CN103940941A - On-line analysis system for automatic pretreatment by adopting ultra high performance liquid chromatography/mass spectrum - Google Patents
On-line analysis system for automatic pretreatment by adopting ultra high performance liquid chromatography/mass spectrum Download PDFInfo
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Abstract
The invention discloses an on-line analysis system for automatic pretreatment by adopting an ultra-high performance liquid chromatography/mass spectrum. The on-line analysis system has an automatic pretreatment mode and a post-column compensation mode, and comprises four chromatography pumps, two high-pressure switch valves, an automatic sample injector, an on-line diluter, an extraction column, an on-line filter, two sample rings, a miniature mixer, a chromatographic column, a tee joint, a mass spectrometry detector and the like. On-line dilution, extraction, desorption, separation, detection and post-column compensation analysis can be carried out on a target analyte in a liquid sample by combination of an on-line dilution/extraction/desorption device, a stigma focusing device, a post-column compensation device and an ultra high performance liquid chromatography/mass spectrum device, the overall analysis process is automatically controlled, and is high in accuracy and precision, and the on-line analysis system can be effectively applied to the analysis detection on trace organic compounds in a complicated liquid sample or a liquid extracting solution.
Description
Technical field
The invention belongs to analytical chemistry sample pre-treatments field, be specifically related to a kind of design and analysis and application of automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system, be applicable to online pre-service, extraction, desorb, the separation and detection of trace organic substance in the fluid samples such as environment, food, medicine, biology or liquid extraction liquid.
Background technology
Ultra Performance Liquid Chromatography (Ultra High Performance Liquid Chromatography, UHPLC) is the quantum jump of liquid chromatography technology, is the development trend of modern compartment analysis.UHPLC obtains higher post effect by reducing the particle diameter of fixed phase stuffing, less internal diameter chromatographic column, reduce analysis time by the length that shortens chromatographic column, therefore the several times that UHPLC analysis speed can reach conventional liquid chromatography are conventionally to decades of times, and peak shape is narrow and high, peak capacity is large, greatly improves detection sensitivity and analysis throughput.But granule particle diameter, narrow chromatographic column internal diameter and high flow rate must improve the pressure of whole liquid phase systems, make its hardware and chromatograph packing material, fiber material to pressure-bearing all propose higher requirement of withstand voltage.
Mass spectroscopy (Mass spectrometry, MS) can provide abundant structural information in once analyzing, and is considered to a kind of universality method that possesses high specific and high sensitivity simultaneously and be widely applied.It is a breakthrough in separation science method that mass spectroscopy is combined with isolation technics.
For the analysis of complex sample, generally need to carry out pre-service, as use various fiber materials to separate and enrichment target analytes in sample, the chromatographic system analysis of reinjecting.Can fiber material be connected to liquid chromatography column cap by specific interface at present, use mobile phase to carry out desorb, realize online desorb and separate.But for Ultra Performance Liquid Chromatography, its pressure, far above the withstand voltage limit of common fiber material, therefore cannot use the method for the direct desorb of column cap.
Summary of the invention
The shortcoming that the present invention is intended to overcome pressure that atmospheric extraction material cannot bear Ultra Performance Liquid Chromatography and carries out desorb before direct post, the shortcoming of large volume strong solvent stripping liquid sample introduction postpeak broadening, and liquid chromatograph-mass spectrometer need to use the specific demand of post post-compensation liquid, design one and can realize fluid sample by atmospheric extraction material auto extractive, desorb, sample introduction, then made object be able to the on-line analysis system of analyzing in Ultra Performance Liquid Chromatography-mass spectrometer separation.
The object of the invention is by realizing by the following technical solutions:
A kind of pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system automatically, it comprises:
On-line dilution/extraction/desorption apparatus, it comprises the first chromatogram pump 1 for pushing load sample solvent, for pushing the second chromatogram pump 2 of stripping workshop, for importing the automatic sampler of sample, for the on-line dilution device of dilute sample, be used for the first high pressure six direction changeover valves of stream switching and connect on it for realizing the extraction column 7 of on-line extraction function, for the connecting pipe of connecting components, wherein, the first chromatogram pump 1 is successively through automatic sampler 5, an interface of rear access the first high pressure six direction changeover valves of on-line dilution device 6, the second chromatogram pump 2 accesses another interface of the first high pressure six direction changeover valves, another two interfaces of the first high pressure six direction changeover valves are accessed respectively at the two ends of extraction column 7, and
Column cap focalizer, it comprises the second high pressure six direction changeover valves 11 that switch for stream and connects on it for trapping the first sample loop 10 of stripping liquid, for diluting the micro-mixer 12 of stripping liquid, for pushing the 3rd chromatogram pump 3 of the first mobile phase, push the 4th chromatogram pump 4 of the second mobile phase, and for the connecting pipe of connecting components, another interface of the first high pressure six direction changeover valves accesses to an interface of the second high pressure six direction changeover valves 11 by pot strainer 9, another two interfaces of the second high pressure six direction changeover valves 11 are accessed respectively at the two ends of the first sample loop 10, the 3rd chromatogram pump 3 accesses another interface of the second high pressure six direction changeover valves 11, another interface access micro-mixer 12 of the second high pressure six direction changeover valves 11, the 4th chromatogram pump 4 also accesses this micro-mixer 12, and
Ultra Performance Liquid Chromatography/mass spectrometric apparatus, it comprises chromatographic column 13, column oven and mass detector, the outflow end of above-mentioned micro-mixer 12 is accessed in one end of chromatographic column 13, another termination mass detector; For chromatographic resolution and Mass Spectrometer Method.
The present invention can further comprise the post post-compensation device of post post-compensation mode-specific, it comprises the three or six direction changeover valve 18 switching for stream and connects the second sample loop 16 on it, and for the connecting pipe of connecting components, third high presses an interface of six direction changeover valves 18 to access between chromatographic column 13 and Mass Spectrometer Method instrument by threeway 14, another two interfaces of six direction changeover valves 18 are accessed respectively third high and press at the two ends of the second sample loop 16, third high presses the another port of six direction changeover valves 18 to access another interface of the first high pressure six direction changeover valves 8, so that above-mentioned the second chromatogram pump 2 passes through switch valve, be linked into post post-compensation device.
This system is using three high pressure six direction changeover valves as connection maincenter, on-line dilution/extraction/desorption apparatus, column cap focalizer, post post-compensation device and liquid chromatograph-mass spectrometer are coupled together, and on-line dilution, extraction, desorb and the chromatogram mass spectrum of realizing fluid sample separate, analyze.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
According to automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system of the present invention, described extraction column is the chromatographic column of inner filler particles, inwall is coated with the hollow posts of stain extraction layer material, inner hollow posts of loading bar-shaped fiber material, extracting fiber, sheet fiber material, independent extraction column, any one in the good integral post of permeability.
According to automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system of the present invention, described on-line dilution device is long column shape, and two ends are the standard screw socket that is suitable for connection standard polyetheretherketone joint or stainless joint, and inside is multiple circular inactive surfaces particles.
According to automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system of the present invention, it is characterized in that: described pot strainer two ends are the standard screw socket that is suitable for connecting polyetheretherketone joint or stainless joint, inner zero dead volume, is furnished with filter or the Filter column core in the 0.5 following aperture of μ m.
According to automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system of the present invention, described the first mobile phase is strong solvent with respect to used chromatographic column, the second mobile phase is Weak solvent, in the time that micro-mixer mixes stripping liquid, the flow velocity of the second mobile phase be at least 9 times of the first mobile phase or more than.
According to automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system of the present invention, described sample loop is that stainless steel more than withstand voltage 50Mpa quantitatively encircles.
According to automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system of the present invention, described micro-mixer is more than withstand voltage 50Mpa, is three-port structure, has three standard screw sockets that can connect polyetheretherketone joint or stainless joint.
According to automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system of the present invention, described the second sample loop 16 is the quantitative rings of 100 μ L with upper volume, stainless steel material, polyetheretherketonematerials materials or teflon material.
According to automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system of the present invention, it is hand sampling valve or six direction changeover valves that are connected to syringe inlet that described third high is pressed six direction changeover valves 18.
This system can be divided into " automatic sample pre-treatment pattern " and " post post-compensation pattern ".Automatic sample pre-treatment pattern is equipped with the extraction column of unlike material for removal of impurities, the enrichment of dissimilar sample, and switch stream and carry various solvents by each chromatogram pump flow velocity, the valve state of different time sections (point) is set, automatically realize dilution, object enrichment, desorb, large volume sample injection and follow-up Ultra Performance Liquid Chromatography-mass spectrum compartment analysis of sample.
Post post-compensation pattern is for the specific demand of mass spectrophotometry, collects through simple solvent reprinting, conveying, threeway, can realize the functions such as solvent compensation after post, post-column derivation, matrix effect evaluation.
The present invention's automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system at least has the following advantages:
1) fluid sample is carried out to on-line dilution, can realize the solvent that turns of desorption to object in bio-matrix and strong solvent solubilized target thing, be conducive to extraction and the enrichment of object in fiber material.
2) remove the danger that fiber material is destroyed by desorption pressures, its operating pressure is generally below 3Mpa, is significantly less than the pressure limit of general material.
3) allow large volume stripping liquid to inject chromatographic column, the full sample introduction of realize target desorb thing, there is no peak broadening phenomenon, raising method sensitivity and reduced detection limit.
4) chromatographic column efflux, without shunting, can arrange the flow rate of mobile phase matching with mass ion source.
5) there is independent desorb stream, can carry out desorption condition optimization for object and fiber material.
6) integrate dilution, extraction, desorb, separation and detection, overall process adopts Mechanical Driven and software control, and automaticity is high, can effectively improve method precision and accuracy.
7) can select different materials, multi-form extraction column according to object character, widen system suitability and range of application.
8) be equipped with MS dedicated columns post-compensation pattern, can be used for matrix effect evaluation, transport column post-compensation liquid, post-column derivation.
In specific embodiment, utilize automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system provided by the invention automatic pre-treatment pattern analysis three kinds of auxin in the fairy bamboo leaf of bamboo, mountain ebony petal and bud three Plant Extracts; And the matrix effect of fairy bamboo extract solution of bamboo leaves that used post post-compensation mode evaluation.The extraction column of native system can also use other except reversed material 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 on-line dilution, extraction, desorb, the separation and detection of trace object in the complex samples such as environment, food, medicine, biology, matrix effect evaluation, post-column derivation etc.
Brief description of the drawings
Fig. 1 is the stream connection figure of automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system provided by the invention.
Wherein, 4: the four chromatogram pumps 45 of 1: the first chromatogram pump 3: the three chromatogram pump of 2: the second chromatogram pumps: automatic sampler 6: on-line dilution device 7: 8: the first high pressure six direction changeover valves 9 of extraction column: 11: the second high pressure six direction changeover valves 12 of 10: the first sample loops of pot strainer: micro-mixer 13: chromatographic column 14: threeway 15: 16: the second sample loops 17 of mass detector: syringe 18: third high is pressed six direction changeover valves
Fig. 2 is the tri-kinds of auxin standard specimen samples of the three kinds of chromatogram that auxin obtains: A, 1 μ g/L that use in the blank plant extraction liquid of the automatic pre-treatment pattern analysis 50 μ L of automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system, B, fairy bamboo leaf of bamboo blank sample, C, mountain ebony petal blank sample, D, mountain ebony bud blank sample; 1, heteroauxin, 2, indolepopionic acid, 3, indolebutyric acid.
Fig. 3 is the tri-kinds of auxin standard specimen samples of three kinds of auxin gained chromatogram: A, 1 μ g/L that use in the plant extraction liquid that the automatic pre-treatment pattern analysis 50 μ L mark-on concentration of automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system are 2ng/g, B, fairy bamboo leaf of bamboo mark-on sample, C, mountain ebony petal mark-on sample, D, mountain ebony bud mark-on sample; 1, heteroauxin, 2, indolepopionic acid, 3, indolebutyric acid.
Fig. 4 is the chromatogram that uses automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system post post-compensation pattern analysis blank solvent to obtain: 1, heteroauxin, 2, indolepopionic acid, 3, indolebutyric acid.
Fig. 5 is the chromatogram that uses automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system post post-compensation pattern analysis fairy bamboo extract solution of bamboo leaves to obtain: 1, heteroauxin, 2, indolepopionic acid, 3, indolebutyric acid.
Embodiment
Technological means and effect of being 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 automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system that the present invention is proposed, be described in detail as follows.
As shown in Figure 1, be automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system provided by the invention, a kind of pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system automatically, has automatic pre-treatment pattern and post post-compensation pattern, and it comprises:
(A) on-line dilution/extraction/desorption apparatus: it comprises the first chromatogram pump 1 for pushing load sample solvent, for pushing the second chromatogram pump 2 of stripping workshop, for importing the automatic sampler of sample, for the on-line dilution device of dilute sample, be used for the first high pressure six direction changeover valves of stream switching and connect on it for realizing the extraction column 7 of on-line extraction function, for the connecting pipe of connecting components, wherein, the first chromatogram pump 1 is successively through automatic sampler 5, an interface of rear access the first high pressure six direction changeover valves of on-line dilution device 6, the second chromatogram pump 2 accesses another interface of the first high pressure six direction changeover valves, another two interfaces of the first high pressure six direction changeover valves are accessed respectively at the two ends of extraction column 7,
On-line dilution and on-line extraction process are carried out simultaneously, and sample is imported by automatic sampler 5, and the load sample liquid propelling movement of being released by the first chromatogram pump 1 enters on-line dilution device 6 and carries out on-line mixing dilution; Enter afterwards the extraction column 7 being connected on described the first high pressure six direction changeover valves 8, object is enriched on extraction column 7; After having extracted, enter desorption process: switch the first high pressure six direction changeover valves 8, after this extraction column 7 is connected with the stripping liquid that the second chromatogram pump 2 pushes, stripping liquid passes through extraction column by object desorb and is dissolved in stripping liquid;
(B) column cap focalizer: it comprises the second high pressure six direction changeover valves 11 that switch for stream and connects on it for trapping the first sample loop 10 of stripping liquid, for diluting the micro-mixer 12 of stripping liquid, for pushing the 3rd chromatogram pump 3 of the first mobile phase, push the 4th chromatogram pump 4 of the second mobile phase, and for the connecting pipe of connecting components, another interface of the first high pressure six direction changeover valves accesses to an interface of the second high pressure six direction changeover valves 11 by pot strainer 9, another two interfaces of the second high pressure six direction changeover valves 11 are accessed respectively at the two ends of the first sample loop 10, the 3rd chromatogram pump 3 accesses another interface of the second high pressure six direction changeover valves 11, another interface access micro-mixer 12 of the second high pressure six direction changeover valves 11, the 4th chromatogram pump 4 also accesses this micro-mixer 12,
Stripping liquid in the first high pressure six direction changeover valves 8 is continued to push through pot strainer 9 by the second chromatogram pump 2, then enter the first sample loop 10 being connected on the second high pressure transfer valve 11, in the time being dissolved with the stripping liquid liquid section of object and entering the first sample loop 10 and also do not flow out, switch the second high pressure six direction changeover valves 11, after this first sample loop 10 is connected with the first mobile phase that the 3rd chromatogram pump 3 pushes, the 3rd chromatogram pump 3 drives the stripping liquid in the first mobile phase and then propelling movement the first sample loop 10 to enter micro-mixer 12, and the second mobile phase pushing with the 4th chromatogram pump 4 mixes in micro-mixer 12, because the flow velocity of the first mobile phase is far below the second mobile phase, make object replaced in a high proportion of the second mobile phase, then continued to push and entered chromatographic column, carry out enrichment at chromatographic column column cap,
(C) Ultra Performance Liquid Chromatography/mass spectrometric apparatus: it comprises chromatographic column 13, column oven and mass detector, the outflow end of above-mentioned micro-mixer 12 is accessed in one end of chromatographic column 13, another termination mass detector; For chromatographic resolution and Mass Spectrometer Method;
(D) the post post-compensation device of post post-compensation mode-specific: it comprises the three or six direction changeover valve 18 switching for stream and connects the second sample loop 16 on it, and for the connecting pipe of connecting components, third high presses an interface of six direction changeover valves 18 to access between chromatographic column 13 and Mass Spectrometer Method instrument by threeway 14, another two interfaces of six direction changeover valves 18 are accessed respectively third high and press at the two ends of the second sample loop 16, third high presses the another port of six direction changeover valves 18 to access another interface of the first high pressure six direction changeover valves 8, so that above-mentioned the second chromatogram pump 2 passes through switch valve, be linked into post post-compensation device,
Post post-compensation device is for post post-compensation pattern.Use syringe 17 to press an interface of six direction changeover valves 18 to inject excessive compensation liquid to third high, compensation liquid enters in the second sample loop 16, switch valve, and compensation liquid is pushed and enters threeway 14 by the second chromatogram pump 2, after converging, enters mass detector with mobile phase.
