JPH09190796A - Porous member for mass spectrometer and its using method - Google Patents

Porous member for mass spectrometer and its using method

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Publication number
JPH09190796A
JPH09190796A JP7354493A JP35449395A JPH09190796A JP H09190796 A JPH09190796 A JP H09190796A JP 7354493 A JP7354493 A JP 7354493A JP 35449395 A JP35449395 A JP 35449395A JP H09190796 A JPH09190796 A JP H09190796A
Authority
JP
Japan
Prior art keywords
porous member
ionization
fab
mass spectrometer
eluent
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.)
Pending
Application number
JP7354493A
Other languages
Japanese (ja)
Inventor
Matsuhiro Hori
松浩 堀
Naohiro Oya
尚洋 大屋
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Kao Corp
Original Assignee
Kao Corp
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Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to JP7354493A priority Critical patent/JPH09190796A/en
Publication of JPH09190796A publication Critical patent/JPH09190796A/en
Pending legal-status Critical Current

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  • Electron Tubes For Measurement (AREA)

Abstract

PROBLEM TO BE SOLVED: To perform fine structural analysis of a trace mixed sample having a wide polar component at a short time by forming a porous member for serving as a target of an ionization part of a mass spectrometer so that a sample solution supply part becomes thinner than its peripheral part. SOLUTION: In a porous member 25, if the central part which is an FAB(fast atom bombardment) ionization target position is made thin, an eluant penetrates in the porous member without problem, and oozes out in the ionization target. The central part of a frit is polished and a recessed porous member is manufactured so that the porous member 25 fits without any gap to a funnel 24 at the tip of an FAB ionization probe. By forming in the recessed structure, decrease in the eluant retaining capacity of the porous member is minimized.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、高速原子衝突（Ｆ
ＡＢ）によりイオン化を行う質量分析装置のイオン化部
のターゲットとなる多孔性部材及びその使用方法に関す
る。TECHNICAL FIELD The present invention relates to a fast atom collision (F
The present invention relates to a porous member that is a target of an ionization section of a mass spectrometer that performs ionization by AB) and a method of using the same.

【０００２】[0002]

【従来の技術】近年、質量分析法に関しては、ＦＡＢ，
ＦＤ，ＴＳＰ，ＡＰＣＩ，ＥＳＩと呼ばれる種々のソフ
トイオン化法、構造解析に非常に有効な方法であるＭＳ
／ＭＳ法、超高分子領域まで質量分析できるＦＴ−ＭＳ
（フ−リエ変換式質量分析装置），ＴＯＦ／ＭＳ（飛行
時間型質量装置）が開発されたことにより、この分野に
おける測定技術や解析理論が急速に進歩している。2. Description of the Related Art Recently, regarding mass spectrometry, FAB,
Various soft ionization methods called FD, TSP, APCI, ESI, and MS, which is a very effective method for structural analysis.
/ MS method, FT-MS capable of mass spectrometry up to ultra-high molecular weight region
Due to the development of (Fourier conversion mass spectrometer) and TOF / MS (time-of-flight mass spectrometer), measurement technology and analysis theory in this field are rapidly advancing.

【０００３】そのようなＭＳ新技術開発の中、高速液体
クロマトグラフィー（ＨＰＬＣ，ＬＣ）の検出器に質量
分析装置（ＭＳ）をオンライン接続したＬＣ／ＭＳが、
新規複合化構造解析技術あるいは新規複合化分離技術と
して急速に発達しており、合成研究から環境衛生研究や
薬物動態研究に至るまで幅広い分野の分析研究に応用さ
れている。Among such new MS technology development, LC / MS in which a mass spectrometer (MS) is online connected to a detector of high performance liquid chromatography (HPLC, LC),
It has been rapidly developed as a new complex structure analysis technology or a new complex separation technology, and has been applied to analytical research in a wide range of fields from synthetic research to environmental hygiene research and pharmacokinetic research.

【０００４】従来より未知化合物の構造解析を行なう場
合、未知成分をカラムクロマトやＨＰＬＣにより分取精
製し、ＮＭＲ，ＩＲ，ＵＶ，ＭＳ等で得られるスペクト
ルにより構造解析を行なっている。この方法は現在のと
ころ最も確実な構造解析が行える方法であるが、解析に
時間や手間がかかり非効率であることが最大の難点であ
る。一方、ＬＣ／ＭＳを構造解析の手段として使用した
場合、ＨＰＬＣ分離後、直接オンラインで質量分析がで
きるため、ＨＰＬＣの極性分離的解析、ＭＳスペクトル
やＭＳクロマトグラム解析、合成あるいは反応経路の推
定等を加味することにより、未知成分を迅速にある程度
まで構造解析ができる。つまり、ＬＣ／ＭＳは、確実に
全ての未知成分の構造解析ができる方法ではないが、未
知成分構造解析の一次スクリーニング的な分析には非常
に迅速かつ有効な方法であるといえる。Conventionally, when structural analysis of an unknown compound is performed, the unknown component is preparatively purified by column chromatography or HPLC, and structural analysis is performed by a spectrum obtained by NMR, IR, UV, MS or the like. This method is currently the most reliable method for structural analysis, but the biggest difficulty is that analysis is time-consuming, time-consuming, and inefficient. On the other hand, when LC / MS is used as a means for structural analysis, mass spectrometry can be directly performed online after HPLC separation, and therefore polar separative analysis of HPLC, MS spectrum or MS chromatogram analysis, estimation of synthesis or reaction route, etc. By taking into account, the structural analysis of unknown components can be rapidly performed to some extent. That is, although LC / MS is not a method that can reliably analyze the structure of all unknown components, it can be said that it is a very rapid and effective method for primary screening-like analysis of unknown component structure analysis.

【０００５】また、混合物の定量分析は、通常ＨＰＬＣ
により極性分離を行ない得られるクロマトグラムのピー
ク面積から算出して行なう。この定量方法は汎用的に行
なわれているが、現在検出器として用いられているＵ
Ｖ，ＲＩ，ＥＬＳＤは未知化合物に対し選択的検出がで
きないことや、混合物中の極微量成分の定量分析ができ
ないことに難点がある。これに対しＬＣ／ＭＳを混合物
の定量分析の手段として使用した場合、ＨＰＬＣだけで
は分離が不十分なピークであっても質量分離によりピー
ク分離ができるため正確に混合物の選択的検出ができ
る。また、ノイズに埋もれている極微量成分ピークであ
っても、ＭＳの高感度かつ選択的な質量分離によりピー
ク抽出をし正確な定量分析ができる。つまり、ＬＣ／Ｍ
Ｓは、ＭＳの高感度に質量分離ができる選択的検出器の
特徴を活かすことにより、より正確に混合成分の定量分
析ができる非常に有効な方法であるといえる。The quantitative analysis of the mixture is usually performed by HPLC.
Polarity separation is performed by calculating the peak area of the obtained chromatogram. Although this quantification method is generally used, U which is currently used as a detector
V, RI, and ELSD have drawbacks in that they cannot be selectively detected with respect to unknown compounds, and they cannot perform quantitative analysis of trace components in a mixture. On the other hand, when LC / MS is used as a means for quantitative analysis of the mixture, even if the peak is not sufficiently separated by HPLC alone, the peak can be separated by mass separation, so that the mixture can be accurately detected selectively. Further, even for a trace amount of component peaks buried in noise, accurate quantitative analysis can be performed by extracting peaks by highly sensitive and selective mass separation of MS. That is, LC / M
It can be said that S is a very effective method that enables more accurate quantitative analysis of mixed components by taking advantage of the characteristics of a selective detector capable of mass separation with high sensitivity of MS.

【０００６】従って、このような高度解析用のＭＳは、
数々の合成物質や配合組成物の成分の構造解析に広く利
用することができると考えられる。しかし、実際にはこ
のシステムでは、以下で述べる問題のため、混合微量成
分の詳細な構造解析や特定成分の微量定量分析など、Ｍ
Ｓの特徴を活かした分析はできていなかった。Therefore, such an MS for altitude analysis is
It is considered that it can be widely used for structural analysis of various synthetic substances and components of compounded compositions. However, in this system, in practice, due to the problems described below, the detailed structural analysis of the mixed trace components and the trace quantitative analysis of the specific components are performed.
We have not been able to analyze the characteristics of S.

【０００７】即ち、ＦＡＢイオン化部のターゲットであ
る多孔性部材（いわゆるフリット板）にロット振れがあ
るため、ＦＡＢイオン化が非常に不安定になり、測定そ
のものが非常に困難になるという問題である。例えば、
ＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳシステムについて言え
ば、測定そのものが難しい状態で、得られるＬＣ／ＭＳ
のトータルイオンクロマトグラムもＳ／Ｎが悪く解析で
きないという大きな問題を抱えていたため、ＬＣ／ＭＳ
を微量混合成分の構造解析などの分析手段として活用す
ることができなかった。従って、このような問題によ
り、正確で詳細なＭＳスペクトルやＭＳクロマトグラム
が得られず、微量混合成分の構造解析を行なうことは不
可能であった。That is, since the porous member (so-called frit plate) which is the target of the FAB ionization part has lot fluctuation, FAB ionization becomes very unstable, and the measurement itself becomes very difficult. For example,
Speaking of the FRIT-FAB-LC / MS system, LC / MS that can be obtained when the measurement itself is difficult
Since the total ion chromatogram of the product also had a big problem that the S / N was poor and it could not be analyzed, LC / MS
Could not be utilized as an analytical means such as structural analysis of trace mixed components. Therefore, due to such problems, accurate and detailed MS spectra and MS chromatograms cannot be obtained, and it has been impossible to carry out structural analysis of a trace amount of mixed components.

【０００８】このようなイオン化の不安定性については
装置メーカーでも認識されており、その改善策として空
気圧スプリッターの改良やＭＳ本体の温度・真空度のコ
ンピュータコントロール化の開発が行われているが、こ
れらの装置の導入には非常にコストがかかることが難点
である。[0008] Such instability of ionization is also recognized by equipment manufacturers, and as a remedy for this, improvement of a pneumatic splitter and development of computer control of temperature / vacuum degree of MS body have been carried out. The disadvantage is that the introduction of this device is very costly.

【０００９】一方、特開平３−１８７１４７号公報に
は、ＦＡＢイオン化部のターゲットである多孔性部材を
周辺よりも中心部の試料通過性が大きくなるように周辺
部を圧密化し、大部分の試料液が多孔性部材の中心部を
流れるようにしてイオン化の効率を高めて感度を向上さ
せる方法が開示されている。しかしながら、かかる方法
では、多孔性部材の中心部での溶離液保持容量が増大
し、ノイズの原因となる問題がある。On the other hand, in Japanese Patent Laid-Open No. 3-187147, the peripheral portion of a porous member, which is a target of the FAB ionization portion, is compacted so that the central portion of the porous member has a greater permeability than the peripheral portion, and most of the sample is sampled. A method is disclosed in which the liquid is caused to flow through the central portion of the porous member to enhance the efficiency of ionization and improve the sensitivity. However, in such a method, there is a problem that the eluent holding capacity in the central portion of the porous member increases, which causes noise.

【００１０】[0010]

【発明が解決しようとする課題】従って、本発明の目的
は、幅広い極性成分を持つ微量混合サンプルを短時間で
詳細な構造解析ができるＬＣ／ＭＳが可能となるような
質量分析装置用多孔性部材及びその使用方法を提供する
ことにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a porous material for a mass spectrometer capable of performing LC / MS capable of performing detailed structural analysis of a minute amount of a mixed sample having a wide range of polar components in a short time. To provide a member and a method of using the member.

【００１１】[0011]

【課題を解決するための手段】本発明者らは、測定の困
難さやクロマトグラムの不明確さは、多孔性部材の個々
の性能差やセッティングのノウハウ的な微妙さ等の２つ
の問題が主因と考え、その問題を解決する手段としてイ
オン化状態を安定に保つためＦＡＢイオン化部を改良し
て凹型の多孔性部材を採用することにより、上記目的が
達成できることを見出し、本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention are mainly responsible for the difficulty of measurement and the indefiniteness of the chromatogram due to two problems such as the difference in performance of individual porous members and the subtlety of setting know-how. Therefore, as a means for solving the problem, it was found that the above object can be achieved by improving the FAB ionization part and adopting a concave porous member in order to keep the ionization state stable, and thus completed the present invention. It was

【００１２】即ち、本発明の要旨は、（１） 高速原子
衝突（ＦＡＢ）によりイオン化を行う質量分析装置のイ
オン化部のターゲットとなる多孔性部材であって、その
形状が、試料液の供給部がその周辺部より薄い厚みを有
するものであることを特徴とする質量分析装置用多孔性
部材、（２） 平板状の多孔性部材の片面もしくは両面
に、試料液の供給部がその周辺部より薄い厚みとなる凹
部を設けたことを特徴とする上記（１）記載の多孔性部
材、（３） 凹部が球面状に加工されたものであり、そ
の最も薄い部分の厚みが５０〜２００μｍである上記
（２）記載の多孔性部材、（４） 凹部が球面状に加工
されたものであり、その最も薄い部分の厚みが平板部分
の１／５〜４／５である上記（２）又は（３）記載の多
孔性部材、（５） ＳＵＳ、セラミック又は有機繊維よ
りなる上記（１）〜（４）いずれか記載の多孔性部材、
（６） 質量分析装置が、液体クロマトグラフの検出器
として試料液が連続的に供給されるよう接続されている
ものである上記（３）〜（５）いずれか記載の多孔性部
材、（７） 高速原子衝突（ＦＡＢ）によりイオン化を
行う質量分析装置のイオン化部のターゲットとして、平
板状の多孔性部材の片面にその最も薄い部分の厚みが５
０〜２００μｍである球面状の凹部を形成した多孔性部
材を、該凹部が試料液の導入管を固定する弾性体の凸部
に圧接するよう設置することを特徴とする多孔性部材の
使用方法、に関する。That is, the gist of the present invention is (1) a porous member which is a target of an ionization section of a mass spectrometer for performing ionization by fast atom collision (FAB), the shape of which is a sample solution supply section. Has a thickness smaller than that of the peripheral portion thereof, and the porous member for a mass spectrometer is characterized in that (2) one or both sides of the flat plate-like porous member is provided with a sample liquid supply portion from the peripheral portion. The porous member according to (1) above, which is provided with a recess having a thin thickness, and (3) the recess is processed into a spherical shape, and the thinnest part has a thickness of 50 to 200 μm. (4) The porous member according to (2) above, (4) the concave portion is processed into a spherical shape, and the thinnest portion thereof has a thickness of 1/5 to 4/5 of the flat plate portion, (2) or ( 3) The porous member as described above, (5) SUS, The porous member according to any one of (1) to (4) above, which is made of ceramic or organic fiber,
(6) The porous member according to any one of (3) to (5), wherein the mass spectrometer is connected as a detector of a liquid chromatograph so that the sample liquid is continuously supplied. ) As a target of an ionization part of a mass spectrometer for performing ionization by fast atom collision (FAB), the thinnest part of the flat plate-shaped porous member has a thickness of 5
A method of using a porous member, characterized in that a porous member having a spherical recess having a diameter of 0 to 200 μm is installed so that the recess is in pressure contact with a protrusion of an elastic body for fixing a sample liquid introduction tube. About.

