JPH047538B2 - - Google Patents
Info
- Publication number
- JPH047538B2 JPH047538B2 JP59153773A JP15377384A JPH047538B2 JP H047538 B2 JPH047538 B2 JP H047538B2 JP 59153773 A JP59153773 A JP 59153773A JP 15377384 A JP15377384 A JP 15377384A JP H047538 B2 JPH047538 B2 JP H047538B2
- Authority
- JP
- Japan
- Prior art keywords
- field
- superimposed
- electric field
- ion
- magnetic field
- 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
Links
- 150000002500 ions Chemical class 0.000 claims description 58
- 230000005684 electric field Effects 0.000 claims description 34
- 238000004949 mass spectrometry Methods 0.000 claims description 13
- 238000004885 tandem mass spectrometry Methods 0.000 claims description 8
- 238000002545 neutral loss scan Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 238000010408 sweeping Methods 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/022—Circuit arrangements, e.g. for generating deviation currents or voltages ; Components associated with high voltage supply
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、２つの質量分析装置を接続した所謂
MS／MS装置に関し、特に互いに直交する方向
を持つ電場と磁場を重畳した重畳場を備えた重畳
場質量分析装置を後段の質量分析装置として用
い、解裂の際特定の質量を持つ中性分子（粒子）
を派生するすべての親イオンを知るいわゆるニユ
ートラルロススキヤンを行うことのできるMS／
MS装置に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a so-called mass spectrometer that connects two mass spectrometers.
Regarding MS/MS devices, in particular, a superimposed field mass spectrometer equipped with a superimposed field in which an electric field and a magnetic field having directions orthogonal to each other are superimposed is used as a subsequent mass spectrometer to detect neutral molecules with a specific mass during disintegration. (particle)
MS/MS that can perform so-called neutral loss scanning to know all the parent ions derived from
This relates to MS equipment.
［従来の技術］
質量分析の分野における分析技術の進歩は著し
く、Ｂ／ＥスキヤンやB2／Ｅスキヤン等のリン
クドスキヤン法が一般に広く行われるようになつ
てきた。このリンクドスキヤン法は、磁場Ｂと電
場Ｅを接続した質量分析装置において、Ｂ／Ｅあ
るいはB2／Ｅの値が一定になるような関係を保
つて磁場Ｂ及び電場Ｅを連動でスキヤンするもの
で、特定の親イオンから派生したすべての娘イオ
ン、あるいは特定の質量の娘イオンを派生するす
べての親イオンを検出する測定方法である。[Prior Art] Analysis technology in the field of mass spectrometry has made remarkable progress, and linked scan methods such as B/E scan and B 2 /E scan have become widely used. In this linked scan method, in a mass spectrometer that connects magnetic field B and electric field E, magnetic field B and electric field E are scanned in conjunction with each other while maintaining a relationship such that the value of B/E or B 2 /E is constant. It is a measurement method that detects all daughter ions derived from a specific parent ion, or all parent ions that derive daughter ions of a specific mass.
［発明が解決しようとする問題点］
一方、近時リンクドスキヤン法の１つとしてニ
ユートラルロススキヤンと呼ばれるスキヤン法が
発表されている。このニユートラルロススキヤン
法は、解裂の際特定の質量を持つ中性分子（粒
子）を派生するすべての親イオンを検出するもの
である。本発明は、重畳場質量分析装置を後段の
質量分析装置として用いたMS／MS装置におい
て、このニユートラルロススキヤン法を行うこと
のできる装置を実現することを目的としている。[Problems to be Solved by the Invention] On the other hand, a scan method called neutral loss scan has recently been announced as one of the linked scan methods. This neutral loss scan method detects all parent ions that, when cleaved, produce neutral molecules (particles) with a specific mass. An object of the present invention is to realize an MS/MS apparatus that uses a superimposed field mass spectrometer as a subsequent mass spectrometer and is capable of performing this neutral loss scan method.
［問題点を解決するための手段］
本発明にかかるMS／MS装置は、イオン源と、
該イオン源で生成されたイオンが導入される少な
くとも磁場を備えた第１の質量分析系と、該第１
の質量分析系の後方に配置され、互いに直交する
方向を持つ電場と磁場を重畳した重畳場を少なく
とも備えた第２の質量分析系と、該第２の質量分
析系を通過したイオンを検出するイオン検出器
と、前記第１と第２の質量分析系の間のイオン通
路に配置される衝突室とから成り、重畳場の電場
電圧をVp、Ｋを定数、ｍを変数としてVp−ｋ／
ｍに比例して掃引すると共に、それに連動して前
記第１の質量分析系の磁場の強度を√に比例し
て掃引するようにしたことを特徴としている。[Means for solving the problems] The MS/MS device according to the present invention includes an ion source,
a first mass spectrometry system comprising at least a magnetic field into which ions generated by the ion source are introduced;
a second mass spectrometry system that is disposed behind the mass spectrometry system and includes at least a superimposed field in which an electric field and a magnetic field having directions orthogonal to each other are superimposed, and detects ions that have passed through the second mass spectrometry system. It consists of an ion detector and a collision chamber placed in the ion path between the first and second mass spectrometry systems, and the electric field voltage of the superimposed field is V p , K is a constant, and m is a variable, and V p - k/
It is characterized in that it is swept in proportion to m, and in conjunction therewith, the intensity of the magnetic field of the first mass spectrometry system is swept in proportion to √.
［実施例］
第１図は本発明の一実施例を示す断面図であ
り、第２図はそのＣ−Ｃ断面図である。両図にお
いて１はイオン源、２は該イオン源で生成された
イオンが導入される磁場、３は該磁場２を通過し
たイオンを衝突解離させる衝突室、４は重畳場、
５はイオンコレクタである。６は磁場２を発生さ
せるための磁場電源、７は重畳場４の磁場を発生
させるための磁場電源、８は重畳場４の電場を発
生させるための電極９，９′に電圧を供給するた
めの電場電源、１０，１１は磁場２と重畳場の電
場を掃引するための信号を演算により求める演算
回路、１２は該演算回路１０，１１へ質量掃引信
号を供給するための質量掃引回路である。[Embodiment] FIG. 1 is a sectional view showing an embodiment of the present invention, and FIG. 2 is a sectional view taken along the line C-C. In both figures, 1 is an ion source, 2 is a magnetic field into which ions generated by the ion source are introduced, 3 is a collision chamber for colliding and dissociating ions that have passed through the magnetic field 2, 4 is a superimposed field,
5 is an ion collector. 6 is a magnetic field power supply for generating the magnetic field 2; 7 is a magnetic field power supply for generating the magnetic field of the superimposed field 4; 8 is for supplying voltage to the electrodes 9 and 9' for generating the electric field of the superimposed field 4. 10 and 11 are arithmetic circuits that calculate signals for sweeping the electric field of the magnetic field 2 and the superimposed field, and 12 is a mass sweep circuit that supplies mass sweep signals to the arithmetic circuits 10 and 11. .
かかる構成において、イオン源１で生成された
試料イオン（親イオン）は、先ず磁場２に入射す
る。該磁場２の強度をH1とすれば、該磁場２を
通過する試料イオンの質量ｍは、ａを定数として
下式で表わされる。 In this configuration, sample ions (parent ions) generated by the ion source 1 first enter the magnetic field 2 . Assuming that the strength of the magnetic field 2 is H1, the mass m of sample ions passing through the magnetic field 2 is expressed by the following formula, where a is a constant.
ｍ＝ａ（H12／Va） (1)
ここで、Vaはイオン加速電圧であり、測定中
一定であるからａ／Va＝A2と置き直して(1)式を
変形すれば下式が得られる。m=a(H1 2 /V a ) (1) Here, Va is the ion acceleration voltage and is constant during the measurement, so if we replace it with a/Va=A 2 and transform equation (1), we get the following equation. is obtained.
H1＝Ａ√ (2)
(1)式又は(2)式に従つて選択された親イオンは衝
突室３に入射するが、衝突室３内にはヘリウム等
の衝突ガスが適当な圧力になるように供給されて
おり、親イオンm+は衝突室内でヘリウム原子と
衝突し、下式に従つて中性粒子mpと娘イオン
m1+に分裂する。従つて、親イオンの質量ｍはｍ
＝（mp＋m1）と表わされる。H1=A√ (2) The parent ions selected according to equation (1) or (2) enter the collision chamber 3, and the collision gas such as helium is at an appropriate pressure in the collision chamber 3. The parent ion m + collides with the helium atom in the collision chamber, and the neutral particle m p and the daughter ion are separated according to the following formula:
Splits into m1 + . Therefore, the mass m of the parent ion is m
It is expressed as = (m p + m1).
重畳場の磁場強度Ho一定、イオン源における
イオン加速電圧Va一定の条件で、先ず重畳場に
おけるニユートラルロススキヤンについて考察す
る。 First, we will consider the neutral loss scan in the superimposed field under the conditions that the magnetic field strength Ho of the superimposed field is constant and the ion acceleration voltage Va in the ion source is constant.
衝突室で解離しなかつた親イオンが重畳場を通
過する条件は下式で示される。 The conditions under which parent ions that have not dissociated in the collision chamber pass through the superimposed field are expressed by the following equation.
（m1＋mp）vp 2／ｒ＝eEp＋evpHp (3)
ここで、voは親イオンの速度、Eoは重畳場に
おける電場強度、ｒは重畳場におけるイオン軌道
半径である。(m1+m p )v p 2 /r=eE p +ev p H p (3) Here, vo is the velocity of the parent ion, Eo is the electric field strength in the superimposed field, and r is the ion orbit radius in the superimposed field.
次に、重畳場の電場強度がE1の時に娘イオン
m1+が重畳場を通過するとすれば、下式が成立す
る。 Next, when the electric field strength of the superimposed field is E1, the daughter ion
If m1 + passes through the superimposed field, the following formula holds true.
m1＋vp 2／ｒ＝eE1＋evpHp (4) (3)式と(4)式から下式が成立する。m1+v p 2 /r=eE1+ev p H p (4) The following equation is established from equations (3) and (4).
mpvp 2／ｒ＝ｅ（Ep−E1） (5)
親イオンの持つエネルギーに関して下式が成立
するので、
mvp 2／２＝eVa (6)
これを(5)式に代入してvoを消去すると下式が
得られる。m p v p 2 /r=e(E p −E1) (5) Since the following formula holds regarding the energy of the parent ion, mv p 2 /2=eV a (6) Substitute this into equation (5) and eliminate vo, the following formula is obtained.
E1＝Ep−2Vamp／rn (7)
この(7)式を電極９，９′に印加する電場電圧で
示す。Ep，E1の時の電場電圧を夫々Vp，V1と
し、電極の間隔をｄとすれば、
Ep＝2Vp／ｄ，E1＝2V1／ｄが夫々成立するか
ら、これを(7)式に代入すると下式が得られる。E1=E p -2V a m p /r n (7) Expression (7) is expressed in terms of the electric field voltage applied to the electrodes 9 and 9'. If the electric field voltages at E p and E1 are V p and V1, respectively, and the electrode spacing is d, then E p = 2V p /d and E1 = 2V1 / d hold, respectively, so this can be expressed as (7) By substituting into the formula, the following formula is obtained.
V1＝Vp−Vampｄ／rm (8)
この(8)式において、Vaｄ／ｒ＝Vppとおくと、
(8)式は下式のように簡単化される。V1=V p −V a m p d/rm (8) In this equation (8), if we set V a d/r=V pp ,
Equation (8) can be simplified as shown below.
V1＝Vp−Vppmp／ｍ (9)
この(9)式においてVppは定数、mpも適宜な値に
設定するものであり定数である。従つて、(9)式は
ｋを定数として下式のように表わすことができ
る。V1=V p -V pp m p /m (9) In this equation (9), V pp is a constant, and m p is also set to an appropriate value and is a constant. Therefore, equation (9) can be expressed as the following equation with k as a constant.
V1＝Vp−ｋ／ｍ (10)
(8)式においてVpは予め測定できて既知である
から、ｍを変数としてV1を(10)式に従つて掃引す
れば、ニユートラルロススキヤンを行うことがで
きる。この時磁場２の強度H1は、質量ｍの親イ
オンを選択するため、(2)式に従つて掃引する必要
があることは言うまでもない。V1=V p −k/m (10) In equation (8), V p can be measured in advance and is known, so if m is a variable and V1 is swept according to equation (10), the neutral loss scan can be obtained. It can be carried out. At this time, it goes without saying that the intensity H1 of the magnetic field 2 needs to be swept according to equation (2) in order to select the parent ion with mass m.
第１図における演算回路１０，１１は上記(2)
式、(10)式に従う掃引を夫々行うためのもので、演
算回路１０は、適宜設定されるＡの値及び質量掃
引回路１２から送られて来るｍの値（時間と共に
掃引される）に基づいて(2)式を演算し、求めた
H1の値を磁場電源２へ送る。又、演算回路１１
は、予め着目した親イオンについて求めたVpと
定数ｋ、及び質量掃引回路１２から送られて来る
ｍの値に基づいて(10)式を演算し、求めたV1の値
を電場電源８へ送る。 The arithmetic circuits 10 and 11 in FIG. 1 are shown in (2) above.
