CN107626286A - A kind of Poly-crown ether functionalized nano-fiber material and preparation method and application - Google Patents
A kind of Poly-crown ether functionalized nano-fiber material and preparation method and application Download PDFInfo
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Abstract
A kind of application the invention discloses Poly-crown ether functionalized nano-fiber material preparation method and in the detection of urine catecholamine, its preparation method include：Prepare Poly-crown ether；Mixed after the Poly-crown ether is dissolved with base material, form mixed solution；The mixed solution is spun into Poly-crown ether functionalized nano-fiber using method of electrostatic spinning.Supermolecular mechanism of the present invention using specific Poly-crown ether functional material to catecholamine, the solid-phase extraction column for the Poly-crown ether functionalized nano-fiber and its filling that there is selective absorption to act on is designed and is prepared for using electrostatic spinning technique, not only there is good extraction effect to object Catecholamines Neurotransmitters in Blood, and most of interfering materials in urine specimen can be removed, realize the superperformance of selective extraction object Catecholamines Neurotransmitters in Blood, it is ensured that the accurate qualitative and quantitative analysis of Catecholamines Neurotransmitters in Blood in urine.
Description
Technical field
The present invention relates to urine sample analyze pre-treatment field of material technology, be related to it is a kind of according to absorption principle design can
With the Poly-crown ether functionalized nano-fiber material of selective absorption Catecholamines Neurotransmitters in Blood and its application.It is particularly a kind of poly-
Crown ether functionalized nano-fiber material and preparation method thereof and the application in the detection of urine catecholamine.
Background technology
Catecholamines Neurotransmitters in Blood mainly includes adrenaline（E), norepinephrine (NE) and dopamine (DA), it is
Important monoamine neurotransmitter in organism, basic physiological function is adjusted in vivo, transmit physiological signal, be normal physiological mistake
Important signal media in journey.Also occurs the respective change of its content in pathologic process simultaneously.Therefore, detect in biological fluid
Catecholamines Neurotransmitters in Blood for pheochromocytoma, neuroblastoma, hypertension, miocardial infarction, adrenal medella increase
The clinical diagnosis of the disease such as raw is significant, and contribute to hyperthyroidism, first to subtract, congestive heart failure, diabetes, renal function not
Entirely, the diagnosis of the disease such as hypoglycemia, it is also significant to basic medical researches such as Electrophysiologies.Currently used youngster
Tea phenol amine neurotransmitters detection method is based on high performance liquid chromatography electrochemical detector or fluorescence detector.Due to human body
Such content of material is extremely low in body fluid, and other endogenous materials often interfere with measure in the biological sample gathered so that raw
Catecholamines Neurotransmitters in Blood directly detection in thing sample does not often reach preferable detection sensitivity, it is impossible to meets accurate point
The needs of analysis.Found in the research of our early stages, some nanofibers with specific crown ether functional group, for catechol
The adsorption effect of amine sample is obvious.
The content of the invention
The present invention solves the technical problem of the preparation method for providing a kind of Poly-crown ether functionalized nano-fiber and its
Application technology, the fibrous material that can adsorb Catecholamine matter in urine sample can be prepared, for selective absorption
Object, remove stroma contaminants, it is ensured that the accuracy of target analyte detection.
In order to solve the above technical problems, one aspect of the present invention is：
A kind of Poly-crown ether functionalized nano-fiber material, it is characterised in that it is by crown ether monomer：Solvent：High polymer material：It is poly-
The ratio of weight and number for closing reagent is 5：30：10：20 are polymerized Poly-crown ether, and Poly-crown ether is again with base material using mass ratio as 5:
1-1:5 mixing, form mixed solution, and mixed solution finally is spun into Poly-crown ether functionalized nano fibre using electrospinning process
Dimension.
The polymerization agent is 2,4,6- tri hydroxy methyl phenols, bisphenol-A, double acyl chlorides, paraformaldehyde, diisocyanate, two
One kind in benzyl bromine, SA, thionyl chloride, multicondensed ethylene glycol；The solvent be 1,1,2,2- tetrachloroethanes, chloroform,
Formic acid, methanol, acetic acid, ethanol, tetrahydrofuran, N,N-dimethylformamide or dimethyl sulfoxide；It is preferred that bisphenol-A, paraformaldehyde, Asia
Chlorosulfuric acid, 1,1,2,2- tetrachloroethanes, acetic acid.
