JPS6326571A - Analyzing instrument directly coupled to ultracritical fluid chromatograph and mass spectrometer - Google Patents
Analyzing instrument directly coupled to ultracritical fluid chromatograph and mass spectrometerInfo
- Publication number
- JPS6326571A JPS6326571A JP61170549A JP17054986A JPS6326571A JP S6326571 A JPS6326571 A JP S6326571A JP 61170549 A JP61170549 A JP 61170549A JP 17054986 A JP17054986 A JP 17054986A JP S6326571 A JPS6326571 A JP S6326571A
- Authority
- JP
- Japan
- Prior art keywords
- standard sample
- ion
- ion source
- mass spectrometer
- sample
- 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
Links
- 239000012530 fluid Substances 0.000 title claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 15
- 238000000451 chemical ionisation Methods 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims description 37
- 238000004458 analytical method Methods 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000004808 supercritical fluid chromatography Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
（嗜 従来技術
質量分析計（マススペクトロメータ）（ＭＳ）は、高感
度、高選択性訃よび化合物の構造決定能力を有する点で
理想的なりロマトグラフの検出器と考えられている。従
って、ガスクロマトグラフ・マススペクトロメータｆＬ
結ＩＬｉｆｌＥ （ＧＣＭＳ）は多成分混合試料の分離
・定量一定性分析のための有力な手段として広範な分野
で利用されている。Detailed Description of the Invention (a) Industrial Application Fields Conventional mass spectrometers (MS) are ideal in that they have high sensitivity, high selectivity, and the ability to determine the structure of compounds. It is considered to be a chromatograph detector.Therefore, a gas chromatograph/mass spectrometer fL
GCMS is used in a wide range of fields as a powerful means for separation and quantitative constant analysis of multi-component mixed samples.
しかし、この方法も非揮発性物質や加熱気化過程で分解
−変性を起こす熱的不安定物質には適用できないという
原理的な制約がある。However, this method also has a fundamental limitation in that it cannot be applied to nonvolatile substances or thermally unstable substances that undergo decomposition and denaturation during the heating vaporization process.
これに対して、高速液体クロマトグラフ（ＨＰＬＣ）Ｋ
は、との制約がなく、熱的不安定物質の多い生化学分野
や医薬品・食品分野等で特に賞月されている。しかし、
ＨＰＬＣとＭ Ｓの直結においては、溶媒除去その他技
術的に解決を要する問題が残されてシシ、数種の市販商
品は現れているが、５ｊ！用土十分満足なＨＰＬＣ・Ｍ
Ｓ直結装置は未だ開発段階にあるとみられている。In contrast, high performance liquid chromatography (HPLC) K
It is especially prized in the biochemistry field, pharmaceutical and food fields, etc., which have many thermally unstable substances, as there are no restrictions. but,
In the direct connection of HPLC and MS, there remain problems such as solvent removal and other technical problems that need to be solved.Although several commercially available products have appeared, 5j! HPLC/M with sufficient soil
It is believed that the S direct connection device is still in the development stage.
一方、ＨＰＬＣに比べて、よシ優れた分離能をもち、か
つガスクロマトグラフに適用できない非揮発性物質や熱
不安定物質も分析対象とし得る超臨界流体クロマトグラ
フ（ｓｔ’ｃ）が最近注目されている。特に、キャピラ
リカラム全周いたＳＦＣでは移動相が低流量であシ、か
つ、高揮発性移動相の使用により、ＳＦＣ−ＭＳの直結
が容易となるメリットを有している。特に、電子衝撃イ
オン化に比して高イオン源圧力下で動作する化学イオン
化（ＣＩ）を用いるＭＳへの直結がよシ容易となる。On the other hand, supercritical fluid chromatography (ST'C) has recently attracted attention because it has superior separation performance compared to HPLC and can also analyze non-volatile substances and thermally unstable substances that cannot be applied to gas chromatography. ing. In particular, SFC with a capillary column all around it has the advantage of requiring a low mobile phase flow rate and using a highly volatile mobile phase, which facilitates direct SFC-MS connection. In particular, direct coupling to MS using chemical ionization (CI), which operates under high ion source pressures, is easier than with electron impact ionization.
第三図に従来行われている一般的な超臨界流体クロマト
グラフ・質楚分析計直結装置の構成図を示す。超臨界ク
ロマトグラフ１は試料注入部、キャピラリーカラム、ク
ロマトグラフ用オーブン。Figure 3 shows a configuration diagram of a conventionally used general supercritical fluid chromatograph/quality analyzer direct connection device. Supercritical chromatograph 1 includes a sample injection section, a capillary column, and a chromatograph oven.
温度制御部、移動相流通用ポンプ、圧力側（資）部等よ
り成っている。カラム出口はカットオフパルプ２と伝送
路３で構成されるインターフェースを介して質量分析計
のイオン源６に接続される。インターフェースもイオン
源も加熱および温度制御されている。イオン源６には、
化学イオン化用試薬ガスがガス供給フィン４から供給さ
れ、イオン源内圧力は圧力モニター５で監視される。イ
オン源６で生成したイオンは四重極マスフィ！レターと
イオン検出器で構成される質量分析部７で測定され。It consists of a temperature control section, a mobile phase circulation pump, a pressure side (supply) section, etc. The column outlet is connected to an ion source 6 of a mass spectrometer via an interface consisting of a cutoff pulp 2 and a transmission line 3. Both the interface and the ion source are heated and temperature controlled. The ion source 6 includes
A reagent gas for chemical ionization is supplied from a gas supply fin 4, and the pressure inside the ion source is monitored by a pressure monitor 5. Ions generated by ion source 6 are quadrupole mass fi! It is measured by a mass spectrometer 7 consisting of a letter and an ion detector.
コンピューターシステム１０でテ゛−タ処理、出力の表
示−記録が行われる。コンピューターシステム１０は分
析装置各部の動作制御・集注設定も行っている。イオン
源６と質量分析部７は排気管８゜９にそれぞれ接続され
た真空ポンプにより排気される。A computer system 10 processes the data and displays and records the output. The computer system 10 also controls the operation and collection settings of each part of the analyzer. The ion source 6 and the mass spectrometer 7 are evacuated by vacuum pumps connected to exhaust pipes 8.9, respectively.
（ハ）発明が解決しようとする問題点
超臨界クロマトグラフが圧力プログラミングによる動作
を行う場合、イオン源に流入する移動相流量が変化し、
その結果、イオン源内圧力も変化するのでイオン化効率
も同様に変化することになる。化学イオン化用試薬ガス
は超臨界流体クロマトグラフの移動相と同じものが用い
られる場合や異なる種類の試薬ガヌが用いられる場合も
ある。特に、移動相と異なる試薬ガスを用いる場合。(c) Problems to be solved by the invention When a supercritical chromatograph operates by pressure programming, the flow rate of the mobile phase flowing into the ion source changes.
As a result, the pressure inside the ion source also changes, so the ionization efficiency also changes. The reagent gas for chemical ionization may be the same as the mobile phase of supercritical fluid chromatography, or a different type of reagent gas may be used. Especially when using a reagent gas different from the mobile phase.
圧力プログラミングに伴う移動相流量変化が試薬ガスの
流量をも変化さすことくなり、化学イオン化における反
応イオン生成効率の変化ひいては試料イオンの生成効率
が変化してしまうことになる。Changes in the mobile phase flow rate due to pressure programming also change the flow rate of the reagent gas, resulting in changes in the reaction ion production efficiency in chemical ionization and, ultimately, in the sample ion production efficiency.
に）問題点を解決するための手段
本発明は上記背景に基づいて、ＳＦＣの圧力プログラミ
ングによる動作時においても、イオン化効率を一定に維
持し、信頼性の高い８ＦＣ・ＭＳ直結装装置−実現する
ことを目的としたものである。B) Means for Solving the Problems Based on the above background, the present invention aims to realize a highly reliable 8FC/MS direct coupling device that maintains constant ionization efficiency even during operation by SFC pressure programming. It is intended for this purpose.
本発明は、超臨界流体クロマトグラフ−化学イオン化質
量分析計直結装置において、化学イオン化のための試薬
ガスをイオン源に供給する手段と。The present invention provides means for supplying a reagent gas for chemical ionization to an ion source in a supercritical fluid chromatograph-chemical ionization mass spectrometer direct connection device.
加熱試料導入装置により一定量の標準試料を定常的にイ
オン源に導入する手段と、この標準試料の特性イオンを
選択的に検出し、特性イオンのピーク強ｆ？一定に保持
するよう、前記試薬ガスの供給量をフィードバック制御
する手段とを備えたことを特徴とする。Means for constantly introducing a fixed amount of a standard sample into an ion source using a heating sample introduction device, selectively detecting characteristic ions of this standard sample, and detecting the peak intensity f? of the characteristic ion. The method is characterized by comprising means for feedback controlling the supply amount of the reagent gas so as to keep it constant.
（ホ）作 用
本発明は、圧力プログラミング条件下で動作する超臨界
流体クロマトグラフに直結した質量分析計で、イオン源
へ定常的に一定の標準試料を導入し、この標準試料から
生成する特性イオンの強度が分析実行中、一定強度を維
持するように。(E) Function The present invention is a mass spectrometer directly connected to a supercritical fluid chromatograph that operates under pressure programming conditions, in which a constant standard sample is constantly introduced into an ion source, and the characteristics generated from this standard sample are The ion intensity remains constant throughout the analysis run.
