspace-solid phase microextraction technical measurement milk powder | |
| CN117603379A (en) | Anion exchange mode polymer separation medium and preparation method and application thereof | |
| Ahn et al. | Malononitrile as a new derivatizing reagent for high‐sensitivity analysis of oligosaccharides by electrospray ionization mass spectrometry | |
| CN112697892B (en) | Method for quantitatively detecting cyclic alkyl sulfonate component and residual oil sulfonate component in petroleum production liquid | |
| CN114200062A (en) | Method for detecting tetraethylene glycol dimethyl ether in leather | |
| CN107899557B (en) | Magnetic molecularly imprinted polymer microsphere and preparation method and application thereof | |
| CN107462651A (en) | The enrichment method of phosphate cpd in biological sample based on titanium immobilization magnetic microsphere | |
| Gao et al. | Design and application of an open tubular capillary reactor for solid-phase permethylation of glycans in glycoprotein | |
| Ba-Isa et al. | Desorption ionization mass spectrometry: Secondary ion mass spectra of phosphonium salts | |
| Prokai | Characterization of Macromolecules by Electrospray lonization Mass Spectrometry | |
| CN113603843B (en) | Limited medium-molecularly imprinted polymer and preparation method and application thereof | |
| Taljūnaitė | Eligibility Criteria for the Upper Middle Class | |
| CN110736792A (en) | Application of polypyrrole nano fibers in extraction of bisphenol F, extraction device based on application and detection method | |
| CN112240905A (en) | Analytical method for molecular composition of thioether compound in petroleum | |
| Xue et al. | Heparin‐like glycosaminoglycan/amine salt‐bridge interactions: A new potential tool for HLGAGs analysis using mass spectrometry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |