CN110102272A - A kind of novel solid phase micro extraction probe and its preparation method and application - Google Patents
A kind of novel solid phase micro extraction probe and its preparation method and application Download PDFInfo
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- CN110102272A CN110102272A CN201910291029.2A CN201910291029A CN110102272A CN 110102272 A CN110102272 A CN 110102272A CN 201910291029 A CN201910291029 A CN 201910291029A CN 110102272 A CN110102272 A CN 110102272A
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- 239000000523 sample Substances 0.000 title claims abstract description 112
- 238000002470 solid-phase micro-extraction Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 54
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 48
- 239000000835 fiber Substances 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 25
- 239000010935 stainless steel Substances 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 150000003233 pyrroles Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- -1 dimethyl siloxane Chemical class 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 206010011224 Cough Diseases 0.000 claims description 2
- 241001465754 Metazoa Species 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 19
- 238000001514 detection method Methods 0.000 abstract description 14
- 239000011159 matrix material Substances 0.000 abstract description 7
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- 238000000034 method Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 11
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 9
- 240000002234 Allium sativum Species 0.000 description 9
- 239000005899 Fipronil Substances 0.000 description 9
- CWFOCCVIPCEQCK-UHFFFAOYSA-N chlorfenapyr Chemical compound BrC1=C(C(F)(F)F)N(COCC)C(C=2C=CC(Cl)=CC=2)=C1C#N CWFOCCVIPCEQCK-UHFFFAOYSA-N 0.000 description 9
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- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 8
- 229940070721 polyacrylate Drugs 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 239000002917 insecticide Substances 0.000 description 6
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- 239000000126 substance Substances 0.000 description 5
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- 239000011550 stock solution Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
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- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000005747 Chlorothalonil Substances 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000004853 microextraction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Classifications
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- 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
-
- 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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention belongs to solid phase microextraction fields, and in particular to a kind of novel solid phase micro extraction probe and its preparation method and application.The solid phase micro extraction probe includes stainless steel fibre and coated on the surface covering on stainless steel fibre, and the surface covering is multi-walled carbon nanotube/polyaniline-polypyrrole@dimethyl silicone polymer composite coating.Solid phase micro extraction probe of the present invention has biocompatibility more preferable, anti- matrix interference ability is stronger, it is more suitable for the pre-treatment of organic matter in complex matrices, and probe of the present invention can be directly exposed to vivo biological tissue and target analytes are extracted and are enriched with.Analysis detection is carried out using probe of the present invention, not only detection limit is low, favorable reproducibility, and compared with existing commercialization fiber, extraction efficiency is higher；Meanwhile solid phase micro extraction probe preparation step of the present invention is simple and quick, preparation cost is low, prepared uniform coating thickness is controllable, and satisfactory mechanical property has fabulous reproducibility.
Description
Technical field
The invention belongs to solid phase microextraction fields, and in particular to a kind of novel solid phase micro extraction probe and preparation method thereof and
Using.
Background technique
Solid phase microextraction (SPME) technology be based on target analytes between sample substrate and extraction phase equilibrium assignmen
Sample Pretreatment Technique.Technology collection sampling, extracts, and concentration, sample introduction does not consume solvent in one, can be in different complicated bases
Body sample Green, efficiently, rapidly process specific trace materials, and can realize on-line coupling with instrument.Therefore SPME
It is widely used in environmental protection, Food Monitoring, the fields such as biomedicine.
The core of solid phase micro-extraction technique is on probe the selection of solid-phase micro-extraction coating and immobilized, the development of coating and
Preparation influences the effect of extraction, the selectivity of detection, sensitivity, service life, reproducibility and application range etc..
The coating being commercialized at present has dimethyl silicone polymer (PDMS), divinylbenzene (DVB), polyacrylate (PA) and
The single of different-thickness such as carbon molecular sieve (CAR), mixture or copolymer coated.Wherein, PDMS and PA is homogeneous polymer painting
Layer, others are porous particle polymer coating.Homogeneous polymer coating extraction selectivity is poor, typically only by increase its
Thickness increases extraction total capacity.It is total can to increase extraction by improving the porosity of coating for porous particle polymer coating
Capacity.However the solid phase micro extraction probe of commercialization uses quartz fibre as carrier more, extracting head frangibility in operating process,
And there is problems: the extraction coat type of commercialization is limited, and expensive (800~900 yuan /), extraction efficiency is inclined
It is low, the disadvantages of extraction selectivity is poor.These unfavorable factors limit solid phase micro-extraction technique further and development, thus be badly in need of
Develop more novel solid phase micro extraction coatings.
Summary of the invention
The present invention is in view of the deficiencies of the prior art, and it is an object of the present invention to provide a kind of novel solid phase micro extraction probe and its preparation side
Method and application.
For achieving the above object, the technical scheme adopted by the invention is as follows:
A kind of novel solid phase micro extraction probe, including stainless steel fibre and coated on the surface covering on stainless steel fibre,
The surface covering is multi-walled carbon nanotube/polyaniline-polypyrrole@dimethyl silicone polymer (MWCNTs/PANI-PPy@PDMS)
Composite coating.
In above scheme, the diameter of the stainless steel fibre is 0.2 ± 0.03mm, and length is 20 ± 3mm.
In above scheme, the length of the surface covering is 1~2cm, with a thickness of 6~10 μm.
The preparation method of above-mentioned novel solid phase micro extraction probe, includes the following steps:
(1) pretreatment of stainless steel fibre: one end of stainless steel fibre is cleaned by ultrasonic and is dried；
(2) multi-walled carbon nanotube aqueous dispersions are taken, deionized water is added, ultrasonic disperse adds aniline and pyrroles, is vortexed
Uniform electrolyte is obtained, two pretreated stainless steel fibres of step (1) is taken to be inserted respectively as anode and cathode,
Anode stainless steel fibre is taken out after electro-deposition in situ, is cleaned and is dried with deionized water, repeats above-mentioned electro-deposition-cleaning-baking
Dry step twice, obtains being coated with multi-walled carbon nanotube/polyaniline-polypyrrole (MWCNTs/PANI-PPy) composite coating
Solid phase micro extraction probe；
(3) step (2) preparation resultant multi-wall carbon nano-tube/poly aniline-Pt/Polypyrrole composite material fiber head is immersed in poly-
It in dimethyl siloxane toluene solution, is taken out after standing, solidification is to get to coated with the poly- pyrrole of multi-walled carbon nanotube/polyaniline-
Cough up the solid phase micro extraction probe of@dimethyl silicone polymer composite coating；
(4) aging of probe: under nitrogen protection, multi-walled carbon nanotube/polyaniline-will be coated with described in step (3)
The solid phase micro extraction probe of polypyrrole@dimethyl silicone polymer (MWCNTs/PANI-PPy@PDMS) composite coating is placed in tube furnace
Middle aging obtains the novel solid phase micro extraction probe.
In above scheme, step (1) stainless steel fibre is cleaned by ultrasonic through acetone, ethyl alcohol and ultrapure water, every time ultrasound
The time of cleaning is 30min.
In above scheme, in electrolyte described in step (2), the concentration of the multi-walled carbon nanotube is 6~12mg/mL,
The concentration of the aniline and pyrroles are 0.1mol/L.
In above scheme, step (2) electro-deposition in situ uses two electrode systems, and electrolyte depth is 1~2cm, 9~
8~10s is deposited under 12V DC electricity；Probe drying temperature and time are as follows: dry 1h at 60 DEG C~80 DEG C.
In above scheme, the concentration of PolydimethylsiloxaneIn In Toluene Solution described in step (3) is 0.4~0.6mg/mL；
The cured temperature and time are as follows: solidify 9~12h at 80 DEG C~100 DEG C.
In above scheme, the temperature and time of aging described in step (4) are as follows: aging 1h at 230 DEG C~250 DEG C.
Application of the above-mentioned novel solid phase micro extraction probe in water body, complex matrices and living body animals and plants extraction field.
Beneficial effects of the present invention: the present invention provides a kind of solid phase micro extraction probe, the probe is with having both porous particle
The MWCNTs/PANI-PPy@PDMS composite material of polymer and homogeneous polymer coating is as solid-phase micro-extraction coating, the material
Physical and chemical stability is good, good mechanical stability；Compared with simple porous particle polymer probe, probe of the present invention
Biocompatibility is more preferable, and anti-matrix interference ability is stronger, is more suitable for the pre-treatment of organic matter in complex matrices；And it can be by this
It invents the probe and is directly exposed to vivo biological tissue and target analytes are extracted and are enriched with, organism can't be made
At lethal damage；Solving porous particle polymer probe cannot be used directly for asking for the biological sample without any pre-treatment
Topic；Also solve the problems, such as that homogeneous polymerization coating loading capacity is inadequate；Analysis detection is carried out using probe of the present invention, not only
Detection limit is low, favorable reproducibility, and compared with existing commercialization fiber, extraction efficiency is higher；Meanwhile solid phase of the present invention
Micro extraction probe preparation step is simple and quick, preparation cost is low, and prepared uniform coating thickness is controllable, and mechanical performance is good
It is good, there is fabulous reproducibility.
Detailed description of the invention
Fig. 1 is the preparation flow figure of MWCNTs/PANI-PPy@PDMS composite material solid phase micro extraction probe.
Fig. 2A, 2B are the field emission scanning electron microscope that MWCNTs/PANI-PPy coating amplifies 10,000 times and 300 times respectively
Figure；Fig. 2 C is the field emission scanning electron microscope figure that MWCNTs/PANI-PPy@PDMS coating amplifies 300 times.
Fig. 3 is MWCNTs/PANI-PPy@PDMS probe and commercialization dimethyl silicone polymer (PDMS), poly dimethyl silicon
Oxygen alkane/divinylbenzene (PDMS/DVB), carbon molecular sieve/dimethyl silicone polymer (CAR/PDMS), the suction of polyacrylate (PA)
Attached effect contrast figure.
Fig. 4 is MWCNTs/PANI-PPy@PDMS and MWCNTs/PANI-PPy probe and the absorption effect for making PDMS probe by oneself
Fruit comparison diagram.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
In following embodiment and comparative example, dimethyl silicone polymer is by the basic of 184 silicon rubber of DOW CORNING SYLGARD
The mixed liquor that component and curing agent are thoroughly mixed by 10:1 weight ratio.
The preparation of 1 MWCNTs/PANI-PPy composite material solid phase micro extraction probe of comparative example
The present invention passes through electro-deposition in situ and prepares MWCNTs/PANI-PPy composite fiber head, specifically includes following step
It is rapid:
(1) pretreatment of stainless steel fibre: being 0.2mm by diameter, and length is 23cm stainless steel fibre one end successively through depth
The acetone, ethyl alcohol and ultrapure water that degree is 5cm are cleaned by ultrasonic 30min, and in 60 DEG C of dry 1h；
(2) measuring mass fraction is 10.36% multi-walled carbon nanotube aqueous dispersions 1.74mL in 40mL sample bottle, is added
Enter 18.26mL deionized water, ultrasonic disperse 10min adds 182 μ L aniline and 139 μ L pyrroles into above-mentioned dilution, is vortexed
0.5min obtains uniform electrolyte；Using two electrode systems, 5mL plastic centrifuge tube is electrolytic cell, with pretreatment in step (1)
In the electrolyte that two stainless steel fibres crossed are 1.5cm respectively as anode and cathode insertion depth, sink in 9V direct current
Anode stainless steel fibre is taken out after product 8s, is cleaned with deionized water and in 60 DEG C of dry 1h；Repeat above-mentioned electro-deposition-cleaning-baking
Twice, obtain length is 1.5cm to dry step, with a thickness of 3.9 μm of MWCNTs/PANI-PPy composite fiber head.
Before use, the needle core in 5 μ L microsyringes is substituted for above-mentioned probe, every time before under nitrogen protection,
250 DEG C of aging 20min.
The preparation of 2 PDMS solid phase micro extraction probe of comparative example
(1) pretreatment of stainless steel fibre: being 0.2mm by diameter, and length is 23cm stainless steel fibre one end successively through depth
The acetone, ethyl alcohol and ultrapure water that degree is 5cm are cleaned by ultrasonic 30min, and in 60 DEG C of dry 1h；
(2) weigh 0.5g dimethyl silicone polymer in plastic centrifuge tube, be added 1mL toluene, vortex 0.5min, stand to
Bubble completely disappears to obtain dimethyl silicone polymer dilution；
(3) by step (1) cleaning stainless steel fibre insertion depth be 1.5cm dimethyl silicone polymer dilution in, it is quiet
It is taken out after setting 5s, dries the visible drop of fiber head surface with filter paper, 100 DEG C of solidification 9h obtain PDMS solid phase micro extraction probe；
(4) aging of probe: under nitrogen protection, solid phase micro extraction probe described in step (2) is placed in tube furnace
250 DEG C of aging 1h.
Before use, the needle core in 5 μ L microsyringes is substituted for the probe after above-mentioned aging, every time using preceding in nitrogen
Under protection, 250 DEG C of aging 20min.
The preparation of 1 MWCNTs/PANI-PPy@PDMS composite material solid phase micro extraction probe of embodiment
The present invention passes through electro-deposition in situ and prepares MWCNTs/PANI-PPy composite coating, then by directly sticking method
Prepare the solid phase micro extraction probe, preparation flow such as Fig. 1, specifically includes the following steps:
(1) MWCNTs/PANI-PPy composite coating is prepared according to the method for comparative example 1；
(2) dimethyl silicone polymer dilution is prepared according to the method for comparative example 2；
It (3) is poly- the two of 1.5cm by MWCNTs/PANI-PPy composite fiber head insertion depth described in step (1)
It in methylsiloxane dilution, is taken out after standing 5s, dries the visible drop of fiber head surface with filter paper, 100 DEG C of solidification 9h,
Coating surface forms the PDMS protective layer with a thickness of 4.1 μm to get compound to MWCNTs/PANI-PPy@PDMS needed for experiment
Material solid phase micro extraction probe；
(4) aging of probe: under nitrogen protection, solid phase micro extraction probe described in step (3) is placed in tube furnace
250 DEG C of aging 1h.
Before use, the needle core in 5 μ L microsyringes is substituted for the probe after above-mentioned aging, every time using preceding in nitrogen
Under protection, 250 DEG C of aging 20min.
Fig. 2A, 2B are the field emission scanning electron microscope that MWCNTs/PANI-PPy coating amplifies 10,000 times and 300 times respectively
Figure；Fig. 2 C is the field emission scanning electron microscope figure that MWCNTs/PANI-PPy@PDMS coating amplifies 300 times, and Fig. 2 shows MWCNTs/
The surface topography of PANI-PPy and MWCNTs/PANI-PPy@PDMS coating, illustrates MWCNTs/PANI-PPy and MWCNTs/
The successful preparation of PANI-PPy@PDMS coating.
Accumulation ability of 2 solid phase micro extraction probe of embodiment to organo-chlorine pesticide and heterocyclic insecticides
Measure MWCNTs/PANI-PPy@PDMS composite material solid phase micro extraction probe and four made from the embodiment of the present invention 1
Enrichment energy of the kind commercialization extraction probe to organo-chlorine pesticide (hexachloro-benzene, Bravo), heterocyclic insecticides (Fipronil, chlorfenapyr)
Power.
Four kinds of commercialization probes are purchased from SUPELCO company, are specifically included: dimethyl silicone polymer (PDMS), thick
100 μm of degree, nonpolar probe, model 57300-U；Dimethyl silicone polymer/divinylbenzene (PDMS/DVB), it is 65 μm of thickness, double
Polarity, model 57310-U；Carbon molecular sieve/dimethyl silicone polymer (CAR/PDMS), 85 μm, bipolarity, model 57334-U；It is poly-
Acrylate (PA), 85 μm of thickness, model 57304, polarity.
Probe made from the embodiment of the present invention 1 and four kinds of commercialization extraction probes are extracted into hexachloro-benzene respectively
(hexachlorobenzene), Bravo (chlorothalonil), Fipronil (fipronil), chlorfenapyr
(chlorfenapyr) hybrid standard aqueous solution.The probe that extraction is finished again is inserted into gas chromatography-mass spectrum (GC-MS) sample introduction
Thermal desorption in mouthful analyzes the peak area of more each substance, to compare different probe to the concentration effect of different analytes.Such as figure
Shown in 3, MWCNTs/PANI-PPy@PDMS composite material solid phase micro extraction probe prepared by the present invention and PDMS/DVB probe pair
The accumulation ability of organo-chlorine pesticide and heterocyclic insecticides is suitable, and is higher than other three kinds commercializations and extracts probe.
3 MWCNTs/PANI-PPy PDMS probe of embodiment with other two kinds from manufacturing probe to organo-chlorine pesticide and heterocycle
The extracting power of insecticide compares
MWCNTs/PANI-PPy@PDMS composite material solid phase micro extraction probe made from the embodiment of the present invention 1 is measured, it is right
PDMS probe made from MWCNTs/PANI-PPy probe made from ratio 1 and comparative example 2 is to organo-chlorine pesticide (hexachloro-benzene, hundred bacterium
Clearly) and the accumulation ability of heterocyclic insecticides (Fipronil, chlorfenapyr).
By probe made from the embodiment of the present invention 1, MWCNTs/PANI-PPy probe and self-control PDMS probe extract six respectively
Chlorobenzene, Bravo, Fipronil, chlorfenapyr hybrid standard aqueous solution.In the probe insertion GC-MS injection port that extraction is finished again
Thermal desorption analyzes the peak area of more each substance, to compare different probe to the concentration effect of different analytes, such as Fig. 4 institute
Show.
Fig. 4 show the adsorption effect of MWCNTs/PANI-PPy@PDMS probe much higher than MWCNTs/PANI-PPy probe and
Make PDMS probe by oneself；Meanwhile from as the result is shown as can be seen that MWCNTs/PANI-PPy@PDMS probe and MWCNTs/PANI-
PPy probe is consistent to the extraction selectivity of each substance, and inconsistent with PDMS coating, this shows that the probe modified through PDMS only exists
It is increased on adsorption effect without the extraction selectivity for influencing original coating.
Analysis detection of 4 solid phase micro extraction probe of embodiment in the standard water sample of organo-chlorine pesticide and heterocyclic insecticides
The MWCNTs/PANI-PPy@PDMS probe and GC-MS that the present invention is prepared using embodiment 1 establish SPME-
GC-MS method.Specifically, with solid phase micro extraction probe extract the hexachloro-benzenes of various concentrations a series of, Bravo, Fipronil,
Chlorfenapyr hybrid standard aqueous solution, then analyzed through GC-MS thermal desorption, 5 groups of each condition parallel testing is a series of by what is obtained
Peak area is mapped with corresponding concentration, obtains institute's manufacturing probe to the standard curve of different analytes.
A series of preparation of various concentration hybrid standard aqueous solutions are as follows:
S1. 2mg hexachloro-benzene, 4mg Bravo, 8mg Fipronil, 2mg chlorfenapyr are weighed in 40mL sample bottle, 20mL is added
Chromatographic grade acetone solution institute reinforcing body, is prepared into the hybrid standard stock solution A of hexachloro-benzene, Bravo, Fipronil, chlorfenapyr；
S2. stock solution A 0.1mL described in S1 is taken, 9.9mL chromatography grade acetone is added, is prepared into hybrid standard stock solution B；
S3. 150 μ L of stock solution B described in S2 is taken, 14.85mL deionized water is added, is prepared into hybrid standard liquid 1.；It takes
1. 2. 7.5mL, addition 7.5mL deionized water are prepared into hybrid standard liquid to hybrid standard liquid；Hybrid standard liquid 1. 3mL is taken, is added
3. 12mL deionized water is prepared into hybrid standard liquid；Hybrid standard liquid 1. 1.5mL is taken, 13.5mL deionized water is added, is prepared into
Hybrid standard liquid is 4.；Hybrid standard liquid 4. 1.5mL is taken, 13.5mL deionized water is added, is prepared into hybrid standard liquid 5.；Take mixing
5. 6. 7.5mL, addition 7.5mL deionized water are prepared into hybrid standard liquid to titer；Hybrid standard liquid 5. 1.5mL is taken, is added
7. 13.5mL deionized water is prepared into hybrid standard liquid；Hybrid standard liquid 7. 1.5mL is taken, 13.5mL deionized water, preparation is added
Obtain hybrid standard liquid 8.；Hybrid standard liquid 1.~8. for preparation mark Qu Suoyong solution.
Standard curve, the range of linearity, the detection limit, quantitative limit for the SPME-GC-MS method that table 1 is established
Wherein y represents chromatographic peak area, and x represents spiked levels.
As shown in table 1, the range of linearity of this method is 0.001~40 μ g/L, linearly dependent coefficient 0.9944~
Between 0.9998, detection limit (S/N=3) is 0.39~2.49ng/L, and quantitative limit (S/N=10) is 1.3~8.3ng/L, wide
The range of linearity and low detection limit illustrate that the material is suitable for the detection of these pesticides.
The mark-on aqueous solution that the present invention chooses basic, normal, high three concentration is respectively measured in parallel 5 times, investigated same probe and
In a few days and in the daytime relative standard deviation (RSD%) of different probe.As shown in table 2, the RSD between same probe and different probe
Smaller (being lower than 13.8%), illustrate that this method has good reproducibility.
Reproducibility of the SPME-GC-MS method that table 2 is established in mark-on aqueous solution
Application of 5 solid phase micro extraction probe of embodiment in garlic matrix
Smash garlic bulbs to pieces homogenate, and in a series of hexachloro-benzene for wherein adding various concentrations, Bravo, Fipronil,
Chlorfenapyr standard mixed solution；The MWCNTs/PANI-PPy@PDMS probe that the embodiment of the present invention 1 is prepared is inserted directly into
It is enriched with and is extracted in mark-on garlic bulbs homogenate tissue, then analyzed through GC-MS thermal desorption, each condition parallel testing 5
Group maps a series of obtained peak areas with corresponding concentration, obtains institute's manufacturing probe to the standard curve of different analytes.
As shown in table 3, in practical matrix, the range of linearity of this method is 1~400ng g-1, linearly dependent coefficient exists
Between 0.9945~0.9993, detection limit (S/N=3) is 0.38~1.9ng g-1, quantitative limit (S/N=10) be 1.27~
6.33ng g-1；The wide range of linearity and low detection limit illustrate detection of the material suitable for the pesticide in complex matrices；It is wide
The range of linearity and the good linear coefficient of determination also illustrate that the anti-matrix pollution capacity of the material is strong, solve large biological molecule
Such as, the problem of protein, lipid etc. block porous particle polymer probe hole and influence probe effect of extracting.
Standard curve, the range of linearity, detection limit, quantitative limit of the SPME-GC-MS method that table 3 is established in mark-on matrix
Application of 6 solid phase micro extraction probe of embodiment in living body garlic
The MWCNTs/PANI-PPy@PDMS probe and GC-MS that the present invention is prepared using embodiment 1 establish living body (in
Vivo)-SPME-GC-MS method.The probe that the embodiment of the present invention 1 is prepared is inserted directly into 5 kinds of garlic bulbs and carries out richness
Collection and extraction, every kind of garlic are measured in parallel 3 times.As shown in table 4, RSD of the probe in garlic bulbs is lower than 15.3%, says
Large biological molecule in bright live plant will not pollute MWCNTs/PANI-PPy@PDMS probe and reduce its effect of extracting, also say
Clear probe does not cause plant stress reaction to generate hormone to influence its extraction ability；This method be not necessarily to garlic bulbs into
Any pre-treatment of row, and mortality will not be caused to injure biology, illustrate MWCNTs/PANI-PPy@PDMS probe bio-compatible
Property is good, and anti-matrix interference ability is strong.
Application of the in vivo-SPME-GC-MS method that table 4 is established in living body garlic
Wherein, that the numerical value in 4 bracket of table represents is RSD, and what ND was represented is that the substance is not detected.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection scope of the invention.
Claims (10)
1. a kind of novel solid phase micro extraction probe, which is characterized in that including stainless steel fibre and coated on stainless steel fibre
Surface covering, the surface covering are multi-walled carbon nanotube/polyaniline-polypyrrole@dimethyl silicone polymer composite coating.
2. novel solid phase micro extraction probe according to claim 1, which is characterized in that the diameter of the stainless steel fibre is
0.2 ± 0.03mm, length are 20 ± 3 mm.
3. novel solid phase micro extraction probe according to claim 1, which is characterized in that the length of the surface covering be 1 ~
2 cm, with a thickness of 6 ~ 10 μm.
4. the preparation method of any novel solid phase micro extraction probe of claim 1 ~ 3, which is characterized in that including walking as follows
It is rapid:
(1) pretreatment of stainless steel fibre: one end of stainless steel fibre is cleaned by ultrasonic and is dried；
(2) multi-walled carbon nanotube aqueous dispersions are taken, deionized water is added, ultrasonic disperse adds aniline and pyrroles, and vortex obtains
Uniform electrolyte takes two pretreated stainless steel fibres of step (1) to be inserted respectively as anode and cathode, through original
Anode stainless steel fibre is taken out after the electro-deposition of position, is cleaned and is dried with deionized water, repeats above-mentioned electro-deposition-cleaning-drying step
Suddenly twice, multi-walled carbon nanotube/polyaniline-Pt/Polypyrrole composite material fiber head is obtained；
(3) step (2) preparation resultant multi-wall carbon nano-tube/poly aniline-Pt/Polypyrrole composite material fiber head is immersed in poly- diformazan
It in radical siloxane toluene solution, is taken out after standing, solidification is to get poly- to multi-walled carbon nanotube/polyaniline-polypyrrole@is coated with
The solid phase micro extraction probe of dimethyl siloxane composite coating；
(4) aging of probe: under nitrogen protection, the poly- pyrrole of multi-walled carbon nanotube/polyaniline-will be coated with described in step (3)
The solid phase micro extraction probe for coughing up@dimethyl silicone polymer composite coating is placed in aging in tube furnace, and it is micro- to obtain the novel solid phase
Extract probe.
5. the preparation method according to claim 4, which is characterized in that step (1) described stainless steel fibre is through acetone, ethyl alcohol
It is cleaned by ultrasonic with ultrapure water, the time being cleaned by ultrasonic every time is 30min.
6. the preparation method according to claim 4, which is characterized in that in electrolyte described in step (2), the multi wall carbon
The concentration of nanotube is 6 ~ 12 mg/mL, and the concentration of the aniline and pyrroles are 0.1 mol/L.
7. the preparation method according to claim 4, which is characterized in that step (2) electro-deposition in situ uses two electrodes
System, electrolyte depth are 1 ~ 2 cm, deposit 8 ~ 10 s under 9 ~ 12 V direct currents；Probe drying temperature and time are as follows: 60 DEG C ~ 80
Dry 1 h at DEG C.
8. the preparation method according to claim 4, which is characterized in that dimethyl silicone polymer toluene described in step (3)
The concentration of solution is 0.4 ~ 0.6 mg/mL；The cured temperature and time are as follows: solidify 9 ~ 12 h at 80 DEG C ~ 100 DEG C.
9. the preparation method according to claim 4, which is characterized in that the temperature and time of aging described in step (4) are as follows:
1 h of aging at 230 DEG C ~ 250 DEG C.
10. any novel solid phase micro extraction probe of claim 1 ~ 3 is extracted in water body, complex matrices and living body animals and plants and is led
The application in domain.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114832800A (en) * | 2022-06-06 | 2022-08-02 | 宁波大学 | Solid phase micro-extraction probe, preparation method and application thereof in biogenic amine detection |
| CN115337670A (en) * | 2022-07-11 | 2022-11-15 | 上海交通大学 | Functionalized solid-phase microextraction probe and application thereof in tetrodotoxin in-vivo detection |
Citations (3)
| 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 |
| CN101637717A (en) * | 2009-08-28 | 2010-02-03 | 南京大学 | Fluorine-doped polyaniline solid-phase microextraction head as well as preparation method and application thereof |
| CN102294131A (en) * | 2011-06-20 | 2011-12-28 | 大连理工大学 | Electricity enhanced molecular imprinting solid phase micro-extraction method |
-
2019
- 2019-04-11 CN CN201910291029.2A patent/CN110102272B/en active Active
Patent Citations (3)
| 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 |
| CN101637717A (en) * | 2009-08-28 | 2010-02-03 | 南京大学 | Fluorine-doped polyaniline solid-phase microextraction head as well as preparation method and application thereof |
| CN102294131A (en) * | 2011-06-20 | 2011-12-28 | 大连理工大学 | Electricity enhanced molecular imprinting solid phase micro-extraction method |
Non-Patent Citations (3)
| Title |
|---|
| ALIREZA GHIASVAND, ET AL.: "A solid-phase microextraction platinized stainless steel fiber coated with a multiwalled carbon nanotube-polyaniline nanocomposite film for the extraction of thymol and carvacrol in medicinal plants and honey", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| LIANGBI CHEN, ET AL.: "Electropolymerized multiwalled carbon nanotubes/polypyrrole fiber for solid-phase microextraction and its applications in the determination of pyrethroids", 《TALANTA》 * |
| YOUHONG AI, ET AL.: "Hydrophobic coating of polyaniline-poly(propylene oxide) copolymer for direct immersion solid phase microextraction of carbamate pesticides", 《JOURNAL OF CHROMATOGRAPHY A》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114832800A (en) * | 2022-06-06 | 2022-08-02 | 宁波大学 | Solid phase micro-extraction probe, preparation method and application thereof in biogenic amine detection |
| CN114832800B (en) * | 2022-06-06 | 2023-08-01 | 宁波大学 | Solid-phase microextraction probe, preparation method and application thereof in biogenic amine detection |
| CN115337670A (en) * | 2022-07-11 | 2022-11-15 | 上海交通大学 | Functionalized solid-phase microextraction probe and application thereof in tetrodotoxin in-vivo detection |
| CN115337670B (en) * | 2022-07-11 | 2023-10-31 | 上海交通大学 | Functionalized solid-phase microextraction probe and application thereof in live detection of tetrodotoxin |
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