WO2016117066A1 - 質量分析装置及びイオン移動度分析装置 - Google Patents
質量分析装置及びイオン移動度分析装置 Download PDFInfo
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- WO2016117066A1 WO2016117066A1 PCT/JP2015/051622 JP2015051622W WO2016117066A1 WO 2016117066 A1 WO2016117066 A1 WO 2016117066A1 JP 2015051622 W JP2015051622 W JP 2015051622W WO 2016117066 A1 WO2016117066 A1 WO 2016117066A1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/622—Ion mobility spectrometry
- G01N27/623—Ion mobility spectrometry combined with mass spectrometry
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0431—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples
- H01J49/0445—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples with means for introducing as a spray, a jet or an aerosol
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/06—Electron- or ion-optical arrangements
- H01J49/061—Ion deflecting means, e.g. ion gates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/06—Electron- or ion-optical arrangements
- H01J49/067—Ion lenses, apertures, skimmers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/165—Electrospray ionisation
Definitions
- the present invention relates to a mass spectrometer and an ion mobility analyzer, and more specifically, a mass spectrometer and an ion mobility analyzer including an ion source that sprays a liquid sample in a substantially atmospheric pressure atmosphere to ionize components in the sample. Relates to the device.
- LC-MS liquid chromatograph mass spectrometer
- APCI chemical ionization method
- APPI atmospheric pressure photoionization method
- the desolvation of the charged droplets is promoted by blowing heated gas onto the charged droplets sprayed from the ionization probe.
- the technology to make it known is known.
- the apparatus described in Patent Document 1 employs a configuration in which heated gas is sprayed so as to intersect the traveling direction of the charged droplet sprayed from the ionization probe.
- the heating gas is ejected coaxially with the spray flow of the charged droplet from the ionization probe, that is, the traveling direction of the charged droplet and the flowing direction of the heating gas are the same direction. The structure which is is taken.
- the spray direction of the droplet from the ionization probe and the vacuum chamber is determined so that the direction of ion introduction to the electrode is orthogonal or oblique. Then, the ions generated from the sample droplet are sucked into the ion introduction part and sent to the vacuum chamber on the gas flow flowing into the ion introduction part from the ionization chamber mainly caused by the differential pressure across the ion introduction part. .
- the jet direction of the heating gas for promoting desolvation described above does not coincide with the direction of the gas flow flowing into the ion introduction portion due to the differential pressure, so that the flow of the heating gas increases the gas flow flowing into the ion introduction portion.
- the flow of the heated gas can be a gas flow orthogonal to the ion introduction direction in the vicinity of the ion introduction port, that is, a gas flow in a direction that prevents ion introduction. Therefore, although the heated gas is effective in increasing the amount of ions generated, it cannot be said that it is effective in terms of improving the efficiency of introducing ions from the ionization chamber into the vacuum chamber.
- Patent Document 2 proposes attracting and collecting in the direction of the mouth.
- the electric field formed in the vicinity of the ion introduction port by such a configuration can sufficiently collect ions against the strong flow of the heated gas flowing in the direction orthogonal to the ion introduction direction. Not strong. Therefore, even if such an electric field is used, it is difficult to greatly improve the efficiency of introducing ions from the ionization chamber to the vacuum chamber.
- the present invention has been made to solve the above problems, and its main purpose is to analyze ions by efficiently introducing ions generated in an atmospheric pressure atmosphere into a vacuum chamber without wasting them as much as possible. It is providing the mass spectrometer which can improve.
- a mass spectrometer made to solve the above-described problems includes an ion source including an ionization probe that sprays a liquid sample into an ionization chamber that is an atmospheric pressure atmosphere, and the ionization generated by the ion source.
- An ion introduction section for sending ions derived from components contained in the sample droplet sprayed from the probe from the ionization chamber to the vacuum chamber, and the spray direction of the liquid sample from the ionization probe and the ion introduction section
- the arrangement of the ionization probe and the ion introduction part is determined so that the direction of ion introduction from the ionization chamber by the a) an auxiliary electrode provided in the spray direction of the sample droplet from the ionization probe and on the front side of the inlet end of the ion introduction portion so as to surround the central axis of the spray flow from the ionization probe; b) a reflective electrode provided in the direction of spraying the sample droplet from the ionization probe and behind the inlet end of the ion introduction portion so as to surround the central axis of the spray flow from the ionization probe; c) a voltage applying unit that applies a voltage that reflects ions to be measured to the reflective electrode with reference to the
- the ion source is, for example, an ESI ion source, an APCI ion source, an APPI ion source, or the like.
