CN106053689B - The sampling time can accurately be obtained arrheas type two-dimensional liquid chromatography and its application manually - Google Patents
The sampling time can accurately be obtained arrheas type two-dimensional liquid chromatography and its application manually Download PDFInfo
- Publication number
- CN106053689B CN106053689B CN201610571942.4A CN201610571942A CN106053689B CN 106053689 B CN106053689 B CN 106053689B CN 201610571942 A CN201610571942 A CN 201610571942A CN 106053689 B CN106053689 B CN 106053689B
- Authority
- CN
- China
- Prior art keywords
- liquid chromatography
- dimension
- relay
- positions
- way valve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/46—Flow patterns using more than one column
- G01N30/461—Flow patterns using more than one column with serial coupling of separation columns
- G01N30/463—Flow patterns using more than one column with serial coupling of separation columns for multidimensional chromatography
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention discloses it is a kind of can accurately obtain the sampling time manually arrhea type two-dimensional liquid chromatography and its application, the chromatogram is used as flow passage selector device using a two-way trigger of Manual multi-way valve series connection, successfully solve and arrhea the problem of type two-dimensional liquid chromatography can not accurately obtain the sampling time and arrhea instantaneous pressure pulse, and there is provided the two-dimensional liquid chromatography system architecture of complete set, so as to dramatically improve the accuracy and repeatability of arrheaing the analysis of type two-dimensional liquid chromatography, and realize the practical application for arrheaing type two-dimensional liquid chromatography.
Description
Technical field
The invention belongs to Instrumental Analysis field, and in particular to one kind arrheas type two-dimensional liquid chromatography, and more particularly to one kind can
Arrhea type two-dimensional liquid chromatography and its application accurately to obtain the manual of sampling time.
Background technology
Two-dimensional liquid chromatography can utilize two kinds of identical or different chromatogram modes simultaneously as a kind of novel liquid-phase chromatogram
Two dimensional separation is carried out to sample component, thus with higher separating degree, it is analyzed and separating capacity is much stronger than one-dimensional liquid phase color
Spectrum.
Two-dimensional liquid chromatography mainly realizes the first dimension liquid chromatogram component to second between bidimensional by switching device
Control between the transfer of dimension liquid chromatogram and bidimensional, thus switching device is very crucial to having in two-dimensional liquid chromatography
Function and significance.Multiple-way valve is as a kind of conventional switching valve, with interface is more, guiding gutter is more, dead volume is small, easy to operate etc.
Many merits, thus it is often used as the core of switching device.
Multiple-way valve is divided into electronic and manual two types, its switching part of the multiple-way valve of both types according to driving type
Structure is basically identical, is constituted by round gasket (rotor) and firm banking (stator), rotor is pivotable parts, rotor table
There is the groove of indent in face, plays the end interface of connectivity slot two, and stator is then fixed, has multiple interfaces to be used for and color above
Spectrum pipeline is connected.Do not have slotted two end interface to completely enclose on rotor, and when motor or manual drive rotor are rotated, water conservancy diversion
Groove rotates therewith, so as to change the connected relation of chromatogram pipeline on stator.
Manual multi-way valve is with electric multi-way valve in addition to type of drive is different, and Manual multi-way valve is produced to reduce manual operation
Raw error, qualitative repeatablity and precision during raising chromatography, Chang Qi valves are embedded in a location sensitive switch
(trigger), location sensitive switch is connected with the line trigger signal of chromatographic work station, is switched when rotating the location sensitive manually
During to inject positions, switch is closed immediately, so that sample introduction (inject) signal of chromatographic work station is triggered rapidly, chromatogram work
Station is recognized after the signal, carries out initialization process to each detector and infusion pump immediately, the timing operation elution ladder since 0
Degree, and the signal of each detector is acquired.This trigger greatly reduces manual operation error, and in all kinds of lists in the early time
Tie up extensive use in liquid chromatogram.
But the trigger can only realize a signal triggering in a flash in switch closure, during while in inject positions
Location sensitive switch is constantly in closure state, can not also realize lasting triggering, when multiple-way valve goes to load positions, switch
Disconnect, equally spread out of without any trigger signal, multiple-way valve must be gone to load positions by being triggered next time, then be turned again
Go back to inject positions.And arrhea type two-dimensional liquid chromatography and be required to accurate time started and end when sampling starting and ending
Time, the sampling volume that two-dimensional liquid chromatography is transferred in liquid chromatogram outflow component is tieed up with accurate calculating first.Thus
Existing Manual multi-way valve, which can not be met, arrheas type liquid chromatographic system service requirement, seriously hinders and high-precision arrheas type manually
Two way chromatograms develop.
