CN101497034B - Solid phase extraction method based on nylon nano fiber film and extractor - Google Patents
Solid phase extraction method based on nylon nano fiber film and extractor Download PDFInfo
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- CN101497034B CN101497034B CN2009100280069A CN200910028006A CN101497034B CN 101497034 B CN101497034 B CN 101497034B CN 2009100280069 A CN2009100280069 A CN 2009100280069A CN 200910028006 A CN200910028006 A CN 200910028006A CN 101497034 B CN101497034 B CN 101497034B
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Abstract
The invention provides solid-phase extraction technology based on a nylon nanometer fibrous membrane and an extraction device thereof. The fibrous membrane is prepared by taking nylon as a raw material and adopting the electrostatic spinning method; the fiber is smooth or porous in surface, and the diameter is between 10 and 1,000nm, and the thickness is between 1 and 20mu m; the technology and the device are suitable for the pre-treatment of biological samples such as water samples, soil, blood, animal tissues, plants and the like, and can extract and enrich the target substances in micro and trace quantities. A small connection pipe(2) of the extraction device is connected with a sample pipe(1) and a collection pipe(3), wherein the middle part of the small connection pipe(2) is provided with a membrane fixed screen, and the nylon nanometer fibrous membrane is arranged and fixed on the screen; and the back end of the sample pipe(1) is closely matched with the front end of the small connection pipe(2), and the back end of the small connection pipe(2) is closely matched with the front end of the collection pipe(3), so that the pipes of the extraction device can be conveniently separated according to operational need. The solid-phase extraction technology and the extraction device thereof related to the invention have the advantages of high efficiency, quickness, stability, the environment friendly realization of the pre-treatment of the samples, easy operation, and simple equipment.
Description
Technical field
It is the solid phase extraction techniques of spe medium with the nylon nano fiber film that the present invention's design relates to a kind of, and corresponding extraction equipment, belongs to analysis technical field.
Background technology
The monitoring of object is concerning the life and health every field, as medical diagnosis on disease, clinical monitoring, medicament research and development, food security, environmental monitoring, legal medical expert's calibrating, the inspection of contraband drugs etc. in the sample.Yet biological sample is a complex system, and coexisting substances wherein is of a great variety, complex shape, character is different, target substance content is atomic.Analyze and detect the composition and the content of these trace even trace target substance, separation and enrichment object are the necessary conditions of high-sensitivity detection effectively.Statistics shows that the sample pretreatment time accounts for 60～80% of The whole analytical process in the biological sample mensuration, this shows the monitoring of object in the sample, be not to lack accurate instrument and equipment, but sample pre-treatments time and effort consuming, make testing result can not be in time, accurately obtain, can not satisfy the needs of social development and people's lives.
Traditional sample-pretreating method (liquid-liquid extraction, resin adsorption, Soxhlet extraction etc.) because environmental pollution, loaded down with trivial details consuming time, be difficult for the many limitations of automation, can not meet the demands, SPE (Solid phase extraction, SPE) technology has obtained significant progress at numerous areas since the later stage seventies comes out.Replace traditional liquid-liquid extraction gradually abroad and become the reliable and effective method of sample pre-treatments.But the SPE scantling mostly is micron order at present, micropore and the limited active group of kind that absorption/enrichment relies on material surface to gather, its adsorption desorption functional efficiency of the chemical analysis of these materials and pattern feature limits, adsorption capacity, selectivity and desorption and regeneration performance also do not reach desired level.
Since the nineties in last century, nanometer material science became a new branch of material science, nanofiber became the research focus in forward position.Compare with other methods (as dry spinning, wet spinning, melt spinning etc.) that prepare nanofiber, the advantage of electrospinning is mainly reflected in and can stably prepares the fiber of diameter at Nano grade, and with low cost, the technological process of equipment is simple, the liquid-solid phase disengaging time is short.
The high-specific surface area of nano material can provide the action site of enormous quantity, lays a good foundation for efficient separation, extraction and enrichment.Fiber-based material is simple and easy to do than particle and powder body material aspect material preparation and subsequent device making, and the adsorption desorption performance is more superior.
Because nanofiber only diameter is nano level, length is that micron, millimeter are longer even, can be made into the goods of variforms such as yarn, line, fabric, film, felt, and still keep the characteristic of nano material, more flexible during use, have the potentiality of the novel absorption material of developing excellent performance.Nanofiber has big specific area, stronger and object interaction ability is arranged, to the adsorption capacity height of object, reaching the effect balance time also significantly reduces, can be efficiently, apace sample is carried out preliminary treatment, the nano fibrous membrane consumption is few and can reuse economical and convenient.
SPE medium raw material of the present invention is a nylon, nylon (Nylon) is being commonly called as of polyamide, the intensity of nylon fiber, elasticity all are better than general fiber greatly, excellent acid and alkali resistance are insoluble to character such as common solvent such as alcohol, ether, acetone and provide feasibility for its pre-treatment that is applied to complex biological sample; Water insoluble, but can be by water infiltration, to the big affinity of low pole or nonpolar target substance, for its SPE medium as high bioaccumulation efficiency provides guarantee.Nylon is a kind of chemical products commonly used, and is cheap and easy to get with its raw material as the preparation electro spinning nanometer fiber membrane, is convenient to industrial productionization from now on.
Summary of the invention
Technical problem: the objective of the invention is to overcome that existing sample-pretreating method complex operation is time-consuming, extraction efficiency is low or shortcoming such as extraction yield instability, solid phase extraction techniques and the corresponding extraction equipment of a kind of novel and effective based on nylon nano fiber film is provided.Utilize the strong adsorption capacity of nanostructured surface, bioaccumulation efficiency is high and stable, and consumption of organic solvent is few, and environmental friendliness can be handled multiple biological specimen, and is easy and simple to handle, with low cost.
Technical scheme: solid phase extraction techniques and corresponding extraction equipment based on nylon nano fiber film provided by the invention are achieved by the following technical solution:
1, the structure of extraction equipment
Device comprises tool lid sample cell, connects tubule and collecting pipe, connects tubule and connects sample cell and collecting pipe; There is a film fixed grit at the middle part that connects tubule, and nylon nano fiber film is mounted and fixed on promptly that this is online; The rear end of tool lid sample cell closely matches with the front end that is connected tubule, connects the rear end of tubule and the front end of collecting pipe and closely matches, and also can conveniently separate during action need.Nylon nano fiber film is raw material with nylon, prepares with method of electrostatic spinning, and fiber surface is smooth or porous, and diameter is 10～1000nm, and tunica fibrosa thickness is 1～20 μ m.
The disposable processing sample volume of aforesaid extraction equipment is 1～10mL, to the more volume sample can adding up property extraction and enrichment.
2, based on the solid phase extraction techniques of nylon nano fiber film
This method comprises the steps:
1) according to the volume of pending sample liquid, select to be fit to the tool lid sample cell and the collecting pipe of specification, nylon nano fiber film is installed on the extraction equipment, handle with the activation solvent,
2) pending sample liquid is placed tool lid sample cell, whole extraction equipment is put into centrifuge, the centrifugal sample solvent that makes flows in the collecting pipe by film, and the target substance in the pending sample liquid is then at the tunica fibrosa surface enrichment, and this film plays the effect of SPE;
3) change collecting pipe, in tool lid sample cell, add eluting solvent, the object of enrichment on the nylon nano fiber film is eluted in the collecting pipe, carry out follow-up analyzing and testing.
The preparation method of nylon nano fiber film is: with nylon and solvent, ultrasonic concussion or magnetic agitation obtain electrospinning solution; Control electrospinning condition and time are so that the tunica fibrosa that makes has required fibre diameter, voidage and film thickness; Nylon nano fiber film is placed on 60～80 ℃ of placement 6～24h in the vacuum drying chamber, removes residual solvent wherein; Described solvent is single solvent or the mixed solvent in formic acid, carrene, a toluene, phenol, calcium chloride-methyl alcohol saturated solution, phenmethylol, glacial acetic acid, the ethylene glycol, or added the single or mixed solvent of surfactant, solubilizer or pH conditioning agent, nylon mass concentration therein is 10～70%.
Described nylon is nylon 6, nylon 66, nylon 11, nylon 12, NYLON610, nylon 612, nylon 1010, nylon 46, nylon 7, nylon 9, nylon 13, new nylon 6I, one or more in nylon 9 T, nylon MXD 6 and the modification of nylon.
Solid phase extraction techniques and corresponding extraction equipment based on nylon nano fiber film provided by the invention, be applicable to the pre-treatment of biological samples such as water body example, soil, blood, animal tissue, plant, to the target substance of trace in the sample and trace extract, enrichment.
Beneficial effect: compare with existing various abstraction techniques, provided by the inventionly be based on the solid phase extraction techniques of nylon nano fiber film and the advantage of extraction equipment:
1) because the specific area of nanofiber is huge, stronger and target molecule interaction force, this technology is only used the spe medium (0.5～5mg) of minute quantity, sorption extraction efficient just can reach more than 80%, and extraction efficiency favorable reproducibility (RSD＜10%, n=6), be 10～1000 to target substance enrichment multiple.
2) target substance be since material molecule two chemical potential energy differences in the homophase not, from a phase (liquid phase, being sample liquid) amount of transferring to another phase (solid phase, i.e. nylon nano fiber film) can reach balance in sufficiently long action time, need not other energy source, in the Membrane Extraction, as long as with in the nylon nano fiber film charging apparatus accessory, use common desk centrifuge low-speed centrifugal, can finish the enrichment and the wash-out of target substance in the sample, easy and simple to handle, equipment is simple.
3) mass transfer velocity of nylon nano fiber film is fast, only needs with seldom (0.1～1mL) solvent by centrifugal force, can elute target substance, compares with existing solid phase extraction, can save the process that organic solvent volatilizes, and effectively avoids environmental pollution; Compare with existing SPME method, loading capacity is big, and the extraction equilibrium time is short, can handle the sample of larger volume, is particularly useful for containing the sample of trace target substance, can finish the sample treatment overall process in the 20min.
Description of drawings
Fig. 1 solid-phase extraction device schematic diagram of the present invention.
The fiber sem photograph of Fig. 2 embodiment of the invention 1.
The fiber sem photograph of Fig. 3 embodiment of the invention 2.
The fiber sem photograph of Fig. 4 embodiment of the invention 3.
The specific embodiment
Solid-phase extraction device based on nylon nano fiber film comprises tool lid sample cell 1, connects tubule 2 and collecting pipe 3, connects tubule 2 and connects sample cell 1 and collecting pipe 3; There is a film fixed grit at the middle part that connects tubule 2, and nylon nano fiber film is mounted and fixed on promptly that this is online; The rear end of tool lid sample cell 1 closely matches with the front end that is connected tubule 2, connects the rear end of tubule 2 and the front end of collecting pipe 3 and closely matches, and also can conveniently separate during action need.Nylon nano fiber film is raw material with nylon, prepares with method of electrostatic spinning, and fiber surface is smooth or porous, and diameter is 10～1000nm, and tunica fibrosa thickness is 1～20 μ m.
This method comprises the steps:
1) according to the volume of pending sample, select to be fit to the sample cell and the collecting pipe of specification, nylon nano fiber film is installed on the extraction equipment, use the appropriate solvent activation processing.
2) pending sample liquid is placed sample cell, whole extraction equipment is put into centrifuge, the centrifugal sample solvent that makes flows in the collecting pipe by film, and the object in the sample liquid is then at the tunica fibrosa surface enrichment, and this film plays the effect of SPE;
3) change collecting pipe, in sample cell, add the eluting solvent (mixture of acid, alkali, organic solvent or aforementioned each solvent) of 0.1～1mL, the object of enrichment on the film is eluted in the collecting pipe, carry out follow-up analyzing and testing.
The preparation method of aforesaid nylon nano fiber film is: with nylon and solvent, ultrasonic concussion or magnetic agitation obtain electrospinning solution; Control electrospinning condition and time are so that the tunica fibrosa that makes has required fibre diameter, voidage and film thickness; Nylon nano fiber film is placed on 60～80 ℃ of placement 6～24h in the vacuum drying chamber, removes residual solvent wherein.
As above the solvent described in the preparation method is formic acid, carrene, a toluene, phenol, calcium chloride-methyl alcohol saturated solution, phenmethylol, glacial acetic acid, ethylene glycol etc., can be single solvent or mixed solvent wherein, or added the single or mixed solvent of surfactant, solubilizer or pH conditioning agent, nylon mass concentration therein is 10～70%.
As above the electrospinning condition of regulating or controlling described in the preparation method comprises the composition of electrospinning solution and concentration, voltage, collection distance and time, ambient humidity.
The as above tunica fibrosa described in the preparation method, its fiber surface is smooth or porous, and diameter is 10～1000nm, and tunica fibrosa thickness is 1～20 μ m.
As above the nylon described in the preparation method is nylon 6, nylon 66, nylon 11, nylon 12, NYLON610, nylon 612, nylon 1010, nylon 46, nylon 7, nylon 9, nylon 13, new nylon 6I, one or more in nylon 9 T, nylon MXD 6 and the modification of nylon.
Further specify the present invention by following examples, but claim of the present invention is not limited only to embodiment.
Embodiment 1:
Sample: environmental water sample sample volume: 1ml target substance: diethylstilbestrol
With nylon 6 is raw material, and formic acid is solvent, and the mass concentration of nylon 6 is 25%, and magnetic agitation obtains electrospinning solution, and electrospinning becomes nano fibrous membrane, and film thickness is 10 μ m.Fiber surface is smooth, and diameter is 200～500nm.
Take by weighing the 1.5mg nano fibrous membrane extraction equipment of packing into, acetonitrile → water → acetonitrile → water (each 200 μ l) activation washing, sample moves into sample cell, the centrifugal 3min of 1000rpm, target substance is enriched on the nano fibrous membrane, and acetonitrile 100 μ l wash-outs are enriched in the diethylstilbestrol on the nanofiber, after measured, calculate extraction efficiency and be 99.0% (RSD=2.1%, n=6).
Embodiment 2:
Sample: plasma in rabbit sample volume: 3ml target substance: Docetaxel
With nylon 6 is raw material, and formic acid is solvent, and the mass concentration of nylon 6 is 44%, and magnetic agitation obtains electrospinning solution, and electrospinning becomes nano fibrous membrane, and film thickness is 15 μ m.Fiber surface is smooth, and diameter is 200～700nm.
Blood sample collection, centrifugal treating obtains blood plasma, dilutes 10 times, gets plasma sample.
Take by weighing the 1.5mg nano fibrous membrane extraction equipment of packing into, acetonitrile → water (each 200 μ l) activation washing, sample moves into sample cell, the centrifugal 3min of 2000rpm, target substance is enriched on the nano fibrous membrane, is enriched in Docetaxel on the nanofiber with acetonitrile 200 μ l wash-outs, after measured, calculate extraction efficiency and be 92.5% (RSD=5.7%, n=6).
Embodiment 3:
Sample: environmental water sample sample volume: 20ml target substance: Methyl Benzene-o-dicarboxylate
With nylon 66 is raw material, and formic acid/metacresol (v/v=3/2) is a solvent, and the mass concentration of nylon 66 is 30%, and the heating magnetic agitation obtains electrospinning solution, and electrospinning becomes nano fibrous membrane, and film thickness is 3 μ m.Fiber surface is smooth, and diameter is 100～1000nm.
Take by weighing the 1.5mg nano fibrous membrane extraction equipment of packing into, acetone → water → acetone → water → acetonitrile → water → acetonitrile → water (each 200 μ l) activation washing, sample moves into sample cell (10mL/ time) at twice, centrifugal 1000 (rpm), each centrifugal 3min, target substance is enriched on the nanofiber, with methyl alcohol 200 μ l wash-outs, after measured, calculate extraction efficiency and be 90.2% (RSD=6.2%, n=6).
Claims (3)
1. the solid-phase extraction device based on nylon nano fiber film is characterized in that this device comprises tool lid sample cell (1), connects tubule (2) and collecting pipe (3), connects tubule (2) and connects tool lid sample cell (1) and collecting pipe (3); There is a film fixed grit at the middle part that connects tubule (2), and nylon nano fiber film is mounted and fixed on promptly that this is online; The rear end of tool lid sample cell (1) closely matches with the front end that is connected tubule (2), connects the rear end of tubule (2) and the front end of collecting pipe (3) and closely matches, and also can conveniently separate during action need;
Nylon nano fiber film is raw material with nylon, prepares with method of electrostatic spinning, and fiber surface is smooth or porous, and diameter is 10～1000nm, and tunica fibrosa thickness is 1～20 μ m.
2. the SPE method based on nylon nano fiber film is characterized in that this method comprises the steps:
1) according to the volume of pending sample liquid, select to be fit to the tool lid sample cell (1) and the collecting pipe (3) of specification, nylon nano fiber film is installed on the extraction equipment, handle with the activation solvent,
2) pending sample liquid is placed tool lid sample cell, whole extraction equipment is put into centrifuge, the centrifugal sample solvent that makes flows in the collecting pipe by film, and the target substance in the pending sample liquid is then at the tunica fibrosa surface enrichment, and this film plays the effect of SPE;
3) change collecting pipe, in tool lid sample cell, add eluting solvent, the object of enrichment on the nylon nano fiber film is eluted in the collecting pipe, carry out follow-up analyzing and testing;
The preparation method of nylon nano fiber film is: with nylon and solvent, ultrasonic concussion or magnetic agitation obtain electrospinning solution; Control electrospinning condition and time are so that the tunica fibrosa that makes has required fibre diameter, voidage and film thickness; Nylon nano fiber film is placed on 60～80 ℃ of placement 6～24h in the vacuum drying chamber, removes residual solvent wherein; Described solvent is single solvent or the mixed solvent in formic acid, carrene, a toluene, phenol, calcium chloride-methyl alcohol saturated solution, phenmethylol, glacial acetic acid, the ethylene glycol, or added the single or mixed solvent of surfactant, solubilizer or pH conditioning agent, nylon mass concentration therein is 10～70%.
3. the SPE method based on nylon nano fiber film as claimed in claim 2 is characterized in that described nylon is nylon 6, nylon 66, nylon 11, nylon 12, NYLON610, nylon 612, nylon 1010, nylon 46, nylon 7, nylon 9, nylon 13, nylon 6I, one or more in nylon 9 T, nylon MXD 6 and the modification of nylon.
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| CN101947393A (en) * | 2010-08-23 | 2011-01-19 | 东南大学 | Split-type nanometer fibre solid-phase extraction column and application thereof |
| CN102338713B (en) * | 2011-07-13 | 2012-12-26 | 东南大学 | Method for simultaneous extraction of a plurality of target substances with different polarity in sample |
| CN102353571B (en) * | 2011-09-20 | 2013-07-10 | 苏州东奇生物科技有限公司 | Viscous biological sample purifier and pre-processing method of viscous biological sample |
| CN103061046A (en) * | 2012-12-29 | 2013-04-24 | 浙江大东南集团有限公司 | Method for manufacturing PA6 porous nanofiber composite membrane |
| CN103163254B (en) * | 2013-02-04 | 2014-11-26 | 国家海洋局天津海水淡化与综合利用研究所 | Method of trace quantity persistent organic pollutant in enrichment and separation seawater |
| CN103614916B (en) * | 2013-11-20 | 2016-02-17 | 苏州东奇生物科技有限公司 | A kind of SPE composite nano-fiber material preparation method |
| CN103816695B (en) * | 2014-02-25 | 2015-10-07 | 东南大学 | The solid phase extraction of phenols endocrine disruptors in a kind of sample |
| CN106669446A (en) * | 2017-01-06 | 2017-05-17 | 宁波大学 | SVOCs solid-phase extraction membrane |
| CN108383289A (en) * | 2018-05-03 | 2018-08-10 | 长春工程学院 | Utilize the device and method of heavy metal in magnetic Nano material treated sewage |
| CN109212010A (en) * | 2018-09-05 | 2019-01-15 | 东南大学 | A kind of sample detection methods of simplicity fast high-flux |
| CN110652749B (en) * | 2019-09-29 | 2021-09-24 | 华中师范大学 | Composite nanofiber online micro solid-phase extraction column and preparation method thereof |
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| CN1806880A (en) * | 2005-12-19 | 2006-07-26 | 东南大学 | Solid phase micro-extraction device based on nanometer fiber |
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| CN1806880A (en) * | 2005-12-19 | 2006-07-26 | 东南大学 | Solid phase micro-extraction device based on nanometer fiber |
| CN1928527A (en) * | 2006-09-15 | 2007-03-14 | 东南大学 | Functional nano-fiber based method for extracting and enriching pollutants in water |
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| JP特开2000-95861A 2000.04.04 |
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