- the ion source is an ESI ion source
- a predetermined DC high voltage for charging the liquid sample is applied to the tip of the ionization probe.
- the ion source is an APCI ion source
- a discharge electrode for generating corona discharge for generating buffer ions is provided between or in the vicinity of the ionization probe and the auxiliary electrode.
- a light source that irradiates light such as ultraviolet light to the spray flow that passes through the space from the ionization probe to the auxiliary electrode is provided.
- the auxiliary electrode when looking forward from the tip of the ionization probe in the spray direction of the sample droplet, the auxiliary electrode is positioned at the foremost side, the reflective electrode is positioned on the other side, and the auxiliary electrode and The inlet end of the ion introduction part is positioned so as to open in a space between the reflective electrode.
- Each of the auxiliary electrode and the reflective electrode may typically be a cylindrical body or a polygonal cylindrical body. Further, these cylindrical bodies may have a shape in which a part in the circumferential direction is notched.
- the ion introduction part is typically an ion introduction tube such as a conductive capillary, and in that case, the inside of the space sandwiched between the space surrounded by the auxiliary electrode and the space surrounded by the reflection electrode. It is preferable that it is in the state extended to.
- the auxiliary electrode and the ion introduction unit are grounded, for example, and the voltage application unit applies a predetermined DC voltage having a polarity corresponding to the polarity of the ion to be measured to the reflection electrode. Due to the potential difference between the potential of the reflective electrode and the potential of the auxiliary electrode and the ion introduction portion (ground potential), the liquid sprayed from the ionization probe is formed in the space surrounded by the reflective electrode and the space between the reflective electrode and the auxiliary electrode. A reflected electric field having an action of pushing back ions generated from the droplets and minute charged droplets (in the case of an ESI ion source) is formed.
- a focusing electric field is formed in a local space between the reflective electrode and the inlet end of the ion introducing portion to focus the ions and charged droplets toward the inlet end of the ion introducing portion.
- the intensity of the reflected electric field and the focused electric field can be adjusted by the voltage applied to the reflective electrode.
- ions and minute charges can be generated from the gas flow that forms the spray flow. Droplets can be separated and attracted to the inlet end of the ion introduction section.
- the auxiliary electrode has a gas ejection part that ejects gas from the outside of the spray flow toward the central axis of the spray flow so as to surround the spray flow from the ionization probe. It is good also as an attached structure.
- the ion motion speed in the ionization chamber in which the gas flow and the electric field are present in a substantially atmospheric pressure atmosphere depends on the ion mobility.
- the ion mobility depends on the mass, valence, collision cross section with neutral particles (for example, residual gas molecules), and the like. Therefore, from the viewpoint of the efficiency of ions that can reach the inlet end of the ion introduction part, the optimum strengths of the reflected electric field and the focused electric field differ depending on the mass-to-charge ratio of the ions. That is, when the intensity of the reflected electric field and the focused electric field is changed by changing the voltage applied to the reflective electrode, the mass-to-charge ratio of the ions that efficiently reach the inlet end of the ion introduction portion changes.
- the voltage application unit may be configured to change the voltage applied to the reflective electrode in accordance with the mass-to-charge ratio of ions to be measured. For example, when a quadrupole mass filter is used as a mass separator and scan measurement is performed over a predetermined mass-to-charge ratio range, the voltage applied to the quadrupole mass filter is synchronized with the scan measurement. The voltage applied to the reflective electrode is preferably scanned.
- the ion introduction efficiency from the ionization chamber to the vacuum chamber can be increased regardless of the mass-to-charge ratio of the ions to be measured.
- the ion mobility analyzer is a) an ion source including an ionization probe for spraying a liquid sample in an atmospheric pressure atmosphere; b) an ion detection unit that is arranged in front of the spray flow from the ionization probe and detects ions derived from components contained in the sample droplet sprayed from the ionization probe generated by the ion source; c) an auxiliary electrode provided in a spraying direction of the sample droplet from the ionization probe and on the front side of the ion detection unit so as to surround a central axis of the spray flow from the ionization probe; d) a reflective electrode provided to surround the central axis of the spray flow from the ionization probe in the spray direction of the sample droplet from the ionization probe and on the back side of the ion detector; e) a voltage applying unit that applies a voltage that reflects ions to be measured to the reflective electrode with reference to the potential of the auxiliary electrode; It is
- the auxiliary electrode is grounded, and the voltage application unit changes the voltage applied to the reflection electrode according to a predetermined sequence. Then, the intensity of the reflected electric field formed in the space surrounded by the reflective electrode and the space between the reflective electrode and the auxiliary electrode changes with time, and accordingly, ions of ions that reach the ion detector most efficiently. Mobility will change. Therefore, an ion mobility spectrum indicating a rough relationship between the ion mobility and the ion intensity can be obtained based on the detection signal from the ion detector. Further, by fixing the voltage applied to the reflective electrode from the voltage application unit to a predetermined value, only ions having a specific ion mobility can be selectively detected. A chromatogram showing the change can be obtained.
- a gas jet that jets gas from the outside of the spray flow toward the central axis of the spray flow so as to surround the spray flow from the ionization probe to the auxiliary electrode. It is good to set it as the structure to which the part is attached.
- ions generated in the ionization chamber that is an atmospheric pressure atmosphere can be efficiently collected and introduced into the vacuum chamber through the ion introduction section.
- the amount of ions used for mass spectrometry increases, so that analysis sensitivity can be improved.
- an ion mobility spectrum or the like can be obtained with a simple configuration, so that the ion mobility analyzer can be reduced in size, weight, and cost. it can.
- the schematic block diagram of the mass spectrometer which is 1st Example of this invention The block diagram of the ion source of the mass spectrometer of 1st Example. The figure which shows the simulation result of an ion orbit. The figure which shows the simulation result of the direction of the force which an electric field acts on. The figure which shows the simulation result of the flow of gas.
- the block diagram of the ion source in the mass spectrometer which is 2nd Example of this invention.
- FIG. 1 is a schematic overall configuration diagram of the mass spectrometer of the first embodiment
- FIG. 2 is a configuration diagram of an ion source in the mass spectrometer.
- the ionization chamber 1 has a substantially atmospheric pressure atmosphere, and the analysis chamber 4 is maintained in a high vacuum atmosphere by evacuation by a high-performance vacuum pump (usually a combination of a turbo molecular pump and a rotary pump) (not shown).
- a high-performance vacuum pump usually a combination of a turbo molecular pump and a rotary pump
- a first intermediate vacuum chamber 2 which is a low vacuum atmosphere
- a second intermediate maintained at a vacuum degree intermediate between the first intermediate vacuum chamber 2 and the analysis chamber 4.
- a vacuum chamber 3 that is, this mass spectrometer has a multistage differential exhaust system configuration in which the degree of vacuum increases stepwise from the ionization chamber 1 in the direction of ion travel.
- a liquid sample containing sample components is sprayed from the ionization probe 5 for ESI while being given a biased charge.
- a heated nebulization gas is ejected from a nebulization gas tube provided in a coaxial cylindrical shape so as to surround a nozzle for spraying the sample, for example, as in the apparatus described in Patent Document 2, and the sample liquid The spraying may be assisted.
- the charged droplet sprayed from the tip of the ionization probe 5 comes into contact with the surrounding atmosphere and is refined, and in the process of evaporating the solvent from the droplet, the sample component jumps out with charge and becomes ions.
- an auxiliary electrode 6 and a reflective electrode 7 having functions to be described later are arranged in front of the spray flow from the ionization probe 5.
- the ionization chamber 1 and the first intermediate vacuum chamber 2 are communicated with each other by a small heating capillary 8 corresponding to the ion introduction portion in the present invention. Since there is a pressure difference between both open ends of the heating capillary 8, a gas flow that flows from the ionization chamber 1 to the first intermediate vacuum chamber 2 through the heating capillary 8 is formed by the pressure difference.
- the ions derived from the sample components generated in the ionization chamber 1 are mainly sucked into the heating capillary 8 along the flow of the gas flow, and discharged from the outlet end into the first intermediate vacuum chamber 2 together with the gas flow.
- a partition wall that separates the first intermediate vacuum chamber 2 and the second intermediate vacuum chamber 3 is provided with a skimmer 10 having a small-diameter orifice at the top.
- a skimmer 10 having a small-diameter orifice at the top.
- an ion guide 9 composed of a plurality of electrode plates arranged so as to surround the ion optical axis C is arranged, and ions introduced into the first intermediate vacuum chamber 2 are caused by the ion guide 9. It is converged in the vicinity of the orifice of the skimmer 10 by the action of the formed electric field, and sent to the second intermediate vacuum chamber 3 through the orifice.
- a multipole (for example, octupole) type ion guide 11 is disposed in the second intermediate vacuum chamber 3, and the ions are converged by the action of a high-frequency electric field formed by the ion guide 11 and enter the analysis chamber 4. It is sent.
- ions are introduced into the space in the long axis direction of the quadrupole mass filter 12 and specified by the action of the electric field formed by the high-frequency voltage and DC voltage applied to the quadrupole mass filter 12. Only ions having the mass-to-charge ratio pass through the quadrupole mass filter 12 and reach the ion detector 13.
- the ion detector 13 generates a detection signal corresponding to the amount of ions that have arrived, and sends the detection signal to a data processing unit (not shown).
- a highly sensitive analysis can be realized by finally entering the ion detector 13 while minimizing the loss of the ions to be measured.
- an auxiliary electrode 6 is disposed closest to the ionization probe 5, and a reflection electrode 7 is disposed at a position far from the ionization probe 5 while maintaining a distance a from the auxiliary electrode 6.
- both the auxiliary electrode 6 and the reflective electrode 7 have a cylindrical shape and are arranged so as to be coaxial with the central axis of the spray flow from the ionization probe 5.
- the heating capillary 8 is provided so that the inlet end 8 a extends to the space between the electrodes 6 and 7.
- the auxiliary electrode 6, the inlet end 8a of the heating capillary 8, and the reflective electrode 7 are positioned in this order from the front.
- the spray flow that progresses while spreading in a substantially conical shape is a hollow portion of the auxiliary electrode 6 (a space surrounded by the auxiliary electrode 6) and a hollow portion of the reflective electrode 7 (a space surrounded by the reflective electrode 7).
- the auxiliary electrode 6 and the reflective electrode 7 have the same inner diameter, but are not necessarily the same.
- the electrodes 6 and 7 do not have to be cylindrical, but may be polygonal cylinders, for example.
- the conductive electrode electrically connected to the auxiliary electrode 6 and the heating capillary 8 is grounded.
- a direct current voltage is applied to the reflective electrode 7 from the reflective electrode power supply unit 21, and a direct current high voltage of about several kV at maximum is applied to the ionization probe 5 from the nozzle power supply unit 20.
- the polarity of the voltage applied to each of the reflective electrode 7 and the ionization probe 5 corresponds to the polarity of the ion to be measured.
- the polarity of the applied voltage is Both are positive.
- the voltage generated in the nozzle power supply unit 20 and the reflective electrode power supply unit 21 is controlled by the control unit 22. In the following description, it is assumed that the measurement target ion is a positive ion. However, when the measurement target ion is a negative ion, only the polarity of the applied voltage is changed.
- v v f + KE ... ( 1)
- K ion mobility. Ion mobility is a parameter that determines the speed of ion motion due to an electric field when collisions with neutral particles are taken into account, and depends on ion mass, valence, collision cross section with neutral particles, gas temperature, etc. To do.
- Non-Patent Document 1 it is reported that the ion mobility of ions having a mass to charge ratio of about 500 m / z is about 1 ⁇ 10 ⁇ 4 [m 2 / Vs].
- Many of the particles sprayed from the ionization probe 5 are considered to be in a state of minute charged droplets containing a solvent. Since the size of the particles is larger than that of the ions, the mobility of the particles is as described above. It is estimated that it is smaller than the mobility value for the obtained ion. In addition, since the desolvation progresses while these charged droplets fly in the atmospheric pressure atmosphere and the size of the charged droplets decreases, it is presumed that the mobility approaches the value of ions.
- the auxiliary electrode 6 and the reflective electrode 7 are provided in order to efficiently generate an electric field in the direction opposite to the gas flow.
- the spray flow from the ionization probe 5 proceeds downward. Ions generated from the sample droplet also travel in substantially the same direction.
- a force that pushes ions upward is exerted on the space between the auxiliary electrode 6 and the reflective electrode 7 by the DC voltage applied to the reflective electrode 7 from the reflective electrode power supply unit 21. A reflected electric field is formed.
- the distance a between the auxiliary electrode 6 and the reflective electrode 7 is relatively short, and the inlet end 8a of the heating capillary 8 is located in the space between the auxiliary electrode 6 and the reflective electrode 7.
- a strong electric field in which a force acts on can be formed.
- an appropriate voltage of about 3 [kV] or less should be applied to the reflective electrode 7 even if electric field leakage is taken into consideration.
- the heating capillary 8 itself extending to the space between the auxiliary electrode 6 and the reflection electrode 7 is also at the ground potential, ions are not allowed to flow between the inlet end 8a of the heating capillary 8 and the reflection electrode 7. A focused electric field is inevitably formed that exerts a force on the ions toward the inlet end 8a.
- ions and charged droplets traveling in the downward direction on the spray flow are separated from the gas flow by the strong reflected electric field as described above and pushed back upward, and are stagnated near the inlet end 8 a of the heating capillary 8. To do. Then, they gather in the vicinity of the inlet end 8a of the heating capillary 8 by the focused electric field. The ions and charged droplets collected in the vicinity of the inlet end 8 a of the heating capillary 8 are sucked into the heating capillary 8 along the gas flow flowing through the heating capillary 8 and sent to the first intermediate vacuum chamber 2.
- FIG. 4 is a diagram showing the simulation result of the direction of the force applied by the electric field
- FIG. 5 is a diagram showing the simulation result of the gas flow.
- FIG. 3 is a diagram showing a result of simulating an ion trajectory based on Equation (1) using a gas flow simulation result and an electric field simulation result.
- the ground potential is the same as that of the auxiliary electrode 6 without applying a voltage to the reflective electrode 7, it can be regarded as a system equivalent to the prior art in which the reflective electrode 7 does not substantially exist.
- FIG. 3A shows an ion trajectory in such a state
- FIG. 3B shows an ion trajectory in a state where a DC voltage of 3.6 [kV] is applied to the reflective electrode 7.
- FIG. 3A when the reflective electrode 7 is not substantially present, it can be seen that a large number of ions pass through the inlet end 8a of the heating capillary 8 while riding on the gas flow.
- FIG. 3B when the reflective electrode 7 is used as in the present invention, as shown in FIG. 3B, almost all ions are separated and reflected from the gas flow and directed toward the inlet end 8a of the heating capillary 8. Are focused. As a result, it can be confirmed that a large number of previously discarded ions can be effectively introduced into the first intermediate vacuum chamber.
- the collection efficiency of ions to the inlet end 8a of the heating capillary 8 depends on the strength of the reflected electric field and the ion mobility. Since the ion mobility depends on the mass-to-charge ratio of the ions, the voltage applied to the reflective electrode 7 is changed in accordance with the mass-to-charge ratio of the ions to be selected by the quadrupole mass filter 12 (that is, ions to be measured). It is effective to improve analysis sensitivity.
- FIG. 9 shows the result of simulating the number of ions having a specific mass-to-charge ratio reaching the inlet end 8a of the heating capillary 8 when the applied voltage (reflected voltage) to the reflective electrode 7 is changed.
- FIG. It can be seen that the reflected voltage has an optimum value for the ions, and that the ion collection efficiency decreases if the reflected voltage deviates from the optimum value.
- an optimal reflection voltage is experimentally obtained in advance for each mass-to-charge ratio of ions to be measured, and a calculation formula or table showing the relationship between the mass-to-charge ratio and the optimal reflection voltage Created and stored in the control unit 22. Then, when performing analysis of the target sample, based on the above calculation formula and table, according to the voltage applied to the quadrupole mass filter 12 (that is, the ions to be selected by the quadrupole mass filter 12). In accordance with the mass-to-charge ratio), the control unit 22 obtains the optimum reflection voltage and controls the reflection electrode power source unit 21 so that the voltage applied to the reflection electrode 7 becomes the optimum reflection voltage.
- the mobility of ions to be observed in the auxiliary electrode 6, the reflective electrode 7, and the heating capillary 8 is observed. It may be used as an ion mobility analysis unit that changes the ion mobility, or as an ion mobility filter that selects only ions having a specific mobility. For example, by scanning the voltage applied to the reflective electrode 7 in a state where the mass-to-charge ratio of ions selected by the quadrupole mass filter 12 is fixed, the ion mobility is different with a specific mass-to-charge ratio. The intensity of various ions can be determined.
- the mass of ions having a specific ion mobility is determined.
- the relationship between charge ratio and ionic strength can be examined.
- FIG. 6A is a configuration diagram of an ion source in the mass spectrometer of the second embodiment
- FIG. 6B is a top view of the auxiliary electrode 60.
- the same components as those of the mass spectrometer of the first embodiment are denoted by the same reference numerals.
- the feature of the mass spectrometer of the second embodiment is that a gas ejection mechanism is provided in the auxiliary electrode 60 that is maintained at the ground potential in order to obtain an ion collecting effect with a smaller reflection voltage.
- the gas ejection mechanism includes a shielding gas outlet 62 formed in a slit shape over the entire inner peripheral surface of the auxiliary electrode 60, a gas flow path 61 for guiding gas supplied from the outside to the shielding gas outlet 62, including.
- the gas may be an inert gas similar to nebulization gas or the like.
- gas is ejected from the annular shielding gas outlet 62 toward the cylindrical central axis of the auxiliary electrode 60, so that the gas flow is substantially orthogonal to the spray flow ejected from the ionization probe 5.
- a curtain-like gas flow is formed that blocks the spray flow. Thereby, the flow velocity of the spray flow ejected from the ionization probe 5 is lowered.
- ions and charged droplets contained in the spray flow are focused near the central axis, diffusion to the surroundings is suppressed, and the convergence effect by the reflected electric field and the focused electric field is easily exhibited.
- the direction of the gas ejected from the shielding gas outlet 62 is substantially perpendicular to the central axis of the auxiliary electrode 60, that is, the central axis of the spray flow from the ionization probe 5.
- the shielding gas outlet 62 may be provided so as to eject the gas in the upward oblique direction in FIG.
- the gas ejected from the shielding gas outlet 62 proceeds so as to face the spray flow from the ionization probe 5, so that the effect of reducing the gas flow rate by the spray flow is increased.
- FIG. 7 is a schematic configuration diagram of the ion mobility analyzer of this embodiment.
- the efficiency with which ions having a specific mass-to-charge ratio reach the inlet end 8a of the heating capillary 8 changes. That is, the collection efficiency of ions to the inlet end 8a of the heating capillary 8 has a dependence on ion mobility. In the ion mobility analyzer of the present embodiment, this is used to separate and detect ions according to the ion mobility.
- the ion detection electrode 30 is provided at the position where the inlet end 8a of the heating capillary 8 is located in the mass spectrometer of the first embodiment.
- the ion current thus obtained is amplified by the amplifier 31 and output as a detection signal.
- the control unit 23 controls the reflective electrode power source unit 21 so that the applied voltage to the reflective electrode 7 is scanned within a predetermined range. To do. Then, since the mobility of ions that reach the ion detection electrode 30 most efficiently changes, an ion mobility spectrum can be created based on the detection signal.
- the control unit 23 applies a voltage to the reflective electrode 7 according to the ion mobility.
- the power supply unit 21 is controlled. Then, since the state where the ions having the ion mobility reach the ion detection electrode 30 most efficiently continues, a chromatogram of the ions having the specific ion mobility can be created based on the detection signal. .
- ions can be separated with high resolution according to the ion mobility, but the structure of the electrode for forming the electric field and the structure for forming the gas flow at a constant flow rate are complicated. Become a big deal.
- the ion mobility analyzer of the present embodiment since the configuration of the part for separating ions according to the mobility is very simple, a small and inexpensive device can be realized, for example, a liquid chromatograph. A suitable device can be provided as an option for the detector.
- FIG. 8 shows an ion mobility analyzer in which an ion detection electrode 30 is provided at a position where the inlet end 8a of the heating capillary 8 is located in the mass spectrometer of the second embodiment shown in FIG. Similar to the mass spectrometer of the second embodiment, in the ion mobility analyzer of the fourth embodiment, even when the flow velocity of the spray flow ejected from the ionization probe 5 is large, the flow velocity is increased by the action of the curtain-like shielding gas. And the voltage applied to the reflective electrode 7 can be lowered.
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Abstract
Description
a)前記イオン化プローブからの試料液滴の噴霧方向で且つ前記イオン導入部の入口端よりも手前側に、該イオン化プローブからの噴霧流の中心軸を囲むように設けられた補助電極と、
b)前記イオン化プローブからの試料液滴の噴霧方向で且つ前記イオン導入部の入口端よりも奥側に、該イオン化プローブからの噴霧流の中心軸を囲むように設けられた反射電極と、
c)前記補助電極の電位を基準として、前記反射電極に測定対象であるイオンを反射させる電圧を印加する電圧印加部と、
を備えることを特徴としている。
例えば、質量分離器として四重極マスフィルタを用い、所定の質量電荷比範囲に亘るスキャン測定を行う場合には、そのスキャン測定に際し四重極マスフィルタに印加する電圧を走査するのに同期して、反射電極に印加する電圧も走査するとよい。
a)大気圧雰囲気中に液体試料を噴霧するイオン化プローブを含むイオン源と、
b)前記イオン化プローブからの噴霧流の前方に配置され、前記イオン源で生成された、前記イオン化プローブから噴霧された試料液滴中に含まれる成分由来のイオンを検出するイオン検出部と、
c)前記イオン化プローブからの試料液滴の噴霧方向で且つ前記イオン検出部よりも手前側に、該イオン化プローブからの噴霧流の中心軸を囲むように設けられた補助電極と、
d)前記イオン化プローブからの試料液滴の噴霧方向で且つ前記イオン検出部よりも奥側に、該イオン化プローブからの噴霧流の中心軸を囲むように設けられた反射電極と、
e)前記補助電極の電位を基準として、前記反射電極に測定対象であるイオンを反射させる電圧を印加する電圧印加部と、
を備えることを特徴としている。
本発明の一実施例(第1実施例)である質量分析装置について説明する。図1は第1実施例の質量分析装置の概略全体構成図、図2は該質量分析装置におけるイオン源の構成図である。
以下の説明では、測定対象イオンが正イオンである場合を想定するが、測定対象イオンが負イオンである場合には印加電圧の極性が変わるだけである。
v=vf+KE …(1)
ここでKはイオン移動度である。イオン移動度は、中性粒子との衝突を考慮した場合の電場によるイオンの運動速度を決定するパラメータであり、イオンの質量、価数、中性粒子との衝突断面積、ガス温度などに依存する。非特許文献1によれば、質量電荷比m/z 500程度のイオンのイオン移動度は1×10-4[m2/Vs]程度の値であると報告されている。
イオン化プローブ5から噴霧される粒子の多くは溶媒を含む微小な帯電液滴の状態であると考えられ、その粒子のサイズはイオンの状態よりも大きいため、該粒子の移動度は上記のように求まるイオンに対する移動度の値よりも小さいと推定される。また、こうした帯電液滴が大気圧雰囲気中を飛行する間に脱溶媒化が進んでそのサイズは小さくなるため、その移動度はイオンの値に近づいていくものと推測される。
|E|=|vf|/K=4[kV/cm] …(2)
従来、イオンや帯電液滴をイオン導入口に引き寄せる目的で、イオン導入口のポテンシャルをその近傍に位置する電極(例えばイオン化プローブ先端部)よりも低くすることでイオン導入口への集束電場を発生させている装置がある。しかしながら、この方法では、ガス流と逆方向の電場の強度を上記の値程度まで大きくすることは難しく、多くのイオンや帯電液滴がガス流に乗って廃棄されてしまうことになる。
また、補助電極6と反射電極7との間の空間にまで延伸している加熱キャピラリ8自体も接地電位であるため、加熱キャピラリ8の入口端8aと反射電極7との間には、イオンを入口端8aに向かわせる力を該イオンに及ぼすような集束電場が必然的に形成されることになる。
次に本発明の他の実施例(第2実施例)である質量分析装置について説明する。図6(a)は第2実施例の質量分析装置におけるイオン源の構成図であり、図6(b)は補助電極60の上面図である。図6では、第1実施例の質量分析装置と同じ構成要素には同じ符号を付してある。
第1実施例の質量分析装置では、イオン化プローブ5から噴出されるガス流の流速が大きい場合、イオンをガス流から分離し反射させるためにより大きな反射電圧が必要となる。この第2実施例の質量分析装置の特徴は、より小さい反射電圧で以てイオンの収集効果を得るために、接地電位に維持される補助電極60にガス噴出機構を設けていることである。
次に本発明の他の実施例(第3実施例)であるイオン移動度分析装置について説明する。図7は本実施例のイオン移動度分析装置の概略構成図である。
上述したように、図2に示した構成において反射電極7への印加電圧を変化させると、特定の質量電荷比を有するイオンが加熱キャピラリ8の入口端8aに到達する効率が変化する。即ち、加熱キャピラリ8の入口端8aへのイオンの収集効率はイオン移動度の依存性を有する。本実施例のイオン移動度分析装置では、このことを利用してイオンをイオン移動度に応じて分離して検出するようにしている。
図8は、図6に示した第2実施例の質量分析装置において加熱キャピラリ8の入口端8aが位置していた箇所にイオン検出電極30を設けたイオン移動度分析装置である。第2実施例の質量分析装置と同様に、この第4実施例のイオン移動度分析装置では、イオン化プローブ5から噴出する噴霧流の流速が大きい場合でも、カーテン状の遮蔽ガスの作用によりその流速を減じることができ、反射電極7に印加する電圧を下げることができる。
2…第1中間真空室
3…第2中間真空室
4…分析室
5…イオン化プローブ
6、60…補助電極
61…ガス流路
62…遮蔽ガス出口
7…反射電極
8…加熱キャピラリ
8a…入口端
9…イオンガイド
10…スキマー
11…イオンガイド
12…四重極マスフィルタ
13…イオン検出器
20…ノズル電源部
21…反射電極電源部
22、23…制御部
Claims (5)
- 大気圧雰囲気であるイオン化室内に液体試料を噴霧するイオン化プローブを含むイオン源と、該イオン源で生成された、前記イオン化プローブから噴霧された試料液滴中に含まれる成分由来のイオンを前記イオン化室から真空室へと送るイオン導入部と、を具備し、前記イオン化プローブからの液体試料の噴霧方向と前記イオン導入部による前記イオン化室内からのイオンの導入方向とが直交又は斜交するように、前記イオン化プローブ及び前記イオン導入部の配置が定められてなる質量分析装置において、
a)前記イオン化プローブからの試料液滴の噴霧方向で且つ前記イオン導入部の入口端よりも手前側に、該イオン化プローブからの噴霧流の中心軸を囲むように設けられた補助電極と、
b)前記イオン化プローブからの試料液滴の噴霧方向で且つ前記イオン導入部の入口端よりも奥側に、該イオン化プローブからの噴霧流の中心軸を囲むように設けられた反射電極と、
c)前記補助電極の電位を基準として、前記反射電極に測定対象であるイオンを反射させる電圧を印加する電圧印加部と、
を備えることを特徴とする質量分析装置。 - 請求項1に記載の質量分析装置であって、
前記補助電極に、前記イオン化プローブからの噴霧流を取り囲むように該噴霧流の外側から該噴霧流の中心軸に向かってガスを噴出するガス噴出部が付設されていることを特徴とする質量分析装置。 - 請求項1又は2に記載の質量分析装置であって、
前記電圧印加部は、測定対象であるイオンの質量電荷比に応じて前記反射電極に印加する電圧を変化させることを特徴とする質量分析装置。 - a)大気圧雰囲気中に液体試料を噴霧するイオン化プローブを含むイオン源と、
b)前記イオン化プローブからの噴霧流の前方に配置され、前記イオン源で生成された、前記イオン化プローブから噴霧された試料液滴中に含まれる成分由来のイオンを検出するイオン検出部と、
c)前記イオン化プローブからの試料液滴の噴霧方向で且つ前記イオン検出部よりも手前側に、該イオン化プローブからの噴霧流の中心軸を囲むように設けられた補助電極と、
d)前記イオン化プローブからの試料液滴の噴霧方向で且つ前記イオン検出部よりも奥側に、該イオン化プローブからの噴霧流の中心軸を囲むように設けられた反射電極と、
e)前記補助電極の電位を基準として、前記反射電極に測定対象であるイオンを反射させる電圧を印加する電圧印加部と、
を備えることを特徴とするイオン移動度分析装置。 - 請求項4に記載のイオン移動度分析装置であって、
前記補助電極に、前記イオン化プローブからの噴霧流を取り囲むように該噴霧流の外側から該噴霧流の中心軸に向かってガスを噴出するガス噴出部が付設されていることを特徴とするイオン移動度分析装置。
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