JPH0614035B2 - Electric field control type liquid chromatograph - Google Patents
Electric field control type liquid chromatographInfo
- Publication number
- JPH0614035B2 JPH0614035B2 JP59064994A JP6499484A JPH0614035B2 JP H0614035 B2 JPH0614035 B2 JP H0614035B2 JP 59064994 A JP59064994 A JP 59064994A JP 6499484 A JP6499484 A JP 6499484A JP H0614035 B2 JPH0614035 B2 JP H0614035B2
- Authority
- JP
- Japan
- Prior art keywords
- electric field
- liquid chromatograph
- stationary phase
- column
- phase carrier
- 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 - Lifetime
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
Description
【発明の詳細な説明】 (イ)産業上の利用分野 この発明は、電場制御型液体クロマトグラフ装置に関す
る。さらに詳しくは、移動相の内容を変えずして分離効
率を改善でき、イオン性物質、極性物質等の分離分析に
有用な液体クロマトグラフ装置に関する。TECHNICAL FIELD The present invention relates to an electric field control type liquid chromatograph device. More specifically, the present invention relates to a liquid chromatograph device which can improve the separation efficiency without changing the content of the mobile phase and is useful for the separation and analysis of ionic substances, polar substances and the like.
(ロ)従来技術 液体クロマトグラフィーにおいてしばしば保持時間が同
一又は類似である成分により充分な分離が得られず定性
や定量が阻害されることがある。この点に関し、吸着、
分配及びイオン交換クロマトグラフィー等においては、
同一カラム及び同一温度条件の際に移動相の塩濃度、p
H、有機溶媒等を変えることにより被検成分の固定相担
体への分配係数を変えて分離を改善する方法が行なわて
いるが、かような移動相の内容を変えて意図する分離を
行なうためには複数の移動相とその切換操作を必要と
し、しかもその条件の最適化も試行錯誤を要するという
不都合があった。(B) Prior art In liquid chromatography, components having retention times that are the same or similar often fail to obtain sufficient separation, and qualitative or quantitative determination may be hindered. In this regard, adsorption,
In partition and ion exchange chromatography, etc.,
Salt concentration of mobile phase under the same column and temperature conditions, p
There is a method to improve the separation by changing the distribution coefficient of the analyte to the stationary phase carrier by changing H, organic solvent, etc., but in order to perform the intended separation by changing the content of such mobile phase. Has a disadvantage that it requires a plurality of mobile phases and its switching operation, and that optimization of the conditions requires trial and error.
(ハ)目的 この発明は、かような状況に鑑みなされたものであり、
移動相の内容を変えることなく、もちろんカラムや温度
条件を変えることなく分離を改善しうる液体クロマトグ
ラフ装置を得ることを目的とするものである。(C) Objective The present invention has been made in view of such a situation,
It is an object of the present invention to obtain a liquid chromatograph capable of improving separation without changing the content of the mobile phase and of course without changing the column or temperature conditions.
(ニ)構成 かくしてこの発明によれば、送液部、試料導入部、分離
カラム及び検出部を順次備えてなる液体クロマトグラフ
装置において、 分離カラムを、チューブ内壁に導電性の固定相担体をコ
ートしてなりかつそのチューブの中心部軸方向に導線を
配設してなるカラムで構成すると共に、上記固定相担体
と導線との間に電場をかけ得る電圧印加手段を付設した
ことを特徴とする電場制御型液体クロマトグラフ装置が
提供される。(D) Structure Thus, according to the present invention, in a liquid chromatograph device sequentially provided with a liquid feeding section, a sample introduction section, a separation column and a detection section, the separation column is coated with a conductive stationary phase carrier on the inner wall of the tube. And a column in which a conductor is arranged in the axial direction of the central part of the tube, and a voltage applying means for applying an electric field is additionally provided between the stationary phase carrier and the conductor. An electric field controlled liquid chromatograph device is provided.
この発明における分離カラムは特定のオープンチューブ
ラー型のものからなる。かかる分離カラムに内壁にコー
トされる固定相担体は導電性であれば、吸着、分配順
相、分配逆相及びイオン交換用のいずれのタイプのもの
でもよく目的に応じて選択すればよい。かような導電性
を有する固定相担体は、通常、金属粉末を担体内に含ま
せることにより得ることができ、導電性樹脂を用いて作
製することも可能である。このカラムの内部空隙に軸方
向に伸びる導線を配設することによりこの発明における
分離カラムが得られる。この際、導線は上記導電性の固
定相担体層と直接接触しないように配設することが必要
でありカラムの中心部に設けるのが適当である。ただし
厳密な中心軸に必ずしも配設する必要はなく中心軸付近
であればよい。かかる導線としては、金属導線を用いる
のが適しており、ことに白金、銅等の電気化学的に貴な
金属線を用いるのが好ましい。The separation column in this invention is of a specific open tubular type. The stationary phase carrier coated on the inner wall of the separation column may be of any type for adsorption, normal distribution phase, reverse distribution phase, or ion exchange as long as it is electrically conductive, and may be selected according to the purpose. Such a stationary phase carrier having conductivity can be usually obtained by incorporating a metal powder into the carrier, and can also be prepared using a conductive resin. The separation column according to the present invention can be obtained by disposing the conductor wire extending in the axial direction in the inner space of the column. At this time, it is necessary to dispose the conducting wire so as not to come into direct contact with the conductive stationary phase carrier layer, and it is suitable to dispose the conducting wire at the center of the column. However, it is not always necessary to dispose on the strict center axis, and it is sufficient if it is near the center axis. As such a conductive wire, it is suitable to use a metal conductive wire, and it is particularly preferable to use an electrochemically noble metal wire such as platinum or copper.
上記分離カラムにおける導電性の固定相担体と導線との
間に測定時に外部電源により電圧を印加することによっ
て分離カラムの中心部から内壁に向かって電場が形成さ
れる。この際形成する電場は、高くても電気泳動等で設
定される程度のもので充分である。もちろんかような電
場の強さは固定相担体、移動相、被検物質等により左右
されるため適宜選択して定めればよい。An electric field is formed between the conductive stationary phase carrier and the conducting wire in the separation column from the center of the separation column toward the inner wall by applying a voltage from an external power source during measurement. The electric field formed at this time is sufficient even if it is high, which is set by electrophoresis or the like. Of course, such strength of the electric field depends on the stationary phase carrier, the mobile phase, the test substance, etc., and may be appropriately selected and determined.
以下、この発明を実施例により説明する。Hereinafter, the present invention will be described with reference to examples.
(ホ)実施例 第１図はこの発明の電場制御型液体クロマトグラフ装置
の一実施例を示す構成説明図である。図において電場制
御型液体クロマトグラフ装置(1)は、移動相貯槽(21)及
び送液ポンプ(22)とを備えた送液部(2)と、試料導入部
(3)と、恒温槽(5)を備えた分離カラム(4)と、検出器(7)
とを順次接続してなる。なお、図中、(8)は廃液槽、(9)
はレコーダー、(10)はインテグレーターである。そし
て、分離カラム(4)は、第２図に示すごとく内径約４mm
のステレスチューブ（41；ガラスチユーブでも可能）の
内壁に、鉄粉を含んだシリカゲルからなる導電性の固定
相担体(42)をコートしてなりかつとのチユーブの中心部
軸方向に直径約０．３mmの白金製（銅も可能）の導線(4
3)を配設してなる。かかる導線(43)は、第３図に示すご
とくカラム(4)の両端にナット(47)によって嵌合螺着合
されてなる絶縁製プラスチック製の固定管(44)によって
張設されており、一方の固定管(44)から端子(45)が引き
出されている。(431)は導線(43)を中心部に配設するた
めの金属製固定具である。また、分離カラム(4)には、
固定相担体(42)に電気接続する端子(46)が引き出されて
いる。そして端子(45)及び(46)は電圧印加手段である外
部電源(6)に接続されており、これにより固定相担体(4
2)と導線(43)との間に所定の電場をかけ得るよう構成さ
れている。(E) Embodiment FIG. 1 is a constitutional explanatory view showing an embodiment of the electric field control type liquid chromatograph device of the present invention. In the figure, an electric field control type liquid chromatograph device (1) includes a liquid feed section (2) including a mobile phase storage tank (21) and a liquid feed pump (22), and a sample introduction section.
(3), separation column (4) equipped with a thermostat (5), and detector (7)
And are connected in sequence. In the figure, (8) is a waste liquid tank, (9)
Is a recorder and (10) is an integrator. The separation column (4) has an inner diameter of about 4 mm as shown in FIG.
The inner wall of the stainless steel tube (41; glass tube is also possible) is coated with a conductive stationary phase carrier (42) made of silica gel containing iron powder, and the central part of the tube has a diameter of about 0. ．3mm platinum wire (copper is also possible) (4
3) is provided. The conducting wire (43) is stretched by a fixed pipe (44) made of an insulating plastic which is fitted and screwed to both ends of the column (4) by a nut (47) as shown in FIG. A terminal (45) is drawn out from one fixed tube (44). Reference numeral (431) is a metal fixture for disposing the conducting wire (43) in the central portion. In addition, the separation column (4)
A terminal (46) is drawn out to electrically connect to the stationary phase carrier (42). The terminals (45) and (46) are connected to an external power supply (6) which is a voltage applying means, whereby the stationary phase carrier (4
It is configured so that a predetermined electric field can be applied between 2) and the lead wire (43).
かかる装置により液体クロマトグラフィーを行なうに当
たり、例えばパラアミノ安息香酸のような分子中に電荷
が非対称に分布している化合物を対称とする場合には、
固定相担体と導線との間に電場をかけることにより第４
図のごとく分子に方向性が生じてくるので固定相との相
互作用が電場の強さ及び極性により変化し、結果的に化
合物の分配係数Ｋを変化させるとができる。またプロピ
レジンアミノのように分子全体として正又は負の電荷を
有する化合物の場合には、第５図のごとく電場自体がイ
オン交換的な作用に相当するため、電場の強さ、極性に
より結果的に化合物の分配係数Ｋを変化させることがで
きる。もちろん固定相担体が分配順相、分配逆相及びイ
オン交換用の担体からなる場合においても同様であり、
場合によっては第６図のごとくイオン交換用の固定相担
体(42′)に逆電場をかけることにより分配係数Ｋを変え
ることも可能である。In carrying out liquid chromatography with such an apparatus, when a compound such as para-aminobenzoic acid in which the charge is asymmetrically distributed in the molecule is symmetrical,
By applying an electric field between the stationary phase carrier and the conductor,
As shown in the figure, since the molecules are oriented, the interaction with the stationary phase changes depending on the strength and polarity of the electric field, and as a result, the partition coefficient K of the compound can be changed. Also, in the case of a compound having a positive or negative charge as a whole molecule such as propylene resin amino, the electric field itself corresponds to an ion-exchange-like action as shown in FIG. The partition coefficient K of the compound can be changed. Of course, the same applies when the stationary phase carrier is composed of a partition normal phase, a partition reverse phase and a carrier for ion exchange.
In some cases, it is also possible to change the distribution coefficient K by applying a reverse electric field to the stationary phase carrier (42 ') for ion exchange as shown in FIG.
より具体的な使用方法としては、例えば、トルイジンと
エチルベンゼンとを含む試料を、Ｃ１８の化学結合型固
定相担体（例えば、ODSカラム）と水−メタノール溶離
液とを用いたクロマトグラフィーに付した際、従来の方
式では第７図(イ)のごとくトルイジンはその極性のため
ソルベントフロントに位置するピークＡに含まれるエチ
ルベンゼンのみがピークＢとして分離される。しかし、
この発明の液体クロマトグラフ装置を用いて固定相担体
を正極とする電場をかけることにより、トルイジンの分
配係数を変化させることができ、第７図(ロ)に示すよう
に、ソルベントフロンＡ１、トルイジンＡ２及びエチル
ベンゼンＢを分離することができる。また、固定相担体
として第６図のごとくスルホン酸基（イオン交換基）を
有するものを用い、プロピルアミンとブチルアミンとを
含む試料をクロマトグラフィーに付した際、従来の方式
ではしばしば第８図(イ)に示すごとき重複したピークＣ
１及びＣ２が得られるが、この場合にも移動相やカラム
温度を変えることなく固定相担体を正極とする電場をか
けることにより炭素鎖と固定相担体との逆相的な作用を
利用して第８図(ロ)に示すごとくプロピルアミンＣ１と
ブチルアミンＣ２とを分離することができる。As a more specific method of use, for example, a sample containing toluidine and ethylbenzene was subjected to chromatography using a C 18 chemically bonded stationary phase carrier (eg, ODS column) and a water-methanol eluent. On the other hand, in the conventional method, as shown in FIG. 7A, due to the polarity of toluidine, only ethylbenzene contained in peak A located at the solvent front is separated as peak B. But,
By applying an electric field with the stationary phase carrier serving as a positive electrode using the liquid chromatograph of the present invention, the distribution coefficient of toluidine can be changed, and as shown in FIG. 7 (b), Solvent Freon A 1 , Toluidine A 2 and ethylbenzene B can be separated. Further, when a stationary phase carrier having a sulfonic acid group (ion exchange group) as shown in FIG. 6 was used and a sample containing propylamine and butylamine was subjected to chromatography, the conventional method often used FIG. Overlapped peak C as shown in (a)
1 and C 2 are obtained, but in this case as well, the reverse phase action of the carbon chain and the stationary phase carrier is utilized by applying an electric field with the stationary phase carrier as the positive electrode without changing the mobile phase or column temperature. As shown in FIG. 8B, propylamine C 1 and butylamine C 2 can be separated.