The crown ether monomer be the ether of 4- nitro benzo -18- crown-s 6,2- aminomethyl-1,2 8- crown-s 6, hexamethylene -18- crown-s 6,
4'- acetyl benzo -18- crown- 6- ethers, phendioxin 8- crown- 6- ethers, 18- crown- 6- ethers, 4'- formyl phendioxin 8- crown- 6- ethers, hexichol
And -18- crown- 6- ethers, trans- 4,5'- dinitros dibenzo-18 crown-6,4'- isocyanic acid phendioxin 8- crown-s 6,4', 4''(5'') -
Diacetyl dibenzo-18 crown-6-ether, 4- carboxyl phendioxin 8- crown- 6- ethers, 4', 4''(5'')-di-t-butyl dicyclohexyl simultaneously-
18- crown-s 6,2- (allyloxy methyl) -18- crown- 6- ethers or 2- hydroxymethyl -18- crown ethers -6；It is preferred that 4- carboxyl phendioxins 8-
Crown- 6- ethers, the ether of 4- nitro benzo-18- crown-s 6, dibenzo-18 crown-6-ether.
The high polymer material is polyoxyethylene, polyaniline, polyvinyl alcohol, polystyrene, PEN, poly-
Acrylic acid, polyacrylonitrile, poly-N-isopropyl acrylamide, XAD resins, polymethyl methacrylate or polyvinyl acetate；It is preferred that
XAD resins, polystyrene.
The cooling reagent is aluminium chloride, magnesium chloride, sodium chloride, magnesium sulfate, aluminum sulfate；It is preferred that aluminium chloride, magnesium chloride.
The base material is polyoxyethylene, polyaniline, polyvinyl alcohol, polystyrene, PEN, poly- third
Olefin(e) acid, polyacrylonitrile, poly-N-isopropyl acrylamide, polymethyl methacrylate or polyvinyl acetate.It is preferred that polyaniline, polyphenyl
Ethene, polyacrylonitrile.
The present invention further discloses the preparation method of Poly-crown ether functionalized nano-fiber material, it is characterised in that by as follows
The step of carry out:
（1）Prepare Poly-crown ether：
Take crown ether monomer to be dissolved in right amount in solvent, add high polymer material and polymerization agent, heating stirring reaction.It is cooled to room temperature
Afterwards, cooling reagent is added, and the solution is preserved into 16-24 hours at 10 DEG C, rear filtration treatment obtains solid Poly-crown ether；Wherein
Crown ether monomer：Solvent：High polymer material：The ratio of weight and number of polymerization agent is 5：30：10：20；The polymerization agent is 2,4,
6- tri hydroxy methyl phenols, bisphenol-A, double acyl chlorides, paraformaldehyde, diisocyanate, dibenzyl bromine, SA, more thionyl chloride, contracting second
One kind in glycol；The solvent is 1,1,2,2- tetrachloroethanes, chloroform, formic acid, methanol, acetic acid, ethanol, tetrahydrochysene furan
Mutter, N,N-dimethylformamide or dimethyl sulfoxide；
（2）By step（1）Poly-crown ether is with base material using mass ratio as 5:1-1:5 mixing, form mixed solution；
（3）Using method of electrostatic spinning by step（2）Mixed solution be fitted into the syringe with stainless pin, with wire connection not
Become rusty draw point and the positive pole of high voltage power supply, and away from the collection screen that connection power cathode is placed at stainless pin 20cm, regulation positive voltage is
20KV, liquor charging speed are 3mL/h, and fiber falls within aluminum and collected on screen, form mesh, and as Poly-crown ether functionalized nano is fine
Dimension.
Wherein described crown ether monomer is the ether of 4- nitro benzo -18- crown-s 6,2- aminomethyl-1,2 8- crown-s 6, hexamethylene -18-
Crown- 6,4'- acetyl benzo -18- crown- 6- ethers, phendioxin 8- crown- 6- ethers, 18- crown- 6- ethers, 4'- formyl phendioxin 8- crown-s 6-
Ether, dibenzo-18 crown-6-ether, trans- 4,5'- dinitros dibenzo-18 crown-6,4'- isocyanic acid phendioxin 8- crown-s 6,4',
4''(5'')-diacetyl dibenzo-18 crown-6-ether, 4- carboxyl phendioxin 8- crown- 6- ethers, 4', 4''(5'')-di-t-butyl two
Cyclohexyl simultaneously -18- crown-s 6,2- (allyloxy methyl) -18- crown- 6- ethers or 2- hydroxymethyl -18- crown ethers -6；It is preferred that 4- carboxyls
Phendioxin 8- crown- 6- ethers, the ether of 4- nitro benzo-18- crown-s 6, dibenzo-18 crown-6-ether.
The base material is polyoxyethylene, polyaniline, polyvinyl alcohol, polystyrene, PEN, poly- third
Olefin(e) acid, polyacrylonitrile, poly-N-isopropyl acrylamide, polymethyl methacrylate or polyvinyl acetate.
The Poly-crown ether functionalized nano-fiber material of the invention that further discloses is in preparing and adsorbing urine sample
Application in terms of Catecholamine matter.It is that Poly-crown ether functionalized nano-fiber is packed into solid-phase extraction column, net to adsorb
Change the Catecholamine matter in urine specimen.The results show：
（1）Poly-crown ether functionalized nano-fiber nearly to the adsorption rate of urine catecholamine 90%, still have more than 60% after solvent cleaning,
Be advantageous to improve the target substance detection of low concentration；
（2）After Poly-crown ether functionalized nano-fiber carries out extraction process to urine catecholamine, background impurity can be effectively removed
Influence, more can guarantee that the Accurate Determining of target substance.