This system is using three high pressure six direction changeover valves as connection maincenter, on-line dilution/extraction/desorption apparatus, column cap focalizer, post post-compensation device and liquid chromatograph-mass spectrometer are coupled together, and on-line dilution, extraction, desorb and the chromatogram mass spectrum of realizing fluid sample separate, analyze.
Described extraction column is the chromatographic column of inner filler particles, inwall is coated with the hollow posts of stain extraction layer material, inner hollow posts of loading bar-shaped fiber material, extracting fiber, sheet fiber material, independent extraction column, any one in the good integral post of permeability.
Described on-line dilution device is long column shape, and two ends are the standard screw socket that is suitable for connection standard polyetheretherketone joint or stainless joint, and inside is multiple circular inactive surfaces particles.
Described pot strainer two ends are the standard screw socket that is suitable for connecting polyetheretherketone joint or stainless joint, and inner zero dead volume is furnished with filter or the Filter column core in the 0.5 following aperture of μ m.
Described the first mobile phase is Weak solvent with respect to used chromatographic column, and the second mobile phase is strong solvent, in the time that micro-mixer mixes stripping liquid, the flow velocity of the second mobile phase be at least 9 times of the first mobile phase or more than.
Described sample loop is that stainless steel more than withstand voltage 50Mpa quantitatively encircles.
Described micro-mixer is more than withstand voltage 50Mpa, is three-port structure, has three standard screw sockets that can connect polyetheretherketone joint or stainless joint.
Described the second sample loop 16 is the quantitative rings of 100 μ L with upper volume, stainless steel material, polyetheretherketonematerials materials or teflon material.
It is hand sampling valve or six direction changeover valves that are connected to syringe inlet that described third high is pressed six direction changeover valves 18.
This system can be divided into " automatic sample pre-treatment pattern " and " post post-compensation pattern ".Automatic sample pre-treatment pattern is equipped with the extraction column of unlike material for removal of impurities, the enrichment of dissimilar sample, and switch stream and carry various solvents by each chromatogram pump flow velocity, the valve state of different time sections (point) is set, automatically realize dilution, object enrichment, desorb, large volume sample injection and follow-up Ultra Performance Liquid Chromatography-mass spectrum compartment analysis of sample.
Embodiment 1:
Taking Shimadzu MAYI-SAX post as extraction column, use three kinds of auxin in the automatic pre-treatment pattern analysis of automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system plant extraction liquid.
Extraction column used is Shimadzu Shim-pack MAYI-SAX (G) 10L × 4.6 in the method, and chromatographic column is Shimadzu Shim-pack XR-ODS III, 2.0mm × 50mm L (1.6 μ m particle diameter).
Coupling stream as shown in Figure 1.
Automatic sampler 5 imports 50 μ L mark-on plant extraction liquid mark-on samples, push 0.01mol ammonium acetate/acetonitrile (95/5 by the first chromatogram pump 1, v/v) load sample solution is sent sample into online diluter 6, and dilute sample enters MAYI-SAX extraction column 7 and carries out on-line extraction subsequently; Complete after extraction, switch the first high pressure six direction changeover valves 8, MAYI-SAX extraction column 7 is switched between the second chromatogram pump 2 and the first sample loop 10, and the second chromatogram pump 2 pushes methyl alcohol through extraction column 7, and object desorb is got off then to continue to move into the first sample loop 10; After desorb completes, switch the second high pressure six direction changeover valves 11, the first sample loop 10 is switched between the 3rd chromatogram pump 3 and micro-mixer 12, the second mobile phase velocity ratio that the first mobile phase that the 3rd chromatogram pump 3 pushes and the 4th chromatogram pump 4 push is 1:10, and stripping liquid enters chromatographic column 13 after being diluted by two kinds of mobile phases and carries out chromatographic resolution detection.
