CN101206197B - System for on-line desalinization, enrichment and mass spectrum of Double tap upgrade liquid chromatogram - Google Patents
System for on-line desalinization, enrichment and mass spectrum of Double tap upgrade liquid chromatogram Download PDFInfo
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- CN101206197B CN101206197B CN2006101349814A CN200610134981A CN101206197B CN 101206197 B CN101206197 B CN 101206197B CN 2006101349814 A CN2006101349814 A CN 2006101349814A CN 200610134981 A CN200610134981 A CN 200610134981A CN 101206197 B CN101206197 B CN 101206197B
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Abstract
The invention relates to a double splitflow nano upgrade liquid phase chromatogram online desalting, enrichment and mass spectrum combination system which comprises a pump, a first splitter, a second splitter, a sample valve, a switching valve, a backpressure valve, a capillary tube separation column and a mass spectrometer, wherein, the pump, the first splitter, the sample valve, the second splitter, the capillary tube separation column and the mass spectrometer are connected in series in turn through pipelines; the split ports of the first splitter and the second splitter are respectively connected with the two inlets of the switching valve through the pipelines; moreover, the outlet of the switching valve is connected in series with the backpressure valve and then is communicated with awaste fluid pool through the pipeline. The system has the advantages that: during the sampling and separation of sample, the system has less pressure fluctuation; with small pre-column dead volume, t he system overcomes the gradient delay effect caused by large-volume sampling adopted in the prior nano upgrade liquid phase separation system; with excellent separation repeatability, the system is particularly suitable for gradient separation; meanwhile, the system can be used in online desalting, enrichment and mass spectrum combination of sample with high salinity and low concentration; moreover, the system has a simple structure, convenient operation and easily realized automation.
Description
Technical field
The present invention relates to differential from system, the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system are received in a kind of specifically double split flow.
Background technology
From the eighties in 20th century, along with the development of chromatographic theory, people come to realise the advantage of differential from system, and are devoted to the research and development of microscale, micrometeor high performance liquid chromatography (HPLC) piece-rate system.In such system, the fused quartz kapillary, PEEK pipe or the PEKSIL pipe that generally use 20-250 μ m internal diameter load filler therein as column jecket.Under the low flow velocity of 0.02-10 μ L/min, carry out the separation of sample, can obtain the post higher and imitate and resolution than conventional H PLC system.Simultaneously, in such micro-dimension system, traditional UV-detector is owing to detect the light path weak point, and detection sensitivity is low, and is no longer suitable.
The appearance of electro-spray ionization (ESI) technology indicates reaching its maturity of liquid-phase separating system and mass spectrometric hyphenated technique.In recent years, development along with the mass spectrometer interface technology, the interface of micrometeor liquid-phase separating system has appearred being suitable in a large number, make the electron spray-mass spectrum (ESI-MS) and the on-line coupling of microtrabeculae HPLC, Capillary Electrophoresis (CE), capillary electric chromatogram (CEC) and pressurization electrochromatography micrometeor (micro updating, the upgrading of receiving) liquid-phase separating systems such as (pCEC) become possibility, and develop into emerging separation detection technology.This combined system has been widely used in fields such as Analysis of environmental samples, medicine and drug metabolism, biological sample, proteomics.
Rise institute's use separating column in the HPLC piece-rate system receiving, its internal diameter is generally below 150 μ m; Flow in the system is generally at 1 μ/below the min.So need more minute sized connecting line, otherwise often cause before the serious post easily and the post aftereffect.But because the restriction of processing technology, the otch of connecting line and the interface of each pipeline are easy to introduce bigger dead volume, influence the separation and the detection of piece-rate system.Particularly when using gradient separations, such influence becomes more serious, simultaneously, uses and is also stopped up by the particulate contaminants in sample or the moving phase easily than the small-bore tubing road.In addition, sample being introduced piece-rate system also is one of reason that causes dead volume.For and system matches, generally can only use miniature sampling valve, the sample size of sample is limited in tens liters of receiving to hundreds of.In order to obtain bigger sample size, also the someone adopts the method sample introduction of off-line.The sample of large volume is directly injected separating column, and then be connected with piece-rate system.But this method troublesome poeration, system's poor repeatability, separating effect is bad, is unfavorable for robotization.The somebody adopts the mode of shunting to come sample introduction, but often needs to waste a large amount of samples.These have all limited the use of this method.
Summary of the invention
The object of the present invention is to provide a kind of double split flow to receive the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system.Utilize the double split flow device, can eliminate the dead volume of system.Liquid-phase chromatographic column can play the effect of desalination and concentrating sample simultaneously, reduces the influence to sample ionsization of salt or other micromolecule.In addition, can also reduce the loss and the pollution of sample, reduce non-volatile salt mass spectral pollution and infringement.Thereby realize online desalination, enrichment and the mass spectrometry of sample.
For achieving the above object, the technical solution used in the present invention is:
Use the form of double split flow that the flow velocity of moving phase in the HPLC separating column received in the upgrading scope.By before separating column, adding two part flow arrangements, make moving phase in the system never distinguish co-located at sample feeding with when separating and shunt.Utilize the reservation of sample on stationary phase, realize online desalination and enrichment salt content height, sample that concentration is low, and and mass spectrometry.
Concrete system comprises: pump, first shunt, second shunt, sampling valve, transfer valve, backpressure valve, capillary separation column and mass spectrometer; Wherein, pump, first shunt, sampling valve, second shunt, capillary separation column and mass spectrometer are contacted successively by pipeline; The diversion port of first shunt and second shunt links to each other with two inlets of transfer valve respectively by pipeline; Feed waste liquid pool by the road behind the outlet of transfer valve and the backpressure valve polyphone.
The flow of described pump is 1 μ L/min.-5mL/min.The upgrading scope flow velocity of receiving can be realized by the pressure limiting device of change system.Pressure limiting device can be backpressure valve, fine inner diameter pipeline, packed column, pressure limiting valve, resistance gauge, pump etc.Can use single pressure limiting device that pressure in the piece-rate system is provided jointly by the stream after the shunting of two part flow arrangements, also can use pressure limiting device that pressure in the piece-rate system is provided respectively.
Described capillary separation column can be reverse-phase chromatographic column, forward chromatographic column, hydrophobic chromatography post, affinity chromatographic column, immobilization metal affinity chromatographic column or size exclusion chromatograph post.
Described first shunt or second shunt can use the multithread pipeline connector to shunt; The multithread pipeline connector can be threeway or four-way.Described sampling valve can be automatic sampler.The shunting of above-mentioned diverse location need at least one be in sampling device before, need at least one be in sampling device after.
Described salt content height, the sample that concentration is low comprise and variously can adsorb on chromatographic column or keep under certain condition, and, comprise protein example, polypeptide sample, biological sample, Chinese medical extract, environmental contaminants and chemical products etc. by the sample that the change condition can wash-out.Be used for sample and when enrichment and wash-out, need change separation condition.These conditions comprise the kind of the kind of moving phase and composition, pH value, ionic strength, direction of an electric field, adjuvant and concentration etc.
The invention has the beneficial effects as follows:
1, the online desalination of upgrading HPLC, enrichment and mass spectrometry system have been realized utilizing conventional liquid chromatography pump to make up receiving.Eliminated the dead volume of introducing by connecting line and sampling device in the system by the double split flow system; Simultaneously, utilize the reservation of sample on liquid-phase chromatographic column, can carry out online desalination and concentrated sample; Make receive the upgrading piece-rate system sampling volume can reach micro updating.
2, realized the online desalination of HPLC, enrichment and and the mass spectrometry of upgrading of receiving of sample.By desalination to sample, can reduce the influence of salt or other micromolecule to sample ionsization, improve the sensitivity of Mass Spectrometer Method.In addition, can also reduce the loss and the pollution of sample, reduce non-volatile salt, can be applicable to the Mass Spectrometer Method of high salt sample mass spectral pollution and infringement.
3, simple, the realization easily of system constructing.Need not use low discharge liquid chromatography pump and little valve, that only need use that conventional pumps can realize piece-rate system receives the upgrading flow; Use general sampling valve can realize a large amount of sample introductions of sample; Utilize the reservation of chromatographic column, can realize sample enrichment and desalination sample.
4, have good versatility, practical, have higher promotional value.This system can be used for the clastotype of multiple and mass spectrum coupling online desalination, enrichment and and mass spectrometry, comprise reverse-phase chromatography, normal-phase chromatography, hydrophobic chromatography, affinity chromatography, immobilization metal affinity chromatography, size exclusion chromatograph etc.
5, applied range.The present invention can be used for two dimension or multi-dimensional chromatograph separates, and comprises the compartment analysis of complex samples such as protein example, polypeptide sample, biological sample, Chinese medical extract, environmental contaminants and chemical products; Can realize conventional piece-rate system and receive the coupling connection of upgrading piece-rate system; Realize robotization easily.
Wherein said conventional piece-rate system can be can't with the piece-rate system of mass spectrum coupling.
Description of drawings
Fig. 1 is the device synoptic diagram of special use of the present invention.System is made up of pump 1, first shunt 2, second shunt 3, sampling valve 4, transfer valve 5, backpressure valve 6, (kapillary) separating column 7 and mass spectrum 8.Can shunt by first shunt 2 and second shunt 3 from the moving phase that pump 1 transports out; Sampling valve 4 is connected between first shunt 2 and second shunt 3, and two shunts link to each other with transfer valve 5 respectively again.At last, path feeds in the waste liquid by backpressure valve 6.Become taper after capillary separation column 7 one of them terminal process heating and the stretching, not only can stationary phase is fixed in the separating column, and can link to each other with mass spectrum; Another end then directly links to each other with second shunt 3.
Fig. 2 receives the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system for using double split flow, the trypsin digestion product of mouse cancer cell albumen is carried out the chromatogram that obtains after the separation detection.
Fig. 3 receives the device synoptic diagram of upgrading HPLC online desalination, enrichment and mass spectrometry system and immobilization affinity chromatography integral post on-line coupling for double split flow of the present invention.
Fig. 4 is that five peptide sections are used immobilization affinity chromatography integral post and double split flow to receive the online desalination of upgrade liquid chromatogram, enrichment and the coupling of mass spectrometry system to carry out the chromatogram that separation detection obtains.Wherein a is total ion current figure, and c and e are the selectivity ion figure of Phosphorylated Peptide, and b, d, f are the selectivity ion figure that does not have the peptide section of reservation on immobilization affinity chromatography integral post.
Fig. 5 uses double split flow to receive the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system, to the separation spectrogram of the bovine serum albumin(BSA) enzymolysis product that contains different salinity.Wherein scheme A and figure C for containing 100mMNH
4HCO
3Sample receive the separation spectrogram that obtains after the online desalination of upgrade liquid chromatogram, the enrichment by double split flow; Figure B is for containing 1MNH
4The sample of Ac is received the separation spectrogram that obtains after the online desalination of upgrade liquid chromatogram, the enrichment by double split flow.
Embodiment
Embodiment 1:
See also Fig. 1, system is made up of pump 1, first shunt 2, second shunt 3, sampling valve 4, transfer valve 5, backpressure valve 6, (kapillary) separating column 7 and mass spectrum 8.Can shunt by first shunt 2 and second shunt 3 from the moving phase that pump 1 transports out; Sampling valve 4 is connected between first shunt 2 and second shunt 3, and two shunts link to each other with transfer valve 5 respectively again.At last, path feeds in the waste liquid by backpressure valve 6.Become taper after capillary separation column 7 one of them terminal process heating and the stretching, not only can stationary phase is fixed in the separating column, and can link to each other with mass spectrum; Another end then directly links to each other with second shunt 3.
When separating column is carried out balance such as Fig. 1-a,, moving phase is shunted at second shunt, 3 places, and first shunt 2 is no longer shunted by control transfer valve 5;
When sample feeding such as Fig. 1-b,, moving phase is shunted at first shunt, 2 places, and second shunt 3 is no longer shunted by control transfer valve 5.Sample enters separating column with the flow velocity in minute fluidization tower, does not shunt, and can guarantee that sample enters separating column fully.Simultaneously, because sample and stationary phase have interaction, can be retained in column cap, the salt in the solution and other do not have material retained then from passing through separating column.By such step, can carry out desalination and enrichment to sample.
When sample is separated,, moving phase is shunted at second shunt, 3 places, and first shunt 2 is no longer shunted by control transfer valve 5; Dead volume by 3-4 introduces under higher flow velocity, can be left in the basket, thereby reaches the effect of eliminating dead volume.
In addition, select for use a backpressure valve 6 as pressure controller in the system, the constant pressure of whole like this system; When transfer valve 5 switches, do not have significant pressure to change, thereby can guarantee the constant of flow velocity in the separating column, can prevent separating column simultaneously because the pressure variation damages.
Fig. 2 receives the online desalination of upgrading HPLC, enrichment and mass spectrometry system for using double split flow, the trypsin digestion product of mouse cancer cell albumen is carried out the chromatogram that obtains after the separation detection.
Embodiment 2:
See also Fig. 3, system is made up of pump 1, first shunt 2, second shunt 3, sampling valve 4, transfer valve 5, backpressure valve 6, (kapillary) separating column 7, immobilization metal affinity chromatography integral post (IMC) 8 and mass spectrum 9.Can shunt by first shunt 2 and second shunt 3 from the moving phase that pump 1 transports out.Sampling valve 4 is connected between first shunt 2 and second shunt 3, and two shunts link to each other with transfer valve 5 respectively again.At last, path feeds in the waste liquid by backpressure valve 6.Become taper after capillary separation column 7 one of them terminal process heating and the stretching, not only can stationary phase is fixed in the separating column, and can link to each other with mass spectrum; Another end then directly links to each other with second shunt 3.
Sample is gone in immobilization metal affinity chromatography (IMAC) integral post 8 by infusion.The polypeptide of phosphorylation and IMAC integrated substrate have specificity to interact can obtain reservation, and other and matrix do not have the material of effect then not to be retained.Use elute soln directly with the Phosphorylated Peptide wash-out, enter the injection annulus of sampling valve 4 after, further compartment analysis again.
Fig. 4 is that 5 polypeptide use double split flows to receive the online desalination of upgrading HPLC, enrichment and mass spectrometry system to carry out resulting chromatogram after the separation detection.2 peptides wherein are after Phosphorylated Peptide is immobilized the selective retention of affinity chromatography integral post, to have obtained Mass Spectrometer Method.
Embodiment 3:
See also Fig. 1, system is made up of pump 1, first shunt 2, second shunt 3, sampling valve 4, transfer valve 5, backpressure valve 6, (kapillary) separating column 7 and mass spectrum 8.Can shunt by first shunt 2 and second shunt 3 from the moving phase that pump 1 transports out.Sampling valve 4 is connected between first shunt 2 and second shunt 3, and two shunts link to each other with transfer valve 5 respectively again.At last, path feeds in the waste liquid by backpressure valve 6.Become taper after capillary separation column 7 one of them terminal process heating and the stretching, not only can stationary phase is fixed in the separating column, and can link to each other with mass spectrum; Another end then directly links to each other with second shunt 3.
When separating column is carried out balance such as Fig. 1-a,, moving phase is shunted at second shunt, 3 places, and first shunt 2 is no longer shunted by control transfer valve 5;
When sample feeding such as Fig. 1-b,, moving phase is shunted at first shunt, 2 places, and second shunt 3 is no longer shunted by control transfer valve 5.Sample enters separating column with the flow velocity in minute fluidization tower, does not shunt, and can guarantee that sample enters separating column fully.Simultaneously, because sample and stationary phase have interaction, can be retained in column cap, the salt in the solution and other do not have material retained then from passing through separating column.By such step, can carry out desalination and enrichment to sample.
When sample is separated,, moving phase is shunted at second shunt, 3 places, and first shunt 2 is no longer shunted by control transfer valve 5.Dead volume by 3-4 introduces can be left in the basket under higher flow velocity, thereby reaches the effect of eliminating dead volume.
In addition, select for use a backpressure valve 6 in the system, can make the constant pressure of whole system as pressure controller.When transfer valve 5 switches, do not have significant pressure to change, thereby both can guarantee the constant of flow velocity in the separating column, can prevent separating column simultaneously again because the pressure variation damages.
Use double split flow to receive the online desalination of upgrading HPLC, enrichment and mass spectrometry system, the bovine serum albumin(BSA) enzymolysis product that contains different salinity is analyzed result such as Fig. 5.In sample, contain NH up to 1M
4During AC (figure B), sample still obtains separation detection.It separates spectrogram and contains 100mM NH
4HCO
3(figure A and scheme C) with the bovine serum albumin(BSA) enzymolysis product to separate spectrogram quite similar, its database retrieval result is no significant difference also.
Claims (7)
1. the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system are received in a double split flow, it is characterized in that: comprise pump (1), first shunt (2), second shunt (3), sampling valve (4), transfer valve (5), backpressure valve (6), capillary separation column (7) and mass spectrometer (8); Wherein, pump (1), first shunt (2), sampling valve (4), second shunt (3), capillary separation column (7) and mass spectrometer (8) are contacted successively by pipeline; One of wherein said capillary separation column (7) terminal through heating with become taper after stretching and link to each other with mass spectrometer; The diversion port of first shunt (2) and second shunt (3) links to each other with two inlets of transfer valve (5) respectively by pipeline; Feed waste liquid pool by the road behind the outlet of transfer valve (5) and backpressure valve (6) polyphone.
2. receive the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system according to the described double split flow of claim 1, it is characterized in that: the flow of described pump is 1 μ L/min.-5mL/min..
3. receive the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system according to the described double split flow of claim 1, it is characterized in that: described capillary separation column (7) is reverse-phase chromatographic column, forward chromatographic column, hydrophobic chromatography post, affinity chromatographic column or size exclusion chromatograph post.
4. receive the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system according to the described double split flow of claim 3, it is characterized in that: described affinity chromatographic column is the immobilization metal affinity chromatographic column.
5. receive the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system according to the described double split flow of claim 1, it is characterized in that: described first shunt (2) or second shunt (3) use the multithread pipeline connector to shunt.
6. receive the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system according to the described double split flow of claim 5, it is characterized in that: described multithread pipeline connector is threeway or four-way.
7. receive the online desalination of upgrade liquid chromatogram, enrichment and mass spectrometry system according to the described double split flow of claim 1, it is characterized in that: described sampling valve (4) is an automatic sampler.
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| EP2524734B1 (en) * | 2011-05-20 | 2015-01-14 | Postnova Analytics GmbH | Apparatus for performing a centrifugal field-flow fractionation comprising a seal which minimizes leakage and method of performing centrifugal field-flow fractionation |
| CN104124131A (en) * | 2013-04-23 | 2014-10-29 | 北京普析通用仪器有限责任公司 | Mass spectrum ion source and mass spectrometer |
| CN105092745B (en) * | 2015-07-31 | 2017-09-12 | 北京市药品检验所 | The method and apparatus for reducing fixedness buffer salt content in LC MS testers |
| CN104991028B (en) * | 2015-07-31 | 2017-10-31 | 北京市药品检验所 | The reduction method of fixedness buffer salt content in LC MS testers |
| CN105891363A (en) * | 2016-04-08 | 2016-08-24 | 厦门大学 | Multi-probe liquid chromatography tandem mass spectrometry point plate device |
| CN110568086A (en) * | 2018-06-05 | 2019-12-13 | 深圳华大生命科学研究院 | Capillary chromatographic column device and liquid chromatographic separation method |
| CN112578017B (en) * | 2020-11-11 | 2022-08-02 | 威海职业学院 | Rapid detection method and detection device for organic matters in high-salinity water |
| CN115931482A (en) * | 2023-01-09 | 2023-04-07 | 深圳中国计量科学研究院技术创新研究院 | Multichannel real-time online sampling device and mass spectrometer |
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| CN1065529A (en) * | 1991-04-01 | 1992-10-21 | 山东省化学研究所 | The method of capillary supercritical fluid chromatography desolventizing and desolventizing split sampling system thereof |
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