CN102288473B - On-line coupling system for dynamic liquid-liquid solid imprinted microextraction-liquid phase chromatogram and application thereof - Google Patents
On-line coupling system for dynamic liquid-liquid solid imprinted microextraction-liquid phase chromatogram and application thereof Download PDFInfo
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Abstract
The invention discloses an on-line coupling system for a dynamic liquid-liquid solid imprinted microextraction-liquid phase chromatogram, which comprises a magnetic agitator, a water bath bottle, an extracting bottle, a draft tube, a peristaltic pump, a high-pressure six-way switching valve, a molecularly imprinted solid phase extracting material, a high-pressure six-way sample valve, a quantifying cup, a sample needle, a liquid phase chromatographic pump, a chromatographic column, a detector, a liquid phase chromatogram and the like. Through the coupling of a dynamic liquid-liquid solid imprinted microextracting device and the liquid phase chromatogram, the on-line overall processes of the preenrichment, the extraction, the desorption, the separation and the detection of a target analyte in a water phase sample are achieved. By using the system, the universality of liquid-liquid extraction, the high selectivity and the high enrichment capability of a molecularly imprinted solid phase microextraction technique, the efficient separation capability and the high sensitivity of the liquid phase chromatogram are combined; the analysis degree of automation is improved; the analysis time is shortened; the accuracy and the precision are improved; and the system can be effectively applied to the analysis and the detection of a trace organic matter in a complicated sample.
Description
Technical field
The invention belongs to analytical chemistry sample pre-treatments field, be specifically related to design and analysis and the application of the liquid-solid trace micro-extraction of a kind of dynamic fluid flow-liquid chromatography on-line coupled system, be applicable to online pre-service, extraction, desorb, the separation and detection of trace organic substance in the complex samples such as environment, food, medicine, biology.
Background technology
Liquid-liquid extraction (liquid-liquid-extraction, LLE) is a kind of traditional universal abstraction technique, and its using method is simple, and applicability is wide, is particularly suitable for extraction and the enrichment of apolar substance in the aqueous sample.But because the selectivity of liquid-liquid extraction mainly determines therefore do not have high specific and extract and separate selectivity by the partition factor of analyte at organic phase and water.When being used for the complex system sample analysis, extract will contain a large amount of nonpolar matrix chaff interferences, thus the accuracy of impact analysis method.
Solid phase micro-extraction technique (solid phase microextraction, SPME) is that centralized procurement sample, extraction, concentrated, sample introduction are in a kind of microminiaturized Sample Pretreatment Technique of one.Thereby the most frequently used solid-phase microextraction form is the fixing little extraction probe of solid phase that forms mutually that has extraction and enrichment performance at the elongated fibers surface-coated at present.Complicated along with analysis system, the solid-phase microextraction that needs the development high selectivity is phase fixedly.Molecularly imprinted polymer (molecularly imprinted polymer, MIP) is the polymkeric substance synthetic take certain compound molecule as template, and template molecule is had specific recognition capability.Molecularly imprinted polymer can be improved the selectivity of solid-phase microextraction as coating, efficiently separation, enrichment target molecule from complex sample.Yet the intermolecular force between most molecularly imprinted polymer recognition sites and the template molecule is take hydrogen bond as main, and when being used for the aqueous sample pre-treatment, its recognition capability can be subject to the intensive polar solvent interference such as water, reduces extracting power and selectivity.On the other hand, at present micro-extraction technique generally is by specific interface with gas chromatography or liquid chromatography coupling, realize online desorb and separate, but can't realize pre-service, extraction, desorb, separation and detection overall process online.
The liquid-phase micro-extraction and the molecular blotting solid phase microextraction combined apparatus that use at present need to increase a hollow-fibre membrane usually in order to isolate organic phase and water, and all be the extraction form of using off-line, carry out online desorb by special-purpose desorption pool again, or directly adopt after the offline mode desorb again sample introduction.Disclose a kind of molecular engram solid micro-extraction-hollow fiber liquid-phase micro-extraction combined apparatus, method and application such as Chinese patent application CN101637668A, wherein relate to the molecular blotting solid phase microextraction probe and insert in the hollow-fibre membrane chamber of loading organic solvent, place again extraction flask.This method required time length, complex operation, error are large, and unfavorable and subsequent analysis technology coupling realizes on-line analysis.
