CN112295264B - Method for manufacturing solid phase micro-extraction probe - Google Patents
Method for manufacturing solid phase micro-extraction probe Download PDFInfo
- Publication number
- CN112295264B CN112295264B CN202011378318.5A CN202011378318A CN112295264B CN 112295264 B CN112295264 B CN 112295264B CN 202011378318 A CN202011378318 A CN 202011378318A CN 112295264 B CN112295264 B CN 112295264B
- Authority
- CN
- China
- Prior art keywords
- stainless steel
- steel wire
- solid phase
- probe
- extraction
- 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.)
- Active
Links
Classifications
-
- 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
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
A method for manufacturing a solid phase micro-extraction probe comprises the following steps: s1, depositing hydroxyl double salt on the stainless steel wire by an electrochemical method; and S2, reacting the stainless steel wire deposited with the hydroxyl double salt with an aqueous solution of 2-methylimidazole and a surfactant at room temperature, and converting the hydroxyl double salt into ZIF in situ to obtain the solid-phase microextraction probe with the ZIF-8 coating. A solid phase micro-extraction method uses the solid phase micro-extraction probe manufactured by the method to carry out solid phase micro-extraction. The method for manufacturing the SPME probe is simple and quick, and the prepared coating is compact and uniform and has better adhesive force with the carrier, so that the service life of the SPME probe can be prolonged. The SPME probe with the ZIF-8 coating can extract polycyclic aromatic hydrocarbons in an environmental water sample, has high extraction efficiency and meets the requirement of trace analysis.
Description
Technical Field
The invention relates to a solid phase microextraction technology for chemical analysis and test, in particular to a method for manufacturing a solid phase microextraction probe.
Background
Solid Phase Microextraction (SPME) integrates sampling, extraction, concentration and sample introduction, and is a novel solvent-free sample treatment technology. Compared with the traditional sample pretreatment technology, the SPME technology finishes extraction, concentration and sample introduction under the condition of no solvent, can be used together with instruments such as GC, HPLC, MS and the like, and can effectively analyze trace organic matters in a sample so as to quickly perform qualitative/quantitative analysis. Current commercial SPME probes are mainly developed and manufactured by Supelco corporation of usa, and the coatings of commercial SPME extraction probes are mainly Polydimethylsiloxane (PDMS), polyethylene glycol/polydimethylsiloxane (CAR/PDMS), Polyacrylate (PA), carbon molecular sieve/vinylbenzene (CW/DVB), and carbon molecular sieve/molecular template resin (CW/TPR). The preparation method of the coatings is that polymers are fixed on the surface of quartz fiber by methods such as illumination or heating, and the SPME probe prepared by taking the quartz fiber as a carrier has low mechanical strength and is easy to break off in the using process; the thermal stability of the coating is poor, and the recommended use temperature is low; easily swell in organic solvents, and the like. These drawbacks limit the scope of application. Therefore, probes having good (thermal, organic solvent) stability and having good mechanical strength, which are rapidly prepared using a simple method, are attracting wide attention of analysts.
Metal-Organic Frameworks (MOFs) are Organic-inorganic hybrid materials with intramolecular pores formed by self-assembly of Organic ligands (imidazole, carboxylic acid, etc.) and Metal ions (zinc, copper, iron, cobalt, etc.) through coordination bonds. Zeolite imidazole-like framework materials (ZIFs) are a subset of MOFs, and are novel MOFs with a zeolite topology formed by divalent transition metal ions and imidazole ligands. The ZIFs material not only has high stability of inorganic zeolite, but also can synthesize ZIFs with different structures by adjusting the types of organic ligands and metal ions. ZIFs not only has the advantages of adjustable pore diameter and large surface area of the MOFs material, but also has greatly improved thermal stability, chemical stability and water stability compared with the MOFs material, so that the ZIFs material can be widely applied to the fields of gas separation, adsorption, storage, catalysis and the like. Among the many ZIFs materials, ZIF-8 is most widely studied and used, and is prepared by synthesizing zinc salt and 2-methylimidazole as raw materials and methanol (or DMF) as a solvent under high temperature and high pressure conditions, wherein the synthesis methods are long in time (generally about 20 hours), and require harsh conditions (high temperature and high pressure) and use of toxic organic solvents (methanol, DMF and the like).
At present, the SPME probe is prepared by taking MOFs (ZIFs) as an adsorption material, and common methods comprise in-situ hydrothermal synthesis, physical adhesion, sol-gel, gluing and the like, and the preparation methods have the defects of long preparation time, difficulty in accurately controlling the thickness of a coating, pore size blockage by sol and the like.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
The main purpose of the present invention is to overcome the above mentioned drawbacks of the background art and to provide a method for manufacturing a solid phase microextraction probe.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for manufacturing a solid phase micro-extraction probe comprises the following steps:
s1, depositing hydroxyl double salt on the stainless steel wire by an electrochemical method;
and S2, reacting the stainless steel wire deposited with the hydroxy double salt with an aqueous solution of 2-methylimidazole and a surfactant at room temperature, and converting the hydroxy double salt into ZIF in situ to obtain the solid-phase microextraction probe with the ZIF-8 coating.
Further:
in step S1, zinc oxide and zinc acetate or zinc acetate dihydrate are used as raw materials, and deionized water is used as a solvent to prepare the (Zn, Zn) hydroxy double salt at room temperature.
In step S1, the dispersion of zinc oxide in water and the aqueous solution of zinc acetate are stirred at room temperature.
In step S1, the stainless steel wire is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum wire is used as a counter electrode, the voltage is controlled, and the deposition is performed for hundreds of seconds at room temperature, so as to obtain the stainless steel wire coated with the (Zn, Zn) hydroxyl double salt coating.
In step S2, the stainless steel wire coated with the (Zn, Zn) hydroxy double salt is immersed in a deionized water solution of 2-methylimidazole and sodium dodecylsulfate, and stirred at room temperature for several tens of seconds to convert the (Zn, Zn) hydroxy double salt into ZIF-8.
The surfactant is sodium dodecyl sulfate.
Before the step S1, the stainless steel wire is ultrasonically cleaned by ethanol and deionized water respectively.
Step S2 is followed by washing with a solvent to remove the ligand and surfactant possibly present on the surface of the stainless steel wire, and drying.
A solid phase micro-extraction method uses the solid phase micro-extraction probe manufactured by the method to carry out solid phase micro-extraction.
Further, the solid phase microextraction probe is used in conjunction with gas chromatography.
And further, taking out a push rod of the micro sample injection needle, replacing the push rod with a stainless steel capillary tube, bending one end of the stainless steel wire without the coating, inserting the end of the stainless steel wire without the coating into the stainless steel capillary tube, exposing one end of the stainless steel wire coated with the coating outside the stainless steel capillary tube to form an extraction device, and performing solid phase micro-extraction by using the extraction device.
The invention has the following beneficial effects:
according to the invention, hydroxyl double salt is deposited on the stainless steel wire by an electrochemical method, and then reacts with the aqueous solution of 2-methylimidazole and an anionic surfactant at room temperature, so that the ZIF-SPME probe can be rapidly manufactured. The method for manufacturing the SPME probe is simple and rapid (only a few minutes), and the prepared coating is compact and uniform and has good adhesive force with the carrier, so that the service life of the SPME probe can be prolonged. The SPME probe with the ZIF-8 coating can extract polycyclic aromatic hydrocarbons in an environmental water sample, has high extraction efficiency and meets the requirement of trace analysis.
The SPME probe with the layered ZIF-8 coating is manufactured by the novel process, has good selectivity on non-polar organic matters, is suitable for being combined with gas chromatography, and has stability and repeatability completely meeting the requirements of quantitative analysis.
Compared with the existing SPME probe manufacturing process, the SPME probe has the following advantages:
1. the electrochemical deposition (Zn, Zn) HDS coating can be finished within hundreds of seconds, the conversion of (Zn, Zn) HDS into ZIF-8 can be finished within tens of seconds, and the manufacturing speed is very high.
2. The (Zn, Zn) HDS coating is prepared on the stainless steel wire by an electrochemical method, the manufacturing process can be accurately controlled by adjusting voltage and deposition time, and the repeatability is good.
3. And (2) adding a surfactant during preparation of the (Zn, Zn) HDS coating, wherein the obtained ZIF with the laminated structure has larger specific surface area.
The solvents used for the preparation of (Zn, Zn) HDS and the conversion of (Zn, Zn) HDS to ZIF-8 are deionized water, and the preparation process is environment-friendly. The preparation and conversion of (Zn, Zn) HDS are carried out at room temperature, the required equipment is simple, and the energy consumption is low.
5. The stainless steel wire is used as a carrier, and the manufactured probe has good mechanical strength.
6. The prepared probe has excellent thermal stability (decomposition temperature is more than 400 ℃), and is more suitable for being used with gas chromatography compared with the existing probe.
7. Through extraction experiments on aqueous solutions of 8 polycyclic aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene and the like, the extraction effect of the probe on organic pollutants in a water sample and the extraction reproducibility are investigated. After multiple extractions, the extraction capacity is not obviously reduced, and the swelling phenomenon does not occur.
Detailed Description
The embodiments of the present invention will be described in detail below. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
The embodiment of the invention provides a method for manufacturing a solid-phase microextraction probe, which comprises the following steps:
s1, depositing hydroxyl double salt on the stainless steel wire by an electrochemical method;
and S2, reacting the stainless steel wire deposited with the hydroxyl double salt with an aqueous solution of 2-methylimidazole and a surfactant at room temperature, and converting the hydroxyl double salt into ZIF in situ to obtain the solid-phase microextraction probe with the ZIF-8 coating.
In a preferred embodiment, in step S1, the (Zn, Zn) hydroxy double salt is prepared at room temperature using zinc oxide and zinc acetate or zinc acetate dihydrate as raw materials and deionized water as a solvent.
In a preferred embodiment, in step S1, the dispersion of zinc oxide in water and the aqueous solution of zinc acetate are stirred at room temperature.
In a preferred embodiment, in step S1, a stainless steel wire is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and the voltage is controlled to deposit for hundreds of seconds at room temperature, so as to obtain the stainless steel wire coated with the (Zn, Zn) hydroxyl double salt coating.
In a preferred embodiment, the stainless steel wire coated with the (Zn, Zn) hydroxy double salt is immersed in a deionized water solution of 2-methylimidazole and sodium dodecylsulfate and stirred at room temperature for several tens of seconds to convert the (Zn, Zn) hydroxy double salt into ZIF-8 in step S2.
In a preferred embodiment, the surfactant is sodium dodecyl sulfate.
In a preferred embodiment, step S1 is preceded by ultrasonically cleaning the stainless steel wire with ethanol and deionized water, respectively.
In a preferred embodiment, step S2 is followed by removing the ligand and surfactant possibly present on the surface of the stainless steel wire by washing with a solvent, and drying.
In another embodiment, a solid phase microextraction method uses a solid phase microextraction probe made by the method of any of the preceding embodiments to perform solid phase microextraction.
In a preferred embodiment, the solid phase microextraction probe is used in conjunction with gas chromatography.
In a preferred embodiment, the push rod of the micro-sampling needle is taken out and replaced by a stainless steel capillary tube, one end of the stainless steel wire without the coating is bent and then inserted into the stainless steel capillary tube, one end of the stainless steel wire coated with the coating is exposed outside the stainless steel capillary tube to form an extraction device, and the extraction device is used for solid phase micro-extraction.
The method for manufacturing the SPME probe with the ZIF coating has the advantages of simplicity, rapidness, low cost and the like, the (Zn, Zn) hydroxyl double salt is deposited by using an electrochemical method, the thickness of the coating can be accurately controlled by changing the deposition voltage and time, and the coating is compact and uniform and has better adhesive force with a carrier. The stainless steel wire is used as a carrier, so that the mechanical strength of the extraction probe is improved. Experiments prove that the SPME probe provided by the invention can be used for extracting 8 kinds of polycyclic aromatic hydrocarbon aqueous solutions to obtain a lower detection limit, and can meet the requirements of trace analysis. The SPME probe prepared by the process has a layered ZIF-8 coating with a large specific surface area, has good selectivity on non-polar organic matters, is combined with gas chromatography, and has stability and repeatability completely meeting the requirements of quantitative analysis. Meanwhile, the probe has longer service life.
Specific embodiments of the present invention are further described below.
The specific embodiments provide a method for rapidly preparing a ZIF coated SPME probe using a hydroxy double salt. The method comprises the steps of depositing hydroxyl double salt on a stainless steel wire by an electrochemical method, and then reacting the hydroxyl double salt with an aqueous solution of 2-methylimidazole and sodium dodecyl sulfate at room temperature to quickly prepare the SPME probe with the ZIF-8 coating.
The (Zn, Zn) hydroxy double salt can be prepared at room temperature by using commercially available zinc oxide and zinc acetate as raw materials and water as a solvent. And (3) taking a stainless steel wire as a working electrode, taking a saturated calomel electrode as a reference electrode and a platinum wire as a counter electrode, controlling a certain voltage, and depositing for hundreds of seconds at room temperature to obtain the stainless steel wire coated with the (Zn, Zn) hydroxyl double-salt coating. The (Zn, Zn) hydroxy double salt can be rapidly converted into ZIF-8 by immersing the stainless steel wire coated with the (Zn, Zn) hydroxy double salt in an aqueous solution of 2-methylimidazole and sodium dodecylsulfate and stirring at room temperature for tens of seconds.
Hydroxy Double Salts (HDSs) are layered compounds consisting of cationic sheets of inorganic (organic) interlaminar anionic linkages. Usually from one divalent metal oxide (MeO) with another different (or the same) divalent cation (M)2+) Reacting to synthesize. HDS has excellent anion exchange property, and by utilizing the characteristic, hydroxyl double salt is taken as an intermediate to perform rapid anion exchange reaction with deprotonated ligand, so that MOF can be rapidly preparedS (ZIFs). Adding (anionic, cationic and nonionic) surfactant into organic ligand, and then reacting with HDS, not only can obtain layered MOFs (ZIFs), but also the surface area of the organic ligand can be improved, thereby improving the extraction capacity of the organic ligand to organic matters.
In some embodiments, a dispersion of zinc oxide in water and an aqueous solution of zinc acetate are stirred at room temperature for a period of time to provide (Zn, Zn) HDS. The method comprises the steps of taking a stainless steel wire as a working electrode, taking a saturated calomel electrode as a reference electrode and a platinum wire as a counter electrode, depositing a (Zn, Zn) HDS coating on the working electrode under optimized voltage and time, and then soaking the stainless steel wire deposited with the (Zn, Zn) HDS coating in an aqueous solution of 2-methylimidazole/anionic surfactant with a certain concentration for reaction to complete conversion of the (Zn, Zn) HDS to ZIF-8. And after the reaction is finished, taking out the stainless steel wire, cleaning the stainless steel wire by using a solvent to remove a ligand and a surfactant which may exist on the surface, and drying to obtain the stainless steel wire with the ZIF-8 coating.
In some embodiments, the extraction device is retrofitted with a 5 microliter microinjection needle: taking out the push rod of the 5 microliter micro-sampling needle, replacing with a stainless steel capillary tube with the same length, the outer diameter of 0.35mm and the inner diameter of 0.15mm, and when in use, bending the end of the stainless steel wire with the ZIF-8 coated on the surface and without the coating at a certain angle, and inserting the end into the stainless steel tube (the end coated with the coating is exposed outside the stainless steel capillary tube). Through the extraction device after the repacking, the fibre probe is convenient for changing according to the sample difference, repeatedly usable.
Examples of the invention
First, pretreatment of the carrier
The straightened stainless steel wire, 0.15mm in diameter, was ultrasonically cleaned with ethanol and deionized water for 10min, respectively, to remove any contaminants that may be present, and then dried in air.
Preparation of bis, hydroxy disalts
1. In a 20mL vial, 10mL of deionized water was added with a magneton, then 0.406g (5mmol) of zinc oxide was added and stirred rapidly for 20min to give a suspension of zinc oxide, designated as solution A.
2. 1.098g (5mmol) of zinc acetate dihydrate were weighed out and dissolved in 5mL of deionized water to obtain solution B.
3. Solution B was added to solution a with rapid stirring and then stirring was continued at room temperature for 24 hours to give a gelatinous viscous liquid indicating formation of (Zn, Zn) HDS.
Electrodeposition of tris, hydroxy bis salts
And (3) adding a proper amount of (Zn, Zn) HDS suspension into a 10mL small weighing bottle, taking a stainless steel wire as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum wire as a counter electrode, controlling the voltage to be-1.5V (relative to the reference electrode), and depositing at room temperature for 240 seconds to obtain the stainless steel wire coated with the (Zn, Zn) HDS coating.
Preparation of four, ZIF-8 coating probe
1. Preparation of transformation liquid
0.082g of 2-methylimidazole is weighed and dissolved in 10mL of deionized water, and then 0.136g of sodium dodecyl sulfate is added to obtain the ZIF-8 conversion solution.
Preparation of ZIF-8 coated Probe
The stainless steel wire coated with the hydroxybis salt was immersed in the conversion solution and stirred at room temperature for 1 minute to complete the conversion of the hydroxybis salt to ZIF-8. After completion of the reaction, the reaction mixture was washed with absolute ethanol 3 times and then dried in an oven at 120 ℃ overnight.
3. Assembly of solid phase micro-extraction device
1) Manufacturing an SPME device by using a 5 microliter micro sample injection needle;
2) taking out the stainless steel push rod of the micro sample injection needle, and replacing the stainless steel push rod with a stainless steel capillary tube with the outer diameter of 0.35mm and the inner diameter of 0.15 mm;
3) the non-coating end of the manufactured ZIF-8 coated stainless steel wire (the diameter is 0.15mm) is bent at a certain angle (the friction force between the stainless steel wire and the stainless steel capillary is increased to ensure that the stainless steel wire cannot fall off in the using process), then the non-coating part is inserted into the stainless steel capillary, and the part (about 10mm) coated with the ZIF-8 is exposed outside.
Fifth, extraction experiment
1. Before the extraction experiment, the extraction probe was aged at 280 ℃ for 2 hours at the gas chromatography injection port to remove impurities that may be present.
2. Extraction experiments were performed with 8 polycyclic aromatic hydrocarbon (naphthalene, acenaphthylene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene) aqueous solutions at a concentration of 10ppb as the simulated target.
3. Extraction conditions are as follows: 10mL of the aqueous target solution, extraction temperature of 60 ℃, time of 40min, sodium chloride addition of 2g, and stirring speed of 800 rpm.
4. Chromatographic conditions are as follows: the separation of the target was performed on an HP-5(30 m.times.250. mu.m.times.0.25 um) capillary column; the column box adopts programmed heating: the initial temperature was 80 deg.C (held for 5min) and then ramped up to 250 deg.C (held for 2min) at a rate of 10 deg.C/min.
Sample inlet temperature: no shunt sampling at 260 ℃; FID detector, temperature 300 ℃.
Carrier gas: high-purity nitrogen with the flow rate of 0.8 mL/min; hydrogen gas: the flow rate is 35 mL/min; air: 300 mL/min.
SPME extraction conditions: the optimized extraction time is 40min, the extraction temperature is 60 ℃, and the salt concentration is 20%.
Analysis conditions: the solution was analyzed at 260 ℃ for 5 min.
The background of the present invention may contain background information related to the problem or environment of the present invention and does not necessarily describe the prior art. Accordingly, the inclusion in the background section is not an admission of prior art by the applicant.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and these substitutions and modifications should be considered to fall within the scope of the invention. In the description herein, references to the description of the term "one embodiment," "some embodiments," "preferred embodiments," "an example," "a specific example," or "some examples" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope of the claims.
Claims (9)
1. A method for manufacturing a solid phase micro-extraction probe is characterized by comprising the following steps:
s1, electro-chemically depositing the (Zn, Zn) hydroxyl double salt on the stainless steel wire;
and S2, immersing the stainless steel wire with the (Zn, Zn) hydroxyl double salt electrodeposited into a deionized water solution of 2-methylimidazole and sodium dodecyl sulfate, stirring for tens of seconds at room temperature, reacting at room temperature, and converting the (Zn, Zn) hydroxyl double salt into ZIF-8 in situ to obtain the solid-phase microextraction probe with the ZIF-8 coating.
