JPH0746596B2 - Mass spectrometry method - Google Patents
Mass spectrometry methodInfo
- Publication number
- JPH0746596B2 JPH0746596B2 JP60287079A JP28707985A JPH0746596B2 JP H0746596 B2 JPH0746596 B2 JP H0746596B2 JP 60287079 A JP60287079 A JP 60287079A JP 28707985 A JP28707985 A JP 28707985A JP H0746596 B2 JPH0746596 B2 JP H0746596B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- ion
- mass
- ions
- energy
- 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.)
- Expired - Fee Related
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- Electron Tubes For Measurement (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Description
【発明の詳細な説明】 イ 産業上の利用分野 本発明は試料分子をイオン化し、試料から生成されたイ
オンが別途導入された中性分子或はイオンとどのような
反応を呈するかを質量分析的方法によつて調査する方法
に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial field of application The present invention mass-analyzes how a sample molecule is ionized and the ion generated from the sample reacts with a neutral molecule or ion introduced separately. The method of investigating by the statistical method.
ロ 従来の技術 質量分析には従来種々の手法が用いられている。最も一
般的なのは試料分子を電子衝撃によつてイオン化し、生
成される多種の断片イオンの質量スペクトルを測定する
もので、断片イオンの質量と強度のデータからもとの試
料分子の構造を再構成しようとするものである。CIイオ
ン化法による質量分析は、イオン化室内で反応ガスを電
子衝撃によりイオン化し、その中に試料分子を導入して
試料分子と反応ガスイオンとを結合させ、この結合によ
つて生じたイオンの質量を測定するもので、試料分子の
分子量を直接的に知ることができる。その他に試料のイ
オン化によつて生成されたイオンが更に自然に或はHeの
ような適当な不活性ガスのガス分子との衝突による衝撃
で開裂が促進されて生じる娘イオンの質量分析を行つ
て、もとのイオンの構造を調べる開裂イオン質量分析法
等が知られている。(B) Conventional technology Various methods have been conventionally used for mass spectrometry. The most common method is to ionize sample molecules by electron impact and measure the mass spectra of various fragment ions produced.The structure of the original sample molecule is reconstructed from the mass and intensity data of the fragment ions. Is what you are trying to do. In the mass spectrometry by CI ionization method, the reaction gas is ionized by electron impact in the ionization chamber, sample molecules are introduced into the ionization chamber to combine the sample molecules with the reaction gas ions, and the mass of the ions generated by this bond is measured. It is possible to directly know the molecular weight of the sample molecule. In addition, mass spectrometry of daughter ions generated by ionization of the sample, which is promoted by natural ionization or collision by collision with gas molecules of a suitable inert gas such as He, is carried out. Cleavage ion mass spectrometry, which investigates the structure of the original ion, is known.
試料の分析においては、単一の分析法で試料の全容が明
かになるものではなく、種々の分析法により得られる情
報を総合して、試料の構成が推測されるのであり、より
多種の情報を得ることによつて推測の確実性が高められ
るものである。この意味で新規な分析手法の開発は常に
望まれている所である。In the analysis of a sample, a single analysis method does not reveal the whole contents of the sample, but the composition of the sample is inferred by combining the information obtained by various analysis methods. By obtaining, the certainty of the guess can be increased. In this sense, the development of new analytical methods is always desired.
ハ 発明が解決しようとする問題点 新規な分析手法の開発が望まれていると云つても、余り
複雑な方法であつたり、特殊な装置を必要とするものは
経済性の面で好ましくない。本発明は通常の質量分析装
置に簡単な付加を行うだけで実行可能であり、手法的に
も簡単な新しい分析方法を提案するものである。C. Problems to be solved by the invention Even though it is desired to develop a new analysis method, a method that is too complicated or requires a special device is not preferable in terms of economical efficiency. The present invention proposes a new analysis method which can be carried out simply by adding a simple mass spectrometer to a general mass spectrometer and is also simple in method.