(ヘ)効果 以上述べたように、この発明の電場制御型液体クロマト
グラフ装置によれば、移動相やカラム温度等の条件をと
くに変えることなく極性基を有する化合物のクロマト分
離を改善することができる。従って、種々の用途に有利
であり例えばアミノ酸分析装置の液体クロマトグラフ部
としても有用である。(F) Effect As described above, according to the electric field control type liquid chromatograph device of the present invention, it is possible to improve the chromatographic separation of the compound having a polar group without particularly changing the conditions such as the mobile phase and the column temperature. it can. Therefore, it is advantageous for various applications and is also useful, for example, as a liquid chromatograph section of an amino acid analyzer.
なお、この発明の装置においては、被検成分の分離の改
善以外に、分離速度を速くしたい場合に電場をかけるこ
とにより移動相流速を変えることなく行なうことがで
き、さらに、カラム洗浄時に逆電場をかけることにより
洗浄が容易となる、という利点もある。In addition, in the device of the present invention, in addition to improving the separation of the components to be tested, it can be performed without changing the mobile phase flow rate by applying an electric field when it is desired to increase the separation speed, and further, the reverse electric field can be applied during column washing. There is also an advantage that cleaning can be facilitated by applying the pressure.
第１図はこの発明の電場制御型液体クロマトグラフ装置
の一実施例を示す構成説明図、第２図は第１図の分離カ
ラムを示す断面を含む斜視図、第３図は第２図の部分断
面図、第４〜６図はそれぞれこの発明の装置における電
場による作用を示す説明図、第７図及び第８図はそれぞ
れこの説明の装置を用いた際のクロマトグラムを比較例
と共に示す模式図である。 (1)…電場制御型液体クロマトグラフ装置、 (2)…送液部、(3)…試料導入部、 (4)…分離カラム、(41)…ステンレスチューブ、 (42)…導電性担体、(43)…導線、 (44)…固定管、(45)(46)…端子、 (47)…ナット、(6)…外部電源。FIG. 1 is a structural explanatory view showing an embodiment of an electric field control type liquid chromatograph device of the present invention, FIG. 2 is a perspective view including a cross section showing a separation column of FIG. 1, and FIG. Partial cross-sectional views, FIGS. 4 to 6 are explanatory views showing the action of the electric field in the device of the present invention, and FIGS. 7 and 8 are schematic views showing chromatograms when the device of this description is used together with comparative examples. It is a figure. (1) ... electric field control type liquid chromatograph, (2) ... liquid feeding section, (3) ... sample introducing section, (4) ... separation column, (41) ... stainless tube, (42) ... conductive carrier, (43)… Conductive wire, (44)… Fixed tube, (45) (46)… Terminal, (47)… Nut, (6)… External power supply.
Claims (1)
部を順次備えてなる液体クロマトグラフ装置において、 分離カラムを、チューブ内壁に導電性の固定相担体をコ
ートしてなりかつそのチューブの中心部軸方向に導線を
配設してなるカラムで構成すると共に、上記固定相担体
と導線との間に電場をかけ得る電圧印加手段を付設した
ことを特徴とする電場制御型液体クロマトグラフ装置。1. A liquid chromatograph comprising a liquid sending part, a sample introducing part, a separation column and a detection part in that order, wherein the separation column is formed by coating a conductive stationary phase carrier on the inner wall of the tube. And a voltage applying means for applying an electric field between the stationary phase carrier and the conducting wire, which is constituted by a column in which a conducting wire is arranged in the central portion of the liquid chromatograph. apparatus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59064994A JPH0614035B2 (en) | 1984-03-30 | 1984-03-30 | Electric field control type liquid chromatograph |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59064994A JPH0614035B2 (en) | 1984-03-30 | 1984-03-30 | Electric field control type liquid chromatograph |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60207055A JPS60207055A (en) | 1985-10-18 |
| JPH0614035B2 true JPH0614035B2 (en) | 1994-02-23 |
Family
ID=13274122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59064994A Expired - Lifetime JPH0614035B2 (en) | 1984-03-30 | 1984-03-30 | Electric field control type liquid chromatograph |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0614035B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989007265A1 (en) * | 1988-02-03 | 1989-08-10 | Wollongong Uniadvice Limited | Chromatography using electrically conductive polymer stationary phase materials |
| EP1048351B1 (en) | 1995-03-03 | 2003-09-10 | Alltech Associates, Inc. | System for generating a high purity eluant |
| US5935443A (en) * | 1995-03-03 | 1999-08-10 | Alltech Associates, Inc. | Electrochemically regenerated ion neutralization and concentration devices and systems |
-
1984
- 1984-03-30 JP JP59064994A patent/JPH0614035B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60207055A (en) | 1985-10-18 |
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