2. The method of claim 1, wherein the (Zn, Zn) hydroxy double salt is prepared at room temperature in step S1 using zinc oxide and zinc acetate as raw materials or using zinc oxide and zinc acetate dihydrate as raw materials and deionized water as a solvent.
3. The method of claim 2, wherein in step S1, the dispersion of zinc oxide in water and the aqueous solution of zinc acetate are stirred together at room temperature.
4. The method of claim 2 or 3, wherein in step S1, the stainless steel wire is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum wire is used as a counter electrode, the voltage is controlled, and the stainless steel wire is deposited at room temperature for hundreds of seconds to obtain the stainless steel wire coated with the (Zn, Zn) hydroxyl double salt coating.
5. The method of any one of claims 1 to 3, wherein step S1 is preceded by ultrasonically cleaning the stainless steel wire with ethanol and deionized water, respectively.
6. The method according to any one of claims 1 to 3, wherein step S2 is followed by removing the ligand and surfactant possibly present on the surface of the stainless steel wire by washing with a solvent and drying.
7. A solid phase microextraction method characterized in that the solid phase microextraction is carried out using the solid phase microextraction probe produced by the method according to any one of claims 1 to 6.
8. The method of claim 7, used in conjunction with gas chromatography.
9. The method of claim 7, wherein the plunger of the micro needle is removed and replaced with a stainless steel capillary, the end of the stainless steel wire without the coating layer is bent and inserted into the stainless steel capillary, the end of the stainless steel wire coated with the coating layer is exposed to the outside of the stainless steel capillary to form an extraction device, and the solid phase micro extraction is performed using the extraction device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011378318.5A CN112295264B (en) | 2020-11-30 | 2020-11-30 | Method for manufacturing solid phase micro-extraction probe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011378318.5A CN112295264B (en) | 2020-11-30 | 2020-11-30 | Method for manufacturing solid phase micro-extraction probe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112295264A CN112295264A (en) | 2021-02-02 |
| CN112295264B true CN112295264B (en) | 2022-04-12 |
Family
ID=74487384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011378318.5A Active CN112295264B (en) | 2020-11-30 | 2020-11-30 | Method for manufacturing solid phase micro-extraction probe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112295264B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114405063B (en) * | 2021-11-12 | 2023-02-24 | 河北大学 | Method for enriching and purifying diosmetin from dandelion on line |
| CN115350591A (en) * | 2022-05-03 | 2022-11-18 | 北京工业大学 | Method for preparing metal organic framework pervaporation composite membrane by hydroxyl salt induction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290307A (en) * | 2008-05-30 | 2008-10-22 | 南京大学 | Polyaniline solid phase micro- extraction head and method for making same |
| CN101530679A (en) * | 2009-02-27 | 2009-09-16 | 南开大学 | Solid phase micro-extraction stainless steel fiber and preparation method thereof |
| CN105274596A (en) * | 2015-10-30 | 2016-01-27 | 西北师范大学 | Method for preparing nano-copper coating through electrodeposition |
| CN107715843A (en) * | 2017-09-30 | 2018-02-23 | 华南理工大学 | A kind of method of the materials of micro-diplopore ZIF 8 in Fast back-projection algorithm at normal temperatures |
| CN110215914A (en) * | 2019-06-10 | 2019-09-10 | 南京大学 | A kind of solid-phase micro-extraction fibre and the preparation method and application thereof based on zeolite imidazole skeleton material ZIF-8 |
-
2020
- 2020-11-30 CN CN202011378318.5A patent/CN112295264B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290307A (en) * | 2008-05-30 | 2008-10-22 | 南京大学 | Polyaniline solid phase micro- extraction head and method for making same |
| CN101530679A (en) * | 2009-02-27 | 2009-09-16 | 南开大学 | Solid phase micro-extraction stainless steel fiber and preparation method thereof |
| CN105274596A (en) * | 2015-10-30 | 2016-01-27 | 西北师范大学 | Method for preparing nano-copper coating through electrodeposition |
| CN107715843A (en) * | 2017-09-30 | 2018-02-23 | 华南理工大学 | A kind of method of the materials of micro-diplopore ZIF 8 in Fast back-projection algorithm at normal temperatures |
