CN102288473A - 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, 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, separation and the detection of trace organic substance in the complex samples such as environment, food, medicine, biology.
Background technology
(liquid-liquid-extraction is a kind of traditional universal abstraction technique LLE), and its using method is simple, and applicability is wide, is particularly suitable for the extraction and the enrichment of apolar substance in the aqueous sample in liquid-liquid extraction.But because therefore the selectivity of liquid-liquid extraction does not have high specific and extract and separate selectivity mainly by the partition factor decision 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) be centralized procurement sample, extraction, concentrate, sample introduction is in a kind of microminiaturized sample pre-treatments technology of one.Thereby the most frequently used solid-phase microextraction form is the little collection probe of stationary phase formation solid phase that has extraction and enrichment performance in the elongated fibers surface coated at present.Complicated along with analysis system needs the solid-phase microextraction stationary phase of development high selectivity.(molecularly imprinted polymer is to be the synthetic polymkeric substance of template with certain compound molecule MIP) to molecularly imprinted polymer, and template molecule is had specific recognition capability.Molecularly imprinted polymer can be improved the selectivity of solid-phase microextraction as coating, from complex sample, separate efficiently, the enrichment target molecule.Yet the intermolecular force between most molecularly imprinted polymer recognition sites and the template molecule is based on hydrogen bond, and when being used for the aqueous sample pre-treatment, its recognition capability can be subjected to intensive polar solvent interference such as water, reduces extracting power and selectivity.On the other hand, micro-extraction technique and gas chromatography or liquid chromatography coupling generally are by specific interface at present, realize online desorb and separate, but can't realize the online of pre-service, extraction, desorb, separation and detection overall process.
Liquid-phase micro-extraction that uses and molecular blotting solid phase microextraction combined apparatus need increase a hollow-fibre membrane usually in order to isolate organic phase and water at present, and all be to use the extraction form of off-line, carry out online desorb by special-purpose desorb pond again, or directly adopt after the offline mode desorb sample introduction again.Disclose a kind of molecular engram solid micro-extraction-hollow fiber liquid-phase micro-extraction combined apparatus, method and application 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 extraction flask again.This method required time length, complex operation, error are big, and unfavorable and subsequent analysis technology coupling is implemented in 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 subjected 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 stationary phase, the extraction time is short, the organic solvent use amount is few, robotization control, highly sensitive, realize the aqueous sample pre-service, extraction, desorb, separate and detect omnidistance 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 the dynamic fluid flow-liquid chromatography on-line coupled system of precision and accuracy.
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 that is used for the water-bath heating and stirs, be fixed on the bubbler on the stirrer, the extraction flask of water and organic phase is housed, be used to stir the magnetic stir bar of aqueous sample, be used to import and derive the drainage tube of organic phase, be used to drive the peristaltic pump of organic phase, be used for high pressure six direction changeover valves and two ends connection polyetheretherketone pipe thereon and the molecular blotting solid phase microextraction material that is used to realize the micro-extraction function that stream switches;
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 stratification state up and down in extraction flask, insert in the last phase organic extraction mutually and import drainage tube and derive drainage tube, organic phase is drawn through deriving drainage tube, flow through in order then molecular blotting solid phase microextraction material in the described polyetheretherketone pipe, peristaltic pump, after import drainage tube and get back in the extraction flask upper organic phase, 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 are isolated in extraction process mutually, then are 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 moving 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 flexible pipe material 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 a 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 the hollow tube of stationary phase and in the permeability good whole post 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, the described quantitative ring body that is used to load stripping liquid is long-pending to be 100 μ L.
The operation of this system comprises liquid-liquid-solid three phase dynamic micro-extraction process, dynamic desorption process and liquid chromatography separation detection process: 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; Dynamic desorption process and liquid chromatography separation detection process need not operation, realize conversion automatically; In liquid-liquid-solid three phase dynamic micro-extraction process, the high pressure six-way injection valve is in the LOAD state, and the polyetheretherketone pipe and the cycling extraction stream that are mounted with the molecular imprinting stationary phase link; In the dynamic desorption process, the high pressure six-way injection valve is in the INJECT state, and the polyetheretherketone pipe and the liquid chromatography stream that are mounted with stationary 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 the solvent of chromatogram flow phase according to the optimization experiment of desorption condition.
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 character are per sample adjusted 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 is formed:
1) carry out liquid-liquid extraction under water-bath heating 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 volume, surface area or the permeability of molecular blotting solid phase microextraction material easily, effectively improve the extracting power of stationary phase and shorten the extraction time, thus the sensitivity of the method for raisinging, quickening analysis speed.
4) whole stripping liquids are injected in the chromatographic column, realize the full sample introduction of target desorb thing, raising method sensitivity and reduced detection limit.
5) overall process adopts Mechanical Driven and software control, and the automaticity height reduces sample contamination and loss.
6) collection pre-separation, extraction, desorb, separate and be detected on one, reduced manual operations, can effectively improve method precision and accuracy.
7) can select different materials, multi-form stationary phase according to object character, widen the applicability and the range of application of liquid-liquid-solid micro-extraction technique.
In specific embodiment, 5 kinds of estrogen in utilized the liquid-solid trace micro-extraction of dynamic fluid flow provided by the invention-liquid chromatography on-line coupled system check and analysis urine sample and the milk.The stationary phase of native system can also use except that molecular engram material other to have the material of extraction ability, but this Apparatus and system is not limited in this preferred application, also can be widely used in online pre-service, extraction, desorb, separation and the detection of trace object in the complex samples such as environment, food, medicine, biology.
Description of drawings
Fig. 1 is that the stream of the liquid-solid trace micro-extraction of dynamic fluid flow provided by the invention-liquid chromatography on-line coupled system connects figure.
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 for being stationary phase with 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 the urine sample direct injected 20 μ L gained chromatograms of 2 μ g/L for mark-on concentration; 1, estradiol, 2, ethinyloestradiol, 3, oestrone, 4, diethylstilbestrol, 5, hexestrol.
Fig. 3 is for being stationary phase with 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 the urine sample direct injected 20 μ L of 1 μ g/L for mark-on concentration; 1, estradiol, 2, ethinyloestradiol, 3, oestrone, 4, diethylstilbestrol, 5, hexestrol.
Fig. 4 is for analyzing 5 kinds of estrogen gained chromatograms in the milk that 2mL mark-on concentration is 2 μ g/L with the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system: 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 2mL mark-on concentration is 2 μ g/L; D is the milk direct injected 20 μ L of 2 μ g/L for mark-on concentration; 1, estradiol, 2, ethinyloestradiol, 3, oestrone, 4, diethylstilbestrol, 5, hexestrol.
Fig. 5 is for being stationary phase with 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 the milk direct injected 20 μ L of 1 μ g/L for mark-on concentration; 1, estradiol, 2, ethinyloestradiol, 3, oestrone, 4, diethylstilbestrol, 5, hexestrol.
Embodiment
For further setting forth the present invention to reach technological means and the effect that predetermined goal of the invention is taked, 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-liquid chromatography on-line coupled system that the present invention is proposed 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 that is used for the water-bath heating and stirs, be fixed on the bubbler 4 on the stirrer, aqueous sample 3 and organic extraction 2 extraction flask mutually is housed, be used to stir the magnetic stir bar 7 of aqueous sample 3, be used to import and derive organic extraction 2 importing drainage tube 6 and derivation drainage tube 1 mutually, be used to drive organic extraction 2 peristaltic pump 8 mutually, be used for high pressure six direction changeover valves 9 and two ends connection polyetheretherketone pipe 11 thereon and the molecular blotting solid phase microextraction material 10 that is used to realize the micro-extraction function that stream switches;
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 stratification state up and down in extraction flask, insert in the last 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, flow through in order then molecular blotting solid phase microextraction material 10 in the described polyetheretherketone pipe 11, peristaltic pump 8, get back to the organic extraction of extraction flask upper strata mutually in 2, thereby realize circulating extraction after import drainage tube 6.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 flexible pipe material of tolerance organic solvent, and internal diameter is 0.5-2.0mm, and polyvinyl chloride pipe more preferably.In addition, be used to connect described cycling extraction loop other connecting pipes, import drainage tube 6 and derive the polyetheretherketone pipe that drainage tube 1 is preferably internal diameter 0.25mm.
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 hollow tube or the permeability good whole post that scribbles stationary 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 described long-pending 100 μ L that are preferably of quantitative ring body that are used to load stripping liquid.The polyetheretherketone pipe 11 of micro-extraction material and quantitatively ring 16 isolation mutually 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 moving 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: with the estradiol molecular engram fiber is stationary phase, uses 5 kinds of estrogen in the liquid-solid trace micro-extraction of dynamic fluid flow-liquid chromatography on-line coupled system analysis urine sample and the milk.
Used in the method stationary phase be 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.With 5mL test tube (internal diameter is about 0.8cm) is liquid-liquid extractor vessel, and pack into 2mL urine sample or milk add 600 μ L normal hexanes thereon, forms immiscible two layers of solution up and down; Add a big magnetic stir bar that is about the about 0.6cm of 1cm external diameter in the test tube earlier, put into a little magnetic stir bar that is about the about 0.4cm of 0.6cm external diameter more thereon, both are with the mutual exclusion of magnetic pole opposite way, the unsettled big 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, the 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, switch high pressure six-way injection valve and high pressure six direction changeover valves then simultaneously, impel system to enter the dynamic desorption process, system enters liquid chromatography separation detection process automatically afterwards.
In the 25mL pattern, use 1 estradiol molecular engram fiber.With 25mL volumetric flask (the upper hind neck internal diameter is about 0.8cm) is liquid-liquid extractor vessel, the 25mL urine sample of packing into (milk); Add a big magnetic stir bar that is about the about 0.6cm of 1cm external diameter in the test tube earlier.Stirring rate is 875rpm.The entire capacity bottle 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, with the estradiol molecular engram fiber is stationary 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 distinguish that easily method sensitivity is improved.
Fig. 4 and Fig. 5 are respectively under 2mL and the 25mL pattern, with the estradiol molecular engram fiber is stationary 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 character is per sample adjusted as source, object sensitivity, equilibration time etc.Though the present invention with the preferred embodiment explanation as above, yet be not in order to limit the present invention, any those skilled in the art, in 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 did according to technical spirit of the present invention.
Claims (10)
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 that is used for the water-bath heating and stirs, be fixed on the bubbler on the stirrer, the extraction flask of water and organic phase is housed, be used to stir the magnetic stir bar of aqueous sample, be used to import and derive the drainage tube of organic phase, be used to drive the peristaltic pump of organic phase, be used for high pressure six direction changeover valves and two ends connection polyetheretherketone pipe thereon and the molecular blotting solid phase microextraction material that is used to realize the micro-extraction function that stream switches;
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 stratification state up and down in extraction flask, insert in the last phase organic extraction mutually and import drainage tube and derive drainage tube, organic phase is drawn through deriving drainage tube, flow through in order then molecular blotting solid phase microextraction material in the described polyetheretherketone pipe, peristaltic pump, after import drainage tube and get back in the extraction flask upper organic phase, 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 are isolated in extraction process mutually, then are 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 moving 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 0.5-2cm.
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 flexible pipe material of tolerance organic solvent, and internal diameter is 0.5-2.0mm;
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 a 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: the connecting pipe in described cycling extraction loop and drainage tube are the polyetheretherketone pipe of internal diameter 0.25mm.
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 the hollow tube of stationary phase and in the permeability good whole post any one on elongated fibers, particulate, stirring rod, the wall.
10. on-line coupled system according to claim 1 is characterized in that: the described quantitative ring body that is used to load stripping liquid is long-pending to be 100 μ L.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103760004A (en) * | 2013-12-31 | 2014-04-30 | 聚光科技(杭州)股份有限公司 | Solvent desorption device and method |
| CN104931609A (en) * | 2015-05-28 | 2015-09-23 | 浙江省中医药研究院 | Hollow-fiber membrane liquid-phase micro-extraction and liquid chromatography coupling device and polysaccharide component on-line quantitative analysis method thereof |
| CN105486777A (en) * | 2016-01-14 | 2016-04-13 | 黄志强 | On-line digestion combined liquid chromatography system and method for detecting coloring agent in tea |
| CN106959349A (en) * | 2017-04-17 | 2017-07-18 | 武汉大学 | A kind of microtrabeculae is enriched with sample injection method |
| CN107121504A (en) * | 2017-04-12 | 2017-09-01 | 岛津企业管理（中国）有限公司 | Multi-functional temperature-pressure extraction trapping chromatographic isolation on-line coupling equipment |
| CN115219606A (en) * | 2021-04-20 | 2022-10-21 | 广州禾信仪器股份有限公司 | Automatic water sample pretreatment device, treatment method and automatic water sample detection system |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103760004A (en) * | 2013-12-31 | 2014-04-30 | 聚光科技(杭州)股份有限公司 | Solvent desorption device and method |
| 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 |
| CN104931609A (en) * | 2015-05-28 | 2015-09-23 | 浙江省中医药研究院 | Hollow-fiber membrane liquid-phase micro-extraction and liquid chromatography coupling device and polysaccharide component on-line quantitative analysis method thereof |
| CN105486777A (en) * | 2016-01-14 | 2016-04-13 | 黄志强 | On-line digestion combined liquid chromatography system and method for detecting coloring agent in tea |
| CN107121504A (en) * | 2017-04-12 | 2017-09-01 | 岛津企业管理（中国）有限公司 | Multi-functional temperature-pressure extraction trapping chromatographic isolation on-line coupling equipment |
| CN107121504B (en) * | 2017-04-12 | 2019-08-20 | 岛津企业管理（中国）有限公司 | Multi-functional temperature-pressure extraction-trapping-chromatographic isolation on-line coupling equipment |
| CN106959349A (en) * | 2017-04-17 | 2017-07-18 | 武汉大学 | A kind of microtrabeculae is enriched with sample injection method |
| CN115219606A (en) * | 2021-04-20 | 2022-10-21 | 广州禾信仪器股份有限公司 | Automatic water sample pretreatment device, treatment method and automatic water sample detection system |
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