Summary of the invention
The object of the invention is intended to overcome liquid-liquid-solid trace micro-extraction technique off-line and stirs extraction and be subject to the shortcoming that the hollow membrane obstruction causes equilibration time length, designing one can be with object in the flow pattern aqueous phase extracted sample, accelerate between water and the organic phase, mass transfer rate between organic phase and the fixing phase, extraction time is short, the organic solvent use amount is few, robotization control, highly sensitive, realize the aqueous sample pre-service, extraction, desorb, the whole process of separation and detection is online, versatility in conjunction with liquid-liquid extraction, the high selectivity of molecular engram micro-extraction technique, high accumulation ability, and the high score of liquid chromatography is from ability and high sensitivity, reduce personal error, improved the liquid-solid trace micro-extraction of dynamic fluid flow of preci-sion and accuracy-liquid chromatography on-line coupled system.
The objective of the invention is by realizing by the following technical solutions:
The liquid-solid trace micro-extraction of a kind of dynamic fluid flow-liquid chromatography on-line coupled system, it comprises:
(A) the liquid-solid trace micro-extraction device of dynamic fluid flow: it comprises the magnetic stirring apparatus for heating water bath and stirring, be fixed on the bubbler on the stirrer, the extraction flask of water and organic phase is housed, be used for stirring the magnetic stir bar of aqueous sample, be used for importing and deriving the drainage tube of organic phase, be used for driving the peristaltic pump of organic phase, be used for the molecular blotting solid phase microextraction material that high pressure six direction changeover valves that stream switches and two ends connect polyetheretherketone pipe thereon and are used for realizing the micro-extraction function;
In the liquid-solid trace micro-extraction of dynamic fluid flow process, the molecular blotting solid phase microextraction material that is connected on described high pressure six direction changeover valves links to each other with drainage tube, bubbler is placed on the magnetic stirring apparatus, extraction flask is immersed in the bubbler, organic extraction phase and aqueous sample are in immiscible up and down stratification state in extraction flask, insert in the upper phase organic extraction mutually and import drainage tube and derive drainage tube, organic phase is drawn through deriving drainage tube, then flow through in order molecular blotting solid phase microextraction material in the described polyetheretherketone pipe, peristaltic pump, get back in the extraction flask upper organic phase finally by importing drainage tube, thereby realize circulating extraction;
(B) liquid-chromatography apparatus: it comprises high pressure six-way injection valve, quantitative ring, sample introduction needle, chromatographic column, detecting device and high pressure liquid phase pump; Wherein, quantitatively encircling two ends is connected on the high pressure six-way injection valve;
Described polyetheretherketone pipe and described quantitative ring be mutually isolation in extraction process, then is in connected state in dynamic desorption/chromatographic separation process; After the liquid-solid trace micro-extraction of dynamic fluid flow process is finished, be written into stripping liquid by sample introduction needle, switch high pressure six direction changeover valves and the high pressure six-way injection valve that is connected with quantitative ring, after this system enters dynamic desorption/chromatographic separation process, the stripping liquid that is written into by sample introduction needle is pushed by the mobile phase that the high pressure liquid phase pump drives, and solid-phase microextraction material, chromatographic column and the detecting device in the quantitative ring in the high pressure six-way injection valve of flowing through successively, high pressure six direction changeover valves is formed on the moving desorb of linear flow, separation, detection stream.
This system with high pressure six direction changeover valves, a high pressure six-way injection valve as the connection maincenter, with the liquid-solid trace micro-extraction device of dynamic fluid flow, stripping liquid quantitatively encircles and liquid chromatography couples together, and realizes that the overall process of pre-separation, extraction, desorb, stratographic analysis of trace materials in the aqueous sample is online.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
The liquid-solid trace micro-extraction of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, described organic phase and water are immiscible, and its relative density compares less than 0.8 with water.
The liquid-solid trace micro-extraction of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, described extraction flask has transparent long-neck structure, and the eck internal diameter is 0.5-2cm.
The liquid-solid trace micro-extraction of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, described extraction flask is test tube or volumetric flask.
The liquid-solid trace micro-extraction of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, the peristaltic tube in the described peristaltic pump is the hose materials of tolerance organic solvent, internal diameter is 0.5-2.0mm;
The liquid-solid trace micro-extraction of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, described peristaltic tube is polyvinyl chloride pipe.
