JP5322385B2 - 質量分析器におけるイオン集団の制御 - Google Patents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
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- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
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Description
本願は、2003年1月24日提出の米国仮出願No.60/442,368および2003年6月5日提出の米国仮出願60/476,473に利益を請求し、その両方を参照により本願に組み込む。
本発明は、質量分析計におけるイオン集団の制御に関する。
ω=qB/m
(式中、ω=角周波数、q=イオン電荷、B=磁場強度、およびm=イオン質量)この単純化した等式は、イオンの周波数に対する電場の影響を無視している。参照により本願に組み込む、Franclら“Experimental Determination of the Effects of Space Charge on Ion Cyclotron Resonance Frequencies”Int.J.Mass Spectrom.Ion Processes,54,1983,p.189−199に記載されるように、ICRセルにおけるイオンのサイクロトロン周波数は、以下のように近似することができる:
ω=qB/m−2αV/a2B−qρGi/ε0B
(式中、αはセル幾何定数であり、Vは捕獲電圧であり、aはセル径であり、ρはイオン密度であり、Giはイオン雲幾何定数であり、ε0は、自由空間の許容度である。)
したがって、FTICR内のイオン集団が変化してもよい場合には、イオンが、セルおよび磁石の場に加えて別のイオンの静電場との相互作用によって移動し、結果として測定ピーク位置が移動する。これによる質量移動はわずか10数ppmであるので、比較的小さな問題とされてきた。しかしながら、分析への要求が進むにつれて、1ppmの範囲の質量精度を得ることが望まれるようになってきた。
本発明は、所定のイオン集団を蓄積させ、蓄積したイオン集団を質量分析計の分析セルまたは一部に移送することにより、質量分析計内でイオン集団を制御する方法および装置を提供する。
図1に示すように、本発明の1つの態様に従う質量分析計130において、イオン集団を制御するために用いることのできる装置/システム100は、イオンアキュムレータ120(イオンアキュムレータ電子部150を付属)と連絡するイオン源115と、検出器125(検出器電子部155を付属)と、質量分析計130とを含む。システム100のいくつかまたはすべての部品は、様々な部品からのデータを受け取って処理し、受け取ったデータに対する分析を実施するように構成してもよい、適切にプログラムされたデジタルコンピュータ145などのシステム制御部に連結してもよい。
T注入-最適=(Q検出-最適 /Q 検出AGC-前実験 )×T注入-前実験
(式中、Tは時間を表し、Qは検出されたイオン電荷(検出イオン電流の積分)を表す)イオンアキュムレータ120および質量分析計130によって課される限定または制限は、最適イオン集団(すなわち、注入時間間隔全体にわたって蓄積されるイオン集団)が、イオンアキュムレータ120内の最適イオン集団か、質量分析計130の分析セル135内の最適イオン集団かのいずれに対応するかを指示するものであってもよい。イオンアキュムレータ120内および/または質量分析計130の分析セル135内のイオン集団を調節することにより、システム100を最適容量で動作するように調整することができる。すなわち、所定の注入時間間隔だけイオンを蓄積させることにより、イオンアキュムレータ120または質量分析計130の分析セル135を、該素子を飽和させないその最大容量まで充填するイオン集団が得られる(すなわち、望ましくない空間電荷効果をもたらすことはない)。
Claims (2)
- 質量分析器の作動方法であって、該方法は、以下:
前駆体イオンを蓄積し、該蓄積された前駆体イオンに由来する生成イオンを該質量分析器に導入することによって、該質量分析器に導入される生成イオン集団を制御する工程を包含し、該前駆体イオンは、イオン蓄積速度と目標前駆体イオン集団とに基づいて決定される期間の間蓄積され、該目標前駆体イオン集団は、最適生成イオン集団を生成する目標前駆体イオンの集団であり、該最適生成イオン集団は、これを超えると該生成イオンが前記質量分析器に導入された際にm/z割り当てに誤差が生じる生成イオン集団であり、該蓄積速度は、前駆体イオン源からイオンアキュムレータへのイオンの流速を表し、該蓄積速度は、イオンビームの一部分を検出器に転向させることによって測定され、一方で該イオンビームの残りの部分が前記イオンアキュムレータに移送される、方法。 - 質量分析器を作動させるために情報担体上で明白に具現されるコンピュータプログラムであって、該コンピュータプログラムは、プログラム可能なプロセッサに作動可能に連結された質量分析計を含む装置に、以下:
a)イオン源から質量分析計に延びるイオン路に沿って、前記イオン源と前記質量分析器との間にあるイオンアキュムレータへイオンサンプルを導入させ、
b)該イオンサンプル由来のイオンをサンプリング時間間隔の間蓄積させ、
c)蓄積されたイオン由来の実質的に全てのイオンを前記イオンアキュムレータから排出し;
d)排出されたイオンの少なくとも一部を検出させ、
e)前記イオンアキュムレータへのイオンの蓄積速度を、前記検出、前記時間間隔及び前記一部に基づいて決定する工程;
f)前記蓄積速度及び目標イオン集団に基づいて注入時間間隔を決定させ、該注入時間間隔は、前記目標イオン集団を前記イオンアキュムレータに蓄積するための時間間隔を表し、該目標イオン集団は、前記イオンアキュムレータ内での衝突誘起解離による前記イオンの解離の間に最適生成イオン集団を生成するイオン集団であり、該最適生成イオン集団は、これを超えると該生成イオンが前記質量分析器に導入された際にm/z割り当てに誤差が生じる生成イオン集団である、
g)該注入時間間隔に対応する時間の間前記装置内の第2のイオンサンプルを蓄積させ、
h)前記装置内において特定の質量電荷比または範囲を有する該第2のイオンサンプルのサブセットを単離し、
i)前記装置内において前記第2のイオンサンプルのサブセットから前記生成イオンを発生させ、そして
j)前記生成イオンを質量分析計に導入させる働きをする命令
を含む、コンピュータプログラム。
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Application Number | Priority Date | Filing Date | Title |
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US44236803P | 2003-01-24 | 2003-01-24 | |
US60/442,368 | 2003-01-24 | ||
US47647303P | 2003-06-05 | 2003-06-05 | |
US60/476,473 | 2003-06-05 | ||
PCT/US2004/001810 WO2004068523A2 (en) | 2003-01-24 | 2004-01-23 | Controlling ion populations in a mass analyzer |
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JP2006517723A JP2006517723A (ja) | 2006-07-27 |
JP5322385B2 true JP5322385B2 (ja) | 2013-10-23 |
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US (1) | US6987261B2 (ja) |
EP (2) | EP2385543B1 (ja) |
JP (1) | JP5322385B2 (ja) |
CN (2) | CN100550275C (ja) |
CA (1) | CA2514343C (ja) |
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CN101685755A (zh) | 2010-03-31 |
US6987261B2 (en) | 2006-01-17 |
WO2004068523A3 (en) | 2005-10-27 |
CN100550275C (zh) | 2009-10-14 |
US20040217272A1 (en) | 2004-11-04 |
EP1586104A2 (en) | 2005-10-19 |
EP2385543B1 (en) | 2013-05-08 |
EP2385543A1 (en) | 2011-11-09 |
CN101685755B (zh) | 2011-12-14 |
CA2514343C (en) | 2010-04-06 |
CA2514343A1 (en) | 2004-08-12 |
CN1777975A (zh) | 2006-05-24 |
WO2004068523A2 (en) | 2004-08-12 |
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