Due to arrheaing type two-dimensional liquid chromatography when carrying out full two-dimension analysis, take longer, and there is pressure pulse etc. and ask
Topic, to accelerate analyze speed, existing chromatogram enterprise have selected continuous loop switch type two-dimensional liquid chromatography system, point of the chromatogram
Analysis speed is exceedingly fast, and resolution ratio is higher.But the type chromatogram cost is high, because the analysis of two-dimensional liquid chromatography is by first
Dimension liquid chromatogram is seriously restricted, and is that this its analytical cycle is extremely short (often even shorter for 30s), this causes its two-dimensional liquid chromatography
System must use supper-fast liquid phase or ultrahigh pressure liquid phase to meet the requirement that it is quickly analyzed.And the high request of hardware device enters
One step result in the sky high cost and maintenance cost of the type chromatographic system.The chromatogram column life of the chromatographic system is extremely short, its pump head
The chromatogram such as sealing ring consumptive material abrasion probability is also high, it is necessary to high maintenance cost.Further, since two-dimensional liquid chromatography is necessary
Run under ultra-high pressure condition, its two-dimensional liquid chromatography can not use can not high pressure resistant and high flow rate gel column as second
Liquid-phase chromatographic column is tieed up, and the type chromatographic column has in point analysis of variance of all kinds of materials such as polypeptide, polysaccharide and protein
Extremely wide application, is that this type two-dimensional liquid chromatography systematic difference field receives extensive limitation.And it is used as one kind two
The complete machine of liquid chromatogram is tieed up, to realize the accurate control of analytical cycle, is equally had to using motor-driven valve control, while to realize
The coordination control of chromatographic system, device chromatographic work station also needs to recompilate.Therefore, having further resulted in existing commercial Two way chromatograms
The high price of system, more than 4 times of almost existing common highly effective liquid phase chromatographic system.
Arrhea type two-dimensional liquid chromatography as a kind of operational mode and be totally different from the commercial two dimension of existing continuous loop switch type
The chromatographic system of liquid chromatogram, with instrument hardware require low, resolution ratio it is high, dead volume is small, it is simple to operate the characteristics of.Arrhea
Any existing two one-dimensional liquid chromatograies composition can be used in type two-dimensional liquid chromatography, and instrument maintenance and the cost run are extremely low.This
Outside, arrhea the two-dimensional liquid chromatography of type two-dimensional liquid chromatography its analysis process not restricted by the first dimension liquid chromatogram completely,
Thus can realize under normal conditions sample component it is long when efficiently separate, it is compatible use any existing chromatographic column, especially
Including gel column.Seldom paid close attention to yet with type two-dimensional liquid chromatography is arrheaed by apparatus manufacture, for grinding for the type chromatogram
Study carefully also few, there are problems in its running can not solve, and seriously hinder the popularization of the type chromatogram.
High performance liquid chromatography is widely present in domestic and international each size research institution as a kind of widely used analytical instrument,
With deepening continuously for scientific research, requirement of the scientific research personnel to the complicated ingredient point analysis of variance is improved constantly, existing one-dimensional liquid phase color
Spectrum has started to that existing analysis demand can not be met, but existing business two-dimensional liquid chromatography price is prohibitively expensive so that vast section
The personnel of grinding hang back, and arrhea concern and research and development of the type two-dimensional liquid chromatography due to lacking opticians, still without any shaping
Commercialization arrhea type two-dimensional liquid chromatography or the upgrading scheme for the type chromatogram, and arrhea manually type two-dimensional liquid chromatography due to
Without the chromatographic work station that can mutually coordinate therewith, it is impossible to obtain the accurate sampling time, and there is pressure pulse in chromatographic system, together
When lack detailed and complete operating structure and guide for method, be that this scientific research personnel must not go on one-dimensional chromatography.
However, the research and development for arrheaing type two-dimensional liquid chromatography has high application value, it will be in complicated ingredient in future
Had broad prospects in terms of separation analysis.
The content of the invention
In order to overcome the existing type two-dimensional liquid chromatography that arrheas can not accurately obtain sampling time and the moment of arrheaing presence
The problem of pressure pulse, and make up relevant art blank both at home and abroad in terms of type two-dimensional liquid chromatography is arrheaed, head of the invention
Syllabus be provide it is a kind of can accurately obtain the sampling time manually arrhea type two-dimensional liquid chromatography, the chromatogram use one
Manual multi-way valve connects two-way trigger as flow passage selector device, successfully solve arrhea type two-dimensional liquid chromatography can not be accurate
The problem of obtaining the sampling time and arrhea instantaneous pressure pulse, and there is provided the two-dimensional liquid chromatography system knot of complete set
Structure, so as to dramatically improve the accuracy and repeatability for arrheaing the analysis of type two-dimensional liquid chromatography, and realizes and arrheas type
The practical application of two-dimensional liquid chromatography.
Another object of the present invention is to provide the above-mentioned purposes for arrheaing type two-dimensional liquid chromatography manually.
The purpose of the present invention is achieved through the following technical solutions：
One kind arrheas type two-dimensional liquid chromatography manually, including first ties up separate section, arrheas switching device and the second dimension point
From detection part；
The first dimension separate section is made up of the first dimension liquid chromatography pump, injector and the first dimension chromatographic column；
Described switching device of arrheaing is made up of Manual multi-way valve one two-way trigger of series connection；
Described two-way trigger is made up of dc source, relay and controlling switch；
The second described dimension separation detection part is made up of the second dimension liquid chromatography pump, the second dimension chromatographic column and detector；
The Control end of the two-way trigger is composed in series with dc source, multiple-way valve location sensitive switch successively
Governor circuit, and relay is connected to form controlled circuit with another controlling switch and chromatographic work station signal wire, its specific connection
Mode is：The normal-closed end of relay controlled terminal and the normally opened end of controlling switch are connected, normally opened end and the control of relay controlled terminal
The normal-closed end connection of switch, the public port of relay controlled terminal and the public port of controlling switch respectively with chromatographic work station
Line trigger signal two ports connection；
During sample states, multiple-way valve is in load positions, and the end position of multiple-way valve and No. 1 position, No. 2 positions and No. 3 positions,
No. 4 positions are connected with No. 5 positions by guiding gutter；The output end of first dimension separate section and the end position of multiple-way valve are connected, and second
Tie up the output end of liquid chromatography pump and No. 2 positions of multiple-way valve are connected, the input of the second dimension chromatographic column and No. 3 positions of multiple-way valve connect
Connect, quantitative loop is connected with 1 and No. 4 position of multiple-way valve respectively, No. 5 positions connection of sewer pipe and multiple-way valve；Remaining port uses stifled
Head closing；Now, the outflow component of the first dimension separate section flows through quantitative loop by multiple-way valve, finally flows to sewer pipe, and double
To the controlling switch now contactor where closing relay normally opened contact of trigger；
When sampling terminate enter detection state after, set first tie up liquid chromatography pump flow velocity be 0, while by multiple-way valve from
Load positions go to inject positions, now, No. 1 position of multiple-way valve and No. 2 positions, No. 3 positions and No. 4 positions, No. 5 positions and No. 6 positions, ends
End position is communicated with penultimate position by guiding gutter；Number position communicated with end position is closed using plug, thus the
The outlet of one-dimensional separate section is closed, so that its pressure is maintained, and the output mobile phase of the second dimension liquid chromatography pump
Quantitative loop is then flowed through by multiple-way valve pour the component in quantitative loop and eluted in the second dimension liquid-phase chromatographic column, and pass through inspection
Device is surveyed to be detected；In addition, when multiple-way valve turns to inject positions, its location sensitive switch closure, now relay is rapid
Energization work, its normally-closed contact is disconnected rapidly, and normally opened contact is connected rapidly, so that chromatographic work station line trigger signal is closed,
Trigger chromatographic work station sample introduction signal, recorded by chromatographic work station rapidly, it is to be triggered after the completion of, by two-way trigger control open
Off-position disconnects in the contact where relay normally open circuit, and the contact where closing relay normally-closed circuit, because of chromatogram work
The disconnection to signal wire stand without response, therefore the second dimension liquid chromatographic system is had no effect；
Treat after the completion of the second dimension liquid-phase chromatographic analysis, multiple-way valve is rotated again and is entered again from inject positions to load positions
Enter sample states, at the same recover first tie up liquid chromatography pump flow velocity, quantitative loop is filled again, and two-way trigger by
The disconnection switched in location sensitive, relay disconnects rapidly its normally opened contact, closes its normally-closed contact, because trigger control is opened
Close circuit where advance closing relay normally-closed contact, therefore chromatographic work station signal wire rapid closing, further trigger into
Sample signal, is recorded rapidly by chromatographic work station, is treated after the completion of signal triggering, two-way trigger controlling switch is located at by continuation
Switch contact disconnects where relay normally-closed circuit, by the closing of contact where relay normally open circuit；
After state to be sampled terminates, then detection state is gone successively to, sample introduction signal will be now triggered again, passes through chromatogram work
Make the data processing stood, can accurately obtain the initial time of the duration sampled every time and Two way chromatograms detection；Treat
After the completion of two dimension is analyzed again, then the first dimension sample states are reentered, sample analysis is recycled to according to this and is terminated.
A number position for the multiple-way valve is only to show system annexation and use, and its specifically used position can supply with manufacturer
Original position difference, its number position name and sequence can be since any interfaces of multiple-way valve according to counterclockwise or clockwise since 1
Sequence name；
The interface of the multiple-way valve is even number, and number of ports must be at least 6, i.e., at least six-way valve, can be eight
Port valve, ten-way valve etc.；
Described multiple-way valve is two multiple-way valves, you can the screens of positive anti-switching；
Described multiple-way valve is Manual multi-way valve, and must have location sensitive switch；
The dc source of the two-way trigger can be battery, or D.C. regulated power supply, its voltage must meet relay
The requirement of device rated operational voltage；
The relay of the two-way trigger at least must open one for one and close relay；The relay can be electromagnetism relay
Any one in device, solid-state relay, reed switch relay, reed relay, temperature relay or optical relay；
The relay rated operational current of the two-way trigger is no more than Manual multi-way valve position inductive switch most
Big operating current；
The controlling switch of the two-way trigger can be the double control switch of a single-pole double throw, also can be by two single control switches
Composition；The controlling switch can be alternatively button switch for toggle switch；
Described chromatogram pump can be many pumps or single pump, can be any one in high pressure, middle pressure or low pressure liquid phase pump；
Described sampling device can be manual or electronic；
The first dimension chromatographic column, the second dimension chromatographic column can be conventional H PLC chromatographic columns；The second dimension chromatographic column will be with
Liquid phase separation condition coupling, if the second dimension liquid chromatography pump is high-pressure pump, and runs under condition of high voltage, then the second dimension liquid phase color
Spectrum post is high pressure liquid chromatography post；
Described two-dimensional detector can be the applicable any detector of existing liquid chromatogram, such as UV-detector, show
The static laser light scattering instrument of difference detector, 18 angles.