The liquid-solid trace micro-extraction of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, the connecting pipe in described cycling extraction loop and drainage tube are the polyetheretherketone pipe of internal diameter 0.25mm.
The liquid-solid trace micro-extraction of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, described organic extraction is in the state of circulating in the extraction loop, whole dynamic extraction time and mobile rate of extraction guarantee that all organic extract liquids circulate once at least, and the organic solvent volume needs greater than the closed circuit dead volume.
The liquid-solid trace micro-extraction of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, described molecular blotting solid phase microextraction material are to scribble in the good integral post of the hollow tube of fixing phase and permeability any one on elongated fibers, particulate, stirring rod, the wall.
The liquid-solid trace micro-extraction of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, described quantitative ring body for loading stripping liquid is long-pending to be 100 μ L.
The operation of this system comprises that liquid-liquid-solid three phase dynamic micro-extraction process, dynamic desorption process separate testing process with liquid chromatography: the conversion of liquid-liquid-solid three phase dynamic micro-extraction process and dynamic desorption process can be by switching the high pressure six-way injection valve and high pressure six direction changeover valves are realized simultaneously; The dynamic desorption process is separated testing process and be need not operation with liquid chromatography, automatically realize conversion; In liquid-liquid-solid three phase dynamic micro-extraction process, the high pressure six-way injection valve is in the LOAD state, and fixedly polyetheretherketone pipe and the cycling extraction stream of phase link to be mounted with molecular engram; In the dynamic desorption process, the high pressure six-way injection valve is in the INJECT state, and being mounted with fixedly, polyetheretherketone pipe and the liquid chromatography stream of phase link.
The liquid-solid trace micro-extraction of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, described stripping liquid can select to be different from according to the Optimal Experimental of desorption condition the solvent of chromatogram flow phase.
The liquid-solid trace micro-extraction device of dynamic fluid flow according to the present invention-liquid chromatography on-line coupled system, described sample volume per sample character are adjusted such as source, object sensitivity, equilibration time etc.
The liquid-solid trace micro-extraction device of dynamic fluid flow of the present invention and have the following advantages at least with on-line coupled system that liquid chromatography forms:
1) carry out liquid-liquid extraction under heating water bath and high-speed stirred, mass transfer rate is fast, and equilibration time is short.
2) use in the liquid-solid extraction process to circulate the extraction mode and replace and stir the extraction mode, reduced the organic solvent use amount, be easy to realize on-line coupling.
3) can increase easily volume, surface area or the permeability of molecular blotting solid phase microextraction material, Effective Raise fixedly phase extracting power and shorten extraction time, thereby the sensitivity of the method for raisinging, quickening analysis speed.
4) whole stripping liquids are injected in the chromatographic column the full sample introduction of realize target desorb thing, raising method sensitivity and reduced detection limit.
5) overall process adopts Mechanical Driven and software control, and automaticity is high, reduces sample contamination and loss.
6) integrate pre-separation, extraction, desorb, separation and detection, reduced manual operations, can Effective Raise method precision and accuracy.
7) can select different materials, multi-form fixedly phase according to object character, widen applicability and the range of application of liquid-liquid-solid micro-extraction technique.
In specific embodiment, utilize the liquid-solid trace micro-extraction of dynamic fluid flow provided by the invention-liquid chromatography on-line coupled system to detect 5 kinds of estrogen having analyzed in urine sample and the milk.Native system fixing can also use except molecular engram material other to have the material of extraction ability mutually, but this Apparatus and system is not limited in this preferred application, also can be widely used in online pre-service, extraction, desorb, the separation and detection of trace object in the complex samples such as environment, food, medicine, biology.
Description of drawings
Fig. 1 is the stream connection figure of the liquid-solid trace micro-extraction of dynamic fluid flow provided by the invention-liquid chromatography on-line coupled system.
