CN108794687A - A kind of molecular engram material and its application in water environment in nonsteroidal anti-inflammatory drug detection - Google Patents
A kind of molecular engram material and its application in water environment in nonsteroidal anti-inflammatory drug detection Download PDFInfo
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- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- 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
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to water environment nonsteroidal anti-inflammatory drug detection technique fields, it is related to a kind of molecular engram material and its application in the detection of water environment nonsteroidal anti-inflammatory drug, and in particular to a kind of for multi-walled carbon nanotube molecularly imprinted material on surface of nonsteroidal anti-inflammatory drug in water environment and preparation method thereof and the application in nonsteroidal anti-inflammatory drug.The present invention uses the molecular engram polymeric material for preparing gained as micro- solid phase extraction adsorbents, using micro- Solid Phase Extraction combination dispersive liquid-liquid microextraction as environmental water sample pretreatment technology, and it is used in conjunction as detector using superelevation liquid chromatography-mass spectrography, the content of loxoprofen sodium, Ketoprofen, naproxen, 5 kinds of Flurbiprofen, brufen aryl propionic non-steroid antiphlogistic objects in rapid and accurate determination water environment.
Description
Technical field
The present invention relates to water environment nonsteroidal anti-inflammatory drug detection technique field, be related to a kind of molecular engram material and its
A kind of application in the detection of environment nonsteroidal anti-inflammatory drug, and in particular to multi wall carbon for nonsteroidal anti-inflammatory drug in water environment
Nanotube surface molecular engram material and preparation method thereof and the application in nonsteroidal anti-inflammatory drug.
Background technology
Non-steroidal anti-inflammatory drugs (NSAIDs) is a kind of anti-inflammatory agent for not containing steroidal structure, has anti-inflammatory, antirheumatic, stops
Bitterly, it brings down a fever and the effects that anticoagulation, is clinically widely used in osteoarthritis, rheumatoid arthritis, a variety of fevers and various
The alleviation of pain symptom.Non-steroidal anti-inflammatory drugs is one of most commonly used medicament categories in the whole world at present.
Environment medicament residue problem is of interest by more and more people at present, these chemical combination are had confirmed in many analysis and research
Object being widely present in water and pedotheque.Non-steroidal anti-inflammatory drugs is mainly discharged into aquatic ring by human and animal's excreta
In border.Although their concentration in aquatic environment are at a fairly low (ng/L to μ g/L), continuous discharge in the environment and length
Time exposure may have an adverse effect to non-target organism.For example, the NSAIDs in industrial wastewater can induce carp
Gene in (Cyprinus carpio) and cytotoxicity, brufen and Diclofenac are in Mytilus
Huge bioaccumulation and cytological effect are shown in galloprovincialis.These are long-term existing residual in water environment
Drug is stayed to constitute potential threat to human health eventually by various modes, the non-steroidal anti-inflammatory drugs controlled in water environment has been carved not
Rong Huan.Therefore, establish environment drug residue measurement novel analysis method played in environment destiny and ecological risk it is important
Effect.It is necessary to develop a kind of sensitive and reliable analysis method, to understand its behavior, destiny, and be human health and life
State system makes accurate risk assessment.
Aquatic environment non-steroid anti-inflammatory drug is usually in extremely low concentration (ng/L to μ g/L).Although in chromatography
Huge development is achieved, but still is difficult to detect micro NSAIDs in water.Therefore, sample pretreatment process becomes extremely
It closes important.Dispersive liquid-liquid microextraction (DLLME) is a kind of simple and quick pre-sample concentration that organic compound is extracted from water sample
Method, quickly, at low cost with easy to operate, the advantages that rate of recovery is high, and enrichment factor is high.And Solid Phase Extraction (SPE) is
Typical sample-pretreating method, due to its separative efficiency height, detergent power is strong, therefore is widely used in the pre- dense of environmental sample
Contracting and purifying.
For Solid Phase Extraction, the property of adsorbent is key factor, and classical adsorbent usually has selectivity low and inhales
The shortcomings of attached energy force difference.Therefore, it is necessary that a kind of highly selective SPE adsorbents are prepared.In the past decade, molecular engram is poly-
Closing object (MIPs) is used as a kind of environmental protection, durable and reusable material to attract the concern of many researchers.In addition, MIPs
Different mal-conditions (such as high pressure, high temperature and extreme pH) have been successfully applied to, there is good biochemical stability, become separation
The ideal material of technology.However, the conventional method of production MIPs has several drawbacks in that, including template leakage, low combination ability are gentle
Slow mass transfer.It is a kind of to be synthesized using the molecular imprinted polymer on surface of virtual template in order to overcome these defects.
Invention content
Technical problem solved by the invention is to provide a kind of many walls nanotube molecular imprinted polymer on surface, the polymer
Aryl propionic non-steroid antiphlogistic in water environment can be detected.
The present invention also provides the preparation methods of the polymer.
Invention further provides the multi-walled carbon nanotube tables for aryl propionic non-steroid antiphlogistic in water environment
Application of the face molecularly imprinted polymer in detection water environment nonsteroidal anti-inflammatory drug detection.
The present invention uses the molecular engram polymeric material for preparing gained as micro- solid phase extraction adsorbents, is extracted using micro- solid phase
It takes in conjunction with dispersive liquid-liquid microextraction as environmental water sample pretreatment technology, and is used in conjunction as inspection using superelevation liquid chromatography-mass spectrography
Device is surveyed, 5 kinds of loxoprofen sodium, Ketoprofen, naproxen, Flurbiprofen, brufen arylpropionic acids in rapid and accurate determination water environment
The content of non-steroid antiphlogistic object.
The present invention is achieved in the following ways：
Multi-walled carbon nanotube surface molecular of the present invention for aryl propionic non-steroid antiphlogistic in water environment
Imprinted polymer is made of following steps：
(1) pseudo- template molecule is selected, the puppet template molecule is the compound with arylpropionic acid structure；
(2) in proportion by amino multi-wall carbon nanotube (MWNTs-NH2), pseudo- template molecule, function monomer, pore-foaming agent it is mixed
Conjunction uniformly prepares pre-polymeric mixture；A certain amount of crosslinking agent, initiator are added in the pre-polymeric mixture of gained and are mixed equal
It is even, Synthesis of Molecular Imprinting Polymers under certain condition.
Pseudo- template molecule described in step (1) is 2- phenylpropionic acids, brufen, Flurbiprofen, Ketoprofen, naproxen；
Function monomer described in step (2) is 4-vinylpridine (4-VP)；The pore-foaming agent is N, N- dimethyl formyls
Amine (DMF)；The initiator is azodiisobutyronitrile (AIBN)；Crosslinking agent is ethylene glycol dimethacrylate (EGDMA)；
The quality of amino multi-wall carbon nanotube described in step (2) is 200-300mg, and the puppet template mole is
0.5-0.6mmol, it is described puppet template molecule, function monomer, crosslinking agent molar ratio be 1：4-6：20-25；The crosslinking agent with
The volume ratio of pore-foaming agent is 1：20-1：30；The initiator quality is the 1%-2% of crosslinking agent quality；
Wherein, the method for preparing pre-polymeric mixture is：In proportion by amino multi-wall carbon nanotube, pseudo- template molecule,
Function monomer, pore-foaming agent are uniformly mixed, and are ultrasonically treated 15-30 minutes, mixture stirs 1-2 hours to obtain at 25-30 DEG C
Pre-polymeric mixture.
The condition of Synthesis of Molecular Imprinting Polymers is：Reacting liquid temperature control stirs 15- under 55-60 DEG C, nitrogen atmosphere
20 hours.
The multi-walled carbon nanotube molecular imprinted polymer on surface that the present invention synthesizes can be used for detecting arylprop in water environment
Acids nonsteroidal anti-inflammatory drug, detection use following steps：
(1) pretreatment of water sample
Collect water sample and use 0.45 μm of nylon membrane filtration, water sample with 0.1M-1M HCl adjusting pH to 5-6, and at room temperature
It is stored in plastic bottle.
(2) micro- Solid Phase Extraction (μ SPE) process
A certain amount of internal standard is added in sample obtained by step (1), is added after mixing and prepares gained molecular engram material, shake
(25-30 DEG C, 250-350rpm) is swung, liquid is filtered and discard supernatant, it is 1 that volume ratio is added in residue:100 formic acid-second
Nitrile, ultrasound, centrifugation are collected supernatant and are dried up, it is spare to obtain residue.
(3) dispersive liquid-liquid microextraction (DLLME) process
With the residue obtained in 5mL water dissolutions step (2), then a certain amount of acetonitrile and dichloroethanes, ultrasound, centrifugation is gone
Except upper water, lower layer's organic phase is dried up with nitrogen, and it is spare to obtain residue.
(4) ultra high efficiency liquid phase-mass spectrum, which is used in conjunction, measures 5 kinds of aryl propionic non-steroid antiphlogistic objects in water environment
Precision measures the residue in 100 μ L dissolving steps (3) of acetonitrile-water (50/50, v/v) solution, takes 10 μ L injection superelevation
Effect liquid phase-mass spectrum is used in conjunction in instrument and is analyzed.
Every part of sample is 500mL in step (2)；Inside it is designated as deuterated brufen or deuterated Ketoprofen or deuterated naproxen；
Molecularly imprinted polymer dosage is 50-100mg；The concussion time is 20-30min；Formic acid-acetonitrile content is 3-5mL；Ultrasonic time
For 10-20min；Centrifugal rotational speed is 10000-12000rpm；Centrifugation time is 5-10min；
Acetonitrile, dichloroethanes dosage are respectively 850-950 μ L, 800-1000 μ L in step (3)；Ultrasonic time is 5-
10min；Centrifugal rotational speed is 4000-12000rpm；Centrifugation time is 5-10min；
Step (4) includes following two processes：
(a) ultra performance liquid chromatography detaches
Water phase is pure water (A), and organic phase is acetonitrile (B), takes isocratic elution program, elution program 0-4.5min：
60% B；Flow velocity is 0.2mLmin-1, column temperature is 25-30 DEG C, and sample size is 10 μ L；
(b) Mass Spectrometer Method
Ion source is electro-spray ionization source (sources ESI), and source temperature is 120 DEG C, capillary voltage 3kV, desolventizing gas
Temperature：350 DEG C, Desolvention gas velocity 700L/hr, sweep time 0.1s, detection mode detects for more reactive ions
(MRM)。
The positive effect of the present invention is as follows：
1. molecular engram material according to the present invention in its building-up process due to introducing pseudo- template so that it overcomes often
Template leakage problem caused by regulation Preparation Method, and make it for having one kind of identical function group with pseudo- template molecule
Compound all has higher selectivity and absorption property, this for molecular engram material in the environment many kinds of substance simultaneously measure in
Application certain feasibility is provided；
2. the present invention prepares molecularly imprinted polymer using surface precipitation polymerization technology in multi-wall carbon nano-tube pipe surface, increase
Mass transfer rate of the target molecule inside the imprinted polymer so that it can from environment rapid extraction target compound；
3. the present invention use imprinted polymer as solid phase extraction adsorbents, overcome that classical adsorbent is selectively low and suction
The shortcomings that attached energy force difference；
4. the step of micro- Solid Phase Extraction and dispersive liquid-liquid microextraction combination are not only simplified sample pre-treatments by this method, also greatly
Enrichment times are increased greatly, reduce influence of the environmental matrices to measurement result, are provided for the development and application of pretreatment technology
New approaches, also for Environmental Trace medicament residue extraction, concentrate and increase new method with detaching.
Description of the drawings
Fig. 1 .MWNT-NH2With the infrared spectrogram (a) of MWNTs@MIPs；MWNTs-NH2, MWNTs@MIPs and MWNTs@
The TGA curves (b) of NIPs；The SEM image of MWNTs@MIPs (c) and MWNTs (d)；
The influence of 5 kinds of 2- phenylpropionic acid NSAIDs drug rate of recovery of ethane nitrile content pair in Fig. 2 sample solutions；
The influence of 5 kinds of 2- phenylpropionic acid NSAIDs drug rate of recovery of Fig. 3 sample pH values pair；
The influence of 5 kinds of 2- phenylpropionic acid NSAIDs drug rate of recovery of Fig. 4 eluting solvents type pair；
The influence of 5 kinds of 2- phenylpropionic acid NSAIDs drug rate of recovery of Fig. 5 eluting solvents volume pair；
The influence of 5 kinds of 2- phenylpropionic acid NSAIDs drug rate of recovery of Fig. 6 extractants type pair；
The influence of 5 kinds of 2- phenylpropionic acid NSAIDs drug rate of recovery of Fig. 7 extractants volume pair；
The influence of 5 kinds of 2- phenylpropionic acid NSAIDs drug rate of recovery of Fig. 8 dispersants pair；
The influence of 5 kinds of 2- phenylpropionic acid NSAIDs drug rate of recovery of Fig. 9 dispersants volume pair.
Specific implementation mode
In the present invention, we establish a kind of accurately and reliably 5 kinds of 2- arylpropionic acid NSAIDs assay methods, to understand
Its environment destiny and risk.For this purpose, using 2- phenylpropionic acids as virtual template, received in multi wall carbon by surface precipitation polymerization method
The molecularly imprinted polymer (MWNTs-MIP) that height combines has been synthesized on nanotube surface, and uses imprinted polymer as μ SPE
Adsorbent.It is concentrated using μ SPE-DLLME methods, extraction and purity analysis object, and it is accurate accurate to develop the progress of LC-MS/MS methods
Determine amount.This research conducts in-depth research and optimizes to the efficiency of μ SPE and DLLME.Finally, the method for exploitation is applied to
Authentic sample is analyzed.
The following examples are that the present invention is described in further detail.
(1) synthesis of multi-walled carbon nanotube molecular imprinted polymer on surface
Using 2- phenylpropionic acids as pseudo- template, 4-VP is as function monomer, and EGDMA is as crosslinking agent, and DMF is as pore
Agent synthesizes MWNTs@MIPs by precipitation polymerization method.In short, by MWNTs-NH2(200mg), 2- phenylpropionic acids
(0.5mmol), 4-VP (2mmol) and 48.0mL DMF are placed in 50mL round-bottomed flasks and mixing, supersound process 15 minutes, then
60min is stirred at 30 DEG C, obtains pre-polymeric mixture.Then in pre-polymeric mixture be added EGDMA (10mmol) and
AIBN (40mg) and mixing stir 15 hours under nitrogen atmosphere in 60 DEG C, obtain molecularly imprinted polymer.First is used after the completion of preparing
Alcohol-acetic acid (9:1, v/v) washing copolymer is to remove pseudo- template and pore-foaming agent, and the drying at 50 DEG C.
(2) collection of water sample and preprocessing process
Collect tap water respectively, river water, lake water, sewage treatment plant's Inlet and outlet water is used in combination 0.45 μm of nylon membrane filtration, water sample to use
1M HCl adjust pH to 6, and are stored in plastic bottle at room temperature.
(3) micro- solid micro-extraction-dispersive liquid-liquid microextraction (μ SPE-DLLME) is enriched with concentration process
The sample 500mL obtained by step (2) is taken, the deuterated brufens of 50ng are added into each water sample as internal standard, mixing
The molecular engram material that 50mg prepares gained is added afterwards, concussion (30 DEG C, 250rpm) 20min is abandoned with 0.45 μm of nylon membrane filtration
Remove supernatant.1% formic acid of 3mL-acetonitrile is added in residue, ultrasonic 10min centrifuges 5min in 12000rpm, supernatant is received
Collect in 10mL centrifuge tubes, it is spare to collect residue for nitrogen drying.
It is above-mentioned residue obtained with 5mL water (pH=6) dissolving, 800 μ L dichloroethanes and 900 μ L acetonitriles are rapidly injected, ultrasound
5min forms turbid solution in pipe.Then mixture is centrifuged into 5min in 12000rpm, removes upper water, lower layer's organic phase
It is dried up with nitrogen, it is spare to obtain residue.
(4) Waters AcquityTM superelevation liquid chromatograies and Xevo TM Triple Quadrupole MS/MS are utilized
Matter
Spectra system measures the concentration of 5 kinds of arylpropionic acid antiinflammatory drugs in water environment.
Chromatographic column：Waters ACQUITYBEH C18(100mm×2.1mm,1.7μm)
Mobile phase：A：Water；B：Acetonitrile
Elution program：0-4.5min：60%B
Column temperature：30℃
Flow velocity：0.2mL/min
Sample size：10μL
Ion source：Electro-spray ionization source (sources ESI)
Detection mode：More reactive ions detect (MRM)
Source temperature：120℃；Desolvation temperature：350℃
Capillary voltage：3kV
Sweep time：0.1s
5 kinds of target analytes and its interior target mass spectrometry parameters are shown in Table 1；
15 kinds of target analytes of table and its interior target Mass Spectrometry Conditions
(5) methodology validation
The calculating of matrix effect
Each water sample is acquired, by above-mentioned steps (2), (3) enrichment concentration, by above-mentioned steps (4) test sample, obtains accordingly result
A：The measurement result of each actual sample, B：A certain concentration standard solution measures gained accordingly result, C：Actual sample is added one
After determining concentration standard solution gained accordingly result, D are measured after step (3) enrichment concentration：Actual sample is rich by step (3)
Gained accordingly result is measured after a certain concentration standard solution is added after collection concentration.Then matrix effect (ME), sample preparation procedure
The rate of recovery (RE) and overall process efficiency (PE) are calculated by following formula respectively：
ME (%)=(D-A)/B × 100%
RE (%)=(C-A)/(D-A) × 100%
PE (%)=ME × RE/100
Enrichment factor (EF) is calculated by following formula：
EF=PE × 5000
Matrix effect the results are shown in Table 2, the results showed that μ SPE-DLLME programs are the effective matrix that reduces to measurement result
It influences.Enrichment factor (EF) the results are shown in Table 3.The sample preparation methods of exploitation all show higher enrichment to several water samples of research
Multiple.
(concentration of standard solution of addition is 500ng mL to matrix effect of the 25 kinds of target analytes of table in each water sample-1)
Sensitivity and the range of linearity
With the accurately weighed Ketoprofen of assay balance, naproxen, Flurbiprofen, loxoprofen sodium and brufen reference substance, use
Chromatographic grade acetonitrile dissolves reference substance, is diluted to the standard solution of series concentration, is measured by above-mentioned chromatographic condition.With a concentration of
Abscissa, it is that ordinate is returned to correspond to the ratio between response and internal standard response, obtains standard curve.Use signal-to-noise ratio method
Determining instrument detection limit (IDL) and quantitative limit (IQL).The method detection limit (LOD) and method quantitative limit (LOQ) of different water samples
It is calculated respectively by following formula：
LOD=(IDL × 100)/(PE × 5000)
LOQ=(IQL × 100)/(PE × 5000)
The standard curve range of each determinand, linear coefficient, quantitative limit, detection limit and method precision the results are shown in Table 3.
The range of linearity and quantitative limit of 35 kinds of target analytes of table detect limit, precision and enrichment times
The calculating of recovery of standard addition
By taking river water as an example, processing river water water sample is collected by above-mentioned steps (2), is added and certain density respectively waits for into the water sample
Object is surveyed, after above-mentioned steps (3) enrichment concentration, by above-mentioned steps (4) test sample, obtains accordingly result A；It acquires water sample and presses above-mentioned step
Suddenly after (3) enrichment concentration, by above-mentioned steps (4) test sample, accordingly result B is obtained；Mixed mark of a certain concentration containing each determinand is molten
Liquid presses above-mentioned steps (4) test sample, obtains accordingly result C, then the calculation formula of the rate of recovery (RE, %) is：
RE (%)=(A-B)/C × 100%
The rate of recovery that this method has investigated 3 concentration basic, normal, high, the result is shown in table 4, the rate of recovery of each determinand exists
75.93-109.38%, the rate of recovery are higher.
The recovery of standard addition of each determinand in 4 river water of table
The measurement of (6) 5 kinds of aryl propionic non-steroid antiphlogistic objects
It is collected by above-mentioned steps (2) and handles each water sample, after above-mentioned steps (3) enrichment concentration, surveyed by above-mentioned steps (4)
The ratio of response and internal standard response obtained by each substance is brought into respective mark song, the results are shown in Table 5 by sample
Measurement result (the ng L of each determinand in 5 each water sample of table-1)
The experimental results showed that：Institute's construction method is successfully applied to 5 kinds of aryl propionic non-steroid antiphlogistics in different water environments
The measurement of object.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of molecular engram material, which is characterized in that be prepared via a method which：
(1) pseudo- template molecule is selected, the puppet template molecule is the compound with arylpropionic acid structure；
(2) amino multi-wall carbon nanotube, pseudo- template molecule, function monomer, pore-foaming agent are uniformly mixed and prepare pre-polymerization in proportion
Close mixture；A certain amount of crosslinking agent, initiator are added in the pre-polymeric mixture of gained and are uniformly mixed, under certain condition
Synthesis of Molecular Imprinting Polymers；
Function monomer described in step (2) is 4-vinylpridine；The pore-foaming agent is n,N-Dimethylformamide；The initiation
Agent is azodiisobutyronitrile；Crosslinking agent is ethylene glycol dimethacrylate.
2. molecular engram material as described in claim 1, which is characterized in that pseudo- template molecule described in step (1) is 2- benzene
Base propionic acid, brufen, Flurbiprofen, Ketoprofen, naproxen.
3. molecular engram material as described in claim 1, which is characterized in that the puppet template molecule, function monomer, crosslinking agent
Molar ratio be 1：4-6：20-25.
4. molecular engram material as described in claim 1, which is characterized in that the volume ratio of the crosslinking agent and pore-foaming agent is 1：
20-1：30；The initiator quality is the 1%-2% of crosslinking agent quality.
5. molecular engram material as described in claim 1, which is characterized in that the quality of the amino multi-wall carbon nanotube is
200-300mg, the puppet template mole is 0.5-0.6mmol.
6. molecular engram material as described in claim 1, which is characterized in that the method for preparing pre-polymeric mixture is：
Amino multi-wall carbon nanotube, pseudo- template molecule, function monomer, pore-foaming agent are uniformly mixed, is ultrasonically treated 15-30 minutes, mixes
It closes object and stirs 1-2 hours at 25-30 DEG C to obtain pre-polymeric mixture.
7. application of the molecular engram material described in claim 1 in water environment in nonsteroidal anti-inflammatory drug detection.
8. the use as claimed in claim 7, which is characterized in that the nonsteroidal anti-inflammatory drug is aryl propionic non-steroid
Anti-inflammatory agent.
9. application as claimed in claim 7 or 8, which is characterized in that use following steps：
(1) pretreatment of water sample
(2) micro- solid phase extraction procedure
Internal standard is added in sample obtained by step (1), is added after mixing and prepares gained molecular engram material, concussion, filtering is simultaneously
Liquid is discarded supernatant, it is 1 that volume ratio, which is added,:100 formic acid-acetonitrile, ultrasound, centrifugation are collected supernatant and are dried up, it is standby to obtain residue
With；It is designated as deuterated brufen or deuterated Ketoprofen or deuterated naproxen in described；
(3) dispersive liquid-liquid microextraction process
With the residue obtained in water dissolution step (2), acetonitrile and dichloroethanes, ultrasound is added, centrifugation removes upper water, lower layer
Organic phase is dried up with nitrogen, and it is spare to obtain residue；
(4) ultra high efficiency liquid phase-mass spectrum, which is used in conjunction, measures 5 kinds of aryl propionic non-steroid antiphlogistic object precisions measurement second in water environment
Residue in nitrile-water (50/50, v/v) solution dissolving step (3) takes 10 μ L injection ultra high efficiencies liquid phases-mass spectrum to be used in conjunction in instrument and carry out
Analysis；
It is pure water (A) that ultra performance liquid chromatography, which detaches water phase, and organic phase is acetonitrile (B), takes isocratic elution program, elutes journey
Sequence is 0-4.5min：60%B；Flow velocity is 0.2mLmin-1, and column temperature is 25-30 DEG C, and sample size is 10 μ L；
Mass Spectrometer Method
Ion source is electro-spray ionization source (sources ESI), and source temperature is 120 DEG C, capillary voltage 3kV, desolvation temperature：
350 DEG C, Desolvention gas velocity 700L/hr, sweep time 0.1s, detection mode is that more reactive ions detect (MRM).
10. application as claimed in claim 9, which is characterized in that the acetonitrile can use methanol, ethyl alcohol, propyl alcohol, methanol-
Acetonitrile (1：1, v/v) it replaces；The dichloromethane can be replaced with chloroform.
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| CN112362797A (en) * | 2020-10-26 | 2021-02-12 | 浙江国正检测技术有限公司 | Method for detecting quinolone drugs in feed |
| CN113777184A (en) * | 2021-08-10 | 2021-12-10 | 青岛理工大学 | Analysis and detection method for five non-steroidal anti-inflammatory drugs in environmental water sample |
| CN116396496A (en) * | 2023-05-19 | 2023-07-07 | 安徽建筑大学 | Molecularly imprinted Zr-MOF fluorescent probe material and preparation method and application thereof |
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| CN112362797A (en) * | 2020-10-26 | 2021-02-12 | 浙江国正检测技术有限公司 | Method for detecting quinolone drugs in feed |
| CN113777184A (en) * | 2021-08-10 | 2021-12-10 | 青岛理工大学 | Analysis and detection method for five non-steroidal anti-inflammatory drugs in environmental water sample |
| CN113777184B (en) * | 2021-08-10 | 2023-06-02 | 青岛理工大学 | Analysis and detection method for five nonsteroidal anti-inflammatory drugs in environmental water sample |
| CN116396496A (en) * | 2023-05-19 | 2023-07-07 | 安徽建筑大学 | Molecularly imprinted Zr-MOF fluorescent probe material and preparation method and application thereof |
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