化学イオン化層試薬ガヌの供給量をフィードバック制御
するようＫしたものである。The supply amount of the chemical ionization layer reagent Ganu is feedback-controlled.
（へ）実施例 本発明の実施例を図により説明する。(f) Example Embodiments of the present invention will be described with reference to the drawings.
第一図は本発明の実施例を示す構成図である。FIG. 1 is a configuration diagram showing an embodiment of the present invention.
図中１〜１０は従来方法を説明した第三図と同等である
。１１は加熱試料導入装置であシ１通常。1 to 10 in the figure are equivalent to the third figure explaining the conventional method. 11 is a heating sample introduction device.
質量分析計において質量軸目盛シの校正、イオン光軸の
軸調整や感度調整のために標準試料導入用に用いられて
いるものである・加熱制御された試料リザーバー、リザ
ーバー内外の圧力差を維持するための出ロオリフイヌお
よびマイクロシリンジで標準試料溶液を導入するための
注入口から成−・ている。この装置により一定量の標準
試料を定常的にイオン源に導入でき、更に標準試料のイ
オン源への導入量を微調整するためニードルパルプ１２
が設けである。It is used to introduce a standard sample in a mass spectrometer to calibrate the mass axis scale, adjust the axis of the ion optical axis, and adjust the sensitivity.Heat-controlled sample reservoir, maintains the pressure difference inside and outside the reservoir. It consists of an exit orifice for the injection and an injection port for introducing the standard sample solution with a microsyringe. This device allows a constant amount of standard sample to be introduced into the ion source, and the needle pulp 12 is used to finely adjust the amount of standard sample introduced into the ion source.
is the provision.
化学イオン化用試薬ガスは、ガスポンベ１４から流量調
節パルプ１３を介してイオン源に供給される。流量調節
パルプ１３は、前記標準試料から生成する特性イオン強
度が一定値を維持するようコンピューターシステム１０
を介してフィードバック制御される。The reagent gas for chemical ionization is supplied from the gas pump 14 to the ion source via the flow rate regulating pulp 13. The flow rate regulating pulp 13 is controlled by the computer system 10 so that the characteristic ion intensity generated from the standard sample maintains a constant value.
Feedback controlled via.
第二図に標準試料から生成する特性イオンの選択検出の
例を説明するための信号の時間関係を示した。（ａ）は
四重極マスフィルターによる質量走査のための掃引電圧
である。縦軸の電圧値はイオン質量数と比例関係にある
。従って、−回の掃引によりマススペクトルが測定でき
る。図はクロマトグラフ動作中、繰シ返し掃引を連続し
て行い、得られた多数のマススペクトル・データをコン
ピューターシステムの記憶装置に蓄積し、必要なイオン
のｍ／ｚ値を指定してマスクロマトグフムを測定する場
合の例である。Figure 2 shows the time relationship of signals to explain an example of selective detection of characteristic ions generated from a standard sample. (a) is the sweep voltage for mass scanning by a quadrupole mass filter. The voltage value on the vertical axis is proportional to the ion mass number. Therefore, a mass spectrum can be measured by -times of sweeping. The figure shows that during chromatograph operation, repeated sweeps are performed continuously, a large amount of obtained mass spectrum data is stored in the storage device of the computer system, and the m/z value of the required ion is specified and the mass chromatograph is This is an example of measuring hum.
（ｂ）は、標準試料の特性イオンの質量数に対応する印
加電圧全中心として一定のウィンドウ幅を設定し、この
ウィンドウ幅に対応する時ｒＷ１ｇのゲートバ／Ｌ’ヌ
である。このゲートバルヌで入力の開ｒ！１’ｉ制御さ
れるホールドアンプにより標準試料の特性イオンのピー
ク値を保持したのがＣ）である。これを差動アンプに入
力し、一定の基準電圧と比較して、誤差ａ＠を最小とす
るようにフィードバック信号により試薬ガスの流１１調
節パルプを制御するものである。マスクロマトグラフィ
ーの他に微量定ｔ＃を目的としたマスクラグメントゲラ
フイーも用いられる。この場合は１分析対象によって設
定される数種類のイオンの質量数をプリセットしておき
、これらに対応する四重極印ｍｖｔ圧をステップ状に繰
返し変化させて、それぞれのイオン強度の時間変化を測
″定するもので、言い換えれば数種類の特定質量数イオ
ンによるクロマトグラムを得るものである。この場合も
、標準試料による特性イオンを設定し、上記と同様にし
て流量調節パルプを制御することができる。In (b), a constant window width is set as the center of all applied voltages corresponding to the mass number of the characteristic ions of the standard sample, and the gate value of rW1g corresponds to this window width. Open the input with this gate varnu! In C), the peak value of the characteristic ion of the standard sample is held by a hold amplifier controlled by 1'i. This is input to a differential amplifier and compared with a constant reference voltage, and the reagent gas flow 11 regulating pulp is controlled by the feedback signal so as to minimize the error a@. In addition to mass chromatography, mask fragment gelatin chemistry is also used for the purpose of determining t# in trace quantities. In this case, the mass numbers of several types of ions set depending on one analysis target are preset, and the corresponding quadrupole stamp mvt pressure is repeatedly changed in a step manner, and the time change of each ion intensity is measured. In other words, it is used to obtain a chromatogram using several types of specific mass number ions.In this case as well, the characteristic ions from the standard sample can be set and the flow rate regulating pulp can be controlled in the same manner as above.
゛（ト）効果
以上説明したように本発明によれば、超臨界流体クロマ
トグラフの圧力プログラミング条件下での動作時【も、
常に一定のイオン化効率が維持されるので再現性や定量
性の良い信頼度の高い分析装置が実現できる。Effects As explained above, according to the present invention, when operating a supercritical fluid chromatograph under pressure programming conditions,
Since a constant ionization efficiency is always maintained, a highly reliable analytical device with good reproducibility and quantitative performance can be realized.
第一図は本発明の一実施例を示す構成図、第二図はイオ
ン化効率を一定に維持するため化学イオン化用試薬ガス
の流量調節のフィードバック制御の方法を説明するため
の信号間の時間関係図。
第三図は従来方法を示す構成図である。
６・−・イオンｉ １０・・・ コンピュータシステ
ム１１−加熱試料導入装置 １３−・流量調節パルプ１
４−ガスボンベFigure 1 is a configuration diagram showing one embodiment of the present invention, and Figure 2 is a time relationship between signals to explain a feedback control method for adjusting the flow rate of chemical ionization reagent gas to maintain a constant ionization efficiency. figure. FIG. 3 is a block diagram showing a conventional method. 6.--Ion i 10... Computer system 11-Heating sample introduction device 13-.Flow rate adjustment pulp 1
4-Gas cylinder
Claims (1)
結装置において、化学イオン化のための試薬ガスをイオ
ン源に供給する手段と、加熱試料導入装置により一定量
の標準試料を定常的にイオン源に導入する手段と、この
標準試料の特性イオンを選択的に検出し、特性イオンの
ピーク強度を一定に保持するよう、前記試薬ガスの供給
量をフィードバック制御する手段とを備えたことを特徴
とする超臨界流体クロマトグラフ・質量分析計直結分析
装置。In a supercritical fluid chromatograph/chemical ionization mass spectrometer direct connection device, a fixed amount of standard sample is constantly introduced into the ion source using a means for supplying reagent gas for chemical ionization to the ion source and a heated sample introduction device. and a means for feedback controlling the supply amount of the reagent gas so as to selectively detect characteristic ions of the standard sample and keep the peak intensity of the characteristic ions constant. Fluid chromatograph/mass spectrometer direct connection analysis device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61170549A JPS6326571A (en) | 1986-07-18 | 1986-07-18 | Analyzing instrument directly coupled to ultracritical fluid chromatograph and mass spectrometer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61170549A JPS6326571A (en) | 1986-07-18 | 1986-07-18 | Analyzing instrument directly coupled to ultracritical fluid chromatograph and mass spectrometer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6326571A true JPS6326571A (en) | 1988-02-04 |
Family
ID=15906936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61170549A Pending JPS6326571A (en) | 1986-07-18 | 1986-07-18 | Analyzing instrument directly coupled to ultracritical fluid chromatograph and mass spectrometer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6326571A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02176458A (en) * | 1988-12-27 | 1990-07-09 | Yokogawa Electric Corp | Inductively coupled plasma mass spectrometer |
| CN111033213A (en) * | 2017-06-19 | 2020-04-17 | V&F分析和测量技术股份有限公司 | Apparatus and method for partial conversion of a fluid sample comprising a plurality of components and method for online determination and analysis of these components |
-
1986
- 1986-07-18 JP JP61170549A patent/JPS6326571A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02176458A (en) * | 1988-12-27 | 1990-07-09 | Yokogawa Electric Corp | Inductively coupled plasma mass spectrometer |
| CN111033213A (en) * | 2017-06-19 | 2020-04-17 | V&F分析和测量技术股份有限公司 | Apparatus and method for partial conversion of a fluid sample comprising a plurality of components and method for online determination and analysis of these components |
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