【００１３】[0013]

【発明の実施の形態】本発明の質量分析装置用多孔性部
材は、高速原子衝突（ＦＡＢ）によりイオン化を行う質
量分析装置のイオン化部のターゲットとなる多孔性部材
であって、その形状が、試料液の供給部がその周辺部よ
り薄い厚みを有するものであることを特徴とするもので
ある。BEST MODE FOR CARRYING OUT THE INVENTION The porous member for a mass spectrometer of the present invention is a porous member which is a target of an ionization part of a mass spectrometer for performing ionization by fast atom collision (FAB), and its shape is It is characterized in that the supply portion of the sample liquid has a thinner thickness than the peripheral portion thereof.

【００１４】まず、かかる多孔性部材が用いられる質量
分析装置（以下、ＭＳと略す場合がある）について説明
する。本発明における質量分析装置は、高速原子衝突
（ＦＡＢ）によりイオン化を行う方式を採用するもので
あれば特に限定されることなく、各種の質量分析装置に
用いることができる。例えば、日本電子製ＪＭＳ−ＳＸ
１０２／ＳＸ１０２タンデム型質量分析装置では、１つ
の装置でＥＩ，ＣＩ，ＦＡＢ，ＦＤのイオン化法を選択
でき、またＧＣ／ＭＳ，ＬＣ／ＭＳ，ＭＳ／ＭＳ等の種
々の測定方法を選択できるが、このような装置も本発明
における質量分析装置に包含される。First, a mass spectrometer (hereinafter sometimes abbreviated as MS) using such a porous member will be described. The mass spectrometer in the present invention is not particularly limited as long as it adopts a method of performing ionization by fast atom collision (FAB), and can be used in various mass spectrometers. For example, JMS-SX manufactured by JEOL
In the 102 / SX102 tandem mass spectrometer, the ionization method of EI, CI, FAB, and FD can be selected with one device, and various measurement methods such as GC / MS, LC / MS, MS / MS can be selected. Such an apparatus is also included in the mass spectrometer of the present invention.

【００１５】上記のうちＬＣ／ＭＳシステムは、ＦＲＩ
Ｔ−ＦＡＢ−ＬＣ／ＭＳと呼ばれるシステムであり、そ
のイオン化方法として高速原子衝突法（ＦＡＢ：ＦＡＳ
ＴＡＴＯＭ ＢＯＭＢＡＲＤＭＥＮＴ）を採用してい
る。Among the above, the LC / MS system is the FRI.
This is a system called T-FAB-LC / MS, and its ionization method is a fast atom collision method (FAB: FAS).
It adopts TATOM BOMBARD MENT).

【００１６】このようなシステムでは、試料それだけで
はイオン化が困難であるため、イオン化効率を向上させ
るためイオン化の際グリセリン等のイオン化促進剤と呼
ばれる添加剤を必要とする。高速原子衝突法は、難揮発
性でかつ高極性物質から中極性物質に対し有効な方法で
あるためＬＣ／ＭＳシステムのイオン化によく用いられ
る。本発明の多孔性部材は、質量分析装置が、液体クロ
マトグラフの検出器として試料液が連続的に供給される
よう接続されている上記のＬＣ／ＭＳシステムに特に好
適に用いることができる。In such a system, since it is difficult to ionize the sample itself, an additive called an ionization accelerator such as glycerin is required at the time of ionization in order to improve the ionization efficiency. The fast atom collision method is often used for ionization of LC / MS systems because it is a method that is difficult to volatilize and is effective for highly polar substances to moderately polar substances. The porous member of the present invention can be particularly suitably used for the above-mentioned LC / MS system in which a mass spectrometer is connected as a detector of a liquid chromatograph so that a sample liquid is continuously supplied.

【００１７】ＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳの原理を説
明すべく、図１に、溶離液組成の変化しないアイソクラ
テックモードでのＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳシステ
ムの装置構成図を示す。In order to explain the principle of FRIT-FAB-LC / MS, FIG. 1 shows an apparatus configuration diagram of the FRIT-FAB-LC / MS system in the isocratic mode in which the eluent composition does not change.

【００１８】この装置では、例えばサンプルは、流速
１．０ｍｌ／ｍｉｎのコンベンショナルなＨＰＬＣ６に
よりカラム７で分離され、カラム分離後に試薬を添加す
るポストカラム法によりイオン化促進剤溶液５が流速
１．０ｍｌ／ｍｉｎで添加され、ミキシングチャンバー
１で混合される。混合後、溶離液は空気圧スプリッター
装置２でスプリットされ、線速度２〜５μｌ／ｍｉｎで
キャピラリー３を通じてＭＳ１０に導入、質量分析デー
タ処理される。なお、ＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳシ
ステムは、そのシステム上溶離液除去用の予備差動排気
室を持たないので、直接溶離液を高真空のＭＳ内部に導
入しなければいけない。従って、溶離液の流速は、ＭＳ
の真空度を維持する必要性から、最大でも５μｌ／ｍｉ
ｎという制限がある。In this apparatus, for example, the sample is separated in the column 7 by the conventional HPLC 6 at a flow rate of 1.0 ml / min, and the ionization accelerator solution 5 is added at a flow rate of 1.0 ml / min by a post-column method in which a reagent is added after the column separation. It is added in min and mixed in the mixing chamber 1. After mixing, the eluent is split by the pneumatic splitter device 2, introduced into the MS 10 through the capillary 3 at a linear velocity of 2 to 5 μl / min, and processed by mass spectrometry data. Since the FRIT-FAB-LC / MS system does not have a preliminary differential evacuation chamber for removing the eluent on the system, the eluent must be directly introduced into the high vacuum MS. Therefore, the flow rate of the eluent is MS
It is necessary to maintain the vacuum degree of
There is a limit of n.

【００１９】また、ＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳのＦ
ＡＢイオン化の原理を、図２に示す。キャピラリー１１
を通じてＭＳイオン化室へ導入された溶離液は、フリッ
ト１２と呼ばれるＳＵＳ製の多孔性部材中を浸透して、
ＦＡＢイオン化ターゲット位置に浸み出す。浸み出した
溶離液は、真空下で溶媒が揮発しサンプルとイオン化促
進剤の混和物に濃縮される。ＭＳイオン化室にキセノン
ガスが供給され、ＦＡＢガン１３により加速され、高速
キセノン原子１４が発生する。この高速キセノン原子と
サンプルが衝突することにより、サンプルがイオン化さ
れ、ＭＳで質量分析される。なお、溶離液の大部分を占
める溶媒はほとんど全てが高真空の環境下で瞬時に揮発
するため、溶媒のＦＡＢイオン化は起こらない。In addition, F of FRIT-FAB-LC / MS
The principle of AB ionization is shown in FIG. Capillary 11
The eluent introduced into the MS ionization chamber through the permeates the SUS porous member called frit 12,
Leach into the FAB ionization target position. The solvent in the leached eluent evaporates under vacuum and is concentrated to a mixture of the sample and the ionization promoter. Xenon gas is supplied to the MS ionization chamber and accelerated by the FAB gun 13 to generate high-speed xenon atoms 14. When the sample collides with the high-speed xenon atom, the sample is ionized and mass-analyzed by MS. Note that almost all of the solvent that occupies most of the eluent volatilizes instantly in a high vacuum environment, so FAB ionization of the solvent does not occur.

【００２０】このように、ＦＲＩＴ−ＦＡＢ−ＬＣ／Ｍ
Ｓシステムは、空気圧スプリッター装置をシステムに組
み込むことで真空中への溶液導入を可能とし、多孔性部
材上でイオン化促進剤と高速キセノン原子によりＭＳイ
オン化することを特徴とするＬＣ／ＭＳシステムであ
る。このようなＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳシステム
のイオン化は、図３に示すプローブを用いて行われる。Thus, FRIT-FAB-LC / M
The S system is an LC / MS system characterized by allowing a solution to be introduced into a vacuum by incorporating a pneumatic splitter device into the system and performing MS ionization by an ionization accelerator and high-speed xenon atoms on a porous member. . Ionization of such a FRIT-FAB-LC / MS system is performed using the probe shown in FIG.

【００２１】即ち、プローブ部において、キャピラリー
２１からの溶離液が多孔性部材中を浸透移動し、ＦＡＢ
イオン化ターゲット位置に浸み出し、ＦＡＢイオン化が
行なわれる。ＦＡＢイオン化が安定して行なわれるため
には、溶離液が滞留することなくキャピラリーから多孔
性部材２５に供給され、均一に多孔性部材中を短時間で
浸透移動し、ＦＡＢイオン化ターゲット位置で安定して
連続的に浸み出すことが必要である。つまり、多孔性部
材の性能やセッティングの仕方がＦＡＢイオン化に影響
を与えるため、多孔性部材はＦＲＩＴ−ＦＡＢ−ＬＣ／
ＭＳシステムの心臓部といえる。That is, in the probe portion, the eluent from the capillary 21 permeates and moves in the porous member, and FAB
Leaching to the ionization target position, FAB ionization is performed. In order for FAB ionization to be performed stably, the eluent is supplied from the capillary to the porous member 25 without stagnation, uniformly permeates and moves in the porous member in a short time, and is stabilized at the FAB ionization target position. It is necessary to continuously ooze it out. In other words, since the performance and setting method of the porous member influences FAB ionization, the porous member is FRIT-FAB-LC /
It can be said to be the heart of the MS system.

【００２２】次に、当該孔性部材について説明する。本
発明の多孔性部材は、試料液の供給部がその周辺部より
薄い厚みを有する形状であることを特徴とするものであ
る。試料液の供給部をその周辺部より薄くする方法とし
ては、その部分の透過性を維持しつつ当該形状となるも
ので有れば特に限定されることなく、最初から当該形状
に成形する方法、及び一旦成形した後に、当該形状に加
工する方法の両者が挙げられる。Next, the porous member will be described. The porous member of the present invention is characterized in that the supply portion for the sample liquid has a shape having a smaller thickness than the peripheral portion thereof. The method for making the supply part of the sample liquid thinner than the peripheral part is not particularly limited as long as it has the shape while maintaining the permeability of the part, and a method of forming the shape from the beginning, And a method of once shaping and then processing into the shape.

【００２３】成形後に加工する方法としては、その部分
の透過性が維持される方法でかかる形状に加工可能であ
れば特に限定されることなく、切削加工、研磨加工等が
挙げられる。従って、圧縮加工、加熱加工による場合は
加工部分の試料液の透過性が悪くなるため、本発明に適
用不可能である。なお、特開平３−１８７１４７号公報
には、ＦＡＢイオン化部のターゲットである多孔性部材
を周辺よりも中心部の試料通過性が大きくする発明が開
示されているが、本発明の多孔性部材は試料液の供給部
の透過性が維持できれば十分であり、多孔性部材の周辺
部と中心部の多孔構造自身の透過性に実質的な差異はな
い。The method of processing after molding is not particularly limited as long as it can be processed into such a shape by the method of maintaining the permeability of the portion, and examples thereof include cutting and polishing. Therefore, in the case of compression processing or heating processing, the permeability of the sample liquid in the processed portion is deteriorated, and it is not applicable to the present invention. In addition, Japanese Patent Laid-Open No. 3-187147 discloses an invention in which a porous member which is a target of the FAB ionization part has greater sample permeability in the central portion than in the peripheral portion. However, the porous member of the present invention is It is sufficient if the permeability of the sample liquid supply portion can be maintained, and there is no substantial difference in the permeability of the porous structure itself at the peripheral portion and the central portion of the porous member.

【００２４】本発明では、加工の容易性、溶離液の浸透
性、イオン化部との密着性の観点から、平板状の多孔性
部材の片面もしくは両面に、試料液の供給部がその周辺
部より薄い厚みとなる凹部を設けたものが好まく、より
好ましくは平板状の多孔性部材の片面に凹部を設けた場
合である。In the present invention, from the viewpoints of easiness of processing, permeability of the eluent, and adhesion to the ionization part, the sample liquid supply part is provided on one or both sides of the flat plate-like porous member from its peripheral part. It is preferable to provide a concave portion having a thin thickness, and more preferably a case where the concave portion is provided on one surface of a flat plate-shaped porous member.

【００２５】また、凹部の形状としては、真球面、長球
面等を含む球面状や、曲面状、円盤状、楕円盤状、円錐
状、多角錐状、多角形状など、いずれの形状でもよい
が、加工の容易性の観点から、球面状、円盤状、円錐状
等が好ましい。また試料液の導入管を固定する弾性体の
凸部に圧接させた時の密着性の観点から、凹部が球面状
に加工されたものが最も好ましい。つまり、多孔性部材
の形状に関しては、溶離液が多孔性部材中を浸透し易
く、ＦＡＢイオン化ターゲット位置で浸み出し易く、Ｆ
ＡＢイオン化プローブと隙間なくセッティングできるよ
うな、中央部が薄型化された凹型構造が理想である。Further, the shape of the concave portion may be any shape such as a spherical shape including a true spherical surface, a long spherical surface, etc., a curved surface shape, a disk shape, an elliptic disk shape, a conical shape, a polygonal pyramid shape, a polygonal shape or the like. From the viewpoint of ease of processing, a spherical shape, a disk shape, a conical shape or the like is preferable. Further, from the viewpoint of adhesiveness when pressed into contact with the convex portion of the elastic body for fixing the sample liquid introduction tube, it is most preferable that the concave portion is processed into a spherical shape. That is, regarding the shape of the porous member, the eluent easily penetrates into the porous member and easily oozes out at the FAB ionization target position.
An ideal structure is a concave structure with a thin central part so that it can be set without a gap with the AB ionization probe.

【００２６】凹部の最も薄い部分の厚みは、溶離液の浸
透性の観点から、５０〜２００μｍが好ましく、７５〜
１２５μｍがより好ましい。なお、凹部以外の部分の厚
みは、イオン化部との密着性、板状構造の維持の観点か
ら、１００〜４００μｍが好ましく、２００〜３００μ
ｍがより好ましい。The thickness of the thinnest portion of the concave portion is preferably 50 to 200 μm, and 75 to 200 μm, from the viewpoint of permeability of the eluent.
125 μm is more preferable. The thickness of the portion other than the concave portion is preferably 100 to 400 μm, and more preferably 200 to 300 μm, from the viewpoint of adhesion to the ionized portion and maintenance of the plate-like structure.
m is more preferred.

【００２７】また、溶離液の透過性およびイオン化部と
の密着性、板状構造の維持の観点から、凹部の最も薄い
部分の厚みが平板部分の１／５〜４／５であることが好
ましく、３／１０〜１／２がより好ましい。From the viewpoint of the permeability of the eluent, the adhesion to the ionization part, and the maintenance of the plate-like structure, the thickness of the thinnest part of the recess is preferably 1/5 to 4/5 of that of the flat plate part. It is more preferably 3/10 to 1/2.

【００２８】なお、本発明の多孔性部材の細孔の平均径
は０．１〜１０μｍ程度が好ましいとされており、１〜
５μｍがより好ましい。また、多孔性部材全体の形状
は、使用される質量分析装置に適合するものであれば特
に限定されないが、通常は円盤状、３角、４角等の多角
形板状のものが用いられている。The average diameter of the pores of the porous member of the present invention is said to be preferably about 0.1 to 10 μm.
5 μm is more preferable. Further, the shape of the entire porous member is not particularly limited as long as it is compatible with the mass spectrometer used, but a disk-shaped, triangular, quadrangular, or other polygonal plate-shaped member is usually used. There is.

【００２９】本発明の多孔性部材の材質としては、従来
より使用されているＳＵＳの他、イオン化傾向の小さい
金属である金・銀・白金、無機的材料であるセラミック
やガラス、天然高分子である紙や天然繊維、合成高分子
であるプラスティックや合成繊維などが挙げられる。こ
れらのうち、加工の容易性、低コスト性、汎用性の観点
から、ＳＵＳ、セラミック又は有機繊維が好ましく用い
られる。As the material of the porous member of the present invention, in addition to SUS which has been used conventionally, gold, silver and platinum which are metals having a small ionization tendency, ceramics and glass which are inorganic materials, and natural polymers are used. Examples include certain papers, natural fibers, synthetic polymers such as plastics and synthetic fibers. Of these, SUS, ceramics or organic fibers are preferably used from the viewpoints of ease of processing, low cost, and versatility.

【００３０】従来より使用されている多孔性部材は、Ｓ
ＵＳ製メッシュをプレス加工した多孔構造板である。Ｆ
ＡＢイオン化はＳＵＳ表面で行なわれており、化合物の
イオン化の際ＳＵＳにより影響を受ける可能性が一部で
指摘されている。多孔性部材の材質に関しては、溶離液
の浸透がスムーズに行えるような多孔構造板に加工で
き、その材質がＦＡＢイオン化に影響を与えなければ良
いので、上記のような種々の素材が多孔性部材の材質と
して応用できる。Conventionally used porous members are S
It is a porous structure plate obtained by pressing a US mesh. F
AB ionization is performed on the surface of SUS, and it has been pointed out in part that AB ionization may be affected by SUS during ionization of a compound. Regarding the material of the porous member, it is sufficient that the porous structure plate can be processed so that the eluent can be smoothly permeated, and the material does not affect FAB ionization. It can be applied as a material.

【００３１】なお、現在よりも連続使用性や耐久性を向
上させるべく、多孔性部材自身の溶離液保持能力やその
溶離液揮発能力向上の目的で、多孔性部材の直径の大型
化あるいは溶離液を多孔性部材からの排除する部分の装
着などが可能と考えられる。For the purpose of improving the eluent retention capacity of the porous member itself and the eluent volatilization capacity thereof, in order to improve the continuous usability and durability, the diameter of the porous member is increased or the eluent is increased. It is considered possible to attach a part that excludes from the porous member.

【００３２】本発明の凹型多孔性部材は、わずかな研磨
加工費（一枚当り８００円程度）だけでＦＡＢイオン化
を効果的に安定にすることができ、ＦＲＩＴ−ＦＡＢ−
ＬＣ／ＭＳシステムの応用範囲を広げることができるた
め非常に有効な方法である。The concave porous member of the present invention can effectively stabilize FAB ionization with a small polishing processing cost (about 800 yen per sheet), and FRIT-FAB-
This is a very effective method because it can expand the application range of the LC / MS system.

【００３３】本発明では、高速原子衝突（ＦＡＢ）によ
りイオン化を行う質量分析装置のイオン化部のターゲッ
トとして、平板状の多孔性部材の片面にその最も薄い部
分の厚みが５０〜２００μｍである球面状の凹部を形成
した多孔性部材を、該凹部が試料液の導入管を固定する
弾性体の凸部に圧接するよう設置することにより、本発
明の効果を好適に得ることができる。In the present invention, as the target of the ionization section of the mass spectrometer for performing ionization by fast atom collision (FAB), the thinnest portion on one side of the flat plate-like porous member is a spherical shape having a thickness of 50 to 200 μm. The effect of the present invention can be favorably obtained by disposing the porous member having the concave portion so that the concave portion is in pressure contact with the convex portion of the elastic body that fixes the sample liquid introduction tube.

【００３４】[0034]

【実施例】以下、実施例、および参考例により本発明を
さらに詳しく説明するが、本発明はこれらの実施例等に
よりなんら限定されるものではない。The present invention will be described in more detail with reference to Examples and Reference Examples, but the present invention is not limited to these Examples.

【００３５】従来より使用している多孔性部材は日本電
子（ＪＥＯＬ）純正品であり、ＳＵＳ製メッシュをプレ
ス加工した円盤型多孔板（直径７９ｍｍ，厚さ０．２５
ｍｍ）である。以前より純正多孔性部材はロット振れが
多く、多孔性部材中の溶離液の浸透性やＦＡＢイオン化
ターゲット位置での溶離液の浸み出し方に良し悪しのロ
ット差が大きいため、測定条件が固定できず、ＬＣ／Ｍ
Ｓ測定のスタートアップに長時間を要していた。また、
連続使用していると多孔性部材のメッシュが目詰まりを
起こし、溶離液の浸透性や浸み出し方に変化を与え、Ｆ
ＡＢイオン化効率が変化することも安定性や再現性の問
題となっていた。The porous member that has been conventionally used is a genuine product of JEOL, and is a disk-shaped porous plate (diameter 79 mm, thickness 0.25) made by pressing a SUS mesh.
mm). Lot fluctuations of pure porous material have been large since before, and the measurement conditions are fixed because there is a large lot difference between the permeability of the eluent in the porous material and the leaching method of the eluent at the FAB ionization target position. Not possible, LC / M
It took a long time to start up the S measurement. Also,
If it is used continuously, the mesh of the porous member will become clogged, changing the permeability of the eluent and the leaching method.
The change in AB ionization efficiency has also been a problem of stability and reproducibility.

【００３６】セッティングの微妙さの問題は、主にＦＲ
ＩＴ−ＦＡＢ−ＬＣ／ＭＳプローブとＪＥＯＬ純正多孔
性部材の取り付け方に起因している。純正多孔性部材
は、そのセッティングの仕方によりＬＣ／ＭＳ測定が可
能な場合と不可能な場合があり、測定者の経験と勘に頼
る部分が多いことや、ＦＡＢイオン化安定待ち時間がか
かることなど、とうてい汎用的な測定をする事は不可能
であった。The problem of subtlety of setting is mainly FR
This is due to the method of attaching the IT-FAB-LC / MS probe and the JEOL genuine porous member. Depending on how the genuine porous member is set, LC / MS measurement may or may not be possible, and there are many parts that rely on the experience and intuition of the measurer, and there is a FAB ionization stabilization wait time. However, it was impossible to make general-purpose measurements.

【００３７】これらの問題は、以下のようなメカニズム
で起こる。図３に示すように、ＨＰＬＣからの溶離液は
キャピラリーを通じて多孔性部材に供給されるが、キャ
ピラリー周辺の隙間から真空漏れを防ぐためにカロレッ
ツ製のフェラル１４でシールする必要がある。このフェ
ラルのシール効果を高めるためフェラル用ナットで強く
締め込むが、フェラルが変形しプローブ先端で凸状に飛
び出した形状となる。この凸状フェラルに多孔性部材１
５をセッティングする際に、フェラルと多孔性部材との
間にわずかであるが隙間ができる。この隙間で溶離液の
滞留が起こり、多孔性部材中での溶離液の均一な浸透を
妨げ、結果的に多孔性部材の目詰まりやクロマトグラム
のベースラインノイズを引き起こす。これらの要因が組
み合わさって、汎用的なＬＣ／ＭＳ測定を困難としてい
た。These problems occur by the following mechanism. As shown in FIG. 3, the eluent from the HPLC is supplied to the porous member through the capillary, but it is necessary to seal it with the ferrule 14 made of Calorets in order to prevent vacuum leakage from the gap around the capillary. In order to enhance the sealing effect of the ferrule, the ferrule nut is tightly tightened, but the ferrule is deformed and the probe tip projects into a convex shape. The porous member 1 is attached to the convex ferrule.
When setting 5, there is a slight gap between the ferrule and the porous member. The retention of the eluent occurs in this gap, hindering the uniform permeation of the eluent in the porous member, resulting in clogging of the porous member and baseline noise in the chromatogram. These factors are combined to make general-purpose LC / MS measurement difficult.

【００３８】本実施例では、汎用的なＬＣ／ＭＳ測定を
簡単に行えるように、「溶離液がＦＡＢプローブ先端で
滞留することなく、均一に多孔性部材中を短時間で浸透
移動し、ＦＡＢイオン化ターゲットで安定して連続的に
浸み出す多孔性部材」、すなわち図４に示すような薄型
多孔性部材（Ｂ）および凹型多孔性部材（Ｃ）について
検討した。In the present embodiment, in order to easily perform general-purpose LC / MS measurement, "the eluent does not stay at the tip of the FAB probe and uniformly permeates through the porous member in a short time, A porous member that stably and continuously exudes with an ionization target, that is, a thin porous member (B) and a concave porous member (C) as shown in FIG. 4 was examined.

【００３９】参考例１（薄型多孔性部材） まず、ＪＥＯＬ純正多孔性部材の問題点である「多孔性
部材での溶離液の浸透性やＦＡＢイオン化ターゲット位
置での浸み出し方の不安定さ」を解決する目的で、薄型
多孔性部材について検討した。Reference Example 1 (Thin Porous Member) First, the problem of the JEOL genuine porous member is that "permeability of the eluent in the porous member and instability in the leaching method at the FAB ionization target position are unstable. For the purpose of solving the above, a thin porous member was examined.

【００４０】即ち、溶離液が多孔性部材中を均一に短時
間で浸透移動しターゲット位置で安定して連続的に浸み
出すことを目的に、図４に示したＪＥＯＬ純正多孔性部
材を薄型加工し（純正品厚さ０．２５ｍｍ→薄型加工品
０．１ｍｍ）、薄型多孔性部材を製作し検討した。That is, the JEOL genuine porous member shown in FIG. 4 is thin for the purpose of allowing the eluent to uniformly permeate and move in the porous member in a short time and stably and continuously ooze out at the target position. After processing (thickness of genuine product: 0.25 mm → thin processed product: 0.1 mm), a thin porous member was manufactured and studied.

【００４１】この薄型多孔性部材を用いて実際にＬＣ／
ＭＳ測定を行ない評価したところ、溶離液は薄型多孔性
部材中を均一に短時間で浸透移動し、ＦＡＢイオン化タ
ーゲット位置で安定して連続的に浸み出していることが
確認できた。しかし、長時間測定（２０分以上）を行な
った場合、イオン化促進剤によるノイズが増加し、得ら
れるクロマトグラムではベースラインの上昇が確認され
た。Using this thin porous member, LC /
As a result of MS measurement and evaluation, it was confirmed that the eluent permeated and moved uniformly in the thin porous member in a short time, and was stably and continuously leached at the FAB ionization target position. However, when the measurement was carried out for a long time (20 minutes or more), noise due to the ionization accelerator increased, and the obtained chromatogram confirmed that the baseline increased.

【００４２】この原因は、薄型多孔性部材とＦＡＢイオ
ン化プローブ先端とのセッティング面に隙間があり溶離
液が滞留すること、多孔性部材の薄型化により溶離液を
保持できる容量が減少したため、ＦＡＢイオン化ターゲ
ット表面に溶離液やイオン化促進剤が滞留することによ
り、サンプル以外の溶離液がイオン化しノイズとして現
われると考えられる。The reason for this is that there is a gap in the setting surface between the thin porous member and the tip of the FAB ionization probe, and the eluent stays there. Since the thin porous member reduces the capacity that can hold the eluent, FAB ionization occurs. It is considered that the eluent other than the sample is ionized and appears as noise due to the retention of the eluent and the ionization accelerator on the target surface.

【００４３】実サンプルでのＬＣ測定は２０分以上必要
なことが多いため、薄型多孔性部材を用いた長時間測定
には限界のあることが確認できた。Since LC measurement with an actual sample often requires 20 minutes or more, it was confirmed that there is a limit to long-time measurement using a thin porous member.

【００４４】実施例１（凹型多孔性部材） 多孔性部材の薄型化により、測定時間２０分程度であれ
ば、溶離液が多孔性部材中を均一に短時間で安定して連
続的に浸み出すことが確認できたが、実サンプルを用い
た長時間測定が可能になるように耐久性についての問題
を解決する必要がある。そこで、薄型多孔性部材の問題
点である「多孔性部材とＦＡＢイオン化プローブ間の隙
間の問題や多孔性部材自体の溶離液保持容量不足」を解
決する目的で、図４に示したような凹型多孔性部材につ
いて検討した。Example 1 (Concave Porous Member) By thinning the porous member, if the measuring time is about 20 minutes, the eluent uniformly and continuously immerses the porous member in a short time in a stable manner. Although it has been confirmed that it is possible to solve the problem, it is necessary to solve the problem of durability so that long-time measurement using an actual sample becomes possible. Therefore, in order to solve the problems of the thin porous member "the problem of the gap between the porous member and the FAB ionization probe and the insufficient eluent holding capacity of the porous member itself", the concave type as shown in FIG. The porous member was examined.

【００４５】図５に、本発明の凹型多孔性部材を取り付
けたＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳ用のＦＡＢイオン化
プローブを示す。FIG. 5 shows a FAB ionization probe for FRIT-FAB-LC / MS to which the concave porous member of the present invention is attached.

【００４６】多孔性部材は、ＦＡＢイオン化ターゲット
位置である中央部が薄型化されていれば、問題なく溶離
液が多孔性部材中を浸透しイオン化ターゲットで浸み出
すため、多孔性部材がＦＡＢイオン化プローブ先端のフ
ェラルと隙間なくフイットするようにフリット中央部を
研磨加工（直径４．０ｍｍ深さ０．１５ｍｍ球面状に研
磨加工）し、凹型多孔性部材を製作した。凹型構造にす
ることにより、多孔性部材自体の溶離液保持容量の減少
を最小限に抑えた。If the central portion of the porous member, which is the FAB ionization target position, is made thin, the eluent penetrates into the porous member and leaches out with the ionization target without any problem, so that the porous member is FAB ionized. A concave porous member was manufactured by polishing the central portion of the frit (the diameter was 4.0 mm and the depth was 0.15 mm into a spherical shape) so as to fit the ferrule at the tip of the probe without leaving a gap. The concave structure minimized the decrease in the eluent holding capacity of the porous member itself.

【００４７】この凹型多孔性部材を用いたプローブを使
い、実際にＬＣ／ＭＳ測定を行ない評価したところ、溶
離液は薄型多孔性部材中を均一に短時間で浸透移動し、
ＦＡＢイオン化ターゲット位置で安定して連続的に浸み
出していることが確認できた。また、長時間測定(120分
以上）を行なった場合でも、イオン化促進剤によるノイ
ズの増加は少なく、得られるクロマトグラムのベースラ
インノイズもほとんど確認されなかった。安定したＦＡ
Ｂイオン化は、イオン化促進剤由来のノイズ低減による
Ｓ／Ｎの良好なＬＣ／ＭＳクロマトグラムが得られるよ
うになった。When an LC / MS measurement was actually carried out and evaluated using a probe using this concave porous member, the eluent permeated and moved in the thin porous member uniformly in a short time.
It was confirmed that the leaching was stable and continuous at the FAB ionization target position. Even when the measurement was performed for a long time (120 minutes or more), the increase in noise due to the ionization promoter was small, and baseline noise in the obtained chromatogram was hardly confirmed. Stable FA
The B ionization can obtain a good LC / MS chromatogram with S / N due to the noise reduction due to the ionization accelerator.

【００４８】図６に、ＪＥＯＬ純正多孔性部材と凹型多
孔性部材（を用いた時の混合物サンプルのＬＣ／ＭＳク
ロマトグラム例を示す。（Ａ）がＪＥＯＬ純正多孔性部
材の場合で、（Ｂ）が凹型多孔性部材の場合である。FIG. 6 shows an example of an LC / MS chromatogram of a mixture sample when using a JEOL genuine porous member and a concave porous member (where (A) is the JEOL genuine porous member and (B) ) Is the case of a concave porous member.

【００４９】その時の分析条件を以下に示す。 使用サンプル：オレイルサルフェートソーダ（Ｃ18Ｈ35
−ＯＳＯ3 Ｎａ）混合物：１重量％メタノール２０μＬ
注入、オレイルアルコール（Ｃ16、Ｃ18、Ｃ18Ｆ混合
物）よりＳＯ3 ガスを用いてオレイルサルフェートソー
ダを得る場合の微量混合成分の解析） ＨＰＬＣ用ポンプ：日立６５５Ａ−１１型ＬＣポンプ、
日立６５５Ａ−７１型プロポーショニングバルブ ポストカラム用ポンプ：日立６５５Ａ−１１型ＬＣポン
プ、日立６５５Ａ−７１型プロポーショニングバルブ 分離用カラム：ＴＳＫ−ｇｅｌ ８０ＴＳ，４．６×１
５０ｍｍ，２５℃（東ソー製） 溶離液：ＭｅＯＨ（関東化学）ＨＰＬＣ用 Ｈ2 Ｏ（Millipore によるＬＣ用イオン交換水） イオンペア試薬：ＣＨ3 ＣＯＯＮＨ4 （片山化学）特級 イオン化促進剤：グリセリン（和光純薬）特級 ミキシングチャンバー：THE LEE COMPANY 製 スプリッター：日本電子製，純正品，スプリット比１／
８００ キャピラリー：日本電子製，純正品，６０μｍI.D.×１
００ｃｍ フリット板：日本電子製、純正品もしくは本発明品The analysis conditions at that time are shown below. Sample used: Oleyl Sulfate Soda (C 18 H 35
-OSO 3 Na) mixture: 1 wt% methanol 20 μL
Injection, analysis of minor mixed components when oleyl sulfate soda is obtained using SO 3 gas from oleyl alcohol (C 16 , C 18 , C 18 F mixture) Pump for HPLC: Hitachi 655A-11 type LC pump,
Hitachi 655A-71 type proportioning valve Post column pump: Hitachi 655A-11 type LC pump, Hitachi 655A-71 type proportioning valve Separation column: TSK-gel 80TS, 4.6 × 1
50 mm, 25 ° C. (manufactured by Tosoh Corporation) Eluent: MeOH (Kanto Kagaku) for HPLC H 2 O (ion exchange water for LC by Millipore) Ion pair reagent: CH 3 COONH 4 (Katayama Chemical) Special grade Ionization accelerator: Glycerin (Wako Pure) Medicine) Special grade mixing chamber: THE LEE COMPANY splitter: JEOL genuine product, split ratio 1 /
800 Capillary: JEOL genuine product, 60μm I.D. x 1
00 cm frit plate: JEOL's genuine product or product of the present invention

【００５０】ＭＳ：日本電子製、ＪＭＳ−ＳＸ102 ／Ｓ
Ｘ102 ，タンデム型質量分析装置 ＜ＭＳの条件＞ IONIZING VOLT 70V CHAMBER TEMP 60 ℃ ACCEL 8.0KV POST ACCELL -10.0KV ION MULTI -1.4 EMISSION CURRENT 10mA POLARITY ── MAGNETIC FIELD HS DETECTOR GAIN 1 SCAN RANGE 300-500 CYCLE TIME 2S ＜グラジエント条件＞MS: JEOL, JMS-SX102 / S
X102, tandem mass spectrometer <MS conditions> IONIZING VOLT 70V CHAMBER TEMP 60 ℃ ACCEL 8.0KV POST ACCELL -10.0KV ION MULTI -1.4 EMISSION CURRENT 10mA POLARITY ── MAGNETIC FIELD HS DETECTOR GAIN 1 SCAN RANGE 300-500 CYCLE TIME 2S <Gradient condition>

【００５１】[0051]

【表１】 [Table 1]

【００５２】従来法であるＪＥＯＬ純正多孔性部材を用
いた場合（Ａ）、測定までのスタートアップに長時間を
要するだけでなく、得られるデータもイオン化促進剤由
来のノイズの影響でＳ／Ｎが悪くなり、サンプル中の微
量混合成分由来のピークの確認が困難になる。また、Ｆ
ＡＢイオン化が安定しないためイオン化促進剤により発
生するノイズも一定にならず、データ処理時にノイズカ
ットを行ってもベースラインノイズを低減することがで
きなかった。そのため、マスクロマトグラム法による解
析が必要となっていた。この方法は微量成分ピークをノ
イズから抽出できるため、実サンプルの微量混合成分の
解析には必要な手段であるが、非常に手間と時間が必要
なこと、また全くの未知成分に対しては解析しきれない
という問題があった。When the conventional JEOL pure porous member is used (A), not only does it take a long time to start up until the measurement, but also the obtained data has an S / N ratio due to the influence of the noise derived from the ionization accelerator. It becomes worse, and it becomes difficult to confirm the peak derived from a trace amount of mixed components in the sample. Also, F
Since the AB ionization was not stable, the noise generated by the ionization accelerator was not constant, and baseline noise could not be reduced even if noise was cut during data processing. Therefore, analysis by the mass chromatogram method has been required. Since this method can extract trace component peaks from noise, it is a necessary method for analyzing trace mixed components in actual samples, but it is extremely laborious and time consuming, and it is also necessary to analyze completely unknown components. There was a problem that I could not do it.

【００５３】それに対し、今回開発した凹型多孔性部材
を用いた場合（Ｂ）、測定までのスタートアップ時間が
短縮され、得られるデータもＳ／Ｎが非常に良くなっ
た。また、ＦＡＢイオン化が安定したことでイオン化促
進剤により発生するノイズも一定になったため、データ
処理時にノイズカットすることにより、更にベースライ
ンノイズを低減することができた。これらにより、サン
プル中の微量混合成分由来のピークがノイズに隠れるこ
とがなくなり、マスクロマトグラム法を使用することな
く簡単にピーク判別や確認が行えるようになった。凹型
多孔性部材の採用により、ＦＡＢイオン化が安定し測定
準備時間が短縮されかつ長時間測定も可能になり、ノイ
ズカット技術を組み合わせて更にＳ／Ｎを向上すること
ができたため、全く未知の微量混合成分でも短時間での
解析が可能となった。On the other hand, when the concave porous member developed this time was used (B), the start-up time until measurement was shortened, and the S / N of the obtained data was also very good. Further, since the FAB ionization was stable and the noise generated by the ionization accelerator was also constant, it was possible to further reduce the baseline noise by cutting noise during data processing. As a result, the peaks derived from the trace mixed components in the sample are not hidden by noise, and the peaks can be easily identified and confirmed without using the mass chromatogram method. By adopting a concave porous member, FAB ionization is stable, measurement preparation time is shortened, and long-term measurement is possible, and noise reduction technology can be combined to further improve S / N. Even mixed components can be analyzed in a short time.

【００５４】[0054]

【発明の効果】本発明の質量分析装置用多孔性部材及び
その使用方法によると、幅広い極性成分を持つ微量混合
サンプルを短時間で詳細な構造解析ができるようなＬＣ
／ＭＳが可能となる。また、本発明の質量分析装置用多
孔性部材は、わずかな研磨加工費でＦＡＢイオン化を効
果的に安定にすることができ、ＦＲＩＴ−ＦＡＢ−ＬＣ
／ＭＳシステムの応用範囲を広げることができる非常に
有効な方法である。EFFECTS OF THE INVENTION According to the porous member for a mass spectrometer of the present invention and the method of using the same, it is possible to carry out a detailed structure analysis of a minute amount of a mixed sample having a wide range of polar components in an LC
/ MS is possible. Further, the porous member for a mass spectrometer of the present invention can effectively stabilize FAB ionization with a small polishing processing cost, and FRIT-FAB-LC.
This is a very effective method that can broaden the application range of the / MS system.

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

【図１】図１は、溶離液組成の変化しないアイソクラテ
ックモードでのＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳシステム
の装置構成図を示すものである。FIG. 1 is a device configuration diagram of a FRIT-FAB-LC / MS system in an isocratic mode in which the eluent composition does not change.

【図２】図２は、ＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳのＦＡ
Ｂイオン化の原理を説明するための図である。FIG. 2 shows FA of FRIT-FAB-LC / MS.
It is a figure for demonstrating the principle of B ionization.

【図３】図３は、ＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳシステ
ムのイオン化が行われるプローブ部分を示すものであ
る。FIG. 3 shows a probe portion of a FRIT-FAB-LC / MS system where ionization is performed.

【図４】図４は、各種の多孔性部材を示す正面図及び側
面図であり、（Ａ）は純正多孔性部材、（Ｂ）は薄型多
孔性部材、（Ｃ）は凹型多孔性部材である。FIG. 4 is a front view and a side view showing various porous members, (A) is a pure porous member, (B) is a thin porous member, and (C) is a concave porous member. is there.

【図５】図５は、本発明の凹型多孔性部材を取り付けた
ＦＲＩＴ−ＦＡＢ−ＬＣ／ＭＳ用のＦＡＢイオン化プロ
ーブを示すものである。FIG. 5 shows a FAB ionization probe for FRIT-FAB-LC / MS to which the concave porous member of the present invention is attached.

【図６】図６は、ＪＥＯＬ純正多孔性部材と凹型多孔性
部材を用いた時の混合物サンプルのＬＣ／ＭＳクロマト
グラム例を示すものであり、（Ａ）がＪＥＯＬ純正多孔
性部材の場合で、（Ｂ）が凹型多孔性部材の場合であ
る。FIG. 6 shows an LC / MS chromatogram example of a mixture sample using a JEOL genuine porous member and a concave porous member, where (A) is a JEOL genuine porous member. , (B) are concave porous members.

【符号の説明】[Explanation of symbols]

１ ミキシングチャンバー ２ 空気圧スプリッター装置 ３ キャピラリー ４ ＨＰＬＣ用溶離液 ５ イオン化促進剤溶液 ６ ＨＰＬＣ ７ カラム ８ ポストカラム用ポンプ ９ 廃液タンク １０ ＭＳ １１ キャピラリー １２ 多孔性部材（フリット板） １３ ＦＡＢガン １４ 高速キセノン原子 １５ イオン ２１ キャピラリー ２２ インシュレーター ２３ フェラル用ナット ２４ フェラル ２５ 多孔性部材（フリット板） 1 Mixing Chamber 2 Pneumatic Splitter Device 3 Capillary 4 Eluent for HPLC 5 Ionization Accelerator Solution 6 HPLC 7 Column 8 Post Column Pump 9 Waste Liquid Tank 10 MS 11 Capillary 12 Porous Member (Frit Plate) 13 FAB Gun 14 High Speed Xenon Atom 15 ion 21 capillary 22 insulator 23 ferrule nut 24 ferrule 25 porous member (frit plate)

Claims (7)

【特許請求の範囲】[Claims] 【請求項１】 高速原子衝突（ＦＡＢ）によりイオン化
を行う質量分析装置のイオン化部のターゲットとなる多
孔性部材であって、その形状が、試料液の供給部がその
周辺部より薄い厚みを有するものであることを特徴とす
る質量分析装置用多孔性部材。1. A porous member which is a target of an ionization section of a mass spectrometer for performing ionization by fast atom collision (FAB), and has a shape such that a supply section of a sample liquid has a thinner thickness than a peripheral section thereof. A porous member for a mass spectrometer, which is characterized in that 【請求項２】 平板状の多孔性部材の片面もしくは両面
に、試料液の供給部がその周辺部より薄い厚みとなる凹
部を設けたことを特徴とする請求項１記載の多孔性部
材。2. The porous member according to claim 1, wherein the flat plate-shaped porous member is provided on one or both sides thereof with a recess having a thickness smaller than that of the peripheral portion of the sample liquid supply portion. 【請求項３】 凹部が球面状に加工されたものであり、
その最も薄い部分の厚みが５０〜２００μｍである請求
項２記載の多孔性部材。3. The recess is processed into a spherical shape,
The porous member according to claim 2, wherein the thinnest portion has a thickness of 50 to 200 µm. 【請求項４】 凹部が球面状に加工されたものであり、
その最も薄い部分の厚みが平板部分の１／５〜４／５で
ある請求項２又は３記載の多孔性部材。4. The concave portion is processed into a spherical shape,
The porous member according to claim 2 or 3, wherein the thickness of the thinnest portion is 1/5 to 4/5 of that of the flat plate portion. 【請求項５】 ＳＵＳ、セラミック又は有機繊維よりな
る請求項１〜４いずれか記載の多孔性部材。5. The porous member according to claim 1, which is made of SUS, ceramic or organic fiber. 【請求項６】 質量分析装置が、液体クロマトグラフの
検出器として試料液が連続的に供給されるよう接続され
ているものである請求項３〜５いずれか記載の多孔性部
材。6. The porous member according to claim 3, wherein the mass spectrometer is connected as a detector of a liquid chromatograph so that the sample liquid is continuously supplied. 【請求項７】 高速原子衝突（ＦＡＢ）によりイオン化
を行う質量分析装置のイオン化部のターゲットとして、
平板状の多孔性部材の片面にその最も薄い部分の厚みが
５０〜２００μｍである球面状の凹部を形成した多孔性
部材を、該凹部が試料液の導入管を固定する弾性体の凸
部に圧接するよう設置することを特徴とする多孔性部材
の使用方法。7. A target of an ionization part of a mass spectrometer for performing ionization by fast atom collision (FAB),
A porous member having a spherical concave portion having a thinnest portion having a thickness of 50 to 200 μm formed on one surface of a flat plate-like porous member is used as a convex portion of an elastic body for fixing the sample liquid introducing tube. A method of using a porous member, characterized in that the porous member is installed so as to be in pressure contact.
JP7354493A 1995-12-28 1995-12-28 Porous member for mass spectrometer and its using method Pending JPH09190796A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7354493A JPH09190796A (en) 1995-12-28 1995-12-28 Porous member for mass spectrometer and its using method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7354493A JPH09190796A (en) 1995-12-28 1995-12-28 Porous member for mass spectrometer and its using method

Publications (1)

Publication Number Publication Date
JPH09190796A true JPH09190796A (en) 1997-07-22

Family

ID=18437942

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7354493A Pending JPH09190796A (en) 1995-12-28 1995-12-28 Porous member for mass spectrometer and its using method

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Country Link
JP (1) JPH09190796A (en)

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