JPS59210358A - Analyzing device coupled with liquid chromatograph-atmospheric ionizing mass spectrometer - Google Patents

Analyzing device coupled with liquid chromatograph-atmospheric ionizing mass spectrometer

Info

Publication number
JPS59210358A
JPS59210358A JP59083722A JP8372284A JPS59210358A JP S59210358 A JPS59210358 A JP S59210358A JP 59083722 A JP59083722 A JP 59083722A JP 8372284 A JP8372284 A JP 8372284A JP S59210358 A JPS59210358 A JP S59210358A
Authority
JP
Japan
Prior art keywords
mass spectrometer
liquid chromatograph
carrier gas
liquid
atmospheric pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP59083722A
Other languages
Japanese (ja)
Other versions
JPS641743B2 (en
Inventor
Hideki Kanbara
秀記 神原
Yasuhiro Mitsui
泰裕 三井
Ichiro Shikamata
鹿又　一郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
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
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Priority to JP59083722A priority Critical patent/JPS59210358A/en
Publication of JPS59210358A publication Critical patent/JPS59210358A/en
Publication of JPS641743B2 publication Critical patent/JPS641743B2/ja
Granted legal-status Critical Current

Links

Classifications

    • 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
    • H01J49/0468—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample
    • H01J49/049—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample with means for applying heat to desorb the sample; Evaporation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
    • G01N30/724—Nebulising, aerosol formation or ionisation
    • G01N30/7246—Nebulising, aerosol formation or ionisation by pneumatic means
    • 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
    • H01J49/0454—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 vaporising using mechanical energy, e.g. by ultrasonic vibrations

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

PURPOSE:To enable measurement of a non-volatile sample, etc. which are previously difficult to measure by atomizing the outflow liquid from a liquid chromatograph and analyzing the same with an atm. ionizing mass spectrometer. CONSTITUTION:The outflow liquid from an LC column 1 is fed through a guide wire 10 onto an ultrasonic oscillating element 9, by which the liquid is atomized. The atomized liquid is fed together with the carrier gas from a carrier gas introducing port 2 into the ionizing part of a mass spectrometer. The carrier gas is heated to assist the disintegration of the fine particles contg. the atomized sample to the cluster attached with several molecules or down to the molecule itself and at the same time the ionizing part is also heated by a heater 5 according to need so that the condenstation of the solvent by the inside wall of the ionizing part is prevented. If the device is constituted in such a way, the material susceptible to thermal decomposition or the material which is hardly evaporatable by heating is fed together with the carrier gas into the ionizing part and is ionized. The easy analysis of such material is thus made possible.

Description

【発明の詳細な説明】 〔発明の利用分野〕 本発明は液体クロマトグラフと大気圧イオン化質景分析
計とを結合した分析装置に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to an analysis device that combines a liquid chromatograph and an atmospheric pressure ionization quality analyzer.

〔発明の背景〕[Background of the invention]

大気圧イオン化質量分析計（以下ＡＰＩＭＳと略称する
）は大気圧下でコロナ放電あるいは”Ｎｉから出るβ線
を用いて効率良く試料をイオン化するもので極微量成分
の分析が可能な質量分析計である。液体クロマトグラフ
（以下ＬＣと略称する）は不揮発性物質あるいは熱的に
不安定な物質を分離検出し得る唯一の機器であり広く普
及して来た。Atmospheric pressure ionization mass spectrometer (hereinafter abbreviated as APIMS) is a mass spectrometer that efficiently ionizes a sample under atmospheric pressure using corona discharge or beta rays emitted from Ni, and is capable of analyzing extremely trace components. Liquid chromatographs (hereinafter abbreviated as LC) are the only instruments capable of separating and detecting non-volatile substances or thermally unstable substances, and have become widely used.