ニ 問題点解決のための手段 質量分析部とエネルギー分析部とよりなる質量分析計を
用い、質量分析部とエネルギー分析部との間に前後にイ
オンビームが通過できる開口を有する反応室を配置し、
この反応室に従来の不活性ガスの代わりにメタンとかア
ンモニア等の反応ガスを導入し、質量分析部で特定質量
のイオンを選択して上記反応室に入射させ、反応室にお
けるイオンと反応ガスとの反応によつて生成されたイオ
ンをエネルギー分析部でエネルギー分析する。D. Means for Solving Problems Using a mass spectrometer composed of a mass analysis section and an energy analysis section, a reaction chamber having an opening through which an ion beam can pass is arranged between the mass analysis section and the energy analysis section. ,
A reaction gas such as methane or ammonia is introduced into this reaction chamber instead of the conventional inert gas, ions of a specific mass are selected by the mass spectrometric unit and made incident on the reaction chamber, and ions and reaction gas in the reaction chamber Ions generated by the reaction of are subjected to energy analysis in the energy analysis unit.
ホ 作用 加速されたイオンと反応ガスとの反応にはイオンの特性
によつて種々な型がある。一つは電荷交換でイオンから
反応ガスに電荷が移り、イオンが中性化して中性分子ビ
ームを作る反応であるが、この反応によつて生ずる中性
分子ビームは本発明方法によつては扱えない。もう一つ
の反応はイオンと反応ガスとの単なる衝突によつてイオ
ンが活性化されて開裂する反応で、これは不活性ガス分
子を衝突させて開裂を促進させる場合と同じであり、こ
の反応で生ずる娘イオンについては衝突活性化法による
MIKE（Ｓ）（Mass analysed Ion Kinetic Energy Spect
roscopy）測定と同じである。本発明が利用する反応は
イオンと活性ガスとが結合し、この結合によつて生じた
イオンがもとと異る種々なイオンと中性分子とに開裂す
る反応で、この反応によつて生じたイオンのエネルギー
スペクトルを測定するものである。今質量分析部で選択
されたイオンの質量をＭ、反応ガスの質量をＮとする。
イオンを質量を表わす文字の右肩に十を付して表わす
と、イオン反応は M+＋Ｎ→（Ｍ＋Ｎ）+ ……………（１） のように書くことができる。ｎはもとのイオンから反応
ガスに移つた部分或は反応ガスからもとのイオンに移つ
た部分を示し、ｎ＝Ｎの場合（開裂を起さない）を含め
たＭ′+の質量を測定する。上記（１）（２）式の各反
応でエネルギーの出入がないものとすると、（２）式の
右辺のイオン及び分子が有する運動エネルギーの和は左
辺のイオン（Ｍ＋Ｎ）+の運動エネルギーと等しく、
（Ｍ＋Ｎ）+の運動のエネルギーは（１）式左辺のイオ
ン及び分子の運動エネルギーと等しく、Ｎの運動のエネ
ルギーはＭ+の運動エネルギーに比し無視できるので、
結句（２）式右辺のイオン及び分子の運動のエネルギー
の和はもとのイオンＭ+の運動のエネルギーと等しく、
これはイオン加速電圧によつて決まり、これをEoとす
る。（Ｍ＋Ｎ）+の開裂によつて生じたＭ′+とＮ′とは
同じ速度を持つているから、速度をＶとしＭ′+の運動
のエネルギーをＥ′とすると 上式から により、エネルギーＥ′のスペクトルからＭ′を求める
ことができる。（３）式のような状況は反応室にイオン
加速電圧と同程度（絶対値が加速電圧より大とならな
い）の電圧を印加した場合に作り易い。Photo-action There are various types of reactions between accelerated ions and reaction gas, depending on the characteristics of the ions. One is a reaction in which the charge is transferred from the ions to the reaction gas and the ions are neutralized to form a neutral molecular beam.The neutral molecular beam generated by this reaction is not generated by the method of the present invention. I can't handle it. The other reaction is a reaction in which the ions are activated and cleaved by mere collision between the ions and the reaction gas.This is the same as the case where an inert gas molecule collides with each other to promote the cleavage. The generated daughter ions are based on the collision activation method.