The arithmetic circuit 10 performs sweeps according to equations (10) and (10), and the calculation circuit 10 performs sweeps based on the value of A that is set appropriately and the value of m (swept over time) sent from the mass sweep circuit 12. Calculate equation (2) using
Send the value of H1 to the magnetic field power supply 2. In addition, the arithmetic circuit 11
calculates equation (10) based on the V p and constant k determined in advance for the parent ion of interest, and the value of m sent from the mass sweep circuit 12, and sends the determined value of V1 to the electric field power source 8. send.
ところで、上記実施例では、後段の重畳場質量
分析装置は重畳場のみから構成されたが、このよ
うな構成では、重畳場に関する(9)式を満足する親
イオンと娘イオンの組合わせが多数存在し得るた
め、目的とする親イオンでない親イオンから派生
した娘イオンが混入して検出されてしまうことが
起こり得る。 By the way, in the above example, the subsequent superimposed field mass spectrometer was constructed from only the superimposed field, but in such a configuration, there are many combinations of parent ions and daughter ions that satisfy equation (9) regarding the superimposed field. Therefore, a daughter ion derived from a parent ion other than the intended parent ion may be mixed in and detected.
第３図は、後段の重畳場質量分析装置として、
電場と重畳場から成る重畳場質量分析装置を用い
た本発明の他の実施例の構成を示し、第１図の実
施例と異なるのは、重畳場４と衝突室３との間に
電場１３が配置される点である。第３図におい
て、１４は電場１３を発生するための電極１５，
１５′に電圧を供給するための電場電源、１６は
該電場１３を掃引するための信号を演算により求
める演算回路である。 Figure 3 shows the superimposed field mass spectrometer in the latter stage.
The configuration of another embodiment of the present invention using a superimposed field mass spectrometer consisting of an electric field and a superimposed field is shown, and the difference from the embodiment shown in FIG. is the point where is placed. In FIG. 3, 14 is an electrode 15 for generating the electric field 13;
An electric field power source 15' supplies voltage, and 16 is an arithmetic circuit that calculates a signal for sweeping the electric field 13.
今、衝突室３で解裂しなかつた親イオンが電場
１３を通過する時には、
mvp 2／re＝−eV20／d1 （11）
が成立し、娘イオンが該電場を通過する時には
（ｍ−mp）vp 2／re＝−eV2／d1 （12）
が成立する。ここで、reは電場１３のイオン軌道
半径、d1は電極１５，１５′の間隔、V20，V2は
親イオン、娘イオンが電場を通過する時の電場電
圧を夫々示す。 Now, when the parent ion that has not disintegrated in the collision chamber 3 passes through the electric field 13, mv p 2 / re = -eV20/d1 (11) holds, and when the daughter ion passes through the electric field, (m −m p )v p 2 / re = −eV2/d1 (12) holds. Here, r e is the ion orbital radius of the electric field 13, d1 is the distance between the electrodes 15 and 15', and V20 and V2 are the electric field voltages when the parent ion and daughter ion pass through the electric field, respectively.
（11）、（12）式からvpとd1を削除すると下式が
得られる。 By deleting v p and d1 from equations (11) and (12), the following equation is obtained.
V2＝V20（ｍ−mo）／ｍ （13）
従つて、磁場２の強度H1を(2)式に従つて、重
畳場の電場電圧V1を(10)式に従つて夫々掃引する
と共に、それに連動して電場１３の電場電圧V2
を（13）に従つて掃引すれば、目的とする親イオ
ンm+のみが磁場２を通過して衝突室３へ入射し、
その目的とする親イオンから派生した娘イオンの
みが電場１３を通過し、更に重畳場を通過するこ
とができ、所望でない娘イオンを除いたニユート
ラルロススキヤンを行うことができる。V2=V20(m-mo)/m (13) Therefore, the strength H1 of magnetic field 2 is swept according to equation (2), the electric field voltage V1 of the superimposed field is swept according to equation (10), and Interlockingly, the electric field voltage V2 of electric field 13
If is swept according to (13), only the target parent ion m + passes through the magnetic field 2 and enters the collision chamber 3,
Only the daughter ions derived from the intended parent ion can pass through the electric field 13 and further through the superimposed field, making it possible to perform a neutral loss scan that excludes undesired daughter ions.
第３図における演算回路１６は、上記（13）式
に従つて電場１３の掃引を行うためのもので、該
演算回路１６は、予め着目した親イオンについて
測定したV20の値とオペレータによつて選ばれた
mpの値、及び質量掃引回路１２から送られて来
るｍの値（時間と共に掃引される）に基づいて
（13）式を演算し、求めたV2の値を電場電源へ送
る。 The calculation circuit 16 in FIG. 3 is for sweeping the electric field 13 according to the above equation (13). Was chosen
Equation (13) is calculated based on the value of m p and the value of m (swept over time) sent from the mass sweep circuit 12, and the calculated value of V2 is sent to the electric field power source.