Fig. 2, for taking Shimadzu MAYI-SAX as extraction column, uses three kinds of chromatograms that auxin obtains in the blank plant extraction liquid of the automatic pre-treatment pattern analysis 50 μ L of automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system; Fig. 3 is three kinds of auxin gained chromatograms in these pattern analysis 50 μ L mark-on concentration plant extraction liquid that is 2ng/g: 1, heteroauxin, 2, indolepopionic acid, 3, indolebutyric acid.The mark-on plant extraction liquid sample that can see low concentration can directly enter this system without any pre-treatment and carry out compartment analysis, obtains chromatogram baseline steady, and chromatographic peak is sharp-pointed, degree of separation is good.
Embodiment 2:
Use the matrix effect evaluation of automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system post post-compensation pattern for rich and honour leaf of bamboo sample.
This system is being reequiped below process on pre-treatment pattern basis automatically, can conveniently realize the analysis of post post-compensation: disconnect threeway 14 and third high and press the direct connecting pipe of six direction changeover valves 18, squeeze into solution with syringe 17 and fill the second sample loop 16, connecting tee 14 and third high are pressed the direct connecting pipe of six direction changeover valves 18 again, analyze for post post-compensation.Extraction column used is Shimadzu Shim-pack MAYI-SAX (G) 10L × 4.6 in the method, and chromatographic column is Shimadzu Shim-pack XR-ODS III, 2.0mm × 50mm L (1.6 μ m particle diameter), and the second sample loop is 1mL stainless steel ring.
Coupling stream as shown in Figure 1.Before use, first disconnect threeway 14 and third high and press the direct connecting pipe of six direction changeover valves 18, squeeze into standard solution with syringe 17 and fill the second sample loop 16, then connecting tee 14 and third high press the direct connecting pipe of six direction changeover valves 18, analyze for post post-compensation.After sample introduction, 1min switching third high is pressed six direction changeover valves 18, and it is 0.1mL/min that the second chromatogram pump 2 flow velocitys are set, and other settings are identical with example 1.
Fig. 4 is the chromatogram that the post post-compensation pattern analysis blank solvent of automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system obtains, Fig. 5 is the chromatogram that this pattern analysis fairy bamboo extract solution of bamboo leaves obtains, can learn that from this two figure the fairy bamboo extract solution of bamboo leaves after native system extraction exists matrix effect hardly, the response of three kinds of auxin is basic identical with the response obtaining in blank solvent.Therefore can reach a conclusion, use the matrix effect that the post post-compensation pattern of native system can objective appraisal sample, whole method is simple, reliable.
The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction, and the whole bag of tricks parameter of the present invention per sample matrix, object sensitivity, equilibration time etc. is adjusted.Although the present invention illustrates as above with preferred embodiment, but not in order to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make when utilizing the technology contents of above-mentioned announcement the equivalent embodiment that changes or modify equivalent variations, in every case be the content that does not depart from technical solution of the present invention, any simple modification, equivalent variations and the modification above embodiment done according to technical spirit of the present invention, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system, it comprises:
On-line dilution/extraction/desorption apparatus, it comprises the first chromatogram pump for pushing load sample solvent, for pushing the second chromatogram pump of stripping workshop, for importing the automatic sampler of sample, for the on-line dilution device of dilute sample, be used for the first high pressure six direction changeover valves of stream switching and connect on it for realizing the extraction column of on-line extraction function, for the connecting pipe of connecting components, wherein, the first chromatogram pump is successively through automatic sampler, after on-line dilution device, access an interface of the first high pressure six direction changeover valves, the second chromatogram pump accesses another interface of the first high pressure six direction changeover valves, another two interfaces of the first high pressure six direction changeover valves are accessed respectively at the two ends of extraction column, and
Column cap focalizer, it comprises the second high pressure six direction changeover valves that switch for stream and connects on it for trapping the first sample loop of stripping liquid, for diluting the micro-mixer of stripping liquid, for pushing the 3rd chromatogram pump of the first mobile phase, push the 4th chromatogram pump of the second mobile phase, and for the connecting pipe of connecting components, another interface of the first high pressure six direction changeover valves accesses to an interface of the second high pressure six direction changeover valves by pot strainer, another two interfaces of the second high pressure six direction changeover valves are accessed respectively at the two ends of sample loop, the 3rd chromatogram pump accesses another interface of the second high pressure six direction changeover valves, another interface access micro-mixer of the second high pressure six direction changeover valves, the 4th chromatogram pump also accesses this micro-mixer, and
Ultra Performance Liquid Chromatography/mass spectrometric apparatus, it comprises chromatographic column, column oven and mass detector, and the outflow end of above-mentioned micro-mixer is accessed in one end of chromatographic column, and another termination mass detector is for chromatographic resolution and Mass Spectrometer Method.
2. automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system according to claim 1, it is characterized in that: the post post-compensation device that also comprises post post-compensation mode-specific, it comprises the three or six direction changeover valve switching for stream and connects the second sample loop on it, and for the connecting pipe of connecting components, third high presses an interface of six direction changeover valves to access between chromatographic column and Mass Spectrometer Method instrument by threeway, another two interfaces of six direction changeover valves are accessed respectively third high and press at the two ends of the second sample loop, third high presses the another port of six direction changeover valves to access another interface of the first high pressure six direction changeover valves, so that above-mentioned the second chromatogram pump passes through switch valve, be linked into post post-compensation device.
3. automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system according to claim 1 and 2, it is characterized in that: the chromatographic column that described extraction column is inner filler particles, inwall is coated with the hollow posts of stain extraction layer material, inner hollow posts of loading bar-shaped fiber material, extracting fiber, sheet fiber material, independent extraction column, any one in the good integral post of permeability.
4. automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system according to claim 1 and 2, it is characterized in that: described on-line dilution device is long column shape, two ends are the standard screw socket that is suitable for connection standard polyetheretherketone joint or stainless joint, and inside is multiple circular inactive surfaces particles.
5. automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system according to claim 1 and 2, it is characterized in that: described pot strainer two ends are the standard screw socket that is suitable for connecting polyetheretherketone joint or stainless joint, inner zero dead volume, is furnished with filter or the Filter column core in the 0.5 following aperture of μ m.
6. automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system according to claim 1 and 2, it is characterized in that: described the first mobile phase is strong solvent with respect to used chromatographic column, the second mobile phase is Weak solvent, in the time that micro-mixer mixes stripping liquid, the flow velocity of the second mobile phase be at least 9 times of the first mobile phase or more than.
7. automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system according to claim 1 and 2, is characterized in that: described sample loop is that stainless steel more than withstand voltage 50Mpa quantitatively encircles.
8. automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system according to claim 1 and 2, it is characterized in that: described micro-mixer is more than withstand voltage 50Mpa, be three-port structure, there are three standard screw sockets that can connect polyetheretherketone joint or stainless joint.
9. automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system according to claim 1 and 2, is characterized in that: described the second sample loop is the quantitative rings of 100 μ L with upper volume, stainless steel material, polyetheretherketonematerials materials or teflon material.
10. automatic pre-treatment-Ultra Performance Liquid Chromatography/mass spectrum on-line analysis system according to claim 2, is characterized in that: it is hand sampling valve or six direction changeover valves that are connected to syringe inlet that described third high is pressed six direction changeover valves.
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| 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 |
| CN106018596A (en) * | 2016-05-17 | 2016-10-12 | 华南理工大学 | Online microwave-assisted chiral derivatization-LC/MS (liquid chromatography/mass spectrometry) analysis system and method |
| CN106501428A (en) * | 2016-10-24 | 2017-03-15 | 南方医科大学 | A kind of substep focuses on the method for combined use of axial mixed high-efficient liquid chromatographic separation system |
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