Wherein, 1: derive drainage tube 2: organic extraction phase 3: aqueous sample 4: bubbler 5: magnetic stirring apparatus 6: import drainage tube 7: magnetic stir bar 8: peristaltic pump 9: high pressure six direction changeover valves 10: molecular blotting solid phase microextraction material 11: polyetheretherketone pipe 12: chromatographic column 13: detecting device 14: sample introduction needle 15: high pressure six-way injection valve 16: quantitatively encircle 17: high pressure liquid phase pump
Fig. 2 is as fixing phase take the estradiol molecular engram fiber, the liquid-solid trace micro-extraction of use dynamic fluid flow-liquid chromatography on-line coupled system is analyzed 5 kinds of estrogen gained chromatograms in the urine sample that 2mL mark-on concentration is 2 μ g/L: curve a is 5 kinds of female sharp mixed standard solutions of 100 μ g/L, and sample size is 20 μ L; B is the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system gained chromatogram; C is 5 kinds of estrogen gained chromatograms in the 2 μ g/L urine samples for using traditional solid phase micro-extraction method to analyze 2mL mark-on concentration; D is that mark-on concentration is the urine sample direct injected 20 μ L gained chromatograms of 2 μ g/L; 1, estradiol, 2, ethinyloestradiol, 3, oestrone, 4, diethylstilbestrol, 5, hexestrol.
Fig. 3 is as fixing phase take the estradiol molecular engram fiber, the liquid-solid trace micro-extraction of use dynamic fluid flow-liquid chromatography on-line coupled system is analyzed 5 kinds of estrogen gained chromatograms in the urine sample that 25mL mark-on concentration is 1 μ g/L: curve a is 5 kinds of female sharp mixed standard solutions of 100 μ g/L, and sample size is 20 μ L; B is the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system gained chromatogram; C is that the traditional solid phase micro-extraction method of use is analyzed 5 kinds of estrogen gained chromatograms in the urine sample that 25mL mark-on concentration is 1 μ g/L; D is that mark-on concentration is the urine sample direct injected 20 μ L of 1 μ g/L; 1, estradiol, 2, ethinyloestradiol, 3, oestrone, 4, diethylstilbestrol, 5, hexestrol.
Fig. 4 is for analyzing the 5 kind estrogen gained chromatograms of 2mL mark-on concentration in the milk of 2 μ g/L take the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system: curve a is as 5 kinds of female sharp mixed standard solutions of 100 μ g/L, and sample size is 20 μ L; B is the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system gained chromatogram; C is that the traditional solid phase micro-extraction method of use is analyzed 5 kinds of estrogen gained chromatograms in the milk that 2mL mark-on concentration is 2 μ g/L; D is that mark-on concentration is the milk direct injected 20 μ L of 2 μ g/L; 1, estradiol, 2, ethinyloestradiol, 3, oestrone, 4, diethylstilbestrol, 5, hexestrol.
Fig. 5 is as fixing phase take the estradiol molecular engram fiber, the liquid-solid trace micro-extraction of use dynamic fluid flow-liquid chromatography on-line coupled system is analyzed 5 kinds of estrogen gained chromatograms in the milk that 25mL mark-on concentration is 1 μ g/L: curve a is 5 kinds of female sharp mixed standard solutions of 100 μ g/L, and sample size is 20 μ L; B is the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system gained chromatogram; C is that the traditional solid phase micro-extraction method of use is analyzed 5 kinds of estrogen gained chromatograms in the milk that 25mL mark-on concentration is 1 μ g/L; D is that mark-on concentration is the milk direct injected 20 μ L of 1 μ g/L; 1, estradiol, 2, ethinyloestradiol, 3, oestrone, 4, diethylstilbestrol, 5, hexestrol.
Embodiment
Technological means and the effect taked to reach predetermined goal of the invention for further setting forth the present invention, below in conjunction with embodiment and accompanying drawing, structure, feature and the embodiment thereof of the liquid-solid trace micro-extraction of dynamic fluid flow that the present invention is proposed-liquid chromatography on-line coupled system are described in detail as follows.
As shown in Figure 1, be the liquid-solid trace micro-extraction of dynamic fluid flow provided by the invention-liquid chromatography on-line coupled system, it comprises: (A) the liquid-solid trace micro-extraction device of dynamic fluid flow and (B) liquid-chromatography apparatus.The liquid-solid trace micro-extraction device of described dynamic fluid flow comprises the magnetic stirring apparatus 5 for heating water bath and stirring, be fixed on the bubbler 4 on the stirrer, mutually 2 extraction flask of aqueous sample 3 and organic extraction is housed, be used for stirring the magnetic stir bar 7 of aqueous sample 3, be used for importing and deriving organic extraction mutually 2 importing drainage tube 6 and derivation drainage tube 1, be used for driving mutually 2 peristaltic pump 8 of organic extraction, be used for the molecular blotting solid phase microextraction material 10 that high pressure six direction changeover valves 9 that stream switches and two ends connect polyetheretherketone pipe 11 thereon and are used for realizing the micro-extraction function;
In the liquid-solid trace micro-extraction of dynamic fluid flow process, the molecular blotting solid phase microextraction material 10 that is connected on described high pressure six direction changeover valves 9 links to each other with drainage tube by high pressure six direction changeover valves 9, bubbler 4 is placed on the magnetic stirring apparatus 5, extraction flask is immersed in the bubbler 4, organic extraction phase 2 and aqueous sample 3 are in immiscible up and down stratification state in extraction flask, insert in the upper phase organic extraction phase 2 and import drainage tube 6 and derive drainage tube 1, organic extraction phase 2 is drawn through deriving drainage tube 1, then flow through in order molecular blotting solid phase microextraction material 10 in the described polyetheretherketone pipe 11, peristaltic pump 8, get back in the extraction flask upper strata organic extraction phase 2 finally by importing drainage tube 6, thereby realize circulating extraction.Described organic extraction is 2 preferred and water is immiscible mutually, and its relative density is less than 0.8.Described extraction flask preferably has transparent long-neck structure, and the eck internal diameter is 0.5-2cm, and more preferably test tube or volumetric flask.Peristaltic tube in the described peristaltic pump is preferably the hose materials of tolerance organic solvent, and internal diameter is 0.5-2.0mm, and polyvinyl chloride pipe more preferably.In addition, be preferably the polyetheretherketone pipe of internal diameter 0.25mm for other connecting pipes that connect described cycling extraction loop, importing drainage tube 6 and derivation drainage tube 1.
Described organic extraction phase 2 is in the state of circulating in the extraction loop, whole dynamic extraction time and mobile rate of extraction preferably all organic extract liquids circulate once at least, and the organic solvent volume needs greater than the closed circuit dead volume.
Described molecular blotting solid phase microextraction material 10 is preferably and scribbles fixedly hollow tube or the good integral post of permeability of phase on elongated fibers, particulate, stirring rod, the wall, and elongated fibers more preferably.
Described liquid-chromatography apparatus comprises high pressure six-way injection valve 15, quantitatively encircles 16, sample introduction needle 14, chromatographic column 12, detecting device 13 and high pressure liquid phase pump 17; Wherein, quantitatively encircling 16 two ends is connected on the high pressure six-way injection valve 15; The long-pending 100 μ L that are preferably of described quantitative ring body for loading stripping liquid.The polyetheretherketone pipe 11 of micro-extraction material and quantitatively ring 16 mutually isolation in extraction process are housed, in dynamic desorption/chromatographic separation process, then are in connected state; After the liquid-solid trace micro-extraction of dynamic fluid flow process is finished, be written into stripping liquid by sample introduction needle 14, switch high pressure six direction changeover valves 9 and the high pressure six-way injection valve 15 that is connected with quantitative ring 16, after this system enters dynamic desorption/detachment process, the stripping liquid that is written into by sample introduction needle 14 pushes through the mobile phase that high pressure liquid phase pump 17 drives, flow through successively molecular blotting solid phase microextraction material 10, chromatographic column 12 and detecting device 13 in high pressure six direction changeover valves 9 are formed on the moving desorb of linear flow, separation, detection stream.
Embodiment: take the estradiol molecular engram fiber as fixing phase, use the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system to analyze 5 kinds of estrogen in urine sample and the milk.
In the method used fixing be mutually 1 or 4 be about 9.5cm, coating thickness is the estradiol molecular engram fiber of 10 μ m, bunchy single or in parallel be loaded into long for 12cm, internal diameter be in the PEEK pipe of 0.5mm.Wherein the estradiol molecular engram fiber is the laboratory self-control.
The coupling stream as shown in Figure 1.Use 2mL and two kinds of sample volume patterns of 25mL.
In the 2mL pattern, use 4 estradiol molecular engram fibers.Take 5mL test tube (internal diameter is about 0.8cm) as liquid-liquid extractor vessel, pack into 2mL urine sample or milk add 600 μ L normal hexanes thereon, form immiscible up and down two layers of solution; Add first one in the test tube and be about the approximately large magnetic stir bar of 0.6cm of 1cm external diameter, put into again one thereon and be about the approximately little magnetic stir bar of 0.4cm of 0.6cm external diameter, both are with the mutual exclusion of magnetic pole opposite way, the unsettled large magnetic stir bar top that rests on of little magnetic stir bar, stirring rate is 1000rpm.Whole test tube is fixed in the middle of the 20mL water bath containers, and bath temperature is 60 ℃.Import drainage tube and derive drainage tube and be immersed in the organic solvent middle section position.In liquid-liquid-solid three phase dynamic micro-extraction process, organic solvent with the flow velocity of 50rpm (approximating 0.56mL/min) via deriving estradiol molecular engram fiber, the peristaltic pump of drainage tube sequential flow on six direction changeover valves, flow back in the test tube by importing drainage tube at last, extraction time is 60min.After this process is finished, use sample introduction needle quantitatively to inject the excessive methanol stripping liquid in the ring to 100 μ L, then switch simultaneously high pressure six-way injection valve and high pressure six direction changeover valves, impel system to enter the dynamic desorption process, system enters liquid chromatography separation testing process automatically afterwards.
In the 25mL pattern, use 1 estradiol molecular engram fiber.Take 25mL volumetric flask (the upper hind neck internal diameter is about 0.8cm) as liquid-liquid extractor vessel, the 25mL urine sample of packing into (milk); Add first one in the test tube and be about the approximately large magnetic stir bar of 0.6cm of 1cm external diameter.Stirring rate is 875rpm.Whole volumetric flask is fixed in the middle of the self-control 300mL water bath containers.All the other conditions are with the 2mL pattern.
Fig. 2 and Fig. 3 are respectively under 2mL and the 25mL pattern, take the estradiol molecular engram fiber as fixing phase, using the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system to analyze 2mL mark-on concentration is 2 μ g/L, and 25mL mark-on concentration is 5 kinds of estrogen gained chromatograms in the urine sample of 1 μ g/L.By contrasting with the traditional solid phase micro-extraction method of use with to the result that the same sample direct injection analysis obtains, can find out obviously that the signal background that uses this on-line coupling method to obtain is simple, baseline steady, 5 kinds of estrogen signal peaks are easily distinguished, method sensitivity is improved.
Fig. 4 and Fig. 5 are respectively under 2mL and the 25mL pattern, take the estradiol molecular engram fiber as fixing phase, using the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system to analyze 2mL mark-on concentration is 2 μ g/L, and 25mL mark-on concentration is 5 kinds of estrogen gained chromatograms in the milk of 1 μ g/L.By contrast, can obtain the conclusion that this method for combined use is better than traditional solid phase micro-extraction method and direct injection analysis method equally.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction, and the volume of the above sample of the present invention per sample character is adjusted such as source, object sensitivity, equilibration time etc.Although the present invention with the preferred embodiment explanation as above, yet be not to limit the present invention, any those skilled in the art, within not breaking away from the technical solution of the present invention scope, make the equivalent embodiment that changes or modify equivalent variations when the technology contents that can utilize above-mentioned announcement, in every case be the content that does not break away from technical solution of the present invention,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment does according to technical spirit of the present invention.
