CN104678015B - A kind of chromatograph of liquid - Google Patents
A kind of chromatograph of liquid Download PDFInfo
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- CN104678015B CN104678015B CN201510071069.8A CN201510071069A CN104678015B CN 104678015 B CN104678015 B CN 104678015B CN 201510071069 A CN201510071069 A CN 201510071069A CN 104678015 B CN104678015 B CN 104678015B
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- 239000007788 liquid Substances 0.000 title claims abstract description 68
- 239000000243 solution Substances 0.000 claims abstract description 62
- 239000002699 waste material Substances 0.000 claims abstract description 36
- 239000012482 calibration solution Substances 0.000 claims abstract description 29
- 238000012937 correction Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims description 11
- 238000004458 analytical method Methods 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 21
- 239000011159 matrix material Substances 0.000 abstract description 20
- 239000000758 substrate Substances 0.000 abstract description 13
- 208000035126 Facies Diseases 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 39
- 239000012071 phase Substances 0.000 description 20
- 238000004780 2D liquid chromatography Methods 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 238000001819 mass spectrum Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000007445 Chromatographic isolation Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002989 correction material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 238000004186 food analysis Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000005220 pharmaceutical analysis Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- REFMEZARFCPESH-UHFFFAOYSA-M sodium;heptane-1-sulfonate Chemical compound [Na+].CCCCCCCS([O-])(=O)=O REFMEZARFCPESH-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
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- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
nullThe invention provides a kind of chromatograph of liquid，This chromatograph of liquid includes the first flow (L3) being connected to the first chromatographic column (C1)、Second runner (L13)、Analyze runner (L14)、Waste liquid runner (L4)、Middle chromatographic column (C2)、Multiple flow passages switching valve (V1)、Deposit valve (V2) and solution replacing valve (V3)、Correction switching valve (V4) etc.，First flowing is spaced with the second flowing mutually by this chromatograph of liquid by introducing gas，Both are avoided mixing to impact，The first flowing phase in middle chromatographic column is replaced again mutually by the second flowing，The impurity avoiding the first flowing facies tract to enter produces matrix effect on the detector，Can also be in the middle of the second flowing is replaced mutually before the first flowing mutually in chromatographic column，Increase chromatographic column function in the middle of modulation solution prewashing，Reduce the impact of substrate further，In analyzing runner, further increase calibration solution，Thus the impact that target components is analyzed by the matrix effect calibrating detector.
Description
Technical field
The invention belongs to liquid chromatograph field, be specifically related to a kind of chromatograph of liquid with solvent replacement function.
Background technology
The material that detector is separated by chromatographic column in the liquid-phase chromatographic analysis detects, and the multiple detector such as existing mass spectrum, fluorescence, electrochemistry is available, and liquid chromatograph and various detection combinations reach the purpose of high sensitivity separation detection.The especially combination (liquid Chromatograph Mass Spectrometer is called for short LC-MS) of liquid chromatograph and Mass Spectrometer Method, frequently as the effective means of detection of complex organic mixture.It is using liquid chromatograph as piece-rate system, and mass spectrum is detecting system.Sample is separated in mass spectrum part and flowing, after being ionized, is separated by mass number by fragment ion through mass spectrographic mass analyzer, and device obtains mass spectrum after testing.Selectivity, high sensitivity are combined by LC-MS with the advantage that can provide relative molecular mass and structural information so that chromatograph and mass spectrum are had complementary advantages, and are widely used in many fields such as pharmaceutical analysis, food analysis and environmental analysis.
Continuous application along with LC-MS, find that detection sensitivity and the stability of different types of detector are had a significant effect by the substrate of sample and the substrate of flowing phase, it is referred to as " matrix effect ", matrix effect refers in sample the impact on determinand measured value of other matrix components in addition to determinand, when changing kind and the concentration of sample substrate, determinand response value on the detector can reduce or increase.Matrix components is derived from chromatographic separation process the material flowed out altogether with the measured object impact on measured object ionization process, and the matrix components currently mainly reported has polymer residue, phthalate, detergent catabolite, ion-pairing agent, organic acid plasma to exchange accelerator and chromatographic column fixed phase h substance etc..The existence of matrix effect can have a strong impact on the quantitative precision to determinand and precision, and influence factor is changeable, is difficult to eliminate.Additionally during the combination of the high sensitivity detector such as liquid chromatograph and fluorescence, detector also can be impacted by flowing phase intermediate ion, Organic substance, solvent.
(2D-LC) developed in recent years, is often used in combination with mass detector, is purified by the multistage chromatography of Two-dimensional Liquid Chromatography, reaches to reduce the purpose of matrix effect.Two-dimensional liquid chromatography is the piece-rate system constituted of being got up by two different and separate for separating mechanism Coupled columns.Sample enters in interface through the chromatographic column of the first dimension liquid phase, by being switched after concentrating, trapping or cut in the chromatographic column and detector entering the second dimension liquid phase, is then detected by rear end mass detector by the material of the second dimension chromatographic isolation.Such first dimension liquid phase removes major part impurity in sample, and salt or sample substrate hence into two-dimensional liquid chromatography are little, such that it is able to " matrix effect " that mass spectrum is caused by minimizing sample and One-Dimensional flows phase mesostroma.
nullBut above technical scheme there is a problem in that sample need to be forced through the first dimension chromatographic column mutually by the flowing of the first dimension liquid chromatograph，Comprise the One-Dimensional flows of the sample object component interface by two-dimensional liquid chromatography，Will enter in the chromatographic column of the second dimension liquid phase，Therefore when the first dimension liquid phase flowing mutually contains high salt concentration (such as phosphate、Acetate) or (such as triethylamine time other improve the modifying agent of chromatographic isolation、Triethylammonium tetrakis、Sodium heptanesulfonate etc.)，These salt or modifying agent also can enter rear end mass detector，Thus cause obvious matrix effect，Especially when One-Dimensional flows phase differs bigger with two-dimensional flow phase constituent，Produced matrix effect becomes apparent from，Thus have a strong impact on quantitative precision and the precision of determinand，The matrix effect that the substrate the most how in online elimination Two-dimensional Liquid Chromatography, One-Dimensional flows brings mutually produces at the second dimension liquid chromatographic system is extremely important.
Summary of the invention
For the deficiencies in the prior art, the problem that present invention seek to address that liquid-phase chromatographic analysis mesostroma effect, mainly realize three below purpose:
An object of the present invention: utilize two-dimensional flow to remove the first flowing phase bringing the second dimension chromatographic system into the most online, it is to avoid the matrix effect that the first flowing causes mutually.
The two of the purpose of the present invention: use assisted solution, clean the prerinse of the middle chromatographic column undertaking capture target components in Two way chromatograms, avoid matrix effect further.
The three of the purpose of the present invention: import calibration solution in two-dimensional liquid chromatography system online, sequential with detected object or simultaneously by detector, thus correct the size that matrix effect produces, further up to the purpose eliminating matrix effect impact.
For achieving the above object, the technical scheme is that
One of technical scheme:
A kind of chromatograph of liquid, including: connect the first flow having the first chromatographic column, for conveying the first flowing phase, and sample is carried out initial gross separation；Second runner, for conveying the second flowing phase；Connect the analysis runner having the second chromatographic column, for the material of capture is separated and detected；First waste liquid runner, is used for getting rid of waste liquid；Also include being provided with multiple interface multiple flow passages switching valve, be provided with multiple port deposit valve, described in deposit to connect between any two ends mouth of valve and have middle chromatographic column；And it being provided with the solution replacing valve of multiple port, connecting between any two ends mouth of described solution replacing valve has gas storage ring；
Any three interfaces one end with the first connecting line, the second connecting line and the 3rd connecting line respectively of described multiple flow passages switching valve is connected, and the other end of described first connecting line and the second connecting line connects with two ports of solution replacing valve respectively；The other end of described 3rd connecting line passes through the manifold any two idle port respectively with the port depositing valve and solution replacing valve and connects；Described first flow, the second runner, analysis runner and waste liquid runner are connected in remaining any one idle interface on multiple flow passages switching valve；Described deposit the 4th connecting line being provided with between valve and solution replacing valve for both being directly connected to；It is also respectively connected with gas input flow road, gas exhaust manifold and the second waste liquid on remaining idle port of described solution replacing valve and discharges runner.