The present invention's arrheas detection of the type two-dimensional liquid chromatography available for characteristic component and poisonous and harmful substance, including food
The detection in product field etc..
The present invention has the following advantages and effect relative to prior art：
1st, the type two-dimensional liquid chromatography that arrheas of the invention realizes Manual multi-way valve come back rotation mistake using two-way trigger
Two-way triggering in journey, so that scientific research personnel can accurately obtain the first dimension liquid chromatogram during chromatographic data Treatment Analysis
The duration sampled and the initial time of the second dimension liquid chromatographic detection, completely solve and arrhea type Two-dimensional Liquid manually
The repeatability of phase chromatogram and accurate sex chromosome mosaicism.
2nd, it is of the invention to arrhea type two-dimensional liquid chromatography during arrheaing, cause the first dimension using the plug of adjacent interface
Pressure of the liquid chromatogram in holding process is maintained, and the problem of instantaneous pressure is mutated is arrheaed so as to solve.
3rd, the type two-dimensional liquid chromatography that arrheas of the invention is carried out using quantitative loop to the outflow component of the first dimension liquid chromatogram
Indirect branch, it is to avoid to the pressure produced by two-dimensional liquid chromatography and detection sign mutation during direct transfer, make it simultaneous
Hold any existing liquid chromatogram detector, such as differential refraction device, UV-detector.
4th, the switching device in two-dimensional liquid chromatography system of the invention is only made up of a multiple-way valve, solves same time control
The problem of repeatability and stability are poor when making multiple valves, dramatically improves the reliability and rapidity of system.
5th, the of the invention point analysis of variance for arrheaing type two-dimensional liquid chromatography its two-dimensional liquid chromatography can be completely by the
The limitation of one-dimensional liquid-phase chromatographic analysis time, the first dimension target components can be carried out using gradient or isocratic analysis mode separation and
Analysis, thus chromatographic resolution rate is higher.
6th, the of the invention type two-dimensional liquid chromatography that arrheas is extremely low to chromatogram hardware device requirement, utilizes two low pressure liquid phase colors
Compose and its carry manual six-way injection valve, then be aided with a two-way trigger and can constitute one and complete arrhea type two dimension manually
Liquid chromatogram.
7th, of the invention type two-dimensional liquid chromatography its two-way trigger materials of arrheaing are extensively and cheap, compatible using all kinds of
Relay and controlling switch are produced, in addition, its versatility is extremely strong, any a liquid phase available for domestic and international all big enterprises
Chromatogram.
8th, of the invention type two-dimensional liquid chromatography system its second dimension liquid-phase chromatographic analysis of arrheaing is not by the first dimension liquid phase color
The limitation of analysis of spectrum, you can run under high pressure-temperature conditions of high flow rate, can also run with the conditions of low-pressure low-temperature low flow velocity, because
And the not high pressure resistant, non-refractory of compatible use and the gel chromatographic columnses intolerant to high flow rate carry out separation point to complex compound
Analysis.
Brief description of the drawings
Fig. 1 is the circuit diagram of two-way trigger in embodiment 1；
Fig. 2 is the circuit diagram of two-way trigger in embodiment 2；
Wherein, i1- dc sources；I2- relays；I3- controlling switches；A- relays i2 magnet coil；B- relays
I2 controlled switch.
Fig. 3 is two-dimensional liquid chromatography connection diagram when embodiment 1 is in sample states；
Fig. 4 is two-dimensional liquid chromatography connection diagram when embodiment 1 is in detection state；
Fig. 5 is two-dimensional liquid chromatography connection diagram when embodiment 2 is in sample states；
Fig. 6 is two-dimensional liquid chromatography connection diagram when embodiment 2 is in detection state；
Wherein, a- chromatogram pumps；B- sampling devices；C- first ties up chromatographic column；D- multiple-way valves；E- quantitative loops；F- chromatogram pumps；g-
Second dimension chromatographic column；H- two-dimensional detectors.
Fig. 7 is the dimension chromatogram of sample first of embodiment 1.
Fig. 8 is the sample two-dimensional chromatogram of embodiment 1.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
One kind arrheas type two-dimensional liquid chromatography manually, as shown in Figure 3-4, including first ties up separate section, arrheas switching dress
Put and the second dimension separation detection part；
The switching device of arrheaing is made up of a manual eight ways valve d of four groove two and a two-way trigger, wherein eight
No. 6 positions and No. 7 positions of port valve are closed using plug.
Two-way trigger (as shown in Figure 1) is by an electromagnetic relay i2, a single-pole double-throw switch (SPDT) i3 and a direct current
Power supply i1 is constituted.Electromagnetic relay i2 control ends are composed in series master with dc source i1, eight ways valve d location sensitive switch successively
Circuit is controlled, and electromagnetic relay i2 and single-pole double-throw switch (SPDT) i3 is connected to form controlled circuit with chromatographic work station signal wire, it has
Body connected mode is：The normal-closed end 2 of relay i2 controlled terminals is connected with single-pole double-throw switch (SPDT) i3 normally opened end 2, relay i2 quilts
The normally opened end 1 at control end is connected with the normal-closed end 1 of controlling switch, and the public port of relay i2 controlled terminals is opened with 3 and single-pole double throw
The public port 3 for closing i3 is connected with two ports of the line trigger signal of chromatographic work station respectively.
When in sample states (Fig. 3), eight ways valve d is in load positions, and its location sensitive switch is off,
The controlling switch i3 of two-way trigger connects its normally-closed contact 1, and relay i2 connects its normally-closed contact 2, now due to chromatogram
The open circuit of work station signal firing line, sends from without trigger signal.Now, first dimension liquid chromatography pump a by mobile phase pump extremely
Automatic sampler b, sample is pumped into chromatographic column c, and it flows out No. 8 positions that component enters the d of eight ways valve, then by No. 1 bit stream
Enter quantitative loop e, then sequentially pass through 4 and No. 5 bit streams to waste liquid barrel.Now, the second dimension liquid chromatography pump f output mobile phase is flowed through
Eight ways valve d 2 and No. 3 positions enter back into waste liquid barrel directly through chromatographic column g and detector h.
At the end of sampling, it is 0 to set the first flow velocity for tieing up liquid chromatography pump a, while eight ways valve d is turned from load positions
Move to inject positions, into detection state (Fig. 4), now, eight ways valve d location sensitive switch closure, master where relay A
Control circuit is powered rapidly work, and controlled switch B normally opened contact 1 is switched on rapidly, so that the triggering of chromatographic work station signal
Line is closed, and is sent trigger signal, is recorded immediately by chromatographic work station, and the acquisition testing device signal number since the time point
According to, it is to be triggered after the completion of, single-pole double-throw switch (SPDT) i3 contact 1 is disconnected, make contact 2, be next time triggering prepare.This
When, the stream of the first dimension liquid chromatogram reaches No. 7 positions by No. 8 positions, because No. 7 positions are closed by plug, so that the first dimension
Chromatogram column pressure is maintained.Meanwhile, the second dimension liquid chromatography pump f output mobile phase is quantitative by No. 2 positions and No. 1 bit stream warp
Ring e, chromatographic column g is poured by the sample component in quantitative loop e by No. 4 positions and No. 3 positions, then by detector h carry out elution and
Detection.
After the second dimension liquid-phase chromatographic analysis terminates, eight ways valve d is rotated further from inject positions to load positions, again
Into sample states, now eight ways valve d location sensitive switch is disconnected immediately, and relay i2 is no longer worked, and its quilt is disconnected rapidly
Control switch B normally opened contact 1, connects its normally-closed contact 2, now chromatographic work station line trigger signal is closed again, is triggered immediately
The sample introduction signal of chromatographic work station, is recorded rapidly by chromatographic work station, it is to be triggered after the completion of, by the normal of single-pole double-throw switch (SPDT) i3
Open contact 2 to disconnect, connect its normally-closed contact 1, prepare sample introduction next time and trigger.Now, eight ways valve d stream situation is adopted with foregoing
Sample state consistency.After end to be sampled, then eight ways valve d is rotated further from load positions to inject positions, will now be touched again
Send out sample introduction signal, it is to be triggered after the completion of, continue operate single-pole double-throw switch (SPDT), connect its normally opened contact 2, disconnect its normally-closed contact 1,
Prepared to trigger next time.The stream situation of eight ways valve then with foregoing detection state consistency.Treat that the second dimension analyzes completion again
Afterwards, then the first dimension sample states are reentered, sample analysis is recycled to according to this and is terminated；By the data processing of chromatographic work station,
The initial time of the duration sampled every time and Two way chromatograms detection can accurately be obtained.
Further to prove the novelty of the present invention, using C18 posts as the first dimension liquid-phase chromatographic column, and use can not be made
The gel chromatographic columnses for tieing up liquid-phase chromatographic column for conventional two-dimensional chromatographic system second tie up liquid-phase chromatographic column as the second of the system, and
So that two-dimensional liquid chromatography gel column is run under the usual operating conditions of low pressure low flow velocity.Two-way trigger is steady using direct current
Voltage source, electromagnetic relay and double control switch assembling.