Claims (1)
1. the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system is characterized in that comprising:
(A) the liquid-solid trace micro-extraction device of dynamic fluid flow: it comprises the magnetic stirring apparatus for heating water bath and stirring, be fixed on the bubbler on the stirrer, the extraction flask of water and organic phase is housed, be used for stirring the magnetic stir bar of aqueous sample, be used for importing and deriving the drainage tube of organic phase, be used for driving the peristaltic pump of organic phase, be used for the molecular blotting solid phase microextraction material that high pressure six direction changeover valves that stream switches and two ends connect polyetheretherketone pipe thereon and are used for realizing the micro-extraction function;
In the liquid-solid trace micro-extraction of dynamic fluid flow process, the molecular blotting solid phase microextraction material that is connected on described high pressure six direction changeover valves links to each other with drainage tube, bubbler is placed on the magnetic stirring apparatus, extraction flask is immersed in the bubbler, organic extraction phase and aqueous sample are in immiscible up and down stratification state in extraction flask, insert in the upper strata organic extraction mutually and import drainage tube and derive drainage tube, organic phase is drawn through deriving drainage tube, then flow through in order molecular blotting solid phase microextraction material in the described polyetheretherketone pipe, peristaltic pump, get back in the extraction flask upper organic phase finally by importing drainage tube, thereby realize circulating extraction;
(B) liquid-chromatography apparatus: it comprises high pressure six-way injection valve, quantitative ring, sample introduction needle, chromatographic column, detecting device and high pressure liquid phase pump; Wherein, quantitatively encircling two ends is connected on the high pressure six-way injection valve;
Described polyetheretherketone pipe and described quantitative ring be mutually isolation in extraction process, then is in connected state in dynamic desorption/chromatographic separation process; After the liquid-solid trace micro-extraction of dynamic fluid flow process is finished, be written into stripping liquid by sample introduction needle, switch high pressure six direction changeover valves and the high pressure six-way injection valve that is connected with quantitative ring, after this system enters dynamic desorption/chromatographic separation process, the stripping liquid that is written into by sample introduction needle is pushed by the mobile phase that the high pressure liquid phase pump drives, and solid-phase microextraction material, chromatographic column and the detecting device in high pressure six direction changeover valves of flowing through successively is formed on the moving desorb of linear flow, separation, detection stream.
2, the liquid-solid trace micro-extraction of dynamic fluid flow according to claim 1-liquid chromatography on-line coupled system, it is characterized in that: described organic phase and water are immiscible, and its relative density compares less than 0.8 with water.
3, the liquid-solid trace micro-extraction of dynamic fluid flow according to claim 1-liquid chromatography on-line coupled system, it is characterized in that: described extraction flask has transparent long-neck structure, and the eck internal diameter is 0.5-2 cm.
4, the liquid-solid trace micro-extraction of dynamic fluid flow according to claim 3-liquid chromatography on-line coupled system, it is characterized in that: described extraction flask is test tube or volumetric flask.
5, the liquid-solid trace micro-extraction of dynamic fluid flow according to claim 1-liquid chromatography on-line coupled system is characterized in that: the peristaltic tube in the described peristaltic pump is the hose materials of tolerance organic solvent, and internal diameter is 0.5-2.0 mm.
6, the liquid-solid trace micro-extraction of dynamic fluid flow according to claim 5-liquid chromatography on-line coupled system, it is characterized in that: described peristaltic tube is polyvinyl chloride pipe.
7, the liquid-solid trace micro-extraction of dynamic fluid flow according to claim 1-liquid chromatography on-line coupled system is characterized in that: other connecting pipes and the drainage tube that are used for connection cycling extraction loop are the polyetheretherketone pipe of internal diameter 0.25 mm.
8, the liquid-solid trace micro-extraction of dynamic fluid flow according to claim 1-liquid chromatography on-line coupled system, it is characterized in that: described organic extraction is in the state of circulating in the extraction loop, whole dynamic extraction time and mobile rate of extraction guarantee that all organic extract liquids circulate once at least, and the organic solvent volume needs greater than the closed circuit dead volume.
9, the liquid-solid trace micro-extraction of dynamic fluid flow according to claim 1-liquid chromatography on-line coupled system is characterized in that: described molecular blotting solid phase microextraction material is to scribble in the good integral post of the hollow tube of fixing phase and permeability any one on elongated fibers, particulate, stirring rod, the wall.
10, the liquid-solid trace micro-extraction of dynamic fluid flow according to claim 1-liquid chromatography on-line coupled system is characterized in that: described quantitative ring body for loading stripping liquid is long-pending to be 100 μ L.
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| CN103760004B (en) * | 2013-12-31 | 2017-02-08 | 聚光科技(杭州)股份有限公司 | Solvent desorption device and method |
| CN104931609B (en) * | 2015-05-28 | 2017-03-01 | 浙江省中医药研究院 | Device associated with a kind of hollow fiber membrane liquid-phase micro extraction liquid chromatograph and its polysaccharide component on-line quantitative analysis method |
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| CN101637668A (en) * | 2009-01-14 | 2010-02-03 | 中山大学 | Device and method for combined use of molecular imprinting solid phase microextraction and hollow fiber liquid phase microextraction, and application thereof |
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