MIKE (S) (Mass analyzed Ion Kinetic Energy Spect
roscopy) Same as measurement. The reaction utilized in the present invention is a reaction in which an ion and an active gas are bound to each other, and the ion generated by this binding is cleaved into various different ions and neutral molecules, which is caused by this reaction. The energy spectrum of the ion is measured. It is assumed that the mass of the ions selected in the mass spectrometric unit is M and the mass of the reaction gas is N.
When an ion is expressed by adding a tens mark to the right shoulder of the character representing mass, the ion reaction is M + + N → (M + N) + …………… (1) Can be written as n represents the part transferred from the original ion to the reaction gas or the part transferred from the reaction gas to the original ion, and the mass of M ′ + including the case where n = N (not causing cleavage) is taking measurement. Assuming that there is no energy input and output in each reaction of the above equations (1) and (2), the sum of the kinetic energies of the ions and molecules on the right side of the equation (2) is equal to the kinetic energy of the ion (M + N) + on the left side. ,
The kinetic energy of (M + N) + is equal to the kinetic energy of the ions and molecules on the left side of equation (1), and the kinetic energy of N is negligible compared to the kinetic energy of M + .
The sum of the kinetic energies of the ions and molecules on the right side of the expression (2) is equal to the kinetic energy of the original ion M + ,
This is determined by the ion acceleration voltage, and this is designated as Eo. Since M ' + and N'generated by the cleavage of (M + N) + have the same velocity, let V be the velocity and E'be the kinetic energy of M' +. From the above formula Thus, M'can be obtained from the spectrum of energy E '. The situation like the formula (3) is easy to make when a voltage of the same level as the ion acceleration voltage (absolute value does not become larger than the acceleration voltage) is applied to the reaction chamber.
衝突活性化によるMIKES測定はもとのイオン単独の性質
に基く開裂パターンを調べるものであるが、本発明はも
とのイオンを反応ガスによつて変成した場合の開裂パタ
ーンを調べるもので、もとのイオンが反応ガスによつて
変性を受けるか受けないか、変性によつて開裂パターン
がどのように変化するか等が新しい分析情報となる。MIKES measurement by collision activation is to investigate the cleavage pattern based on the property of the original ion alone, but the present invention is to investigate the cleavage pattern when the original ion is denatured by the reaction gas. The new analytical information is whether or not the ions with and are not modified by the reaction gas, and how the cleavage pattern is modified by the modification.
ヘ 実施例 図は本発明方法を実施する装置の一例で磁場先行型二重
収束質量分析計である。Ｂは質量分析部の磁場、Ｅはエ
ネルギー分析部の電場、Ｉはイオン源、Ｄはイオン検出
器で、Ａが反応室である。反応室は前後に開口を有する
箱で、磁場Ｂにより形成される特定質量イオンのイオン
束の収束点に配置される。反応室にはガス導入管Ｇが接
続されていて、メタン、アンモニア等の反応ガスが供給
できるようになつている。F. Example FIG. 1 shows an example of an apparatus for carrying out the method of the present invention, which is a magnetic field precedent type double-focusing mass spectrometer. B is a magnetic field of the mass analysis unit, E is an electric field of the energy analysis unit, I is an ion source, D is an ion detector, and A is a reaction chamber. The reaction chamber is a box having openings in the front and back, and is arranged at the convergence point of the ion flux of the specific mass ions formed by the magnetic field B. A gas introduction pipe G is connected to the reaction chamber so that reaction gases such as methane and ammonia can be supplied.
上述装置で試料をイオン化して生成される断片イオンか
ら選択した特定質量のイオンが反応室Ａの中央に収束す
るように磁場を設定し、反応室に反応ガスを導入して選
択された質量のイオンと反応させる。反応によつて生じ
たイオンは反応室を通り抜けエネルギー分析部の電場Ｅ
に入射し、電場Ｅを掃引することによつて、反応によつ
て生じたイオンのエネルギースペクトルが求まり、この
スペクトルは前記（３）式によつて質量スペクトルに変
換される。The magnetic field is set so that the ions of a specific mass selected from the fragment ions generated by ionizing the sample with the above-described device are converged in the center of the reaction chamber A, and the reaction gas is introduced into the reaction chamber to introduce the selected mass React with ions. The ions generated by the reaction pass through the reaction chamber and the electric field E of the energy analysis unit
The energy spectrum of the ions generated by the reaction is obtained by injecting into and the electric field E is swept, and this spectrum is converted into a mass spectrum by the above equation (3).