| CN110215914A (en) * | 2019-06-10 | 2019-09-10 | 南京大学 | A kind of solid-phase micro-extraction fibre and the preparation method and application thereof based on zeolite imidazole skeleton material ZIF-8 |
Non-Patent Citations (2)
| Title |
|---|
| Facile Conversion of Hydroxy Double Salts to Metal-Organic Frameworks Using Metal Oxide Particles and Atomic Layer Deposition Thin Film Templates;Junjie Zhao;《Journal of the American Chemical Society》;ACS publications;20151011;13756-13759 * |
| Hierarchicallystructuredmetal–organic frameworksassembledbyhydroxydoublesalt–templatesynergywithhighspace–timeyields;Chongxiong Duan;《CrystEngComm》;20171217;1057-1064 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112295264A (en) | 2021-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112295264B (en) | Method for manufacturing solid phase micro-extraction probe | |
| Pang et al. | Development of a solid-phase microextraction fiber by chemical binding of polymeric ionic liquid on a silica coated stainless steel wire | |
| CN102814195B (en) | Load type acidic ionic liquid catalyst and preparation method and application thereof and preparation method of ethyl acetate and methyl oleate | |
| CN112316929A (en) | Covalent organic framework material, solid-phase microextraction probe, and preparation method and application thereof | |
| CN109174012B (en) | Surface-modified metal organic framework compound and preparation method and application thereof | |
| CN108311125B (en) | Solid phase micro-extraction coating based on hollow carbon nano material and preparation method thereof | |
| CN102989432A (en) | Preparation of solid-phase microextraction (SPME) fiber and extraction device assembled by same | |
| CN110215914B (en) | Zeolite imidazole framework material ZIF-8-based solid-phase microextraction fiber and preparation method and application thereof | |
| Du et al. | Template-directed fabrication of zeolitic imidazolate framework-67-derived coating materials on nickel/titanium alloy fiber substrate for selective solid-phase microextraction | |
| Zhang et al. | Covalent organic frameworks-based paper solid phase microextraction combined with paper spray mass spectrometry for highly enhanced analysis of tetrabromobisphenol A | |
| Ghani et al. | In-syringe extraction using dissolvable layered double hydroxide-polymer sponges templated from hierarchically porous coordination polymers | |
| CN112341578A (en) | Molecularly imprinted polymer coated porous silica gel chromatographic packing and preparation method thereof | |
| US9259708B2 (en) | Device and method for enhanced collection and assay of chemicals with high surface area ceramic | |
| CN109174020B (en) | Preparation method of polydopamine modified cellulose aerogel coating solid-phase microextraction fiber | |
| Mandemaker et al. | Nanoweb surface‐mounted metal–organic framework films with tunable amounts of acid sites as tailored catalysts | |
| CN103203187A (en) | A preparation method for solid film dip-coated with a novel chiral recognition agent | |
| Hussein et al. | Switching on palladium catalyst electrochemical removal from a palladium acetate–acetonitrile system via trace water addition | |
| Mao et al. | Highly efficient conversion of renewable levulinic acid to n-butyl levulinate catalyzed by sulfonated magnetic titanium dioxide nanotubes | |
| Han et al. | ZIF-8/h-BN coated solid-phase microextraction fiber via physical coating technology and sol-gel technology for the determination of nitro polycyclic aromatic hydrocarbons from water samples | |
| CN108997898B (en) | Cis-jasmone molecularly imprinted polymer coating and preparation method and application thereof | |
| Dong et al. | A solid-phase microextraction coating of sol–gel-derived perhydroxy cucurbit [6] uril and its application on to the determination of polycyclic aromatic hydrocarbon | |
| CN104874380A (en) | Graphene oxide doped molecular imprinted polymer stirring rod as well as preparation method and application thereof | |
| CN112547030A (en) | Super-crosslinked polymer nanoparticle solid-phase microextraction biocompatible probe and application thereof in-vivo analysis | |
| CN108414637B (en) | Method for detecting volatile disinfection byproducts in water by utilizing solid phase microextraction-gas chromatography-mass spectrometry combined technology | |
| CN113774447B (en) | Porphyrin-based covalent organic framework solid-phase microextraction coating prepared by one-step electrodeposition and application thereof |
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 | ||
| GR01 | Patent grant |