Sample：Peanut peptide
First dimension separate section includes：Mesolow infusion pump a (AKTA Explorer10 (P900)), automatic sampler b
The chromatographic column c of (Waters 2707), the first Vc 18 (Waters Xselect CSH130,4.5 × 250mm, 5 μm).Mobile phase by
Acetonitrile (12%), water (88%) and trifluoroacetic acid (0.08%) composition, using isocratic elution, sample states flow velocity 0.3mL/min,
It is 0 to arrhea state flow velocity, and each sampling time length is 0.5min.Two-dimensional liquid chromatography is not connect, directly tie up chromatogram first
Result such as Fig. 7 during access UV-detector (Detection wavelength 220nm) one-dimensional continuous Run sample of post rear end.
Arrhea switching device to be made up of a manual eight ways valve (Valco C8W) and two-way trigger, two-way trigger master
Will by a D.C. regulated power supply (5V 1Amax, millet company), an electromagnetic relay (Omron, G2R-1-5VDC) and
One double control switch (wheat praises 1121 small-sized 3 pin of ON-ON, 2 grades of single-pole double throw power switches of shaking the head) composition.
Second dimension separation detection part includes：Middle pressure infuser pump f (Waters 600), the second dimension gel chromatographic columnses g
(Thermo Biobasic SEC 60), the second dimension UV-detector h (Waters 2487).It is using chromatographic work station
Empower 2.0 and Astra 6.1.Mobile phase is made up of acetonitrile (20%), water (80) and trifluoroacetic acid (0.04%), using etc.
Degree elution, flow velocity 1.8mL/min, Detection wavelength：220nm, run time interval 10min.When Two way chromatograms are run, selection first
Chromatographic isolation elution fraction 9.5-10.5min is tieed up as two-dimension analysis target, analysis result such as Fig. 8.
The peptide composition of peanut peptide can once be divided under one-dimensional chromatographic condition from C18 posts in Fig. 7 and 8, Fig. 7
From, and separating effect is preferable.But combine Fig. 8 and understand, it is of the invention arrhea type two-dimensional liquid chromatography manually can be in one-dimensional liquid phase
Further realized on the basis of chromatogram in secondary separation, Fig. 7 it is separated to unimodal enter one in two-dimensional liquid chromatography
Step is separated into for more peaks, pure this further illustrates being not necessarily by unimodal obtained by one-dimensional liquid chromatogram
Product.
In addition, as shown in Figure 8, it can make to arrhea type two-dimensional liquid chromatography manually using two-way trigger and accurately remember respectively
The starting and ending time of sample states and detection state is recorded, type two-dimensional liquid chromatography is arrheaed manually so as to dramatically improve
Repeatability and accuracy.Embodiments of the invention have absolutely proved the innovation for arrheaing type two-dimensional liquid chromatography manually of the present invention
Property and its complicated ingredient separate analysis broad prospect of application.
Embodiment 2
One kind arrheas type two-dimensional liquid chromatography, as seen in figs. 5-6, as different from Example 1, and it arrheas switching device institute
It is two grooves, two six-way valves (7725i) with multiple-way valve d, the power supply i1 of two-way trigger (as shown in Figure 2) used is battery, used
The controlling switch i3 of two-way trigger is made up of two single control switches 1 and 2, respectively with embodiment 1 controlling switch i3 it is normally closed
Contact 1 and normally opened contact 2 are corresponding.In addition, its sampling device b uses manual injector, the second dimension liquid chromatography pump f is using single
Pump.In addition, its construction and operation principle are consistent with embodiment 1.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of arrhea type two-dimensional liquid chromatography manually, including first ties up separate section, arrheas switching device and two dimensional separation
Detection part；It is characterized in that：
Described switching device of arrheaing is made up of Manual multi-way valve one two-way trigger of series connection；
Described two-way trigger is made up of dc source, relay and controlling switch；
The Control end of the two-way trigger is composed in series master control with dc source, multiple-way valve location sensitive switch successively
Circuit, and relay is connected to form controlled circuit with another controlling switch and chromatographic work station signal wire, its specific connected mode
For：The normal-closed end of relay controlled terminal and the normally opened end of controlling switch are connected, the normally opened end of relay controlled terminal and controlling switch
Normal-closed end connection, the public port of relay controlled terminal and the public port of controlling switch are touched with chromatographic work station respectively
Two ports connection of signalling line；
During sample states, multiple-way valve is in load positions, and the end position of multiple-way valve and No. 1 position, No. 2 positions and No. 3 positions, No. 4
Position is connected with No. 5 positions by guiding gutter；The output end of first dimension separate section and the end position of multiple-way valve are connected, Two-dimensional Liquid
The output end of phase chromatogram pump and multiple-way valve No. 2 positions are connected, and the input of the second dimension chromatographic column and No. 3 positions of multiple-way valve are connected,
Quantitative loop is connected with 1 and No. 4 position of multiple-way valve respectively, No. 5 positions connection of sewer pipe and multiple-way valve；Remaining port is sealed using plug
Close；Now, the outflow component of the first dimension separate section flows through quantitative loop by multiple-way valve, finally flows to sewer pipe, and two-way tactile
Send out the controlling switch of device now contactor where closing relay normally opened contact；
After sampling terminates to enter detection state, it is 0 to set the first flow velocity for tieing up liquid chromatography pump, while by multiple-way valve from load
Position goes to inject positions, now, No. 1 position of multiple-way valve and No. 2 positions, No. 3 positions and No. 4 positions, No. 5 positions and No. 6 positions, ends number
Position is communicated with penultimate position by guiding gutter；Number position communicated with end position is closed using plug, thus the first dimension
The outlet of separate section is closed, so that its pressure is maintained, and the output mobile phase of the second dimension liquid chromatography pump is then led to
Cross multiple-way valve and flow through quantitative loop and pour the component in quantitative loop and eluted in the second dimension liquid-phase chromatographic column, and pass through detector
Detected；In addition, when multiple-way valve turns to inject positions, its location sensitive switch closure, now relay is powered rapidly
Work, its normally-closed contact is disconnected rapidly, and normally opened contact is connected rapidly, so as to close chromatographic work station line trigger signal, is triggered
Chromatographic work station sample introduction signal, is recorded rapidly by chromatographic work station, it is to be triggered after the completion of, by two-way trigger controlling switch position
Disconnected in the contact where relay normally open circuit, and the contact where closing relay normally-closed circuit, because of chromatographic work station pair
The disconnection of signal wire has no effect without response to the second dimension liquid chromatographic system；
Treat after the completion of the second dimension liquid-phase chromatographic analysis, rotation multiple-way valve is reentered from inject positions to load positions again adopts
Sample state, while recovering the first flow velocity for tieing up liquid chromatography pump, is filled to quantitative loop again, and two-way trigger is due to position
The disconnection of inductive switch is put, relay disconnects rapidly its normally opened contact, closes its normally-closed contact, because trigger controlling switch is
Circuit where advance closing relay normally-closed contact, therefore chromatographic work station signal wire rapid closing, further trigger sample introduction letter
Number, recorded rapidly by chromatographic work station, treat after the completion of signal triggering, continue two-way trigger controlling switch being located at relay
Switch contact disconnects where device normally-closed circuit, by the closing of contact where relay normally open circuit；
After state to be sampled terminates, then detection state is gone successively to, sample introduction signal will be now triggered again, passes through chromatographic work station
Data processing, can accurately obtain the duration sampled every time and Two way chromatograms detection initial time；Treat the second dimension
After the completion of analyzing again, then the first dimension sample states are reentered, sample analysis is recycled to according to this and is terminated；
The first described dimension separate section is made up of the first dimension liquid chromatography pump, injector and the first dimension chromatographic column；
The second described dimension separation detection part is by the second dimension liquid chromatography pump, the second dimension chromatographic column and two-dimensional detector group
Into.
2. according to claim 1 arrhea type two-dimensional liquid chromatography manually, it is characterised in that：The interface of the multiple-way valve is
Even number, and number of ports is at least 6.
3. according to claim 1 arrhea type two-dimensional liquid chromatography manually, it is characterised in that：The two-way trigger after
Electrical equipment is at least out one and closes relay.
4. according to claim 1 arrhea type two-dimensional liquid chromatography manually, it is characterised in that：The two-way trigger after
Electrical equipment is in electromagnetic relay, solid-state relay, reed switch relay, reed relay, temperature relay or optical relay
Any one.
5. according to claim 1 arrhea type two-dimensional liquid chromatography manually, it is characterised in that：
The controlling switch of the two-way trigger is the double control switch of a single-pole double throw, or by two single control switch groups
Into；
The controlling switch is toggle switch or button switch.
6. according to claim 1 arrhea type two-dimensional liquid chromatography manually, it is characterised in that：Described chromatogram pump is many pumps
Or single pump.
7. according to claim 1 arrhea type two-dimensional liquid chromatography manually, it is characterised in that：Described chromatogram pump is high
Pressure, it is middle pressure or low pressure liquid phase pump in any one.
8. according to claim 1 arrhea type two-dimensional liquid chromatography manually, it is characterised in that：The first described dimension chromatogram
Post, the second dimension chromatographic column are conventional H PLC chromatographic columns.
9. according to claim 1 arrhea type two-dimensional liquid chromatography manually, it is characterised in that：Described two-dimensional detector
It is the static laser light scattering instrument of UV-detector, Composition distribution or 18 angles.
10. arrhea application of the type two-dimensional liquid chromatography in venomous injurant quality detection described in claim any one of 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610571942.4A CN106053689B (en) | 2016-07-18 | 2016-07-18 | The sampling time can accurately be obtained arrheas type two-dimensional liquid chromatography and its application manually |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610571942.4A CN106053689B (en) | 2016-07-18 | 2016-07-18 | The sampling time can accurately be obtained arrheas type two-dimensional liquid chromatography and its application manually |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106053689A CN106053689A (en) | 2016-10-26 |
| CN106053689B true CN106053689B (en) | 2017-10-20 |
Family
ID=57188191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610571942.4A Active CN106053689B (en) | 2016-07-18 | 2016-07-18 | The sampling time can accurately be obtained arrheas type two-dimensional liquid chromatography and its application manually |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106053689B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6402946B1 (en) * | 2000-10-26 | 2002-06-11 | Bruker Analytik Gmbh | Device for feeding a chromatography flow |
| CN102253141A (en) * | 2011-06-24 | 2011-11-23 | 上海药明康德新药开发有限公司 | High performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) system and method |
| CN202501076U (en) * | 2012-02-27 | 2012-10-24 | 大连中汇达科学仪器有限公司 | GC valve controller |
| CN105277641A (en) * | 2014-06-20 | 2016-01-27 | 北京普源精电科技有限公司 | Control method of n-element proportioning valve, and liquid chromatograph provided with n-element proportioning valve |
| CN205898747U (en) * | 2016-07-18 | 2017-01-18 | 华南理工大学 | Manual type two dimension liquid chromatogram that arrheas that can accurate sampling time of acquireing |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5630943A (en) * | 1995-11-30 | 1997-05-20 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Discontinuous countercurrent chromatographic process and apparatus |
-
2016
- 2016-07-18 CN CN201610571942.4A patent/CN106053689B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6402946B1 (en) * | 2000-10-26 | 2002-06-11 | Bruker Analytik Gmbh | Device for feeding a chromatography flow |
| CN102253141A (en) * | 2011-06-24 | 2011-11-23 | 上海药明康德新药开发有限公司 | High performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) system and method |
| CN202501076U (en) * | 2012-02-27 | 2012-10-24 | 大连中汇达科学仪器有限公司 | GC valve controller |
| CN105277641A (en) * | 2014-06-20 | 2016-01-27 | 北京普源精电科技有限公司 | Control method of n-element proportioning valve, and liquid chromatograph provided with n-element proportioning valve |
| CN205898747U (en) * | 2016-07-18 | 2017-01-18 | 华南理工大学 | Manual type two dimension liquid chromatogram that arrheas that can accurate sampling time of acquireing |
Non-Patent Citations (3)
| Title |
|---|
| A novel stop-flow two-dimensional liquid chromatography–mass spectrometry method for lipid analysis;Shuangyuan Wang et al.;《Journal of Chromatography A》;20131029;第1321卷;page 65-72 * |
| Development of different comprehensive twodimensional systems for the separation of phenolic antioxidants;Francesco Cacciola et al.;《J. Sep. Sci. 》;20061231;第29卷;page 2500-2513 * |
| 二维液相色谱接口技术;丁坤 等;《色谱》;20101231;第28卷;page 1117-1122 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106053689A (en) | 2016-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11656208B2 (en) | Multi-injection mode valve module | |
| CN102460145B (en) | Sample injector with metering device balancing pressure differences in an intermediate valve state | |
| CN104781675B (en) | General changeover valve | |
| US5630943A (en) | Discontinuous countercurrent chromatographic process and apparatus | |
| CN205898747U (en) | Manual type two dimension liquid chromatogram that arrheas that can accurate sampling time of acquireing | |
| CN108037233A (en) | The multidimensional liquid chromatographic separation system of full on-line checking based on same detector | |
| CN106075954B (en) | Arrhea type two-dimensional liquid chromatography and its application using a multiple-way valve as switching device | |
| CN110455970A (en) | Sample introduction fraction collector and system | |
| CN107485891B (en) | Improved chromatographic device and method for continuous flow chromatography | |
| CN108562678B (en) | Three-dimensional liquid chromatographic separation system based on full online detection of same detector | |
| CN207586196U (en) | The multidimensional liquid chromatographic separation system of full on-line checking based on same detector | |
| CN102961892A (en) | Preparative multidimensional liquid chromatographic instrument | |
| CN103235074B (en) | High performance liquid chromatography online analysis method and application thereof | |
| CN109655561A (en) | A kind of three-dimensional chromatographic fractionation system based on two ten-way valves | |
| Dus et al. | Continuous amino acid analysis: Elution programming and automatic column selection by means of a rotating valve | |
| CN205844281U (en) | What a kind of bidimensional analysis was carried out simultaneously arrheas type two-dimensional liquid chromatography | |
| CN106053689B (en) | The sampling time can accurately be obtained arrheas type two-dimensional liquid chromatography and its application manually | |
| CN102507764A (en) | Automatic washing device and method for high-efficient liquid phase chromatograph | |
| CN205786515U (en) | A kind of arrhea type two-dimensional liquid chromatography with two multiple-way valves as switching device | |
| CN105891369B (en) | Arrhea type two-dimensional liquid chromatography and its application using two multiple-way valves as switching device | |
| CN110168362A (en) | Chromatogram arrangement control device | |
| CN205759878U (en) | A kind of arrhea type two-dimensional liquid chromatography with multiple-way valve as switching device | |
| CN106053668A (en) | Stopped-flow two-dimensional liquid chromatography allowing two-dimensional analysis to be simultaneously carried out and application thereof | |
| CN106841404B (en) | A kind of high temperature Comprehensive two-dimensional LC device and its application method | |
| CN105974026B (en) | Can overall process ultralow pressure shunting arrhea type two-dimensional liquid chromatography and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |