CN209247685U - A kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device - Google Patents
A kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device Download PDFInfo
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Abstract
The utility model discloses a kind of transient state capillary isotachophoresis-electron spray-mass spectrometry devices, comprising: Capillary Electrophoresis unit comprising outer wall is coated with the electrophoresis capillary outlet end as EFI atomizing nozzle of homogenous metal layer；Metal tube is set in outside electrophoresis capillary outlet end；Removable connecting tube, is sheathed on metal tube, and electrophoresis capillary outlet end is made to expose removable connecting tube or disposed within；Electrolyte feed liquor unit, outlet end are connected to metal tube, make electrolyte full of metal tube；High voltage source unit, including the reversible high voltage power supply of polarity and electron spray high voltage power supply；Gas sampling unit, including first gas sampling device and second gas sampling device；Mass spectrograph.The utility model is converted based on polarity of voltage, and sample ions are concentrated back and forth movement and in a manner of isotachophoresis, are able to ascend sampling volume, and concentrated effect is good, and separation window is long, is separated when improving with electron spray, mass spectrometry and detection performance.
Description
Technical field
The utility model relates to Capillary Electrophoresis and mass spectrometry field more particularly to a kind of transient state capillary constant speed electricity
Swimming-electron spray-mass spectrometry device.
Background technique
Capillary electrophoresis-laser-induced fluorescence is high with separative efficiency, separating rate is fast, sample good compatibility, detection sensitivity
The advantages that high, has been widely used in the various fields such as proteomics, metabolism group, Pharmaceutical Analysis, food inspection.
1987, Smith et al. was for the first time coupled Capillary Electrophoresis by electron spray with mass spectrum, constituted capillary electricity
Swimming-electron spray-mass spectrometry becomes the milestone of Capillary Electrophoresis development.Electron spray is Soft ionization techniques, how electric can produce band
The large biological molecule ion of lotus can accurately obtain the molecular mass and structural information of biological sample through Mass Spectrometer Method.Electron spray from
Sub-ization process is to be atomized sample solution to form gaseous ion, thus by coupling with electron spray, Capillary Electrophoresis can will be separated
The ionic liquid phase of completion is direct, is efficiently converted into gaseous ion, to Mass Spectrometer Method.Thus electron spray is still capillary so far
The ionization techniques of electrophoresis-mass spectrometry most mainstream, Capillary Electrophoresis-electron spray-mass spectrometry are widely used in polypeptide, egg
The detection and analysis of the macromoleculars biological sample such as white.
Interface in Capillary Electrophoresis-electron spray-mass spectrometric hyphenated technique is that can Capillary Electrophoresis and electron spray effective coupling
It closes, realization simultaneously efficiently separates and the key of highly sensitive detection.The difficult point of Interface design is to provide one for sample flow path
Reliable electron spray high pressure forms the electron spray of stability and high efficiency, simultaneously to be closed Capillary Electrophoresis circuit and electron spray circuit
Sample is avoided to dilute.Interface has been broadly divided into sheath liquid interface and without sheath liquid interface two major classes.Sheath liquid interface mainly passes through coaxial sheath
Liquid or tip interflow sheath fluid mix at capillary outlet with sample solution, to provide electron spray high pressure, but this mode is deposited
Problem is diluted in sample, will cause loss of sensitivity.Due to there is no sheath fluid auxiliary in no sheath liquid interface, reliable electron spray is provided
High pressure is more challenged.Jet rose is a kind of typically without sheath liquid interface without sheath liquid interface, and capillary outlet end uses hydrogen
Pipe thickness is etched to 5~10 microns of formation jet roses by fluoric acid, is enabled conduction liquid by stephanoporate thin wall and is managed interior solution
A small amount of ion exchange is generated, to establish reliable and stable electron spray high pressure.Currently, such jet rose without sheath liquid interface
Device is commercially used.But jet rose is frangible, and its chemically etching process in laboratory environment is difficult to control, again
Renaturation is poor.
Although Capillary Electrophoresis-electron spray-mass spectrometry detection limit is extremely low, up to 1 × 10-21Mole, but its sample introduction body
Product is only nanoliter magnitude, and this severely limits the sample volumes of low concentration sample, so that target sample is still difficult to be detected.It passes
The sampling volume for capillary zone electrophoresis of uniting is only 1% or so of capillary column volume, according to typical 30 micron inside diameter, 1 meter
Long capillary calculates, and the sampling volume of sample is only 7 nanoliters.Therefore, carrying out pre-concentration to sample is to improve Capillary Electrophoresis
The effective ways of sampling volume, pre-sample concentration method generally comprise under line, online and in three kinds of modes of column.Wherein, in column side
The pre-sample concentration method of formula is most widely used without changing interface structure.
Wherein, transient state capillary isotachophoresis is a kind of pre-sample concentration method in column mode, is commonly used for capillary
Electrophoresis-mass spectrometry.Transient state capillary isotachophoresis is the mixing of isotachophoresis and zone electrophoresis, and sample solution is first by constant speed electricity
Swimming separated in column pre-concentration, then by zone electrophoresis, thus the sample concentration of big sampling volume can be achieved at the same time and divide
From.Transient state capillary isotachophoresis can be improved sample feeding volume to 30% by the capillary column volume of zone electrophoresis 1%, from
And greatly improve Capillary Electrophoresis-electron spray-mass spectrometry detection limit.
But the further promotion of transient state capillary isotachophoresis sampling volume will cause separation and concentrated effect decline.
Transient state capillary isotachophoresis is first to be concentrated to separate afterwards on same capillary, increases sampling volume and residue is made to be used to be concentrated
Shorten with isolated capillary pipe length；The sample concentration time can be extended simultaneously by increasing sampling volume, on the one hand make sample can not
Concentration completely, sample area band is moved to export direction so as to isolated capillary pipe length into one in another aspect concentration process
Step shortens.Therefore, further increase sampling volume will cause transient state capillary isotachophoresis separator window and peak capacity reduce,
The problem of resolution ratio decline, concentrated effect are deteriorated.The transient state capillary isotachophoresis sampling volume limit is limited in 30% as a result,
The column volume of left and right.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the utility model provides a kind of transient state capillary constant speed electricity
Swimming-electron spray-mass spectrometry device can further promote transient state capillary isotachophoresis sampling volume, and concentrated effect is good, point
It is long from window, to improve the separation and detection performance with electron spray, mass spectrometry.
Technical solution adopted by the utility model to solve the above technical problems is as follows: a kind of transient state capillary isotachophoresis-
Electron spray-mass spectrometry device, comprising:
Capillary Electrophoresis unit, the Capillary Electrophoresis unit includes electrophoresis capillary, the electrophoresis capillary packet
The electrophoresis capillary outlet end that outer wall is coated with homogenous metal layer is included, the electrophoresis capillary outlet end is used as EFI atomizing nozzle；
Metal tube, the metal pipe sleeve is located at outside the electrophoresis capillary outlet end, and makes the electrophoresis capillary
The slightly prominent metal tube in pipe outlet end；
Removable connecting tube, the removable connecting pipe box are set on the metal tube, make the electrophoresis capillary
Pipe outlet end is exposed the removable connecting tube or is placed in the removable connecting tube, for switching transient state capillary etc.
Fast electrophoresis state or capillary zone electrophoresis-electron spray-mass spectrometry state；
The outlet end of electrolyte feed liquor unit, the electrolyte feed liquor unit is connected to the metal tube, and makes electricity
It solves liquid and is full of the metal tube and the removable connecting tube；
High voltage source unit, the high voltage source unit include the reversible high voltage power supply of polarity and electron spray high-voltage electricity
Source, the reversible high voltage power supply of the polarity are electrically connected with the Capillary Electrophoresis unit, for for the capillary
Electrophoretic cell provides the reversible high direct voltage of polarity, and the electron spray high voltage power supply is electrically connected with the metal tube, uses
In to the metal tube load high direct voltage；
Gas sampling unit, the gas sampling unit include for the Capillary Electrophoresis unitary gas pressure
The first gas sampling device of sample introduction and for the second gas sample introduction to the electrolyte feed liquor unitary gas hydrodynamic injection
Device；
Mass spectrograph, the position alignment of the mass spectrometric injection port and the EFI atomizing nozzle.
In some embodiments, the gas sampling unit further includes the first digital altimeter and the second digital air pressure
Meter, first digital altimeter are used to control sample introduction gas pressure and sample introduction liquid flow in the Capillary Electrophoresis unit
Speed；Second digital altimeter is used to control sample introduction gas pressure and sample introduction liquid flow in the electrolyte feed liquor unit
Speed.
In some embodiments, the Capillary Electrophoresis unit further includes the first air-tight bottle, metal electrode and first
The holding in liquid of first air-tight bottle, the metal electrode are protruded into capillary, the sample introduction end of the electrophoresis capillary
One end protrude into the holding in liquid of first air-tight bottle, the other end is electrically connected with the reversible high voltage power supply of the polarity
Connect, one end of first capillary, which is protruded into first air-tight bottle, is placed in ullage, the other end successively with institute
The first digital altimeter stated is connected with the first gas sampling device.
In some embodiments, the electrolyte feed liquor unit further includes the second air-tight bottle, the second capillary and
Three capillary, the arrival end of second capillary protrude into the holding in liquid of second air-tight bottle, and described second mao
The outlet end of tubule is connected to the metal tube, and one end of the third capillary is protruded into second air-tight bottle simultaneously
It is placed in ullage, the other end is successively connect with second digital altimeter and the second gas sampling device.
It in some embodiments, further include three-way connector, the electrophoresis capillary outlet end is through the threeway
The first end of connector is stretched out after being inserted through the metal tube from the second end of the three-way connector, and described the
The third end of the two capillaries insertion three-way connector, the outlet end of second capillary are led to by described three
Fitting is connected to the metal tube, and the electrophoresis capillary, the metal tube and second capillary lead to respectively
Three-way connection is crossed to fix with the three-way connector.Thus the structure has preferably effect.
Compared with the prior art, the advantages of the utility model are: passing through the reversible high voltage power supply of setting polarity and phase
Structure is answered, dipole inversion is based on, on the one hand making sample ions, back and forth movement is simultaneously in electrophoresis capillary in a manner of isotachophoresis
Thus concentration increases the length of the electrophoresis capillary to sample concentration, increase sampling volume, improves detection sensitivity；It is another
Aspect the utility model can be such that the sample ions after concentration separate in a manner of zone electrophoresis near the sample introduction end of electrophoresis capillary,
And it is unconventional be just initially separated in electrophoresis capillary posterior segment so that increase to isolated electrophoresis capillary length,
It is long so as to increase separation window, separation peak capacity is improved, can be improved transient state capillary isotachophoresis and electron spray-on the whole
The separation and detection performance of mass spectrometry.
Detailed description of the invention
Fig. 1 is a kind of transient state capillary isotachophoresis-electron spray-one embodiment of mass spectrometry device of the utility model
Structural schematic diagram；
Fig. 2 is the implementation process schematic diagram using the electrophoresis method of utility model device；
Fig. 3 is sample concentration process schematic after dipole inversion in the implementation process of Fig. 2.
Wherein, electrophoresis capillary 1, EFI atomizing nozzle 2, metal tube 3 move connecting tube 4, the reversible high-voltage electricity of polarity
Source 5, electron spray high voltage power supply 6, first gas sampling device 7, second gas sampling device 8, mass spectrograph 9, the first digital air pressure
Meter 10, the second digital altimeter 11, the first air-tight bottle 12, metal electrode 13, the first capillary 14, the second air-tight bottle 15, second
Capillary 16, third capillary 17, three-way connector 18, three-way connection 19.
Specific embodiment
A kind of the utility model transient state capillary isotachophoresis-electron spray-mass spectrometry device is made below in conjunction with attached drawing
It is further described, but not as the restriction to the utility model.
Embodiment one
A kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device of the utility model, comprising:
Capillary Electrophoresis unit, Capillary Electrophoresis unit include electrophoresis capillary 1, and electrophoresis capillary 1 is coated with including outer wall
The electrophoresis capillary outlet end of homogenous metal layer, electrophoresis capillary outlet end are used as EFI atomizing nozzle 2；Wherein, metal layer is optional
With materials such as platinum, gold, silver, copper.
Metal tube 3, metal tube 3 are set in outside EFI atomizing nozzle 2, and make the slightly prominent metal tube 3 of EFI atomizing nozzle 2.
Removable connecting tube 4, removable connecting tube 4 are sheathed on metal tube 3, and EFI atomizing nozzle 2 is made to expose removable connect
Adapter tube 4 is placed in removable connecting tube 4, for switching transient state capillary isotachophoresis state or capillary zone electrophoresis-electricity
Spraying-mass spectrometry state.
The outlet end of electrolyte feed liquor unit, electrolyte feed liquor unit is connected to metal tube 3, and makes electrolyte full of metal
Pipe 3 and removable connecting tube 4；When EFI atomizing nozzle 2 (i.e. electrophoresis capillary outlet end) is placed in removable connecting tube 4, electricity
It solves liquid and fluid-tight is formed to electrophoresis capillary outlet end, be used for transient state capillary isotachophoresis state at this time, when EFI atomizing nozzle 2 reveals
When moving connecting tube 4 out, electrolyte, which is conducted by conductive high pressure to EFI atomizing nozzle 2, to be exported, and is realized without sheath liquid interface, at this time
For capillary zone electrophoresis-electron spray-mass spectrometry state.
High voltage source unit, high voltage source unit include the reversible high voltage power supply 5 of polarity and electron spray high voltage power supply 6,
The reversible high voltage power supply 5 of polarity is electrically connected with Capillary Electrophoresis unit, can be anti-for providing polarity for Capillary Electrophoresis unit
The high direct voltage turned, electron spray high voltage power supply 6 are electrically connected with metal tube 3, for loading high direct voltage to metal tube 3.
Gas sampling unit, gas sampling unit include for the first gas to Capillary Electrophoresis unitary gas hydrodynamic injection
Body sampling device 7 and for the second gas sampling device 8 to electrolyte feed liquor unitary gas hydrodynamic injection.
Mass spectrograph 9, the injection port of mass spectrograph 9 and the position alignment of EFI atomizing nozzle 3.
Embodiment two
As shown in Figure 1, a kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device, remaining structure and embodiment
One is identical, the difference is that: in the present embodiment, gas sampling unit further includes the first digital altimeter 10 and the second number
Barometer 11, the first digital altimeter 10 is for controlling sample introduction gas pressure and sample introduction flow rate of liquid in Capillary Electrophoresis unit；
Second digital altimeter 11 is for controlling sample introduction gas pressure and sample introduction flow rate of liquid in electrolyte feed liquor unit.
In the present embodiment, Capillary Electrophoresis unit further includes the first air-tight bottle 12, metal electrode 13 and the first capillary 14,
The sample introduction end of electrophoresis capillary 1 is protruded into the background electrolyte that the first air-tight bottle 12 is held, and one end of metal electrode 13 protrudes into
In the background electrolyte of one air-tight bottle 12, the other end is connect with the reversible high voltage power supply 5 of polarity by conducting wire, the first capillary
14 one end, which is protruded into the first air-tight bottle 12, is placed in ullage, the other end successively with the first digital altimeter 10 and the first gas
Body sampling device 7 connects.In the present embodiment, metal electrode 13 selects platinum electrode, has corrosion-resistant, the advantage of service life length.
In the present embodiment, electrolyte feed liquor unit further includes the second air-tight bottle 15, the second capillary 16 and third capillary
17, the arrival end of the second capillary 16 protrudes into the background electrolyte that the second air-tight bottle 15 is held, the outlet of the second capillary 16
End is connected to metal tube 3, and one end of third capillary 17, which is protruded into the second air-tight bottle 15, is placed in ullage, and the other end is successively
It is connect with the second digital altimeter 11 and second gas sampling device 8.
In the present embodiment, combined apparatus further includes three-way connector 18, and electrophoresis capillary outlet end is through three-way connector 18
First end be inserted through after metal tube 3 from the second end of three-way connector 18 and stretch out, the second capillary 16 insertion three is led to
The outlet end at the third end of fitting 18, the second capillary 16 is connected to by three-way connector 18 with metal tube 3, electrophoresis capillary 1,
Metal tube 3 and the second capillary 16 are fixed by three-way connection 19 and three-way connector 18 respectively.In the present embodiment, the company of moving
Adapter tube 4 selects teflon pipe, and teflon pipe is movably sheathed on metal tube 3.
The second air-tight bottle 15 is inserted into second capillary, 16 one end, and the other end is inserted into three-way connector 18 and fixed, the second gas
Conductive background electrolyte is full of metal tube 3 and teflon pipe by gas pressure sample introduction in close bottle 15, so that loading on metal tube 3
On electron spray high pressure be able to pass through conductive background electrolyte and conduct through metal coating to EFI atomizing nozzle 2 to export, realize
Without sheath liquid interface.
Embodiment three
Electrophoresis is carried out using a kind of transient state capillary isotachophoresis device based on polarity of voltage conversion of the utility model
Method, comprising:
1. keeping voltage value constant, the method inverted by polarity, by sample ions with transient state capillary isotachophoresis
Mode carries out back and forth movement and is concentrated in electrophoresis capillary；
2. the sample solution after concentration is separated in a manner of zone electrophoresis, sample is gasificated by stable electron spray
Product gaseous ion, into spectrometer analysis.
In the present embodiment, 1. keep voltage value constant, the method inverted by polarity, by sample with transient state capillary constant speed
The mode of electrophoresis carries out back and forth movement and is concentrated to specifically include in electrophoresis capillary:
1. it is -1, that removable connecting tube is mobile to the outlet extreme direction of electrophoresis capillary, so that EFI atomizing nozzle is placed in one；
1. -2, being packed into background electrolyte in the first air-tight bottle, start first gas sampling device, it will be in the first air-tight bottle
Background electrolyte loaded by gas pressure sample introduction to electrophoresis capillary, and make background electrolyte full of electrophoresis capillary；
1. -3, being packed into background electrolyte in the second air-tight bottle, start second gas sampling device, it will be in the second air-tight bottle
Background electrolyte loaded by gas pressure sample introduction to metal tube, and make background electrolyte full of metal tube and removable connection
Pipe；
1. -4, replacement first equipped with sample solution (including leading electrolyte and trailing electrolyte in sample solution) is airtight
Bottle, sample solution is loaded by gas pressure sample introduction to electrophoresis capillary；
1. the first air-tight bottle equipped with background electrolyte -5, is more gained, by the background electrolyte in the first air-tight bottle by gas
Body hydrodynamic injection is loaded to electrophoresis capillary；
1. -6, by the first digital altimeter and the second digital altimeter, respectively by the first air-tight bottle and the second air-tight bottle
The pressure control of middle load is to zero, so that the flow rate of liquid in electrophoresis capillary and the second capillary is zero；
1. -7, closing electron spray high voltage power supply, the reversible high voltage power supply of polarity is opened and applies high direct voltage, sample
Ion starts to be concentrated in electrophoresis capillary in a manner of isotachophoresis；
1. being carried out -8, before isotachophoresis mode transits to zone electrophoresis mode to the reversible high voltage power supply of polarity
Polarity of voltage conversion, so that sample ions back and forth movement and are concentrated in capillary in a manner of isotachophoresis；Wherein, polarity of voltage
Conversion need to keep even-times to invert, to ensure that sample ions are moved towards the outlet extreme direction of capillary；Even-times reversal voltage pole
Property specifically refer to one positive one negative/negative one and just twice or so repeat switching polarity of voltage；
1. switching to zone electrophoresis after the completion of -9, being concentrated and starting to separate sample ions.
As shown in Fig. 2, describing the implementation process of the transient state capillary isotachophoresis method based on dipole inversion.Wherein,
BGE indicates that background electrolyte, S indicate that sample solution, LE indicate that leading electrolyte, TE indicate to trail electrolyte.According to transient state hair
Capillary isotachclcctzoophorcsis principle, T1Moment powers on rear sample ions (cation) and moves right under electric field action, and based on leading
Electrolyte (LE) ion, sample (S) ion, trail electrolyte (TE) ion ionic mobility difference formed non-uniform intensity electricity
Field distribution causes sample to be concentrated in a manner of isotachophoresis, while sample is concentrated, due to background electrolyte zone and sample area
The unstable moving boundary formed between band, causes background electrolyte ion and sample segment Ar ion mixing；T2Moment voltage pole
Sex reversal, sample ions are moved downward and are concentrated, T3、T4... circulation conversion polarity of voltage repeatedly, until TNMoment,
Background electrolyte is thoroughly mixed with sample, carries electric current by background electrolyte ion in the band of sample area, sample ions are in background electricity
The uniform electric field effect that solution liquid ion determines is lower to be started to separate in a manner of zone electrophoresis.
The feasible key of transient state capillary isotachophoresis method based on dipole inversion is sample ions after polarity reversion
Still it can be concentrated in a manner of isotachophoresis.T in Fig. 22Moment sample do not complete concentration, sample area band can be divided into non-enrichment region band and
Enrichment region band two parts, enlarged drawing are as shown in Figure 3.Polarity reversion after, non-enrichment region band can in the way of isotachophoresis after
Continuous concentration.For enrichment region band, ionic mobility is indicated with μ, trail electrolyte ion, sample ions, leading electrolyte ion
Ionic mobility relationship is μTE<μS<μLE, equation is adjusted according to Kohlrausch, conductivity is indicated with σ, trails electrolyte ion, sample
Product ion, leading electrolyte ion conductivity relation be σTE<σS<σLE, constant in current density j according to Ohm's law j=σ E
Under the conditions of, trail electrolyte ion, sample ions, leading electrolyte ion electric field strength E be distributed as ETE>ES>ELE, according to from
Sub- electrophoretic velocity v meets v=μ E, for leading electrolyte ion, is trailing the movement velocity v in electrolyte zoneLEinTE、
Its movement velocity v in the band of sample areaLEinS, its movement velocity v in leading electrolyte zoneLEinLEMeet vLEinTE>
vLEinS>vLEinLE, therefore leading electrolyte ion can accelerate across sample area band and trailing electrolyte zone is dense without will form
Contracting, i.e., between trailing electrolyte zone and sample area band, the interface between sample area band and leading electrolyte zone is non-steady
Determine moving boundary.Equally, sample ions, which can also accelerate across, trails electrolyte zone, is finally completed the reconstruct of isotachophoresis.It is comprehensive
Upper described, for not completing the sample of concentration, sample ions still are able to be concentrated in a manner of isotachophoresis after polarity reversion.
In the present embodiment, 1. step opens the reversible high voltage power supply of polarity in -7 applies high direct voltage, and polarity can be anti-
The high direct voltage size that the high voltage power supply turned applies is 10~30 kilovolts.
In the present embodiment, 1. step carries out polarity of voltage conversion to the reversible high voltage power supply of polarity in -8, so that sample
Ion back and forth movement and is concentrated in capillary in a manner of isotachophoresis, specifically meets the following conditions: dipole inversion being made to occur to exist
Sample ions are run out of before the both ends of electrophoresis capillary.Thus, it is possible to prevent sample loss.
In the present embodiment, 1. step carries out polarity of voltage conversion to the reversible high voltage power supply of polarity in -8, so that sample
Ion back and forth movement and is concentrated in capillary in a manner of isotachophoresis, is specifically included: control last time dipole inversion occurs
At sample introduction end of the sample area band close to electrophoresis capillary, and it is electric by constant speed in sample area band at the time of last time dipole inversion
It swims near at the time of being converted into zone electrophoresis.Thus when carrying out the separation of subsequent zone electrophoresis, reach to isolated capillary
Longest, separation window is long maximum, and separating effect is optimal.
Example IV
Electrophoresis is carried out using a kind of transient state capillary isotachophoresis device based on polarity of voltage conversion of the utility model
Method, remaining is identical as embodiment three, the difference is that: it is 2. that the sample after concentration and separation is molten in the present embodiment
Liquid is gasificated into sample gaseous ion by stable electron spray, includes: into spectrometer analysis
2. it is -1, that removable connecting tube is mobile to the sample introduction extreme direction of electrophoresis capillary, keep EFI atomizing nozzle protrusion removable
Dynamic connecting tube, device are switched to no sheath fluid interface arrangement, start zone electrophoresis-electron spray-mass spectrometry experiment；
2. apply high direct voltage to Capillary Electrophoresis unit -2, by the reversible high voltage power supply fixed voltage polarity of polarity,
Sample ions after concentration are separated in a manner of zone electrophoresis；
Apply in high direct voltage to metal tube 2. -3, opening electron spray high voltage power supply；
2. -4, first gas sampling device continues to load certain gas pressure to the first air-tight bottle, by the first digital air pressure
Gas pressure size in meter the first air-tight bottle of control, makes to form stable flow rate of liquid in electrophoresis capillary, to be formed steady
Fixed electron spray, sample ionic liquid phase, which is gasificated into sample gaseous ion and enters mass spectrograph, to be analyzed；
2. -5, being continued to load certain gas pressure to the second air-tight bottle from second gas sampling device, by the second digital gas
Gas pressure size in pressure meter the second air-tight bottle of control, makes background electrolyte shape conductive in metal tube and removable connecting tube
At stable flow rate of liquid, so that electron spray high pressure be made to keep stablizing；
2. -6, detect all samples ion to mass spectrograph, by first gas sampling device, second gas sampling device,
The reversible high voltage power supply of polarity and electron spray high voltage power supply are closed, and operation is completed.
In the present embodiment, 2. step opens electron spray high voltage power supply in -3 applies in high direct voltage to metal tube, EFI
The high direct voltage size that mist high voltage power supply applies is 1~3 kilovolt.
In the present embodiment, 2. step makes in -4 to form the stable flow rate of liquid of 10~500nL/min, step in electrophoresis capillary
So that background electrolyte conductive in metal tube and removable connecting tube is formed the stable liquid flow of 0.5~5 μ L/min suddenly
Speed.
It is dense that the experimental provision of the utility model can successively be used as the transient state capillary isotachophoresis sample based on dipole inversion
Contracting experiment and zone electrophoresis-electron spray-mass spectrometry experiment.Transient state capillary isotachophoresis-electron spray-based on dipole inversion
Sample is first concentrated by the transient state capillary isotachophoresis based on dipole inversion in mass spectrometry, then by zone electrophoresis-EFI
Mist-mass spectrometry tests and analyzes.In the transient state capillary isotachophoresis method implementation process of dipole inversion, sample ions are initial
It back and forth movement and is concentrated in capillary in a manner of isotachophoresis, until background electrolyte ion is thoroughly mixed with sample ions,
Sample ions are initially separated in a manner of zone electrophoresis.
A kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device of the utility model, can be anti-by setting polarity
The high voltage power supply turned, dipole inversion is carried out in electrophoresis process, on the one hand makes sample ions in a manner of isotachophoresis in electrophoresis
It back and forth movement and is concentrated in capillary, thus increases the length of the electrophoresis capillary to sample concentration, increased sampling volume, mention
High detection sensitivity；Another aspect the utility model can make concentration after sample ions near the sample introduction end of electrophoresis capillary with
Zone electrophoresis mode separates, and it is unconventional be just initially separated in electrophoresis capillary posterior segment so as to isolated electricity
Capillary pipe length of swimming increases, long so as to increase separation window, improves separation peak capacity, can be improved transient state capillary on the whole
Isotachophoresis and the separation of electron spray-mass spectrometry and detection performance.
It is worth noting that, the above is only the preferred embodiment of the present invention, it is practical new not thereby to limit this
The scope of patent protection of type, the utility model can also carry out the improvement of material and structure to the construction of above-mentioned various components,
Either it is replaced using technically equivalent ones.Therefore, the specification of the utility model is applied and diagramatic content made by equivalent knot
Structure variation, directly or indirectly applies to other correlative technology fields and is similarly all contained in the range that the utility model is covered
It is interior.
Claims (5)
1. a kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device characterized by comprising
Capillary Electrophoresis unit, the Capillary Electrophoresis unit includes electrophoresis capillary, and the electrophoresis capillary includes outer
Wall is coated with the electrophoresis capillary outlet end of homogenous metal layer, and the electrophoresis capillary outlet end is used as EFI atomizing nozzle；
Metal tube, the metal pipe sleeve is located at outside the electrophoresis capillary outlet end, and goes out the electrophoresis capillary
The slightly prominent metal tube in mouth end；
Removable connecting tube, the removable connecting pipe box are set on the metal tube, go out the electrophoresis capillary
Mouth end is exposed the removable connecting tube or is placed in the removable connecting tube, for switching transient state capillary constant speed electricity
Swimming state or capillary zone electrophoresis-electron spray-mass spectrometry state；
The outlet end of electrolyte feed liquor unit, the electrolyte feed liquor unit is connected to the metal tube, and makes electrolyte
Full of the metal tube and the removable connecting tube；
High voltage source unit, the high voltage source unit include the reversible high voltage power supply of polarity and electron spray high voltage power supply,
The reversible high voltage power supply of the polarity is electrically connected with the Capillary Electrophoresis unit, for for the Capillary Electrophoresis
Unit provides the reversible high direct voltage of polarity, and the electron spray high voltage power supply is electrically connected with the metal tube, is used for pair
The metal tube loads high direct voltage；
Gas sampling unit, the gas sampling unit include for the Capillary Electrophoresis unitary gas hydrodynamic injection
First gas sampling device and for the second gas sampling device to the electrolyte feed liquor unitary gas hydrodynamic injection；
Mass spectrograph, the position alignment of the mass spectrometric injection port and the EFI atomizing nozzle.
2. a kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device according to claim 1, feature exist
In the gas sampling unit further includes the first digital altimeter and the second digital altimeter, the described first digital air pressure
It counts for controlling sample introduction gas pressure and sample introduction flow rate of liquid in the Capillary Electrophoresis unit；The digital air pressure of described second
It counts for controlling sample introduction gas pressure and sample introduction flow rate of liquid in the electrolyte feed liquor unit.
3. a kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device according to claim 2, feature exist
In the Capillary Electrophoresis unit further includes the first air-tight bottle, metal electrode and the first capillary, the electrophoresis capillary
Sample introduction end protrude into the holding in liquid of first air-tight bottle, it is airtight that described first is protruded into one end of the metal electrode
Bottle is held in liquid, and the other end is electrically connected with the reversible high voltage power supply of the polarity, one end of first capillary
Protrude into first air-tight bottle and be placed in ullage, the other end successively with first digital altimeter and described
The connection of first gas sampling device.
4. a kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device according to claim 2, feature exist
In the electrolyte feed liquor unit further includes the second air-tight bottle, the second capillary and third capillary, second capillary
The arrival end of pipe protrudes into the holding in liquid of second air-tight bottle, the outlet end of second capillary and the metal
Pipe connection, one end of the third capillary are protruded into second air-tight bottle and are placed in ullage, and the other end is successively
It is connect with second digital altimeter and the second gas sampling device.
5. a kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device according to claim 4, feature exist
In further including three-way connector, the electrophoresis capillary outlet end is inserted into and is worn through the first end of the three-way connector
It is stretched out after crossing the metal tube from the second end of the three-way connector, the second capillary insertion threeway
The outlet end at the third end of connector, second capillary is connected by the three-way connector and the metal tube
Logical, electrophoresis capillary, the metal tube and second capillary passes through three-way connection and described three respectively
Lead to fitting to fix.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201821798184.0U CN209247685U (en) | 2018-11-01 | 2018-11-01 | A kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109444247A (en) * | 2018-11-01 | 2019-03-08 | 宁波大学 | A kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device and method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109444247A (en) * | 2018-11-01 | 2019-03-08 | 宁波大学 | A kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device and method |
| CN109444247B (en) * | 2018-11-01 | 2024-01-09 | 宁波大学 | Transient capillary isotachophoresis-electrospray-mass spectrometry combined device and method |
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