しかし、現在、高感度なＬＣ検出器が存在しないこと、
試料の質量など分子構造に関する情報が得られないこと
などのため、質量分析計との結合が試みられている（Ａ
ｎａｌ、　Ｃｈｅｍ、　５１Ｌ　、　６８２　Ａ（１９
７９））、。However, there is currently no highly sensitive LC detector;
Since information regarding the molecular structure such as the mass of the sample cannot be obtained, attempts have been made to combine it with a mass spectrometer (A
nal, Chem, 51L, 682 A (19
79)),.

ところで、」二連したように大気圧イオン化質量分析計
（ＡＰＩＭＳ　）は高感度であり、かつ、大気圧下でイ
オン化が行なわれるなどＬＣと結びつけるには非常に都
合が良い。Ｈｏｒｎｉｎｇら（Ａｎａｌ。By the way, the atmospheric pressure ionization mass spectrometer (APIMS) is highly sensitive and ionization is performed under atmospheric pressure, so it is very convenient to combine with LC. Horning et al. (Anal.

Ｃｈｅｍ、４　７　　、　２３６９（１９７５）、　　
Ｊ　　、　　Ｃｈｒｏｍａｔｏｇｒ、９　９　　。Chem, 4 7, 2369 (1975),
J, Chromatogr, 99.

１３　（１９７４））はＬＣとＡＰＩＭＳとを結びつけ
た分析装置を提案している。第１図はこの装置の概要構
成を示したものである。ＬＣ流出液はＬＣカラム１を経
由してヒーター５によって加熱されたガラス製ベーパラ
イザ管４中に導入され、加熱気化される。気化した溶液
はキャリアガス導入バイブ２から導入され、加熱された
キャリヤーガスと共にイオン化室に送られコロナ放電電
極６によるコロナ放電によりイオン化され、細孔から真
空中に取り出され分析される。なお、３はガラスウール
であり、大きな粒子の除去と、小さな粒子をより小さく
する機能をもっている。８はガス出口である。13 (1974)) proposed an analysis device that combined LC and APIMS. FIG. 1 shows the general configuration of this device. The LC effluent is introduced through the LC column 1 into a glass vaporizer tube 4 heated by a heater 5, where it is heated and vaporized. The vaporized solution is introduced from the carrier gas introducing vibe 2, sent to the ionization chamber together with the heated carrier gas, ionized by corona discharge by the corona discharge electrode 6, and taken out into the vacuum through the pores and analyzed. Note that 3 is glass wool, which has the function of removing large particles and making small particles smaller. 8 is a gas outlet.

この構成では溶液を加熱気化させるため熱分解しやすい
ものあるいは加熱しても気化しない物質の測定が行なえ
ないという難点があった。This configuration has the disadvantage that since the solution is heated and vaporized, it is not possible to measure substances that are easily thermally decomposed or substances that do not vaporize even when heated.

〔発明の目的〕[Purpose of the invention]

従って、本発明の目的は熱分解しやすい物質、あるいは
加熱気化しにくい物質であっても容易に取扱える液体ク
ロマトグラフと大気圧イオン化質量分析計とを結合した
分析装置を提供することにある。Accordingly, an object of the present invention is to provide an analysis device that combines a liquid chromatograph and an atmospheric pressure ionization mass spectrometer, which can easily handle even substances that are easily thermally decomposed or that are difficult to heat and vaporize.

〔発明の概要〕[Summary of the invention]

上記目的を達成するための本発明においては液体クロマ
トグラフからの流出液を超音波霧化装置で霧化させて大
気圧イオン化質量分析計で分析するように構成したこと
を特徴としている。以下、本発明を図面を用いて詳細に
述べる。To achieve the above object, the present invention is characterized in that the effluent from a liquid chromatograph is atomized by an ultrasonic atomizer and analyzed by an atmospheric pressure ionization mass spectrometer. Hereinafter, the present invention will be described in detail using the drawings.

〔発明の実施例〕[Embodiments of the invention]

第２図は本発明によるＬＣとＡＰＩＭＳとを結合した分
析装置の結合部構成例である。ＬＣカラム１からの流出
液はＬＣ溶液ガイド用ワイヤー１０を伝って連続的に超
音波発振素子９上に送られる。FIG. 2 is an example of a configuration of a coupling section of an analysis device combining an LC and an APIMS according to the present invention. The effluent from the LC column 1 is continuously sent onto the ultrasonic oscillation element 9 along the LC solution guide wire 10.

この超音波発振素子９の表面でＬＣカラム１がらの流出
液は霧化され、キャリヤガス導入口２がらのキャリヤー
ガスと共にイオン化部に送り込まれる。ワイヤ１０と超
音波発振素子９との位置関係は互いに接触しているが、
非常に接近した状態にある。霧化した試料を含んだ微粒
子がより細かくなり分子が数個ついたクラスターあるい
は分子そのものにまでなるのを補助するようキャリヤー
ガスは加熱されると共にイオン化部も必要に応じてヒー
ター５によって加熱し、イオン化部の内壁で溶媒が凝縮
するのを防止している。試料はイオン化部で効率良くイ
オンとなり分析器へ導入されるが余分の溶媒およびキャ
リヤーガスはガス出口８から外部へ排出される。本発明
によれば試料を加熱して気化させるのではないために熱
に弱く物質あるいは不揮発性試料でもキャリヤーガスと
いっしょにイオン化部に送り込みイオンとして分析でき
る利点がある。本発明においてもイオン化部を加熱して
いるがこれは溶媒の凝縮を防ぐためのもので一般に気化
しやすい溶媒が気化できれば十分な低度の低い温度で良
い。The effluent from the LC column 1 is atomized on the surface of the ultrasonic oscillation element 9, and sent to the ionization section together with the carrier gas from the carrier gas inlet 2. Although the wire 10 and the ultrasonic oscillation element 9 are in contact with each other,
are in very close condition. The carrier gas is heated to help the fine particles containing the atomized sample become finer and become clusters with several molecules attached or even molecules themselves, and the ionization section is also heated by the heater 5 as necessary. This prevents the solvent from condensing on the inner wall of the ionization section. The sample is efficiently ionized in the ionization section and introduced into the analyzer, but excess solvent and carrier gas are discharged to the outside from the gas outlet 8. According to the present invention, since the sample is not vaporized by heating, there is an advantage that even heat-sensitive substances or non-volatile samples can be sent to the ionization section together with a carrier gas and analyzed as ions. In the present invention, the ionization section is also heated, but this is to prevent condensation of the solvent, and generally a sufficiently low temperature may be used as long as a solvent that is easily vaporized can be vaporized.

第３図は本発明の分析装置の変形例で超音波発振素子９
′をＬＣカラム１の端部に取り付けて構成したものであ
り、より一層効果的な霧化を行なうことができる特徴を
もっている。FIG. 3 shows a modification of the analyzer of the present invention, in which an ultrasonic oscillation element 9
' is attached to the end of the LC column 1, and has the feature of being able to perform even more effective atomization.

〔発明の効果〕〔Effect of the invention〕

以上述べたように本発明によれば不揮発性試料を溶液状
で超音波により霧化して空中にまで浮遊させるために、
これまで測定が困難であった不揮発性試料あるいは熱に
対して不安定な試料でも、大気圧イオン化を行ない、そ
の質量スペクトルを測定することが可能となる。As described above, according to the present invention, in order to atomize a nonvolatile sample in solution form using ultrasonic waves and suspend it in the air,
Even non-volatile samples or samples that are unstable to heat, which have been difficult to measure up until now, can now be ionized at atmospheric pressure and their mass spectra measured.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は従来のＬＣ−Ａ、ＰＩ結合分析装置の概略構成
図、第２図および第３図はそれぞれ本発明の一実施例に
よるＬ　Ｃ−ＡＰＩＭＳ結合分析装置の概略構成図であ
る。 １・・・ＬＣカラム、２・・・キャリヤガス導入パイプ
、３・・ガラスウール、４・・・ベーパライザーガラス
管、５・・・ヒーター、６・・・コロナ放電電極、７・
・・真空フランジ、８・・ガス出口、９・・・超音波発
振素子、第　）　図 γ　２　図 第　３　ＺFIG. 1 is a schematic diagram of a conventional LC-A and PI bond analyzer, and FIGS. 2 and 3 are schematic diagrams of an LC-APIMS bond analyzer according to an embodiment of the present invention. DESCRIPTION OF SYMBOLS 1... LC column, 2... Carrier gas introduction pipe, 3... Glass wool, 4... Vaporizer glass tube, 5... Heater, 6... Corona discharge electrode, 7...
...Vacuum flange, 8...Gas outlet, 9...Ultrasonic oscillation element, Fig. γ 2 Fig. 3 Z

Claims (1)

【特許請求の範囲】 ■、液体クロマトグラフと、上記液体クロマトグラフか
らの流出液をθ化する霧化装置と、上記霧化装置からの
霧を導入して分析する大気圧イオン化質量分析計とを具
備したことを特徴とするクロマトグラフ−大気圧イオン
化質屋分析計結合分析装置。 ２、上記霧化装置が上記大気圧イオン質量分析計のイオ
ン化部に設けられていることを特徴とする特許請求の範
囲第１項の液体クロマトグラフ−大気圧イオン化質量分
析計結合分析装置。 ３、上記霧化装置が上記液体クロマトグラフからの流出
液を案内する溶液ガイド用ワイヤと上記ワイヤの先端近
傍かあるいは上記ワイヤに接して設けられた超音波発振
素子とからなることを特徴とする特許請求の範囲第２項
の液体クロマトグラフ−大気圧イオン化質量分析計結合
分析装置。 ４、上記霧化装置が上記液体クロマトグラフからの流出
液を下方から案内するコラムと上記コラムの端部に設け
ら九た超音波振動素子とからなることを特徴とする特許
請求の範囲第２項の液体クロマトグラフ−大気圧イオン
質量分析計結合分析装置。[Claims] (1) A liquid chromatograph, an atomizer that converts the effluent from the liquid chromatograph into θ, and an atmospheric pressure ionization mass spectrometer that introduces and analyzes the mist from the atomizer. A combined chromatograph-atmospheric pressure ionization pawnshop analyzer analyzer, characterized in that it is equipped with: 2. The liquid chromatograph-atmospheric pressure ionization mass spectrometer coupled analysis device according to claim 1, wherein the atomization device is provided in the ionization section of the atmospheric pressure ionization mass spectrometer. 3. The atomizing device is characterized by comprising a solution guide wire for guiding the effluent from the liquid chromatograph and an ultrasonic oscillation element provided near the tip of the wire or in contact with the wire. A liquid chromatograph-atmospheric pressure ionization mass spectrometer coupled analysis device according to claim 2. 4. Claim 2, wherein the atomizing device comprises a column that guides the effluent from the liquid chromatograph from below, and an ultrasonic vibration element provided at the end of the column. Liquid chromatograph-atmospheric pressure ion mass spectrometer coupled analysis device.
JP59083722A 1984-04-27 1984-04-27 Analyzing device coupled with liquid chromatograph-atmospheric ionizing mass spectrometer Granted JPS59210358A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59083722A JPS59210358A (en) 1984-04-27 1984-04-27 Analyzing device coupled with liquid chromatograph-atmospheric ionizing mass spectrometer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59083722A JPS59210358A (en) 1984-04-27 1984-04-27 Analyzing device coupled with liquid chromatograph-atmospheric ionizing mass spectrometer

Publications (2)

Publication Number Publication Date
JPS59210358A true JPS59210358A (en) 1984-11-29
JPS641743B2 JPS641743B2 (en) 1989-01-12

Family

ID=13810403

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59083722A Granted JPS59210358A (en) 1984-04-27 1984-04-27 Analyzing device coupled with liquid chromatograph-atmospheric ionizing mass spectrometer

Country Status (1)

Country Link
JP (1) JPS59210358A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5368727A (en) * 1991-10-03 1994-11-29 Hitachi, Ltd. Liquid chromatograph mass spectrometer
WO1998023952A1 (en) * 1996-11-26 1998-06-04 Anglo American Research Laboratories (Proprietary) Limited Nebulizer
KR20010069390A (en) * 2001-03-16 2001-07-25 류재정 Cabinet for ultrasonic radiation and temperature control
GB2546407A (en) * 2015-12-22 2017-07-19 Micromass Ltd Secondary Ultrasonic Nebulisation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS533290A (en) * 1976-06-30 1978-01-12 Hitachi Ltd Analytical device combining liquid chromatography and mass spectrometer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS533290A (en) * 1976-06-30 1978-01-12 Hitachi Ltd Analytical device combining liquid chromatography and mass spectrometer

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5368727A (en) * 1991-10-03 1994-11-29 Hitachi, Ltd. Liquid chromatograph mass spectrometer
WO1998023952A1 (en) * 1996-11-26 1998-06-04 Anglo American Research Laboratories (Proprietary) Limited Nebulizer
KR20010069390A (en) * 2001-03-16 2001-07-25 류재정 Cabinet for ultrasonic radiation and temperature control
GB2546407A (en) * 2015-12-22 2017-07-19 Micromass Ltd Secondary Ultrasonic Nebulisation
US10466213B2 (en) 2015-12-22 2019-11-05 Micromass Uk Limited Secondary ultrasonic nebulisation
GB2546407B (en) * 2015-12-22 2020-04-08 Micromass Ltd Secondary Ultrasonic Nebulisation
GB2579144A (en) * 2015-12-22 2020-06-10 Micromass Ltd Secondary ultrasonic nebulisation
GB2579144B (en) * 2015-12-22 2020-10-14 Micromass Ltd Secondary ultrasonic nebulisation
US10859544B2 (en) 2015-12-22 2020-12-08 Micromass UK Limite Secondary ultrasonic nebulisation

Also Published As

Publication number Publication date
JPS641743B2 (en) 1989-01-12

Similar Documents

Publication Publication Date Title
US4935624A (en) Thermal-assisted electrospray interface (TAESI) for LC/MS
US4861988A (en) Ion spray apparatus and method
US4298795A (en) Method and apparatus for introducing samples to a mass spectrometer
CA2443540C (en) A method of and apparatus for ionizing an analyte and ion source probe for use therewith
US5898175A (en) Mass spectrometer and mass spectrometry method for analyzing compounds contained in a solution
US4977785A (en) Method and apparatus for introduction of fluid streams into mass spectrometers and other gas phase detectors
US6759650B2 (en) Method of and apparatus for ionizing an analyte and ion source probe for use therewith
US4762995A (en) Monodisperse aerosol generator
US4570068A (en) Interface for liquid chromatograph and mass spectrometer
JPH07159377A (en) Device and method for directly connecting liquid chromatograph and mass spectrometer, mass spectrometry following liquid chromatography, and liquid chromatograph-connected type mass spectroscope
US4996424A (en) Atmospheric pressure ionization mass spectrometer
JPS59210358A (en) Analyzing device coupled with liquid chromatograph-atmospheric ionizing mass spectrometer
JPS6257067B2 (en)
JP2000162188A (en) Mass spectrometry and device for analyzing sample in solution
Hirata et al. The application of a new sampling technique using an atomizer for chemical ionization mass spectrometry to free amino acids, drug components, higher phthalates and oligomers of styrene and ethyleneglycol
JP3238488B2 (en) Mass spectrometer
JPS6253903B2 (en)
JP3242264B2 (en) Ion source and mass spectrometer using the same
US5526682A (en) Method and apparatus for analyzing sample solutions
US20080104064A1 (en) Electrospray Ionization Mass Spectrometer Interface
JPH07306193A (en) Ion source and mass spectrograph
JP3238450B2 (en) Mass spectrometer
JP3870870B2 (en) Method and apparatus for mass spectrometry of solutions
JPH0314137B2 (en)
JP3379510B2 (en) Liquid chromatograph coupled mass spectrometer