［効果］
以上詳述した如く、本発明によれば(2)式と(10)
式、又は(2)式と(10)式と（13）式に従う簡単な掃引
を行うことにより、容易にニユートラルロススキ
ヤンを行うことのできる重畳場質量分析装置を後
段の質量分析装置として用いたMS／MS装置が
実現される。[Effect] As detailed above, according to the present invention, formula (2) and (10)
A superimposed field mass spectrometer that can easily perform a neutral loss scan can be used as a subsequent mass spectrometer by performing a simple sweep according to the following equations, or equations (2), (10), and (13). A new MS/MS device will be realized.
第１図は本発明の一実施例を示す断面図、第２
図はそのＡ−Ａ断面図、第３図は本発明の他の実
施例の構成を示す断面図である。
１：イオン源、２：磁場、３：衝突室、４：重
畳場、５：イオンコレクタ、６，７：磁場電源、
８，１４：電場電源、９，９′，１５，１５′：電
極、１０，１１，１６：演算回路、１２：質量掃
引回路、１３：電場。
FIG. 1 is a cross-sectional view showing one embodiment of the present invention, and FIG.
The figure is a sectional view taken along the line AA, and FIG. 3 is a sectional view showing the structure of another embodiment of the present invention. 1: ion source, 2: magnetic field, 3: collision chamber, 4: superimposed field, 5: ion collector, 6, 7: magnetic field power supply,
8, 14: Electric field power source, 9, 9', 15, 15': Electrode, 10, 11, 16: Arithmetic circuit, 12: Mass sweep circuit, 13: Electric field.
Claims (1)
が導入される少なくとも磁場を備えた第１の質量
分析系と、該第１の質量分析系の後方に配置さ
れ、互いに直交する方向を持つ電場と磁場を重畳
した重畳場を少なくとも備えた第２の質量分析系
と、該第２の質量分析系を通過したイオンを検出
するイオン検出器と、前記第１と第２の質量分析
系の間のイオン通路に配置される衝突室とから成
り、重畳場の電場電圧を、Vp、ｋを定数、ｍを
変数としてVp−ｋ／ｍに比例して掃引すると共
に、それに連動して前記第１の質量分析系の磁場
の強度を√に比例して掃引するようにしたこと
を特徴とするMS／MS装置。 ２ 前記第２の質量分析系は電場と重畳場とから
成り、該電場の強度を、前記磁場及び重畳場の電
場の掃引に連動して（ｍ−mp）／ｍに比例して
掃引するようにしたことを特徴とする特許請求の
範囲第１項記載のMS／MS装置。[Scope of Claims] 1. An ion source, a first mass spectrometry system equipped with at least a magnetic field into which ions generated by the ion source are introduced, and an ion source disposed behind the first mass spectrometry system and arranged at a distance from each other. a second mass spectrometry system that includes at least a superimposed field in which an electric field and a magnetic field having orthogonal directions are superimposed; an ion detector that detects ions that have passed through the second mass spectrometry system; and a collision chamber placed in the ion passage between the mass spectrometer systems, and sweeps the electric field voltage of the superimposed field in proportion to V p -k/m with V p and k as constants and m as a variable. , an MS/MS apparatus characterized in that, in conjunction with this, the strength of the magnetic field of the first mass spectrometry system is swept in proportion to √. 2 The second mass spectrometry system consists of an electric field and a superimposed field, and sweeps the intensity of the electric field in proportion to (m-m p )/m in conjunction with the sweep of the electric field of the magnetic field and the superimposed field. An MS/MS apparatus according to claim 1, characterized in that the MS/MS apparatus is configured as follows.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59153773A JPS6132344A (en) | 1984-07-24 | 1984-07-24 | Ms/ms system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59153773A JPS6132344A (en) | 1984-07-24 | 1984-07-24 | Ms/ms system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6132344A JPS6132344A (en) | 1986-02-15 |
| JPH047538B2 true JPH047538B2 (en) | 1992-02-12 |
Family
ID=15569819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59153773A Granted JPS6132344A (en) | 1984-07-24 | 1984-07-24 | Ms/ms system |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6132344A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118297B2 (en) * | 1988-04-01 | 1995-12-18 | 日本電子株式会社 | MS / MS device |
-
1984
- 1984-07-24 JP JP59153773A patent/JPS6132344A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6132344A (en) | 1986-02-15 |
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