Preferably connected mode: described multiple flow passages switching valve includes interface a, interface b, interface c, interface d, interface e, interface f, interface g and interface j；Described interface a is connected with first flow, and described interface b is connected with waste liquid runner, and described interface c and the first connecting line connect, described interface d is connected with analyzing runner, described interface e and the second runner connect, and described interface f and the second connecting line connect, and described interface j and the 3rd connecting line connect.
Described multiple flow passages switching valve can also include that interface h and interface i, described interface h and interface i are sealed condition.
Preferably connected mode: described in deposit valve and include port a, port b, port c, port d, port e, port f；Being provided with middle chromatographic column (C2), described port e and the 3rd connecting line between described port a and port d to connect, described port f and the 4th connecting line connect.Described port b and port c is sealed condition.
Preferably connected mode: described solution replacing valve includes port g, port h, port i, port j, port k, port l, port m, port n, port o, port p；Being provided with gas storage ring between described port m and port j, on port l, connection has gas input flow road, and on port k, connection has gas exhaust manifold；The first connecting line, the second connecting line, the 4th connecting line, the second waste liquid discharge runner, and the two articles of branch lines being connected with the 3rd connecting line it are connected on remaining port.
Check valve preferably it is equipped with on described two branch lines.
This chromatograph of liquid, by selecting the conducting direction of solution replacing valve port, pushes the gas through gas storage rings with air pump or gases at high pressure；By selecting solution replacing valve another location, select multiple flow passages switching valve and the position depositing valve simultaneously, the second flow paths downstream, gas storage rings, middle chromatographic column is made to communicate, in the middle of now, the solution in chromatographic column and the second runner solution are separated by gas in gas storage rings, avoid the mutually immiscible of two kinds of solution, second runner solution is under infusion pump promotes, in middle chromatographic column, original solution is first released by the gas in gas storage rings, then the second runner solution enters middle chromatographic column, has kept away the replacement of solution in middle chromatographic column.
The two of technical scheme:
A kind of chromatograph of liquid, on the basis of technical scheme one, also includes modulating runner, is used for carrying modulation solution, and described modulation runner is connected in an idle interface of multiple flow passages switching valve, and this idle interface is adjacent with connecting the interface having the second connecting line.Preferably, modulation runner is connected on the interface g of multiple flow passages switching valve.
By cleaning solvent (usually water or the organic solvent of low concentration), the material being captured within middle chromatographic column is carried out prewashing, remove the material that water solublity is bigger, then carry out solution replacement, the impact of substrate can be eliminated further.
The three of technical scheme:
A kind of chromatograph of liquid, on the basis of technical scheme one, also includes the correction switching valve being provided with multiple port, and two ports of described correction switching valve are connected on described analysis runner, and are positioned at the front-end position of the second chromatographic column；Connecting between any two idle port of described correction switching valve and have calibration solution storage ring, remaining idle port has been also respectively connected with calibration solution runner and the 3rd waste liquor stream road.
Preferably connected mode is: described correction switching valve (V4) includes port q, port r, port s, port t, port u, port v；Connecting between described port s and port v and have calibration solution storage rings, described port q and port r to be connected to analyze on runner, described port t, port u are connected with calibration solution runner and the 3rd waste liquor stream road respectively.
Further preferred, described middle chromatographic column is chosen reserve capability and is better than the fixing phase of the first chromatographic column reserve capability.
Calibration solution is imported by correction switching valve analyzing in runner, sequential with detected object or simultaneously by detector, carry out the correction that detector affect by substrate, further up to eliminating the purpose that matrix effect affects.
Technical scheme two and technical scheme three are separate, can be separately added in technical scheme one, it is also possible to be simultaneously introduced in technical scheme one.
In addition to special instruction, multiple flow passages of the present invention switches valve, deposits valve, solution replacing valve and corrects the switching general port of valve or interface is only connected with a pipeline.Multiple flow passages of the present invention switches valve, all and correction switching valve is two switching valves to deposit valve.
In addition to the port being in closed state or interface, the port of connecting line or interface is not had to be referred to as idle port or idle interface.
Compared with prior art, present invention have an advantage that the substrate using the second flowing to remove the first flowing facies tract the most online, simple in construction, and do not introduce other solvents, reduce Operating Complexity；Introduce gas by gas storage ring, the first flowing is the most thoroughly separated with the second flowing mutually, it is to avoid the scavenging period caused that is mutually mixed of two solution extends；Using cleaning solution to clean substrate compatible in intermediolateral column further, the substrate making One-Dimensional flows bring into mutually in the second dimension flowing mutually is less, and the effect reducing " matrix effect " is more preferable；Further increase calibration solution, revise the substrate impact on target components by the change on the detector of the material in calibration solution, further reduce " matrix effect " impact on testing result.
Accompanying drawing explanation
Fig. 1 is the chromatograph of liquid structural representation of embodiment 1；
Fig. 2 is a kind of working state figure of the chromatograph of liquid of embodiment 1；
Fig. 3 is a kind of working state figure of the chromatograph of liquid of embodiment 1；
Fig. 4 is a kind of working state figure of the chromatograph of liquid of embodiment 1；
Fig. 5 is a kind of working state figure of the chromatograph of liquid of embodiment 1；
Fig. 6 is a kind of working state figure of the chromatograph of liquid of embodiment 1；
Fig. 7 is the structural representation of the chromatograph of liquid of embodiment 2；
Fig. 8 is a kind of working state figure of the chromatograph of liquid of embodiment 2；
Fig. 9 is a kind of working state figure of the chromatograph of liquid of embodiment 3；
Figure 10 is a kind of working state figure of the chromatograph of liquid of embodiment 3；
Wherein, 1 is interface a, and 2 is interface b, and 3 is interface c, and 4 is interface d, and 5 is interface e, and 6 is interface f, and 7 is interface g, and 8 is interface h, and 9 is interface i, and 10 is interface j, and 11 is port a, and 12 is port b, and 13 is port c, and 14 is port d, and 15 is port e, and 16 is port f；17 it is port g, 18 is port h, 19 is port i, 20 is port, 21 is port k, 22 is port l, 23 is port m, 24 is port n, 25 is port o, 26 is port p；27 it is port q, 28 is port r, 29 is port s, 30 is port t, 31 is port u, 32 is port v；
AS is injector, and W1 is the first waste port, and W2 is the first waste port, and DE is detector；S1 is the first flowing phase, and S2 is the second flowing phase, and S3 is modulation solution, and S4 is calibration solution；P1 be delivery pump I, P2 be delivery pump II, P3 be delivery pump III, P4 be delivery pump IV, P5 be gasing pump,；C1 is the first chromatographic column, and C2 is middle chromatographic column, and C3 is the second chromatographic column；L3 is first flow, and L13 is the second runner, and L14 is to analyze runner, and L4 is waste liquid runner, and L11 is the first connecting line, and L18 is the second connecting line, and L5 is the 3rd connecting line, and L10 is the 3rd connecting line, and L17 is modulation runner；T1 be threeway I, T2 be threeway II；L7 is the first branch flow passage, and L20 is the second branch flow passage, and L24 is the 3rd branch flow passage, Z1 be check valve I, Z2 be check valve II；L26 is gas input flow road, and L27 is gas exhaust manifold, and L25 is that the second waste liquid discharges runner, and L31 is calibration solution runner, and L34 is the 3rd waste liquor stream road；V1 is that multiple flow passages switches valve, and V2 is to deposit valve, and V3 is solution replacing valve, and V4 is correction switching valve；B1 is gas storage ring, and B2 is calibration solution storage ring；In figure, real point represents that sealed condition, heavy line represent flowing phase glide path.
Detailed description of the invention
The present invention will be further explained with embodiment below in conjunction with the accompanying drawings
Embodiment 1
As it is shown in figure 1, a kind of chromatograph of liquid, including: it is connected with the first flow L3 of injector AS and the first chromatographic column C1 in turn, for conveying the first flowing phase S1, and sample is carried out initial gross separation；Second runner L13, for conveying the second flowing phase S2；Connect the analysis runner L14 having the second chromatographic column C2, for the material of capture is separated and detected；First waste liquid runner L4, is used for getting rid of waste liquid；
Also include being provided with multiple interface multiple flow passages switching valve V1, be provided with multiple port deposit valve V2, described in deposit to connect between any two ends mouth of valve V2 and have middle chromatographic column C2；And it being provided with the solution replacing valve V3 of multiple port, connecting between any two ends mouth of described solution replacing valve V3 has gas storage ring B1；Being connected to the first connecting line L11, the second connecting line L18 and one end of the 3rd connecting line L5 on any three interfaces of described multiple flow passages switching valve V1, the other end of described first connecting line L11 and the second connecting line L18 connects with two ports of solution replacing valve V3 respectively；The other end of described 3rd connecting line L5 can be with the replacement of four-way by threeway IT1, two threeways of threeway IIT2() respectively any two idle port with the port depositing valve V2 and solution replacing valve V3 connect；Described first flow L3, the second runner L13, analysis runner L14 and waste liquid runner L4 are connected in remaining any one idle interface on multiple flow passages switching valve V1；Described depositing is provided with the 4th connecting line L10 for both being directly connected between valve V2 and solution replacing valve V3；It is also respectively connected with gas input flow road L26, gas exhaust manifold L27 on remaining idle port of described solution replacing valve V3 and the second waste liquid has discharged runner L25.
Concrete connected mode:
Described multiple flow passages switching valve V1 includes interface a1, interface b2, interface c3, interface d4, interface e5, interface f6, interface g7, interface h8, interface i9 and interface j10；Described interface a1 is connected with first flow L3, described interface b2 is connected with waste liquid runner L4, described interface c3 and the first connecting line L11 connects, described interface d4 is connected with analyzing runner L14, described interface e5 and the second runner L13 connects, described interface f6 and the second connecting line L18 connects, and described interface j10 and the 3rd connecting line L5 connects.Described interface h8 and interface i9 is sealed condition.Described deposit valve V2 include described in deposit valve V2 and include port a11, port b12, port c13, port d14, port e15, port f16；Being provided with middle chromatographic column C2 between described port a11 and port d14, described port e15 and the 3rd connecting line L5 connects, and described port f16 and the 4th connecting line L10 connects.Described port b12 and port c13 is sealed condition.Described solution replacing valve V3 includes port g17, port h18, port i19, port j20, port k21, port l22, port m23, port n24, port o25, port p26；Being provided with gas storage ring B1 between described port m23 and port j20, on port l22, connection has gas input flow road L26, and on port k21, connection has gas exhaust manifold L27；The first connecting line L11, the second connecting line L18, the 4th connecting line L10, the second waste liquid discharge runner L25, and the two articles of branch lines being connected with the 3rd connecting line L5 it are connected on remaining port.Check valve preferably it is equipped with on described two branch lines.
Function describes:
As shown in Figure 2, first chromatographic column separation function: open delivery pump IP1, make the first flowing phase S1 downstream under the promotion of IP1, sample imports in the first flowing mutually by injector AS, the first flowing containing sample enters the first chromatographic column C1 mutually, and in sample, each component is initially separated under the chromatographic isolation mechanism of the first chromatographic column in the first flowing, conducting multiple flow passages switching valve V1 port a1 and port b2, make the first flowing flow to waste liquid runner L4 mutually, discharge.
nullAs shown in Figure 3，Middle chromatographic column capturing function: open delivery pump IP1，Carry the first flowing phase S1 to downstream，Sequentially pass through injector AS and the first chromatographic column C1，After sample imports to the first flowing mutually by AS，In sample, target components is separated with the chromatographic effect power of the first chromatographic column mutually by the first flowing，When in sample, target components will flow out from the first chromatographic column when，Conducting multiple flow passages switching valve V1 port a1 and port j10，The first flowing containing target components is made to communicate the 3rd connecting line L5、Threeway TI、First branch line L7 flows into and deposits valve V2，After passing through middle chromatographic column C2，The target components having relatively high forces with the second chromatographic column C2 can be captured by the second chromatographic column C2，The component not captured continues downstream in succession with the first flowing，After the 4th connecting pipeline L10 and the first connecting pipeline L11，Flow to multiple flow passages switching valve V1 port c3 and port b2,The first flowing is made to flow to waste liquid runner L4 mutually，Discharge.
As shown in Figure 4, gas storage function: this process can complete in the random time section that gas storage rings are connected with air pump, i.e., open gas transfer pump P5, gas is flowed into, the port l22 and port m23 of conducting solution replacing valve V3 from gas input flow road L26 so that gas is by after gas storage rings B1, after gas exhaust manifold L27 enters the second waste liquid discharge runner L25, discharge.
nullAs shown in Figure 5，Solution replacement function: on the premise of the gas storage function shown in Fig. 4 completes，Open delivery pump IIP2，Second flowing phase S2 is delivered to multiple flow passages switching valve V1，Through interface e5 and interface f6，Solution replacing valve V3 is flowed into after second connecting line L18，Stream is after gas storage ring B1，The gas prestored in gas storage ring B1 is promoted mutually by follow-up second flowing，Continue downstream，From Three branched pipe road L24、Third connecting pipe L5 is flowed into after threeway T2，Flow into after threeway T1 and the first branch line L7 again and deposit valve V2，In the middle of entering after chromatographic column C2，Originally the liquid comprised in middle chromatographic column C2 is first released by gas，The second follow-up flowing enters middle chromatographic column C2 mutually，Complete solution replacement function，The solution being replaced and gas continue to flow into the 4th connecting line L10 and return to solution replacing valve V3，Runner L25 is discharged again through the second waste liquid，Discharge.
As shown in Figure 6, after completing the replacement of solution shown in Fig. 5, the function being analyzed: open delivery pump IIP2, second runner L13 is delivered to multiple flow passages switching valve V1, through interface e5 and interface f6, solution replacing valve V3 is flowed into after second connecting line L18, again through the second branch line L20, flow into after threeway T1 and the first branch line and deposit valve V2, after flowing through middle chromatographic column C2, the target components that middle chromatographic column C2 is captured is by the second flowing phase eluting, the second flowing containing target components continues downstream in succession, flow into the 4th connecting line L10 and return to solution replacing valve V3, again after the first connecting line L11, flow into multiple flow passages switching valve V1, flow into after analyzing runner L14 again, target components separates in the second chromatographic column C3, detected by downstream detector DE.
Embodiment 2
As it is shown in fig. 7, a kind of chromatograph of liquid, on the basis of embodiment 1, also include modulating runner L17, for carrying modulation solution, described modulation runner L17 is connected on any one interface of multiple flow passages switching valve V1, and described interface is the interface adjacent with L18 connectivity port.Preferably, modulation runner L17 is connected on the interface g7 of multiple flow passages switching valve V1.By cleaning solution (usually water or the solvent of low concentration), the material being captured within middle chromatographic column is carried out prewashing, then carry out solution replacement, the impact of substrate can be eliminated further.
nullAs shown in Figure 8，Prewashing function describes: between as shown in Figure 3 after chromatographic column capturing function，Before solution replacement function shown in Fig. 5，A step can be added，Capture material of capture in middle chromatographic column C2 is carried out prerinse，Open delivery pump IIIP3，By assisted solution S3 through auxiliary flow L17 input multiple flow passages switching valve V1，Flow into through the second connecting line again，Solution replacing valve V3 is flowed into after second connecting line L18，Again through the second branch line L20、Flow into after threeway T1 and the first branch line and deposit valve V2，After flowing through middle chromatographic column C2，Cleaned by assisted solution by the component mixed with assisted solution S3 in the component of middle chromatographic column C2 capture，Flow into the 4th connecting line L10 and return to solution replacing valve V3，Again after the first connecting line L11，Flow into multiple flow passages switching valve V1，Waste liquid runner L4 it is flow to mutually again from the first flowing，Discharge.
Embodiment 3
As shown in Figure 9, Figure 10, a kind of chromatograph of liquid, on the basis of embodiment 1, also includes the correction switching valve V4 being provided with multiple port, two ports of described correction switching valve V4 are connected on described analysis runner L14, and are positioned at the front-end position of the second chromatographic column；Connecting between any two idle port of described correction switching valve V4 and have calibration solution storage ring B2, remaining idle port has been also respectively connected with calibration solution runner L31 and the 3rd waste liquor stream road L34.
Concrete connected mode is: described correction switching valve V4 includes port q27, port r28, port s29, port t30, port u31, port v32；Connecting between described port s29 and port v32 and have calibration solution storage rings B2, described port q27 and port r28 to be connected to analyze on runner L14, described port t30, port u31 are connected with calibration solution runner L31 and the 3rd waste liquor stream road L34 respectively.
Calibration function describes:
As shown in Figure 9, calibration solution storage function: opening delivery pump IV P4 will switch valve V4 containing calibration solution S4 of correction component by calibration solution runner L31 entrance correction, after the most corrected solution storage ring B2, make in calibration solution storage ring B2 containing calibration solution, unnecessary calibration solution, from the 3rd waste liquor stream road L34, is discharged.
nullAs shown in Figure 10，Calibration function: open delivery pump IIP2，Second runner L13 is delivered to multiple flow passages switching valve V1，Through interface e5 and interface f6，Solution replacing valve V3 is flowed into after second connecting line L18，Again through the second branch line L20、Flow into after threeway T1 and the first branch line and deposit valve V2，After flowing through middle chromatographic column C2，Flow into the 4th connecting line L10 and return to solution replacing valve V3，Again after the first connecting line L11，Flow into multiple flow passages switching valve V1，(the 4 of V1 can also be turned on、5 ports，It is that the second flowing phase S1 is directly entered analysis runner L14,It is not necessarily required to through depositing valve and replacing valve) entrance correction switching valve V4 after the flows into and analyze runner L14，Enter back into calibration solution storage ring B2，Promote the calibration solution downstream in calibration solution storage ring B2，Correction material enters the second chromatographic column C3 and separates，Detected by downstream detector DE.
Claims (10)
1. a chromatograph of liquid, including:
Connect the first flow (L3) having the first chromatographic column (C1), for conveying the first flowing phase (S1), and sample is carried out initial gross separation；
Second runner (L13), for conveying the second flowing phase (S2)；
Connect the analysis runner (L14) having the second chromatographic column (C3), for the material of capture is separated and detected；
First waste liquid runner (L4), is used for getting rid of waste liquid；
It is characterized in that, also include being provided with multiple interface multiple flow passages switching valve (V1), be provided with multiple port deposit valve (V2), described in deposit to connect between any two ends mouth of valve (V2) and have middle chromatographic column (C2)；And it being provided with the solution replacing valve (V3) of multiple port, connecting between any two ends mouth of described solution replacing valve (V3) has gas storage ring (B1)；
Any three interfaces of described multiple flow passages switching valve (V1) one end with the first connecting line (L11), the second connecting line (L18) and the 3rd connecting line (L5) respectively is connected, and described first connecting line (L11) connects with two ports of solution replacing valve (V3) respectively with the other end of the second connecting line (L18)；The other end of described 3rd connecting line (L5) passes through the manifold any two idle port respectively with the port depositing valve (V2) and solution replacing valve (V3) and connects；Described first flow (L3), the second runner (L13), analysis runner (L14) and waste liquid runner (L4) are connected in remaining any one idle interface on multiple flow passages switching valve (V1)；
Described deposit the 4th connecting line (L10) being provided with between valve (V2) and solution replacing valve (V3) for both being directly connected to；
It is also respectively connected with gas input flow road (L26), gas exhaust manifold (L27) and the second waste liquid on remaining idle port of described solution replacing valve (V3) and discharges runner (L25).
Chromatograph of liquid the most according to claim 1, it is characterized in that, also include modulating runner (L17), for carrying modulation solution, described modulation runner (L17) is connected in an idle interface of multiple flow passages switching valve (V1), and this idle interface has the interface of the second connecting line (L18) adjacent with connection.
Chromatograph of liquid the most according to claim 1 or claim 2, it is characterized in that, also include correction switching valve (V4) being provided with multiple port, two ports of described correction switching valve (V4) are connected on described analysis runner (L14), and are positioned at the front-end position of the second chromatographic column (C3)；Connecting between any two idle port of described correction switching valve (V4) and have calibration solution storage ring (B2), remaining idle port has been also respectively connected with calibration solution runner (L31) and the 3rd waste liquor stream road (L34).
Chromatograph of liquid the most according to claim 1 or claim 2, it is characterized in that, described multiple flow passages switching valve (V1) includes interface a (1), interface b (2), interface c (3), interface d (4), interface e (5), interface f (6), interface g (7) and interface j (10)；Described interface a (1) is connected with first flow (L3), described interface b (2) is connected with waste liquid runner (L4), described interface c (3) is connected with the first connecting line (L11), described interface d (4) is connected with analyzing runner (L14), described interface e (5) is connected with the second runner (L13), described interface f (6) is connected with the second connecting line (L18), and described interface j (10) is connected with the 3rd connecting line (L5).
The most according to claim 4, chromatograph of liquid, is characterized in that, described interface g (7) is connected with modulation runner (L17).
Chromatograph of liquid the most according to claim 1 or claim 2, it is characterized in that, described in deposit valve (V2) and include port a (11), port b (12), port c (13), port d (14), port e (15), port f (16)；Middle chromatographic column (C2) it is provided with between described port a (11) and port d (14), described port e (15) is connected with the 3rd connecting line (L5), and described port f (16) is connected with the 4th connecting line (L10).
The most according to claim 6, chromatograph of liquid, is characterized in that, described port b (12) and port c (13) are sealed condition.
Chromatograph of liquid the most according to claim 1 or claim 2, it is characterized in that, described solution replacing valve (V3) includes port g (17), port h (18), port i (19), port j (20), port k (21), port l (22), port m (23), port n (24), port o (25), port p (26)；It is provided with gas storage ring (B1) between described port m (23) and port j (20), the upper connection of port l (22) has gas input flow road (L26), and the upper connection of port k (21) has gas exhaust manifold (L27)；The first connecting line (L11), the second connecting line (L18), the 4th connecting line (L10), the second waste liquid discharge runner (L25), and the two articles of branch lines being connected with the 3rd connecting line (L5) it are connected on remaining port.
The most according to claim 8, chromatograph of liquid, is characterized in that, described two branch lines are equipped with check valve.
Chromatograph of liquid the most according to claim 3, it is characterized in that, described correction switching valve (V4) includes port q (27), port r (28), port s (29), port t (30), port u (31), port v (32)；Connect between described port s (29) and port v (32) and have calibration solution storage rings (B2), described port q (27) and port r (28) are connected to analyze on runner (L14), and described port t (30), port u (31) are connected with calibration solution runner (L31) and the 3rd waste liquor stream road (L34) respectively.
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| DE102016121516B4 (en) * | 2016-11-10 | 2019-03-28 | Dionex Softron Gmbh | Method and apparatus for sample loading |
| CN114324698A (en) * | 2021-11-19 | 2022-04-12 | 贵阳学院 | Liquid chromatograph pump flow calibrating device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1666878A1 (en) * | 2003-09-05 | 2006-06-07 | Sumitomo Chemical Company, Limited | Liquid chromatographic apparatus |
| CN104330502A (en) * | 2014-11-27 | 2015-02-04 | 王峰 | Liquid chromatograph |
| CN204405612U (en) * | 2015-02-11 | 2015-06-17 | 王峰 | A kind of liquid chromatograph |
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| JP4980740B2 (en) * | 2007-01-31 | 2012-07-18 | 株式会社 資生堂 | Two-dimensional liquid chromatography analysis method and sorting flow path switching unit |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1666878A1 (en) * | 2003-09-05 | 2006-06-07 | Sumitomo Chemical Company, Limited | Liquid chromatographic apparatus |
| CN104330502A (en) * | 2014-11-27 | 2015-02-04 | 王峰 | Liquid chromatograph |
| CN204405612U (en) * | 2015-02-11 | 2015-06-17 | 王峰 | A kind of liquid chromatograph |
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