WO2020055133A1 - Unité d'interface - Google Patents

Unité d'interface Download PDF

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Publication number
WO2020055133A1
WO2020055133A1 PCT/KR2019/011778 KR2019011778W WO2020055133A1 WO 2020055133 A1 WO2020055133 A1 WO 2020055133A1 KR 2019011778 W KR2019011778 W KR 2019011778W WO 2020055133 A1 WO2020055133 A1 WO 2020055133A1
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WO
WIPO (PCT)
Prior art keywords
unit
region
opening
sample
dart
Prior art date
Application number
PCT/KR2019/011778
Other languages
English (en)
Korean (ko)
Inventor
유현식
배용진
임영희
윤여영
Original Assignee
주식회사 엘지화학
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from KR1020190110755A external-priority patent/KR20200035859A/ko
Priority claimed from KR1020190111487A external-priority patent/KR102577694B1/ko
Priority claimed from KR1020190112165A external-priority patent/KR20210030699A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2020552313A priority Critical patent/JP7294620B2/ja
Priority to US17/049,105 priority patent/US11488816B2/en
Priority to CN201980024368.2A priority patent/CN111954917B/zh
Priority to EP19860396.1A priority patent/EP3852129A4/fr
Publication of WO2020055133A1 publication Critical patent/WO2020055133A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes

Definitions

  • the present invention relates to an interface unit that can be used in a laser ablation (LA) -DART-MS system, and more specifically, DART (direct) to improve detection sensitivity of a sample that is laser ablation. It relates to an interface unit that can be provided between an analysis in real time (MS) unit and a mass spectrometry (MS) unit.
  • LA laser ablation
  • MS mass spectrometry
  • DART-MS direct analysis in real time-mass spectrometry
  • DART-MS uses desorption and ionization of the target material using heated metastable He gas from an ion source and reactive ions generated therefrom. It is a device that can perform molecular weight and structure analysis of materials.
  • concentration of the sample in the atmosphere increases and the resulting signal-to-interference ratio of the spectrum (Signal-to-noise ratio) technical development is required to improve.
  • desorption efficiency of the sample, ionization efficiency, and efficient collection and transmission of generated ions may be important factors for improving detection sensitivity.
  • laser ablation techniques have been applied to increase the concentration of samples in the atmosphere, but due to the exposed space in the atmosphere, efficient collection and mass analysis units of desorption and ionized components are still available. Improvement for transmission to spectrometer is needed.
  • the laser was detached at the irradiation point of each laser beam through the introduction of a quartz tubing interface between the exit of the DART and the inlet of the MS.
  • a method is required to limit the flow of components and generated ions to improve detection sensitivity.
  • the present invention is to provide an interface unit that can be used in a laser ablation (LA) -DART-MS system, and more specifically, DART for improving detection sensitivity of a sample that is laser ablation with a laser beam. It is intended to provide an interface unit that can be provided between a (direct analysis in real time) unit and a mass spectrometry (MS) unit.
  • LA laser ablation
  • MS mass spectrometry
  • the interface unit of the present invention comprises a tube-shaped body that can be located between the exit of the DART ionization unit (direct analysis in real time ionization unit) and the inlet of the mass spectrometry unit; And a first opening provided on one side of the main body, the first opening provided so that an analyte detached from a sample flows into the main body, and the interface unit includes a laser desorption-DART-MS system (laser ablation).
  • the main body may be a helium beam emitted from the DART ionization unit and an analyte detached from the sample may be introduced and delivered to the mass spectrometry unit.
  • a laser desorption-DART-MS system using the interface unit of the present invention comprising: a sample mounting unit on which the sample is mounted; An optical unit including a laser unit that irradiates a laser beam to the sample so that the sample is detached; A DART ionization unit providing a helium beam to ionize the analyte detached from the sample; And a mass spectrometer (MS) for performing analysis on the ionized analyte, and an optical unit supporting member capable of supporting the optical unit and being capable of mounting the optical unit at a desired position.
  • the optical unit support member may be fixed to the mass spectrometry unit.
  • the desorbed components and generated ions at the irradiation point of each laser beam through the introduction of a quartz tube interface between the exit of the DART and the inlet of the MS
  • the detection sensitivity can be improved by restricting the flow.
  • the body of the first region of the present invention is formed to be narrower as it is adjacent to the second region, so that the analyte desorbed from the sample and the helium gas emitted from the DART ionization unit are collected in a sufficient amount, and the second ion component is generated. It is focused and sent to the region, and the inner diameter of the body of the second region is formed to be equal to or smaller than the inner diameter of the body at the other end of the first region, so that the gas stream received from the first region is Since it is transported to the inlet of the mass spectrometry unit in a radially compressed state, it is possible to efficiently collect and deliver the component to be analyzed.
  • the present invention in the laser desorption-DART-MS system, it is possible to improve the reproducibility of the experiment by fixing the relative positional relationship between the laser and the sample. In addition, there is an advantage that it is possible to perform system optimization for improving the detection sensitivity of a sample by adjusting the position of optical units such as a laser unit using a laser support member. In addition, it is possible to increase the convenience of operation of the laser desorption-DART-MS system.
  • FIG. 1 is a schematic diagram of a laser desorption-DART-MS system to which the interface unit of the present invention is applied.
  • FIG. 2 is a longitudinal sectional view showing an embodiment of the interface unit of the present invention.
  • FIG. 3 is a longitudinal sectional view showing another embodiment of the interface unit of the present invention.
  • FIG. 4 is a longitudinal sectional view showing an embodiment in which a protruding tube is included in the interface unit of the present invention.
  • FIG. 5 is a longitudinal sectional view showing another embodiment in which a protruding tube is included in the interface unit of the present invention.
  • FIG. 6 is a bottom view showing the interface unit of FIG. 4.
  • FIG. 7A is a conceptual diagram illustrating dimensions of each part according to an embodiment of the interface unit.
  • 7B is a conceptual diagram illustrating dimensions of each part according to another embodiment of the interface unit.
  • FIG. 8 shows a case where an experiment is performed in a laser detachable-DART-MS system equipped with the interface unit of FIG. 2.
  • 9A is a graph showing experimental results in a laser desorption-DART-MS system without an interface unit applied.
  • 9B and 9C are graphs showing experimental results in a laser desorption-DART-MS system to which an interface unit is applied.
  • FIG. 10 is a schematic view of the optical unit of the laser desorption-DART-MS system of FIG. 1;
  • FIG. 11 is a front view of a member for supporting the optical unit.
  • FIG. 12 is a view showing an interface flange by way of example.
  • FIG. 13 is a view exemplarily showing a case where the bottom plate is mounted on the interface flange.
  • FIG. 14 is a conceptual view showing a member for supporting the optical unit and a portion of the optical units mounted on the interface flange.
  • the interface unit of the present invention includes a tube-shaped body that can be located between an exit of a DART ionization unit (Direct analysis in real time ionization unit) and an inlet of a mass spectrometry unit; And a first opening provided on one side of the main body, the first opening provided so that an analyte detached from a sample flows into the main body, and the interface unit includes a laser desorption-DART-MS system (laser ablation).
  • the main body may be a helium beam emitted from the DART ionization unit and an analyte detached from the sample may be introduced and delivered to the mass spectrometry unit.
  • the main body is connected to the first region where the helium beam emitted from the DART ionization unit and the analyte detached from the sample are introduced, and the gas stream of the first region is connected to the first region. It includes a second region that is injected and delivered to the mass spectrometry unit, and a helium beam emitted from the DART ionization unit flows into one end of the first region, and the other end of the first region is connected to the second region
  • the inner diameter of the main body in the first region may be reduced as it goes from the one end of the first region to the other end of the first region.
  • the inner space of the main body may be formed to be tapered.
  • the first opening may be provided in the first region.
  • the interface unit of the present invention further includes a protruding tube extending from the first opening toward the sample mounting unit perpendicular to the longitudinal direction of the interface unit, and the analytes detached from the sample mounted on the sample mounting unit are the It may be introduced into the interface unit through the first opening through the protruding tube.
  • a second opening is provided to allow a laser beam emitted from the laser unit to pass, and the second opening faces the first opening, and the laser The beam may be irradiated to the sample through the first opening and the second opening.
  • At least one third opening for corona pins to be inserted into the body may be provided.
  • the inlet of the mass spectrometry unit is an analysis space provided inside the mass spectrometry unit and includes an orifice provided with a hole through which an analyte outside the mass spectrometry unit flows, and an interface flange connected to the orifice.
  • an orifice provided with a hole through which an analyte outside the mass spectrometry unit flows
  • an interface flange connected to the orifice.
  • one end of the second region is connected to the other end of the first region, the other end of the second region is connected to the inlet of the mass spectrometry unit, the body of the other end of the second region
  • the outer diameter of may be smaller than the inner diameter of the suction hole formed to face the hole of the orifice on the interface flange.
  • the interface unit of the present invention further includes a second opening provided to pass the laser beam emitted from the laser unit, the second opening is located at a point opposite to the first opening of the side of the body, and the laser beam is The second opening and the first opening may be irradiated with the sample.
  • the interface unit of the present invention may further include at least one third opening provided so that an end of the corona pin is inserted into the main body of the interface unit, and the third opening may be located near the second opening.
  • the laser detachable-DART-MS system using the interface unit of the present invention includes a sample mounting unit on which the sample is mounted; An optical unit including a laser unit that irradiates a laser beam to the sample so that the sample is detached; A DART ionization unit providing a helium beam to ionize the analyte detached from the sample; And a mass spectrometer (MS) that performs analysis on the ionized analyte, and includes an optical unit supporting member capable of supporting the optical unit and being capable of mounting the optical unit at a desired position.
  • the optical unit support member may be fixed to the mass spectrometry unit.
  • the inlet of the mass spectrometry unit is an analysis space provided inside the mass spectrometry unit.
  • An interface flange is connected, the interface flange is fixed to the surface of the mass spectrometer unit in which the orifice is provided, and the optical unit support member may be fixed to the interface flange.
  • the optical unit support member of the laser detachable-DART-MS system of the present invention includes a plurality of fasteners, and the plurality of fasteners are at least one interface flange connector provided at a position corresponding to a tab portion of the interface flange.
  • each interface flange connection portion may be one that can be coupled to the first fastening member in the tab portion of each interface flange.
  • the plurality of fastening parts further include at least one optical unit connection part to which the optical unit can be coupled, and each optical unit connection part comprises a fastening part of the optical unit. It is combined with two fastening members, and the optical unit may further include at least one of a mirror, a translation stage, an iris, and lenses.
  • the optical unit support member is composed of an upper plate and a lower plate, and the plurality of fastening parts include at least one upper and lower end to which the upper plate and the lower plate can be coupled to each other. It may include a plate coupling portion, and the upper and lower plate coupling portions of the lower plate and the upper and lower plate coupling portions of the upper plate may be fixed by a third fastening member.
  • DART ionization unit 10 DART ion source
  • He beam helium beam
  • the laser desorption-DART-MS system 1 includes a DART ionization unit 10, a mass spectrometer 20, a sample mounting unit 30, a laser unit 41, and a corona discharge unit (not shown). It includes.
  • the analyte detached from the sample 2 mounted on the sample mounting unit 30 by irradiating a laser beam from the laser unit 41 to the helium beam of the DART ionization unit 10 (He beam) and reactive ions generated therefrom.
  • the helium beam is emitted from the exit 11 of the DART ionization unit 10 so that the analyte detached from the sample 2 mounted on the sample mounting unit 30 is ionized.
  • the DART ionization unit 10 may be, for example, DART-SVP from IonSense.
  • the mass spectrometry unit (MS) 20 accepts the ionized analyte to perform molecular weight and structure analysis of the ionized analyte.
  • the mass spectrometry unit 20 may be, for example, LTQ Orbitrap Elite from Thermo Fisher Scientific.
  • the sample mounting unit 30 is located between the outlet of the DART ionization unit 10 and the inlet 21 of the mass spectrometry unit 20.
  • the inlet 21 of the mass spectrometry unit 20 is an orifice 21a and an orifice in which a hole through which an external analyte is introduced is provided as an analysis space provided inside the mass spectrometry unit 20. It may include an interface flange (21b) that is connected to (21a). The interface flange 21b at the inlet 21 of the mass spectrometry unit 20 may be selectively provided according to the analysis situation.
  • the sample mounting unit 30 is a DART ionization unit It may be located a predetermined distance apart from a virtual straight line connecting the inlet 21 of the mass spectrometry unit 20 with the outlet of (10).
  • the sample mounting unit 30 may be located below the path between the outlet of the DART ionization unit 10 and the inlet 21 of the mass spectrometry unit 20.
  • the sample mounting unit 30 is, for example, a stainless steel sample plate, on which a glass substrate or a thin layer chromatography (TLC) substrate on which the sample 2 is present may be placed.
  • the laser unit 41 irradiates a laser beam to the sample 2 to detach the analyte from the sample 2.
  • the laser unit 41 may be, for example, LMD-XT series from LASOS.
  • the corona discharge unit includes a corona pin.
  • the direction of the corona fin is directed to the path between the outlet of the DART ionization unit 10 and the inlet 21 of the mass spectrometry unit 20. That is, the helium beam emitted from the DART ionization unit 10 is directed to an area where the analyte detached from the sample 2 meets.
  • the ionization of the analyte detached from the sample 2 is promoted by supplying a high voltage of the corona discharge unit, for example, a positive DC voltage of 1 kV or more. Accordingly, it is possible to increase the ionization efficiency of the analyte.
  • the relative position of the laser unit 41 or the irradiation angle and power of the laser beam can be adjusted so that the ionic peak intensity of the analyte originating from the sample 2 is maximized.
  • the interface unit 100 of the present invention may be located between the outlet of the DART ionization unit 10 and the inlet 21 of the mass spectrometry unit 20 in the laser desorption-DART-MS system 1.
  • 2 is a longitudinal sectional view of the interface unit 100 according to an embodiment of the present invention.
  • the interface unit 100 may have a tube-shaped body having both ends opened, and may be a tube including a plurality of openings as described later.
  • the interface unit 100 may be, for example, a quartz tube including a plurality of openings.
  • the material of the interface unit 100 may be a tube made of glass or ceramic material in addition to the above-described quartz.
  • One end 101 of both ends of the interface unit 100 is disposed to overlap with the distal end of the outlet of the DART ionization unit 10 (i.e., the DART ionization unit into the inside of one end 101 of the interface unit 100) 10) may include some or all of the distal portion of the outlet.
  • one end 101 of both ends of the interface unit 100 may directly contact or adjoin the outlet of the DART ionization unit 10.
  • the helium beam emitted from the outlet of the DART ionization unit 10 flows into the interface unit 100 through the opened one end 101 of the interface unit 100.
  • the other end 102 of both ends of the interface unit 100 may be combined with the inlet of the mass spectrometry unit 20.
  • the inlet 21 of the mass spectrometry unit 20 may include an interface flange 21b for connecting the external piping and the mass spectrometry unit 20, and the other end 102 of the interface unit 100 ) Is inserted into the interface flange, the interface unit 100 and the inlet 21 of the mass spectrometry unit 20 may be combined.
  • the interface unit 100 may be connected to the inlet 21 of the mass spectrometry unit 20 so as to be in contact with the orifice 21a or to be spaced a predetermined distance (about 2 mm).
  • the inlet 21 of the mass spectrometry unit 20 is further fixed to the interface flange 21b and further includes an extension tube 21c for delivering a gas stream to the orifice 21a, and the extension tube 21c ),
  • the interface unit 100 may be fixed.
  • the interface unit 100 of the present invention is a tube-shaped body that can be located between the outlet of the DART ionization unit 10 and the inlet 21 of the mass spectrometry unit 20.
  • the main body is connected to the first region 110 and the first region 110 to which the analyte detached from the helium beam and the sample 2 emitted from the DART ionization unit 10 flows, the first region 110 It may include a second region 120 that receives the gas stream of the region 110 and delivers it to the mass spectrometry unit 20.
  • the gas stream can include helium gas and desorption and ionized components from the sample.
  • the body of the second region 120 may be combined with the inlet 21 of the mass spectrometry unit 20.
  • one end 111 of the first region 110 faces adjacent to the DART ionization unit 10, and the other end 112 of the first region 110 is one end of the second region 120. It is connected to (121), the other end 122 of the second region 120 may face to be adjacent to the mass spectrometry unit 20. That is, [DART ionization unit 10]-[first region 110]-[second region 120]-[mass spectrometry unit 20] may be arranged in this order.
  • the interface unit 100 may be formed to have a uniform inner diameter along the longitudinal direction.
  • the inner diameter of the body in the first region 110 is the other end 112 of the first region 110 from one end 111 of the first region 110 ).
  • the interior space of the body in the first region 110 may be formed to be tapered. That is, the interior space of the body in the first region 110 may be conical.
  • the body of the first region 110 of the present invention is formed to be narrower as it is adjacent to the second region 120, so that the analyte detached from the sample 2 and the helium gas emitted from the DART ionization unit 10 is sufficient.
  • the positively collected and generated ionic component may be focused and sent to the second region 120.
  • the inner diameter of the body at one end 111 of the first region 110 may be larger than the inner diameter of the inlet of the mass spectrometry unit 20.
  • the inner diameter of the body of the second region 120 is formed to be the same as or smaller than the inner diameter of the body of the other end 112 side of the first region 110, a gas stream received from the first region 110 (gas stream) ) Can be transported to the inlet of the mass spectrometry unit 20 in a radially compressed state.
  • the inner diameter of the main body may be kept constant. Specifically, since the gas stream is delivered in a radially compressed state through the second region 120, loss in the vicinity of the inlet of the mass spectrometry unit 20, which is a sub-ambient pressure region, is reduced. You can.
  • the first region 110 is formed on one side of the body adjacent to the sample mounting unit 30 (more specifically, the sample 2).
  • the opening 130, the second opening 140 formed on the other side of the body so that the laser beam emitted from the laser unit 41 passes, and at least one or more third openings for inserting the corona pin into the body ( 150) may be provided.
  • the analyte detached from the sample 2 mounted on the sample mounting unit 30 may be introduced into the interface unit 100 of the first region 110 through the first opening 130.
  • the analyte introduced into the interface unit 100 may be ionized by a helium beam entering through the opened one end 101 of the interface unit 100 and reactive ions generated therefrom.
  • the first opening 130 is also a path through which the laser beam entering through the second opening 140 to be described later passes toward the sample 2. That is, the laser beam emitted from the laser unit 41 may first pass through the second opening 140 and pass through the first opening 130 to be irradiated to the sample 2 mounted on the sample mounting unit 30.
  • the first opening 130 may have a circular shape, for example.
  • the second opening 140 may be located at a point facing the first opening 130. . That is, the second opening 140 may face the first opening 130.
  • the second opening 140 may have a circular shape, for example. The laser beam may penetrate the center of the second opening 140.
  • the second opening 140 may be covered with a flat cover of a material that transmits light in a wavelength range irradiated with a laser beam.
  • the flat cover may cover the second opening 140 so that the flat surface of the flat cover is perpendicular to the light path of the laser beam.
  • the gas stream can be prevented from leaking through the second opening 140 while irradiating the sample without the laser beam being refracted or scattered.
  • At least one third opening 150 is included in a portion of the side surface of the interface unit 100 toward the corona pin of the corona discharge unit.
  • the third opening 150 may be located near the second opening 140.
  • the end of the corona pin of the corona discharge unit may be positioned near the third opening 150 to face the interior of the interface unit 100, or the end of the corona pin of the corona discharge unit may interface through the third opening 150. It may be inserted into the unit 100.
  • the third opening 150 applied to the corona pin may be provided in one piece or may be provided in plural pieces.
  • the distance between the laser beam and the corona pin may be variously changed.
  • the third opening 150 may have a circular shape, for example.
  • the first opening 130 further includes a protruding tube 131 extending vertically in the longitudinal direction of the interface unit 100.
  • the protruding tube 131 extends from the first opening 130 in the direction of the sample mounting unit 30.
  • the protruding tube 131 extends downward and has a protruding shape. That is, the protruding tube may be a tube extending toward the sample mounting unit 30 perpendicular to the longitudinal direction of the interface unit 100 in the first opening.
  • the protruding tube 131 may be, for example, a tube shape as shown in FIGS. 4 and 5.
  • the present invention is not limited to the above, and various modifications and changes are possible, such as a taper shape extending from the first opening 130 toward the sample mounting unit 30.
  • one end 121 of the second region 120 is connected to the other end 112 of the first region 110, and the other end 122 of the second region 120 is When connected to the inlet of the mass spectrometry unit 20, the outer diameter of the body of the other end 122 of the second region 120 is greater than the inner diameter of the suction hole formed to face the hole of the orifice 21a in the interface flange 21b. It can be small.
  • the other end portion 102 of the interface unit 100 is inserted into the suction hole so that the interface unit 100 can be fixed to the mass spectrometry unit 20.
  • a guide protrusion for securing a length in which the interface unit 100 is inserted may be provided on the suction hole side of the interface flange 21b.
  • the specification of the other end 102 of the interface unit 100 coupled to face the inlet 21 of the mass spectrometry unit 20 directly conforms to the structure and specification of the inlet 21 of the mass spectrometry unit 20. While being formed to be coupled with the inlet 21, the outer diameter and inner diameter of one end portion 101 of the interface unit 100 are formed to be larger, and detached from the helium beam and the sample 2 emitted from the DART ionization unit 10 It is possible to ensure sufficient flow of the analyte into the interface.
  • DART in the process in which the analyte detached from the sample 2 is ionized and flows into the inlet of the mass spectrometry unit 20 Desorption and ionized components may be lost due to the space exposed in the air between the outlet of the ionization unit 10 and the inlet of the mass spectrometry unit 20, and thus there is a problem in that detection sensitivity of an analyte is low.
  • the interface unit ( 100) has a tube shape positioned between the outlet of the DART ionization unit 10 and the inlet 21 of the mass spectrometry unit 20, and has a first opening 130 in a portion adjacent to the sample 2 Includes. Since the interface unit 100 is connected to the outlet of the DART ionization unit 10 (that is, adjacent to the outlet or may include some or all of the ends of the outlet), the flow of the helium beam is limited and detached. It has the advantage of being able to effectively meet the ingredients.
  • the main body of the first region 110 of the present invention is formed to be narrower as it is adjacent to the second region 120, so that the analyte detached from the helium gas and the sample 2 emitted from the DART ionization unit 10
  • the ionic component collected and generated in this sufficient amount is focused and sent to the second region 120, and the inner diameter of the body of the second region 120 is the other end 112 of the first region 110. Since it is formed to be equal to or smaller than the inner diameter of the side body, the gas stream received from the first region 110 is transported to the inlet of the mass spectrometry unit 20 in a radially compressed state, so that the analysis target is It has the advantage of efficiently collecting and delivering the ingredients.
  • the analyte detached from the sample 2 flows into the interface unit 100 through the first opening 130. Accordingly, there is an advantage that the desorbed analyte can be collected more effectively and led to an ionization region that meets the helium beam.
  • the analyte introduced into the interface unit 100 is ionized and flows into the inlet 21 of the mass spectrometry unit 20 by minimizing losses along the tubular interface unit 100. Accordingly, the laser desorption-DART-MS system 1 to which the interface unit 100 of the present invention is applied has an advantage of significantly increasing detection sensitivity compared to a conventional laser desorption-DART-MS system.
  • the interface unit 100 includes a first region 110 in which the inner diameter of the body varies along the longitudinal direction and a second region 120 in which the inner diameter of the body is uniform along the longitudinal direction. A specific embodiment will be described.
  • the inner diameter of the main body at one end 111 of the first region 110 is a type in which helium gas is discharged from the DART ionization unit 10 and a degree at which it is introduced into one end 101 of the interface unit 100 is laser. It can be determined taking into account the effect on the detection sensitivity of the desorption-DART-MS system 1.
  • the inner diameter C of the body at one end 111 of the first region 110 may be 1 mm to 10 mm or 2 mm to 8 mm.
  • the length from one end 111 of the first region 110 to the other end 112 of the first region 110 and the inner diameter of the body at the other end 112 of the first region 110 are gas streams ( The degree of focusing of the gas stream may be determined in consideration of the effect on the detection sensitivity of the laser desorption-DART-MS system 1.
  • the length A from one end 111 of the first region 110 to the other end 112 of the first region 110 is 10 mm to 200 mm or 10 mm to 150 mm
  • the inner diameter D of the body at the other end 112 of 110 may be greater than 0 mm and less than or equal to 8 mm or 0.5 mm to 5 mm.
  • the length from one end 121 of the second region 120 to the other end 122 of the second region 120, and the inner diameter of the body in the second region 120 The degree of radial compression of the silver gas stream can be determined in consideration of the effect on the detection sensitivity of the laser desorption-DART-MS system 1.
  • the length B from one end 121 of the second region 120 to the other end 122 of the second region 120 is greater than or equal to 0 mm and less than or equal to 190 mm or greater than or equal to 0 mm and less than or equal to 140 mm.
  • the inner diameter E of the body adjacent to the mass spectrometry unit 20 in the two regions 120 may be greater than 0 mm and less than or equal to 8 mm or 0.5 mm to 5 mm.
  • the other end 112 of the first region 110 may be coupled to the inlet 21 of the mass spectrometry unit 20.
  • the first opening 130, the second opening 140, and the third opening 150 may function as follows.
  • the diameter H of the first opening 130 may be 1 mm to 5 mm or 2 mm to 5 mm.
  • the second opening 140 serves to enable effective desorption of the sample 2 by the laser beam being irradiated to the sample 2 without scattering or refraction and reflection.
  • the size and formation of the diameter of the second opening 140 may be detached and ionized through the degree of scattering and power loss of the laser beam vs (contrast) the second opening 140.
  • the degree to which the analyte deviates from the interface unit 100 ie, the extent to which an analyte loss occurs out of the path between the outlet of the DART ionization unit 10 and the inlet of the mass spectrometry unit 20) depends on the detection sensitivity. It can be determined taking into account the impact.
  • the diameter F of the second opening 140 may be more than 0 mm and 5 mm or less, or 2 mm to 5 mm.
  • the third opening 150 allows the corona pin to be inserted into the interface unit 100 to facilitate ionization through a high voltage supply in a region where helium beams and detached components meet and ionize.
  • the size, formation, and number of diameters of the third opening 150 are the effect of increasing the ionization efficiency due to corona discharge vs (contrast) the analyte desorbed and ionized through the third opening 150 is the interface unit 100 ), That is, the degree of deviation from the path between the outlet of the DART ionization unit 10 and the inlet of the mass spectrometry unit 20 may be determined in consideration of the effect on detection sensitivity.
  • the diameter G of the third opening 150 may be greater than 0 mm and less than or equal to 5 mm or 1 mm to 3 mm.
  • the presence and length of the protruding tube 131 is such that the detached analyte is introduced into the interface unit 100 to effectively meet the helium gas beam, and more specifically, the extent of the limitation of the detached analyte (sample The degree to which the analytes desorbed in (2) does not flow to a portion other than the area where the helium gas beam meets) and guiding (ie, the flow of the desorbed analytes flows along the structure of the interface unit 100)
  • the degree to which the gas beam meets the interface center) vs. the (contrast) sample 2 may be determined according to the influence of the desorption point on the sample 2 and the relative distance between the interface unit 100 on the detection sensitivity. .
  • the length M of the protruding tube protruding from the first opening 130 may be greater than 0 mm and less than or equal to 20 mm or greater than or equal to 0 mm and less than or equal to 10 mm.
  • the interface unit 100 of the present invention can be applied to the laser desorption-DART-MS system 1 so that the laser beam penetrates the center of the second opening 140, and one end 111 of the first area 110
  • the length I from the center to the center of the second opening 140 is 5 mm to 175 mm or 5 mm to 125 mm, from the center of the second opening 140 to the other end 112 of the first region 110.
  • the length J can be 5 mm to 195 mm or 5 mm to 145 mm.
  • the distance L from the center of the body of the interface unit 100 to the center of the third opening 150 may be -3 mm to 3 mm or -2 mm to 2 mm.
  • the distance from the center of the second opening 140 to the center of the third opening 150 may be determined in consideration of the effect of the relative distance between the laser beam and the corona pin on the detection sensitivity.
  • the distance K from the center of the second opening 140 to the center of the third opening 150 may be 1 mm to 10 mm or 2 mm to 6 mm.
  • Bs means the distance between the outlet of the DART ionization unit 10 and the inlet of the mass spectrometry unit 10, and may be, for example, 10 mm to 200 mm or 10 mm to 150 mm.
  • Bs means the distance between the center of the second opening 140 and the outlet of the DART ionization unit 10, and may be, for example, 5 mm to 175 mm or 5 mm to 125 mm.
  • Bs' means the distance between the center of the second opening 140 and the inlet of the mass spectrometry unit 20, and may be, for example, 5 mm to 195 mm or 5 mm to 145 mm.
  • Cs means the length of the portion fixed to the inlet of the mass spectrometry unit 20, and may be, for example, 10 mm to 190 mm or 10 mm to 140 mm.
  • Ds means the inner diameter of one end of the DART ionization unit 10 side of the interface units 100 and 100 ', and may be, for example, 1 mm to 10 mm or 2 mm to 8 mm.
  • Es means the diameter of the second opening 140 for passing through the laser beam, and may be, for example, more than 0 mm and 5 mm or less, or 2 mm to 5 mm.
  • Fs means the diameter of the third opening 150, and may be, for example, greater than 0 mm and less than or equal to 5 mm or 1 mm to 3 mm.
  • Gs means a distance between the center of the second opening 140 and the center of the third opening 150, and may be, for example, 1 mm to 10 mm or 2 mm to 6 mm.
  • Hs means the height from the center of the interface unit 100, 100 'to the center of the third opening 150 and may be, for example, -3 mm to 3 mm or -2 mm to 2 mm.
  • Is means the diameter of the first opening 130 for the analyte to be desorbed through the laser beam, and may be, for example, 1 mm to 5 mm or 2 mm to 5 mm.
  • Js means the length (height) of the protruding tube 131 extending from the first opening 130, and may be, for example, more than 0 mm and less than or equal to 10 mm or more than 0 mm and less than or equal to 20 mm.
  • J is 0 mm, the first opening 130 is not provided with a protruding tube 131.
  • the present invention is not limited to the above-described dimensions, and may be variously changed according to various environments in which the present invention is implemented.
  • UV absorber material C 14 H 16 N 2 O 2 , ethyl (Z) -2-cyano-3- (4- (dimethylamino) phenyl) acrylate
  • ionic liquid at a concentration of 10 mg / mL ( It is completely dissolved in (ionic liquid) (PYR13-FSI, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide).
  • the ionic liquid is a solvent having properties such as low vapor pressure, good solubility, thermal stability, and high viscosity, so that the solute is evenly mixed, and the solute volatilizes. In terms of preventing it from being prevented, it can be used as a matrix having the advantages of a liquid matrix and a solid matrix at the same time.
  • the analyte was dissolved in an ionic liquid to ensure homogeneity of the sample and shot-to-shot reproducibility. Therefore, when performing experiments using laser desorption-DART-MS, the signal reduction due to the continuous consumption of the sample 2 during the analysis time was reduced to a minimum, so that a signal sensitivity of a certain size was maintained.
  • the laser power is 180 mW, continuous wave, DC voltage is applied to the needle with 0 to 1.5 kV, the DART source temperature is 400 ° C., and the mass spectrometry unit 20 has a positive mode (ionization mode), FTMS (analyzer), It was set to 240,000 (resolution).
  • the inside of the main body of the first region 110 is formed in a conical shape, and the non-prepared interface unit 100 is applied to the protruding tube 131.
  • the laser power is 180 mW, continuous wave, DC voltage is applied to the needle with 0 to 1.5 kV, the DART source temperature is 400 ° C., and the mass spectrometry unit 20 has a positive mode (ionization mode), FTMS (analyzer), It was set to 240,000 (resolution).
  • the protruding tube 131 is not provided, and as shown in FIG. 3, an interface unit 100 having a uniform inner diameter in the longitudinal direction is applied.
  • 9A is a graph showing an experiment result when an experiment is performed without the interface unit 100 according to the present invention.
  • FIG. 9B is a graph showing the experimental results of Example 2
  • FIG. 9C is a graph showing the experimental results of Example 1;
  • the optical unit support member 400 supporting the optical unit 40 including the laser unit 41 Will be described in detail.
  • the interface flange 21b transfers ions generated by the DART ionization unit 10 to the mass spectrometry unit (MS) 20 and the DART ionization unit 10 is mounted to the mass spectrometry unit 20. So, it is mounted on the mass spectrometry unit 20. Specifically, the interface flange 21b may be fixed to the surface of the mass spectrometer unit in which the orifice 21a is provided.
  • the interface flange 21b may further include a tab portion 22a as shown in FIG. 12.
  • the optical unit support member 400 which will be described later, can be fixed to the tab portion 22a of the interface flange 21b.
  • the interface flange 21b may or may not be provided with a tap portion 22a. If the tap portion 22a is not provided in the interface flange 21b, a tap portion (tap) may be provided at a desired position. 22a) to fix the optical unit support member 400.
  • the optical units 40 include a laser unit 41, a mirror 42, a translation stage 43, an iris 44, and lenses 45 And the like.
  • the laser unit 41 irradiates a laser beam to the sample 2 to detach the analyte from the sample.
  • the beam size at the desorption point ie, the point at which the laser beam hits the sample 2 and desorption occurs
  • alignment and focusing of the laser beam may be adjusted through the optimized arrangement of the optical units 40.
  • the head portion of the optical fiber may be mounted on the optical unit support member 400 regardless of the size of the laser module 41. .
  • the mirror 42 serves to adjust the path of the laser beam so that the laser beam generated from the laser unit 41 can reach the sample 2. That is, when the laser beam does not reach the straight path from the laser unit 41 to the sample 2, the path of the laser beam is adjusted by changing the traveling direction of the laser beam with at least one mirror 42.
  • the translation stage 43 is a stage movable along at least one axial direction.
  • it may be an XY stage movable on a plane.
  • the lens 45 is mounted on the moving stage 43 so that the lens 45 can move in a certain direction. Accordingly, the position of the lens 45 can be adjusted to change the focus of the laser beam relative to the sample 2.
  • the focus may be on the sample, or may be slightly away from the sample.
  • the aperture 44 serves as a guide for laser beam alignment to a desired path.
  • the beam size may be adjusted by adjusting the aperture size of the aperture 44.
  • the lens 45 can control the degree of focusing of the laser beam on the surface of the sample 2.
  • the relative distance between the focal point of the laser beam and the surface of the sample may affect the detection sensitivity, so when the sample is present at the focal point, the degree of desorption of the sample per area can be increased. , The desorption area may be reduced, and detection sensitivity of fragment ions compared to molecular ions may be increased.
  • the degree of desorption of the sample per area may be low. The more the off-center, the larger the beam size for the sample, the larger the desorption area, and the higher the detection sensitivity of molecular ions compared to the fragment.
  • the present invention is provided with a plurality of fastening portions 410 on the optical unit support member 400, the above-mentioned object to the plurality of fastening portions 410 on the optical unit support member 400 There is an advantage that can be combined to be arranged in various ways.
  • the laser desorption-DART-MS system 1 of the present invention comprises an optical unit support member 400 for supporting the optical units 40.
  • the optical unit support member 400 may be, for example, manufactured in a plate shape.
  • the optical unit support member 400 includes a plurality of fastening parts 410 arranged at predetermined intervals.
  • the plurality of fastening parts 410 may be, for example, an M6 tab or a through-hole shape.
  • the plurality of fastening parts 410 include at least two interface flange connection parts 410a.
  • some of the plurality of fastening portions 410 made of the above-described predetermined intervals may function as the interface flange connection portion 410a, or may be provided at positions corresponding to the tab portion 22a of the interface flange. have.
  • the interface flange connection portion 410a may be positioned at a position corresponding to the tab portion 22a of the interface flange of FIG. 12.
  • Each interface flange connection portion 410a may be fixed to the tab portion 22a of each interface flange with a first fastening member.
  • the tab flange 22a of the interface flange may have an inner circumferential surface of a female screw shape
  • the first fastening member may have a male screw shape coupled to the inner circumferential surface of the tab portion 22a.
  • the first fastening member may be, for example, an M6 bolt.
  • the optical unit support member 400 is positioned at a desired position on the front surface of the interface flange 21b of the mass spectrometer unit 20 and the tab portion 22a of the interface flange 21b among the plurality of fastening parts 410
  • the optical unit support member 400 is fixed to the front surface of the interface flange 21b by inserting the first fastening member in the fastening parts corresponding to the position (ie, the interface flange connecting part 410a).
  • the plurality of fastening parts 410 include an optical unit connection part 410b. That is, some of the plurality of fastening parts 410 may function as the optical unit connection part 410b.
  • the optical units 40 the above-described laser unit 41, mirror 42, translation stage 43, iris 44, lenses (45) and the like.
  • Each of the optical units 40 (laser unit 41, mirror 42, translation stage 43, iris 44, lenses 45) ), Etc.) may include at least one fastening portion to be connected to the optical unit connection portion 410b.
  • the fastening portion may be, for example, a clear hole shape, or an inner circumferential surface of a female thread shape.
  • each optical unit 40 and the optical unit connecting portion 410b may be fixed with a second fastening member.
  • the second fastening member may have an optical unit connection portion 410b and a male screw shape coupled to the fastening portion.
  • the second fastening member may be, for example, an M6 bolt or an M6 tanned bolt.
  • the second fastening member may be, for example, a nut provided behind a bolt.
  • each of the optical units 40 is disposed at a desired position on the optical unit support member 400, and the fastening portions (that is, corresponding to the fastening portion of each optical unit 40 among the plurality of fastening portions 410) , By inserting the second fastening member to the optical unit connecting portion (410b), each of the optical units 40 are fixed to the optical unit support member 400.
  • the corona discharge unit 50 may be fixed to the optical unit support member 400.
  • the corona discharge unit 50 may also include at least one fastening portion.
  • the fastening portion may be, for example, a through-hole shape, or may be a through-hole shape in which an inner circumferential surface has a female thread shape.
  • the fastening portions corresponding to the fastening portions of the corona discharge unit 50 that is, fixed to the corona discharge unit connecting portion 410c by a second fastening member
  • the corona discharge unit 50 can be fixed to a desired position of the optical unit support member 400.
  • the optical unit support member 400 is largely composed of the bottom plate 401 and the top plate 402, the bottom plate 401 and the top plate 402 It may be combined.
  • some of the plurality of fastening parts 410 may be upper and lower plate coupling parts 410d. That is, the upper portion of the lower plate 401 and the lower portion of the upper plate 402 overlap, a plurality of fastening portions 410 of the lower plate 401 and a plurality of fastening portions 410 of the upper plate 402 overlap. It can be fixed to the paper portion with a third fastening member.
  • the third fastening member may be, for example, an M6 bolt.
  • the hole of the lower plate of the upper and lower plate coupling portion 410d is a counterbore shape for the M6 bolt so that the head portion of the M6 bolt does not protrude above the plate.
  • four holes located in the uppermost row of the lower plate 401 and four holes located in the next row may be upper and lower plate coupling portions 410d.
  • the drawing number is indicated on the leftmost hole.
  • four holes in the lowermost row of the upper plate 402 and four holes in the next row may be the upper and lower plate coupling portions 410d.
  • the lower plate 401 is fixed to the tab portion 22a of the interface flange 21b, and each of the optical units 40 can be fixed to a desired position among the lower plate 401 and the upper plate 402.
  • the load of the upper plate 402 is applied to the bolt and the interface flange (by allowing the upper plate 402 to rest on the interface flange 21b).
  • 21b) has the advantage of being able to be dispersed on top.
  • the material of the optical unit support member 400 may be made of, for example, metal, etc., and may be made of stainless steel, aluminum, etc. as the metal.
  • FIG. 12 is a front view exemplarily showing an interface flange 21b that can be used in the laser desorption-DART-MS system 1 of FIG. 1, and FIG. 13 is a bottom plate 401 of the interface flange 21b of FIG. It is a view showing an example mounted on the.
  • the interface flange 21b includes a tab portion 22a.
  • 14 is a conceptual diagram showing that the member 400 and the optical units 40 for supporting the optical unit are mounted on the interface flange 21b.
  • the bottom plate 401 has a width X height X thickness of 190 mm X 130 mm X 10 mm, 15 mm, respectively.
  • the lower plate 401 is composed of a portion connected with the interface flange 21b and a first portion 401a having a thickness of 10 mm and a portion connected with the upper plate 402 and a second portion 401b having a thickness of 15 mm. .
  • the reason why the thickness is different as above is that the second plate 401b at the bottom is made slightly thicker to secure the minimum distance between the laser beam irradiated to the sample and the mass spectrometry unit 20 as short as possible. It was positioned more inward.
  • the distance between the mass spectrometer unit 20 and the sample desorption point can be increased as desired through the spacer 46 to suit the environment in which the present invention is implemented, but reducing the size of the laser unit 41 and the optical unit support member 400 ) May be restricted depending on the dimensions.
  • the second portion 401b may be made thicker and the upper plate 402 may be positioned inward. Referring to FIG. 11, the first portion 401a and the second portion 401b are illustrated by dotted lines for convenience.
  • the shape of the bottom plate 401 can be variously modified and changed, such as can be made according to the structure or shape of the interface flange 21b coupled to the mass spectrometry unit 20.
  • the top plate 402 has a width X height X thickness of 190 mm X 310 mm X 10 mm, respectively.
  • the lower plate 401 and the upper plate 402 may be made of, for example, aluminum.
  • a plurality of fastening portions 410 are arranged, for example, 12.5 mm or 25 mm apart, so that the optical units 40 can be installed.
  • the interface flange connecting portion 410a is provided at a position corresponding to the tab portion 22a of the interface flange of FIG. 12, and for example, four.
  • the present invention is not limited to the above-described embodiment, and the spacing, the position of the plurality of fastening portions 410 to match the position of the tab portion 22a of the interface flange 21b or the setting of the optical units 40, and The number can be varied.
  • An extension tube 21c may be connected to the suction port 24 formed in the interface flange 21b. One end of the extension tube 21c is connected to the suction port 24, and the other end of the extension tube 21c can be extended in a direction facing the discharge port 11 of the DART ionization unit 10.
  • the interface unit 100 may be connected to the other end of the extension tube 21c, or may be directly coupled to the inlet 24 of the interface flange 21b without the extension tube 21c.
  • the other end of the extension tube 21c is spaced a certain distance from the outlet 11 of the DART ionization unit 10, preventing the laser beam irradiated from the laser unit 41 from being irradiated to the sample mounting unit 30 side. You may not. That is, the extension tube 21c can be extended to a distance that does not invade the optical path of the laser beam. By providing the extension tube 21c, it is possible to reduce the amount of ionized analytes lost before entering the mass spectrometry unit 20.
  • the desorbed components and generated ions at the irradiation point of each laser beam through the introduction of a quartz tube interface between the exit of the DART and the inlet of the MS
  • the detection sensitivity can be improved by restricting the flow.
  • the body of the first region of the present invention is formed to be narrower as it is adjacent to the second region, so that the analyte desorbed from the sample and the helium gas emitted from the DART ionization unit are collected in a sufficient amount, and the second ion component is generated. It is focused and sent to the region, and the inner diameter of the body of the second region is formed to be equal to or smaller than the inner diameter of the body at the other end of the first region, so that the gas stream received from the first region is Since it is transported to the inlet of the mass spectrometry unit in a radially compressed state, it is possible to efficiently collect and deliver the component to be analyzed.
  • the present invention in the laser desorption-DART-MS system, it is possible to improve the reproducibility of the experiment by fixing the relative positional relationship between the laser and the sample. In addition, there is an advantage that it is possible to perform system optimization for improving the detection sensitivity of a sample by adjusting the position of optical units such as a laser unit using a laser support member. In addition, it is possible to increase the convenience of operation of the laser desorption-DART-MS system.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

La présente invention concerne une unité d'interface pouvant servir dans un système ablation laser-analyse directe en temps réel-spectrométrie de masse (LA-DART-MS) et, plus particulièrement, est destinée à fournir une unité d'interface, qui peut être disposée entre une unité de DART et une unité de MS afin d'améliorer la sensibilité de détection d'un échantillon ayant fait l'objet d'une ablation laser par un faisceau laser.
PCT/KR2019/011778 2018-09-11 2019-09-11 Unité d'interface WO2020055133A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2020552313A JP7294620B2 (ja) 2018-09-11 2019-09-11 インターフェースユニット
US17/049,105 US11488816B2 (en) 2018-09-11 2019-09-11 Interface unit
CN201980024368.2A CN111954917B (zh) 2018-09-11 2019-09-11 接口单元
EP19860396.1A EP3852129A4 (fr) 2018-09-11 2019-09-11 Unité d'interface

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
KR10-2018-0108208 2018-09-11
KR20180108208 2018-09-11
KR20180114885 2018-09-27
KR10-2018-0114885 2018-09-27
KR1020190110755A KR20200035859A (ko) 2018-09-27 2019-09-06 레이저 탈착-코로나-dart-ms 시스템 및 이에 사용되는 광학 유닛들을 지지하기 위한 부재
KR10-2019-0110755 2019-09-06
KR10-2019-0111487 2019-09-09
KR1020190111487A KR102577694B1 (ko) 2018-09-11 2019-09-09 검출 감도 향상을 위한 레이저 탈착-dart-ms 시스템 및 이에 사용되는 인터페이스 유닛
KR1020190112165A KR20210030699A (ko) 2019-09-10 2019-09-10 인터페이스 유닛
KR10-2019-0112165 2019-09-10

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WO2020055133A1 true WO2020055133A1 (fr) 2020-03-19

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PCT/KR2019/011778 WO2020055133A1 (fr) 2018-09-11 2019-09-11 Unité d'interface

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WO (1) WO2020055133A1 (fr)

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KR20180114885A (ko) 2018-10-12 2018-10-19 (주)세종이엠씨 전자파 공급장치
KR20190110755A (ko) 2018-03-21 2019-10-01 삼성중공업 주식회사 액화가스 운송선박
KR20190112165A (ko) 2017-02-22 2019-10-02 바스프 코포레이션 질소 산화물 저감을 위한 배기 가스 처리 촉매
KR20190111487A (ko) 2018-03-23 2019-10-02 현대자동차주식회사 무단변속기 차량의 풀리 제어방법

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JP2010014539A (ja) * 2008-07-03 2010-01-21 Tokyo Metropolitan Univ 液体試料イオン化法、質量分析法及びそれらの装置
JP2014209066A (ja) * 2013-04-16 2014-11-06 株式会社 資生堂 質量分析方法、イオン生成装置及び質量分析システム
JP2015165243A (ja) * 2014-02-04 2015-09-17 株式会社バイオクロマト 質量分析装置用連結デバイス
CN105021718B (zh) * 2014-04-28 2017-06-30 南京工业大学 一种液相色谱与敞开式离子化质谱在线联用接口和检测方法
KR20190112165A (ko) 2017-02-22 2019-10-02 바스프 코포레이션 질소 산화물 저감을 위한 배기 가스 처리 촉매
KR20180108208A (ko) 2017-03-24 2018-10-04 도레이케미칼 주식회사 2가 양이온에 대한 선택적 제거능을 가지는 코팅 조성물 및 이를 이용한 분리막
KR20190110755A (ko) 2018-03-21 2019-10-01 삼성중공업 주식회사 액화가스 운송선박
KR20190111487A (ko) 2018-03-23 2019-10-02 현대자동차주식회사 무단변속기 차량의 풀리 제어방법
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