In a preferred embodiment of the present invention, the crown ether monomer is the ether of 4- nitro benzo -18- crown-s 6,2- amino first
Base -18- crown-s 6, hexamethylene -18- crown-s 6,4'- acetyl benzo -18- crown- 6- ethers, phendioxin 8- crown- 6- ethers, 18- crown- 6- ethers,
4'- formyl phendioxin 8- crown- 6- ethers, dibenzo-18 crown-6-ether, trans- 4,5'- dinitros dibenzo-18 crown-6,4'- isocyanides
Sour phendioxin 8- crown-s 6,4', 4''(5'')-diacetyl dibenzo-18 crown-6-ether, 4- carboxyl phendioxin 8- crown- 6- ethers, 4',
4''(5'')-di-t-butyl dicyclohexyl-18-crown-6,2- (allyloxy methyl) -18- crown- 6- ethers or 2- hydroxymethyls -
18- crown ethers -6.
In a preferred embodiment of the present invention, the base material is polyoxyethylene, polyaniline, polyvinyl alcohol, polyphenyl
Ethene, PEN, polyacrylic acid, polyacrylonitrile, poly-N-isopropyl acrylamide, polymethyl methacrylate or
Polyvinyl acetate.
In a preferred embodiment of the present invention, the mixed volume ratio of the Poly-crown ether and the base material is 5:1-
1:5。
Possessed good effect is Poly-crown ether composite nano fiber disclosed by the invention compared with prior art：
（1）Poly-crown ether functionalized nano-fiber disclosed in this invention is with existing Poly-crown ether nanofiber in urine catecholamine
There is advantage in terms of extraction, it is higher to the extraction efficiency of target substance and more preferable to the impurity clean-up effect in matrix, it is ensured that urine
The Accurate Determining of catecholamine in liquid.
（2）Poly-crown ether functionalized nano-fiber disclosed in this invention is with existing Poly-crown ether resin material in urine catechu
There is advantage in terms of the extraction of phenol amine, it is more preferable to the clean-up effect of coexistent impurity while ensureing the high efficiency extraction of target substance.
（3）Poly-crown ether functionalized nano-fiber solid-phase extraction column disclosed in this invention and existing nanofiber extraction column
It is easy to operate compared to achievable high flux sample pre-treatments, it is with the obvious advantage.
Brief description of the drawings
The sem test collection of illustrative plates of Fig. 1 Poly-crown ether functionalized nano-fibers；
Fig. 2 A MULTI-SPE M96 microwell plates are intubated column extracting instrument；The 96 of B filling Poly-crown ether functionalized nano-fibers
Microwell plate is intubated post；The micropores of C 96 are intubated post plate；
Fig. 3 urine specimens are extracted using Poly-crown ether functionalized nano-fiber and use the front and rear comparison diagram of solvent cleaning；
Using the actual urine liquid chromatography figure contrast of Poly-crown ether functionalized nano-fiber processing under Fig. 4 different detectors；Fluoroscopic examination
The front and rear testing result contrast of actual urine extraction under device；The front and rear testing result pair of actual urine extraction under electrochemical detector
Than；
Two kinds of Poly-crown ether nanofiber posts of Fig. 5 contrast to the measurement result of actual urine；The Poly-crown ether of 1 document report is compound to be received
Rice fiber；2 be Poly-crown ether functionalized nano-fiber；
Fig. 6；Poly-crown ether resin and Poly-crown ether functionalized nano-fiber contrast to the measurement result of actual urine；1 is Poly-crown ether tree
Fat, 2 be Poly-crown ether functionalized nano-fiber.
Embodiment
Presently preferred embodiments of the present invention is described in detail below so that advantages and features of the invention can be easier to by
It will be appreciated by those skilled in the art that apparent clearly defined so as to be made to protection scope of the present invention.In the present patent application
Used reagent, raw material are by commercially available in file.Such as crown ether monomer, polymerization agent, high polymer material, base material, XAD
Resin etc. is commercially available.
The embodiment of the present invention includes：
A kind of preparation method of Poly-crown ether functionalized nano-fiber material, comprises the following steps:
（1）Prepare Poly-crown ether；Take crown ether monomer to be dissolved in right amount in solvent, add high polymer material and polymerization agent, heating stirring
Reaction.After being cooled to room temperature, cooling reagent is added, and the solution is preserved into 16-24 hours at 10 DEG C, rear filtration treatment obtains
Solid Poly-crown ether；Wherein crown ether monomer：Solvent：High polymer material：The ratio of weight and number of polymerization agent is 5：30：10：20；It is described
Crown ether monomer be the ether of 4- nitro benzo -18- crown-s 6,2- aminomethyl-1,2 8- crown-s 6, hexamethylene -18- crown-s 6,4'- acetyl benzo -
18- crown- 6- ethers, phendioxin 8- crown- 6- ethers, 18- crown- 6- ethers, 4'- formyl phendioxin 8- crown- 6- ethers, dibenzo-18 crown-6-
Ether, trans- 4,5'- dinitros dibenzo-18 crown-6,4'- isocyanic acid phendioxin 8- crown-s 6,4', 4''(5'')-diacetyl hexichol
And -18- crown- 6- ethers, 4- carboxyl phendioxin 8- crown- 6- ethers, 4', 4''(5'')-di-t-butyl dicyclohexyl-18-crown-6,2-
(allyloxy methyl) -18- crown- 6- ethers or 2- hydroxymethyl -18- crown ethers -6.The polymerization agent is 2,4,6- trihydroxy methyls
One in phenol, bisphenol-A, double acyl chlorides, paraformaldehyde, diisocyanate, dibenzyl bromine, SA, thionyl chloride, multicondensed ethylene glycol
Kind；The solvent be 1,1,2,2- tetrachloroethanes, chloroform, formic acid, methanol, acetic acid, ethanol, tetrahydrofuran, N, N- diformazans
Base formamide or dimethyl sulfoxide；The high polymer material is polyoxyethylene, polyaniline, polyvinyl alcohol, polystyrene, poly- naphthalene diformazan
Sour second diester, polyacrylic acid, polyacrylonitrile, poly-N-isopropyl acrylamide, XAD resins, polymethyl methacrylate or poly-vinegar
Sour ethene；The cooling reagent is aluminium chloride, magnesium chloride, sodium chloride, magnesium sulfate, aluminum sulfate.
（2）The Poly-crown ether and base material are dissolved separately in solvent, then mixed solution is formed with certain volume ratio；
The base material is polyoxyethylene, polyaniline, polyvinyl alcohol, polystyrene, PEN, polyacrylic acid, poly-
Acrylonitrile, poly-N-isopropyl acrylamide, polymethyl methacrylate or polyvinyl acetate.
（3）The mixed solution is spun into Poly-crown ether functionalized nano-fiber using method of electrostatic spinning.
The application technology of Poly-crown ether functionalized nano-fiber material, above-mentioned Poly-crown ether functionalized nano-fiber is packed into solid
Phase extraction column, with the Catecholamine matter in adsorption cleaning urine specimen.
Embodiment 1
5g 4- carboxyl phendioxin 8- crown-s 6 are taken, add 20g thionyl chloride, and add the polystyrene of a part（10g）With
Heated after 30mL 1,1,2,2- tetrachloroethanes.After being cooled to room temperature, aluminium chloride is added, and the solution is preserved 16 at 10 DEG C
Hour.By solution 1,1,2,2- tetrachloroethanes, methanol, and alkaline aqueous solution filtering.It is polymeric crown ether to obtain solid product.
The above-mentioned g of crown ether polymer 0.2 is taken in 50mL narrow-mouthed bottles, 6mL dimethyl sulfoxide solvents is added, is put into stirrer
It is slowly stirred at a room temperature to making it be completely dissolved (2h).Take polystyrene（PS, Mw=185000）1g in 50mL narrow-mouthed bottles,
Add dimethylformamide-tetrahydrofuran（4:6, v/v）Mixed solvent, it is put into stirrer and is slowly stirred at a room temperature to completely molten
Solve (2h), prepare 10%（w/v）PS solution 10mL.Stirring is simultaneously closed bottleneck with sealed membrane, prevents solvent from volatilizing.By poly- hat
Ether dimethyl sulphoxide solution is slowly dropped into 10%（w/v）In PS solution, uniform (about 4h) is slowly stirred at a room temperature, prepares electrostatic
Spinning solution.Take electrostatic spinning solution to be fitted into the syringe with stainless pin, stainless pin and high voltage power supply are connected with wire
Positive pole, away from stainless pin 20cm place connection power cathode collection screen.Regulation positive voltage is 20KV, and liquor charging speed is
3mL/h.Fiber falls within aluminum and collected on screen, forms mesh, as Poly-crown ether functionalized nano-fiber.Poly-crown ether functionalization is received
Rice average fibre diameter is 1569 ± 609 nm.
Embodiment 2
5g dibenzo-18 crown-6s-ether is taken, adds 20g double acyl chlorides, and adds the polystyrene of a part（10g）With
Heated after 30mL chloroforms.After being cooled to room temperature, magnesium chloride is added, and the solution is preserved 16 hours at 10 DEG C.Will be molten
Liquid chloroform, ethanol, and alkaline aqueous solution filtering.It is polymeric crown ether to obtain solid product.
The above-mentioned g of crown ether polymer 0.2 is taken in 50mL narrow-mouthed bottles, 6mL DMF solvents is added, is put into
Stirrer is slowly stirred at a room temperature to making it be completely dissolved (2h).Take polystyrene（PS, Mw=185000）1g is in the thin mouths of 50mL
In bottle, dimethylformamide-tetrahydrofuran is added（4:6, v/v）Mixed solvent, be put into stirrer be slowly stirred at a room temperature to
It is completely dissolved (2h), prepares 10%（w/v）PS solution 10mL.Stirring is simultaneously closed bottleneck with sealed membrane, prevents solvent from volatilizing.
Poly-crown ether dimethyl sulphoxide solution is slowly dropped into 10%（w/v）In PS solution, uniform (about 4h) is slowly stirred at a room temperature, is matched somebody with somebody
Electrostatic spinning solution processed.Take electrostatic spinning solution to be fitted into the syringe with stainless pin, stainless pin and height are connected with wire
The positive pole of voltage source, away from the collection screen that connection power cathode is placed at stainless pin 20cm.Regulation positive voltage is 20KV, and liquor charging is fast
Spend for 3mL/h.Fiber falls within aluminum and collected on screen, forms mesh, as Poly-crown ether functionalized nano-fiber.Poly-crown ether function
It is 1569 ± 609 nm to change nanofiber average diameter.
Embodiment 3
The ether of 5g 4- nitro benzo -18- crown-s 6 is taken, adds 20g thionyl chloride, and adds the XAD resins of a part（10g）
Heated with after 30mL tetrahydrofurans.After being cooled to room temperature, magnesium chloride is added, and the solution is preserved 16 hours at 10 DEG C.Will
Solution tetrahydrofuran, ethanol, and alkaline aqueous solution filtering.It is polymeric crown ether to obtain solid product.
The above-mentioned g of crown ether polymer 0.2 is taken in 50mL narrow-mouthed bottles, 6mL dimethyl sulfoxide solvents is added, is put into stirrer
It is slowly stirred at a room temperature to making it be completely dissolved (2h).Polyoxyethylene 1g is taken in 50mL narrow-mouthed bottles, adds dimethyl formyl
Amine-tetrahydrofuran（4:6, v/v）Mixed solvent, it is put into stirrer and is slowly stirred at a room temperature to being completely dissolved (2h), prepare 10%
（w/v）Polyoxyethylene solution 10mL.Stirring is simultaneously closed bottleneck with sealed membrane, prevents solvent from volatilizing.By Poly-crown ether dimethyl
Sulfoxide solution is slowly dropped into 10%（w/v）In polyoxyethylene solution, uniform (about 4h) is slowly stirred at a room temperature, prepares Static Spinning
Silk solution.Take electrostatic spinning solution to be fitted into the syringe with stainless pin, stainless pin and high voltage power supply are connected with wire
Positive pole, away from the collection screen that connection power cathode is placed at stainless pin 20cm.Regulation positive voltage is 20KV, and liquor charging speed is 3mL/
h.Fiber falls within aluminum and collected on screen, forms mesh, as Poly-crown ether functionalized nano-fiber.
Embodiment 4
5g 2- aminomethyl-1,2 8- crown-s 6 are taken, add 20g SA, and add the polystyrene of a part（10g）With
Heated after 30mL dimethyl sulfoxide (DMSO)s.After being cooled to room temperature, magnesium chloride is added, and the solution is preserved 16 hours at 10 DEG C.Will
Solution dimethyl sulfoxide (DMSO), ethanol, and alkaline aqueous solution filtering.It is polymeric crown ether to obtain solid product.
The above-mentioned g of crown ether polymer 0.2 is taken in 50mL narrow-mouthed bottles, 6mL dimethyl sulfoxide solvents is added, is put into stirrer
It is slowly stirred at a room temperature to making it be completely dissolved (2h).Polyaniline 1g is taken in 50mL narrow-mouthed bottles, addition dimethylformamide-
Tetrahydrofuran（4:6, v/v）Mixed solvent, it is put into stirrer and is slowly stirred at a room temperature to being completely dissolved (2h), prepare 10%（w/
v）Polyaniline solutions 10mL.Stirring is simultaneously closed bottleneck with sealed membrane, prevents solvent from volatilizing.Poly-crown ether dimethyl sulfoxide (DMSO) is molten
Liquid is slowly dropped into 10%（w/v）In polyaniline solutions, uniform (about 4h) is slowly stirred at a room temperature, prepares electrostatic spinning solution.Take
Electrostatic spinning solution is fitted into the syringe with stainless pin, stainless pin and the positive pole of high voltage power supply is connected with wire, away from not
The collection screen of connection power cathode is placed at rust draw point 20cm.Regulation positive voltage is 20KV, and liquor charging speed is 3mL/h.Fiber falls
Collected in aluminum on screen, form mesh, as Poly-crown ether functionalized nano-fiber.
Embodiment 5
The method that catecholamine in urine sample is detected based on Poly-crown ether functionalized nano-fiber selective separation enrichment：
（1）The filling of solid-phase extraction column
This experiment is used as solid-phase extraction column using the microwell plates of 1 mL 96 intubation.Packing method is as follows：Take prepared nanofiber
In right amount, intubation bottom is loaded on by several times, is compacted with the thin rod of a diameter of 0.5 mm stainless steel.The elastic preferably appropriateness of packed column, filling
Cross loose target compound to be extracted completely, then sample solution is difficult to pass through filling tension.Solid-phase extraction column divides before use
It is stand-by after not cleaned with 100 μ L methanol activation, 100 μ L ultra-pure water.
Equally take the microwell plates of 1 mL 96 intubation to be used as solid-phase extraction column, the plug carried with intubation, Poly-crown ether resin is filled
Fill out in interlude, pillar is made.Equally treated respectively with after 100 μ L methanol activates, 100 μ L ultra-pure water cleans using preceding
With.Accompanying drawing 2B and C are arranged on 96 orifice plates after illustrating 96 microwell plates intubation filling nanofiber with 96 microwell plates intubation.
（2）Urine specimen processing：Urine takes 200 μ L to add 200 μ L pH 7.8 phosphorus after 0.22 μm of water film filtering
Phthalate buffer mixes, and adds 50 μ L biphenylboronic acids 2-amino-ethyl esters（DPBA, catecholamine complexometric reagent）With 50 μ L IS
Mixed again after (200 ng/mL), treat SPE column extracting.
（3）96 microwell plates are intubated column solid phase extraction
Divide solution after taking urine process to be extracted to be intubated in right amount to 96 microwell plates in post, delay solution using positive pressure of nitrogen mode
Slowly it is forced out dropwise, adds the methanol of 50 μ L 10% and 50 μ L ultra-pure waters to clean post bed successively, then add 50 μ L eluents（1
Mol/L acetic acid）, pressurizeed with 5 mL syringes draw airs, it is slowly flowed across nanofiber elution object, collect elution
Liquid.Take 50 μ L ultra-pure waters to be added in eluent to mix, take 50 μ L to carry out high performance liquid chromatography-electrochemical or fluoroscopic examination.It is attached
Fig. 2A shows that 96 microwell plates are intubated column extracting instrument, can be very easily by solution pressure in column jecket using positive pressure of nitrogen mode
Go out, once operable 96 extraction columns, efficiency high, save time for sample pretreatment.
Poly-crown ether functionalized nano-fiber is to urine catecholamine（Norepinephrine NE；Adrenaline E；3,4- dihydroxies
Base phenyl ethylamine hydrobromic acid IS；Dopamine D A）Adsorption rate nearly 90%, solvent cleaning after still have more than 60%, data are as shown in table 1.
As shown in Figure 3, the impurity after being cleaned using solvent in urine specimen has been reduced, particularly second target material E and
At four target substance DA chromatographic peak, the larger impurity of concentration was co-exist originally, is greatly reduced through solvent cleaning rear impurity, is protected
Demonstrate,prove the Accurate Determining of target substance.
As shown in Figure 4, the not extracted direct injected of urine, interfering material is more and amount is big, it is virtually impossible to differentiates and wants
Several objects of measure；And the PFSPE that actual urine is loaded through Poly-crown ether functionalized nano-fiber（packed fiber
solid phase extraction）Sample introduction after post extraction, interfering material are eliminated mostly, three kinds of objects and a kind of internal standard
Material is all high-visible.As can be seen here, the PFSPE pillars of Poly-crown ether functionalized nano-fiber filling not only extract to object imitates
Fruit is good, and can remove most interfering material, embodies the characteristic of good selective extraction object.
The cleaning agent of table 1. influences on the absorb-elute of catecholamine
Embodiment 6
Contrast experiment
By Poly-crown ether functionalized nano-fiber disclosed in this invention and the existing Poly-crown ether nanofiber of document report and gather
Crown Ether Resin solid-phase extraction column carries out the extraction and cleaning of catecholamine in urine, as a result sees accompanying drawing 5-6.It was found that document report has
Poly-crown ether nanofiber to E enrichment purification problem be present, this nanofiber is very low to E recovery rate after cleaning（It is shown in Table
2）, but E position chromatographic peak is higher in actual urine（As shown in accompanying drawing 5）, this explanation coexistent impurity, which, not to be cleaned up.
And the result after Poly-crown ether functionalized nano-fiber enrichment purification disclosed in this invention is preferable, E position chromatographic peak is normal, together
Result difference very little obtained by the multiple parallel laboratory test of one sample, test result also with most of normal value phases reported in the literature
Meet.And extracted with existing Poly-crown ether resin solid phase extraction column and find that extraction of the Poly-crown ether resin material to E in urine is too high,
The coexistent impurity in urine may also be extracted simultaneously, also have absorption to other impurity for going out peak position in addition, so
Still there is larger interference in the urine after being extracted using Poly-crown ether resin, Poly-crown ether functionalization not as disclosed in the present invention is received
The enrichment good purification of rice fiber.
Compared with the material that two kinds have been reported, Poly-crown ether functional nano-fiber disclosed in this invention is in urine catechol
Extraction efficiency is higher in the pre-treatment of amine, and impurity removal effect is even more better than the Poly-crown ether nanofiber having been reported and poly- hat
Ether resin material.And it is shorter to have the pre-treatment time concurrently, can high flux batch processing urine specimen the advantages that.
The catecholamine that the cleaning agent of table 2. adsorbs on the Poly-crown ether composite nano fiber of document report, which elutes, to be influenceed
Existing Poly-crown ether nanofiber（See reference document Liqin chen, et al. Analytical and
Bioanalytical chemistry, 2016,408：4987-4994.）；
Existing Poly-crown ether resin（See reference document M. Lee, et al. Journal of chromatography. A,
2007; 1160 :340-344.）；
Conclusion：
（1）Poly-crown ether functionalized nano-fiber nearly to the adsorption rate of urine catecholamine 90%, still have more than 60% after solvent cleaning,
Be advantageous to improve the target substance detection of low concentration；
（2）After Poly-crown ether functionalized nano-fiber carries out extraction process to urine catecholamine, background impurity can be effectively removed
Influence, more can guarantee that the Accurate Determining of target substance.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
The equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, it is included within the scope of the present invention.
Claims (6)
1. a kind of Poly-crown ether functionalized nano-fiber material, it is characterised in that it is made up of Poly-crown ether, base material, wherein poly-
The mass ratio of crown ether and base material is 5:1-1:5, Poly-crown ether composite nano fiber average diameter is 1569 ± 609 nm；
Wherein described base material is polyoxyethylene, polyaniline, polyvinyl alcohol, polystyrene, PEN, poly- third
Olefin(e) acid, polyacrylonitrile, poly-N-isopropyl acrylamide, polymethyl methacrylate or polyvinyl acetate；
Described Poly-crown ether be by crown ether monomer, solvent, high polymer material and polymerization agent score ratio by weight be 5：30：10：
20 are polymerized Poly-crown ether；
The crown ether monomer is the ether of 4- nitro benzo -18- crown-s 6,2- aminomethyl-1,2 8- crown-s 6, hexamethylene -18- crown-s 6,4'-
Acetyl benzo -18- crown- 6- ethers, phendioxin 8- crown- 6- ethers, 18- crown- 6- ethers, 4'- formyl phendioxin 8- crown- 6- ethers, dibenzo -
18- crown- 6- ethers, trans- 4,5'- dinitros dibenzo-18 crown-6,4'- isocyanic acid phendioxin 8- crown-s 6,4', 4''(5'')-two
Acetyl dibenzo-18 crown-6-ether, 4- carboxyl phendioxin 8- crown- 6- ethers, 4', 4''(5'')-di-t-butyl dicyclohexyl simultaneously-
18- crown-s 6,2- (allyloxy methyl) -18- crown- 6- ethers or 2- hydroxymethyl -18- crown ethers -6；
The solvent is 1,1,2,2- tetrachloroethanes, chloroform, formic acid, methanol, acetic acid, ethanol, tetrahydrofuran, N, N- diformazans
Base formamide or dimethyl sulfoxide；
The high polymer material is polyoxyethylene, polyaniline, polyvinyl alcohol, polystyrene, PEN, polypropylene
Acid, polyacrylonitrile, poly-N-isopropyl acrylamide, XAD resins, polymethyl methacrylate or polyvinyl acetate；
The polymerization agent be 2,4,6- tri hydroxy methyl phenols, bisphenol-A, double acyl chlorides, paraformaldehyde, diisocyanate, dibenzyl bromine,
SA, thionyl chloride or multicondensed ethylene glycol.
2. a kind of preparation method of Poly-crown ether functionalized nano-fiber material, it is characterised in that carried out by the steps:
（1）Prepare Poly-crown ether：
Take crown ether monomer to be dissolved in right amount in solvent, add high polymer material and polymerization agent, heating stirring reaction；
After being cooled to room temperature, cooling reagent is added, and the solution is preserved into 16-24 hours at 10 DEG C, rear filtration treatment obtains
Solid Poly-crown ether；Wherein crown ether monomer：Solvent：High polymer material：The ratio of weight and number of polymerization agent is 5：30：10：20；
Wherein described polymerization agent is 2,4,6- tri hydroxy methyl phenols, bisphenol-A, double acyl chlorides, paraformaldehyde, diisocyanate, two
One kind in benzyl bromine, SA, thionyl chloride, multicondensed ethylene glycol；
The solvent is 1,1,2,2- tetrachloroethanes, chloroform, formic acid, methanol, acetic acid, ethanol, tetrahydrofuran, N, N- diformazans
Base formamide or dimethyl sulfoxide；
The high polymer material is polyoxyethylene, polyaniline, polyvinyl alcohol, polystyrene, PEN, polypropylene
Acid, polyacrylonitrile, poly-N-isopropyl acrylamide, XAD resins, polymethyl methacrylate or polyvinyl acetate；
The cooling reagent is aluminium chloride, magnesium chloride, sodium chloride, magnesium sulfate or aluminum sulfate；
（2）By step（1）Poly-crown ether is with base material using mass ratio as 5:1-1:5 mixing, form mixed solution；
（3）Using method of electrostatic spinning by step（2）Mixed solution be fitted into the syringe with stainless pin, with wire connection not
Become rusty draw point and the positive pole of high voltage power supply, and away from the collection screen that connection power cathode is placed at stainless pin 20cm, regulation positive voltage is
20KV, liquor charging speed are 3mL/h, and fiber falls within aluminum and collected on screen, form mesh, and as Poly-crown ether functionalized nano is fine
Dimension.
3. the preparation method of Poly-crown ether functionalized nano-fiber material described in claim 2, it is characterised in that the crown ether monomer
For the ether of 4- nitro benzo -18- crown-s 6,2- aminomethyl-1,2 8- crown-s 6, hexamethylene -18- crown-s 6,4'- acetyl benzo -18- crown-s 6-
Ether, phendioxin 8- crown- 6- ethers, 18- crown- 6- ethers, 4'- formyl phendioxin 8- crown- 6- ethers, dibenzo-18 crown-6-ether, trans- 4,
5'- dinitros dibenzo-18 crown-6,4'- isocyanic acid phendioxin 8- crown-s 6,4', 4''(5'')-diacetyl dibenzo -18- crown-s
6- ethers, 4- carboxyl phendioxin 8- crown- 6- ethers, 4', 4''(5'')-di-t-butyl dicyclohexyl-18-crown-6,2- (allyloxys
Methyl) -18- crown- 6- ethers or 2- hydroxymethyl -18- crown ethers -6.
4. the preparation method of Poly-crown ether functionalized nano-fiber material described in claim 2, it is characterised in that base material used
It is different for polyoxyethylene, polyaniline, polyvinyl alcohol, polystyrene, PEN, polyacrylic acid, polyacrylonitrile, poly- N-
Propylacrylamide, polymethyl methacrylate or polyvinyl acetate.
5. the Catecholamine matter in absorption urine sample is prepared of Poly-crown ether functionalized nano-fiber material described in claim 1
The application of aspect.
6. the application described in claim 5, it is characterised in that load the Poly-crown ether functionalized nano-fiber described in claim 1
Into solid-phase extraction column, with the Catecholamine matter in adsorption cleaning urine specimen.
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| CN108469489A (en) * | 2018-02-12 | 2018-08-31 | 东南大学 | A kind of highly polar matter selective separation enrichment pretreatment reagent kit and its application |
| CN109709239A (en) * | 2019-01-28 | 2019-05-03 | 天津医科大学 | A kind of detection method using the online pre-treatment urine sample of Poly-crown ether functionalized nano-fiber |
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| CN104020167A (en) * | 2014-06-19 | 2014-09-03 | 天津医科大学 | Method for detecting iodine in sample by utilizing polypyrrole nano fiber membrane |
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| CN108469489A (en) * | 2018-02-12 | 2018-08-31 | 东南大学 | A kind of highly polar matter selective separation enrichment pretreatment reagent kit and its application |
| CN112368405A (en) * | 2018-07-06 | 2021-02-12 | 莫赛尔科技有限责任公司 | Methods and compositions for recovering lithium from liquid solutions using nanoparticles |
| US11993827B2 (en) | 2018-07-06 | 2024-05-28 | Moselle Technologies, Llc | Methods and compositions for recovery of lithium from liquid solutions with nanoparticles |
| CN109709239A (en) * | 2019-01-28 | 2019-05-03 | 天津医科大学 | A kind of detection method using the online pre-treatment urine sample of Poly-crown ether functionalized nano-fiber |
| CN110530958A (en) * | 2019-08-30 | 2019-12-03 | 烟台富美特信息科技股份有限公司 | A kind of food inspection electrochemical detector |
| CN110530958B (en) * | 2019-08-30 | 2021-06-15 | 烟台富美特信息科技股份有限公司 | Electrochemical detector for food detection |
| CN111545172A (en) * | 2020-05-11 | 2020-08-18 | 清华大学 | Supported adsorbent and preparation method and application thereof |
| CN111545172B (en) * | 2020-05-11 | 2021-05-28 | 清华大学 | Supported adsorbent and preparation method and application thereof |
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