衝突活性化或は自然開裂による開裂反応の場合のMIKES
測定では開裂イオンの質量Ｍ″、エネルギーＥ″、もと
のイオンの質量Ｍ、エネルギーEoとすると で表わされ、前記（３）式による反応イオンのエネルギ
ースペクトルと上式による開裂イオンのエネルギースペ
クトルの中には重なるもの（例えばＭ′+＝（Ｍ＋Ｎ）+
の場合と未開裂イオンＭは同じエネルギーEoを有する）
がある。上述実施例では直接的にはこの重なりを識別で
きないが、エネルギー分析用電場の後に更に質量分析用
磁場を配置した構成を用いると上述した識別ができる。MIKES in the case of cleavage reaction by collision activation or spontaneous cleavage
In the measurement, it is assumed that the fragmented ion mass M ″, energy E ″, original ion mass M, and energy Eo The energy spectrum of the reaction ion according to the above formula (3) and the energy spectrum of the cleavage ion according to the above formula overlap (for example, M ′ + = (M + N) +
And the uncleaved ion M has the same energy Eo.
There is. In the above-mentioned embodiment, this overlap cannot be directly identified, but the above-mentioned identification can be performed by using a configuration in which the magnetic field for mass analysis is further arranged after the electric field for energy analysis.
ト 効果 本発明方法は上述したような内容で、装置としては二重
収束型質量分析計に反応室を付加するだけでよく、この
付加によつて質量分析計の従来の用法は妨げられない
上、反応室は導入ガスの選択により衝突活性化法による
MIKES測定にも利用できるので、本発明方法は他の質量
分析手法と容易に併用できる利点があり、分析情報の拡
大に非常に有効である。The effect of the method of the present invention is as described above, and as a device, it is sufficient to add a reaction chamber to the double-focusing mass spectrometer, and this addition does not hinder the conventional usage of the mass spectrometer. , The reaction chamber is based on collision activation method by selecting the introduced gas
Since it can also be used for MIKES measurement, the method of the present invention has an advantage that it can be easily used in combination with other mass spectrometry methods, and is very effective for expanding analysis information.
図面は本発明方法を実施する装置の一例の平面図であ
る。The drawing is a plan view of an example of an apparatus for carrying out the method of the present invention.
Claims (1)
置を用い、質量分析部とエネルギー分析部との間に反応
室を配置してメタンとかアンモニア等の反応ガスを導入
し、質量分析部で選択された特定質量のイオンが上記反
応室を通過する際に同反応室内で行われる上記イオンと
反応ガスとの反応によって生成されるイオンについてエ
ネルギー分析部でエネルギースペクトル測定を行うこと
を特徴とする質量分析方法。1. A device having a mass spectrometric section and an energy spectroscopic section is used, a reaction chamber is arranged between the mass spectrometric section and the energy spectroscopic section, and a reaction gas such as methane or ammonia is introduced into the mass spectrometric section. It is characterized in that an energy spectrum measurement is performed by an energy analysis unit for an ion generated by a reaction between the ion and the reaction gas performed in the reaction chamber when the selected ion having a specific mass passes through the reaction chamber. Mass spectrometric method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60287079A JPH0746596B2 (en) | 1985-12-20 | 1985-12-20 | Mass spectrometry method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60287079A JPH0746596B2 (en) | 1985-12-20 | 1985-12-20 | Mass spectrometry method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62168332A JPS62168332A (en) | 1987-07-24 |
| JPH0746596B2 true JPH0746596B2 (en) | 1995-05-17 |
Family
ID=17712781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60287079A Expired - Fee Related JPH0746596B2 (en) | 1985-12-20 | 1985-12-20 | Mass spectrometry method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0746596B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60253964A (en) * | 1984-05-31 | 1985-12-14 | Shimadzu Corp | Method for analyzing and recording ion cleavage reaction |
-
1985
- 1985-12-20 JP JP60287079A patent/JPH0746596B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62168332A (en) | 1987-07-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |