JPS63210766A - Capillary column - Google Patents
Capillary columnInfo
- Publication number
- JPS63210766A JPS63210766A JP62044768A JP4476887A JPS63210766A JP S63210766 A JPS63210766 A JP S63210766A JP 62044768 A JP62044768 A JP 62044768A JP 4476887 A JP4476887 A JP 4476887A JP S63210766 A JPS63210766 A JP S63210766A
- Authority
- JP
- Japan
- Prior art keywords
- capillary column
- capillary
- crosslinking agent
- column
- temp
- 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
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 8
- -1 tetramethyl divinyl siloxane Chemical class 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 238000004193 electrokinetic chromatography Methods 0.000 claims description 10
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 claims description 4
- PMSZNCMIJVNSPB-UHFFFAOYSA-N bis(ethenyl)silicon Chemical group C=C[Si]C=C PMSZNCMIJVNSPB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 229920006254 polymer film Polymers 0.000 abstract 1
- 238000010926 purge Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract 1
- 238000005370 electroosmosis Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000007853 buffer solution Substances 0.000 description 7
- 239000012086 standard solution Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 239000005350 fused silica glass Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012491 analyte Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- XJWOWXZSFTXJEX-UHFFFAOYSA-N phenylsilicon Chemical group [Si]C1=CC=CC=C1 XJWOWXZSFTXJEX-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 1
- RMZNXRYIFGTWPF-UHFFFAOYSA-N 2-nitrosoacetic acid Chemical compound OC(=O)CN=O RMZNXRYIFGTWPF-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 238000005515 capillary zone electrophoresis Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HPYJIGCCYQMQDL-UHFFFAOYSA-N cyano(phenyl)silicon Chemical compound N#C[Si]C1=CC=CC=C1 HPYJIGCCYQMQDL-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000002218 isotachophoresis Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、界面動電クロマトグラフ装置等に使用される
キャピラリーカラムに関する。ここに、界面動電クロマ
トグラフ装置とは、キャピラリー（毛細管）に緩衝液と
イオン化ミセルとからなる溶媒を流し、該ミセルと注入
された一定員の試料との溶解現象並びに毛細管電気泳動
法とを組合せて、該試料中の被測定成分を分離・分析す
る装置である。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a capillary column used in an electrokinetic chromatography device or the like. Here, an electrokinetic chromatography device refers to a method in which a solvent consisting of a buffer solution and ionized micelles is passed through a capillary, and a dissolution phenomenon between the micelles and a certain number of injected samples is detected, as well as capillary electrophoresis. In combination, this is an apparatus that separates and analyzes the components to be measured in the sample.
〈従来の技術〉
上述のようなキャピラリーカラムとしては、例えば、フ
ユーズドシリカ（溶融シリカ）でなる内径１０〜２０μ
ｍ程度のキャピラリーカラムが使用されている。このよ
うなフユーズドシリカでなるキャピラリーカラムが用い
られるのは、該フユーズドシリカの表面に界面動電クロ
マトグラフィを行なうのに適したシラノール基が存在し
ているからである。即ち、界面動電クロマトグラフィー
における物質移動は、上記キャピラリーカラムの両端に
高電圧を印加し該カラムの上記緩衝液に電気浸透流を与
えると共に上記試料が電気泳動によって上記ｌｌｌ液液
流れと逆方向に移動すること等を利用するものであり、
しかも該電気浸透流がフユーズドシリカ表面のシラノー
ル基に依存しているからである。<Prior art> The above-mentioned capillary column is, for example, made of fused silica and has an inner diameter of 10 to 20 μm.
A capillary column of about m is used. A capillary column made of such fused silica is used because silanol groups suitable for electrokinetic chromatography are present on the surface of the fused silica. That is, mass transfer in electrokinetic chromatography involves applying a high voltage to both ends of the capillary column to give an electroosmotic flow to the buffer solution in the column, and causing the sample to move in the opposite direction to the liquid flow by electrophoresis. It takes advantage of things like moving.
Moreover, this is because the electroosmotic flow depends on the silanol groups on the surface of the fused silica.
〈発明が解決しようとする問題点〉
然し乍ら、上記従来例においては、フユーズドカラム表
面のシラノール基に、蛋白質１重金属。<Problems to be Solved by the Invention> However, in the above conventional example, proteins and heavy metals are present in the silanol groups on the surface of the fused column.
若しくはアミン等の試料中成分が吸着し易く、上記電気
浸透流が大きく変化し究極的にキャピラリーカラムの分
離特性に再現性がなくなるという欠点があった。このよ
うな現象は、試料中成分のみならず移動相中の成分（不
純物）によっても同様に生じ、しかも、これら成分が一
旦キャピラリーカラム内に吸着すると、洗浄しても簡単
に脱離せず結果的にキャピラリーカラムが使用不能にな
ったりする欠点もあった。一方、上記キャピラリーカラ
ムを長く保存すると、上記電気浸透流が小さくなって被
測定成分の保持時間が長くなり、試料の分析を開始して
もキャピラリーカラム保存前の状態に容易に復帰しない
という欠点があった。また、このように長期間保存した
キャピラリーカラムは、試料を分析している間も被測定
成分の保持時間変動が大きく分離特性の再現性が悪いと
いう欠点もあった。Alternatively, components in the sample such as amines are likely to be adsorbed, and the electroosmotic flow changes greatly, ultimately resulting in a loss of reproducibility in the separation characteristics of the capillary column. This phenomenon occurs not only due to components in the sample but also due to components (impurities) in the mobile phase. Moreover, once these components are adsorbed within the capillary column, they cannot be easily desorbed even after washing, resulting in There was also the drawback that the capillary column became unusable. On the other hand, if the capillary column is stored for a long time, the electroosmotic flow becomes smaller and the retention time of the analyte becomes longer, and there is a drawback that the state before the capillary column is not easily restored even after starting sample analysis. . In addition, capillary columns stored for a long period of time have the disadvantage that the retention time of the analyte varies greatly even during sample analysis, and the reproducibility of separation characteristics is poor.
本発明はかかる従来例の欠点に鑑みてなされたものであ
り、その目的は、内壁面へ不純物等が吸着し難くて寿命
が長く且つ分離特性の再現性も優れているキャピラリー
カラムを提供することにある。The present invention was made in view of the drawbacks of the conventional examples, and its purpose is to provide a capillary column that is difficult to adsorb impurities to the inner wall surface, has a long life, and has excellent reproducibility of separation characteristics. be.
く問題点を解決するための具体的手段〉上述のような問
題点を解決する本発明の特徴は、キャピラリーカラムに
おいて、メチルシリコン系シリコンポリマー溶液と架橋
剤溶液とを封入して架橋反応を行なわせ前記内壁面に一
定膜厚を有する高分子膿をコーティングさせたことにあ
る。Specific Means for Solving the Problems> The feature of the present invention that solves the problems described above is that a methyl silicone silicone polymer solution and a crosslinking agent solution are sealed in a capillary column to perform a crosslinking reaction. The inner wall surface is coated with polymeric pus having a constant thickness.
〈実施例〉
以下、本発明について図を用いて詳しく説明する。第１
図は本発明に係るキャピラリーカラムを説明するための
製法説明図である。第１図において、最初に、例えば、
メチルシロキサン（末端基がハイドライド基）、メチル
シロキサン（末端基がシラノール基）、ジビニルシラン
、ジビニルシロキサン、若しくはビス（アミノプロピル
）シロキサン等でなる架橋剤を用意する。次に、シリコ
ン系ポリマー、ポリエチレングリコール、ポリアルキレ
ンゲリコール、メチロール化ポリスチレン。<Example> Hereinafter, the present invention will be explained in detail using the drawings. 1st
The figure is an explanatory diagram of a manufacturing method for explaining a capillary column according to the present invention. In FIG. 1, first, for example,
A crosslinking agent made of methylsiloxane (terminal group is a hydride group), methylsiloxane (terminal group is a silanol group), divinylsilane, divinylsiloxane, bis(aminopropyl)siloxane, or the like is prepared. Next, silicone polymers, polyethylene glycol, polyalkylene gelicol, and methylolated polystyrene.
ビニルシラン共重合物、若しくはポリスチレン等でなる
オリゴマーを用意する。その後、例えばジクロロメタン
でなる溶剤に、上記オリゴマー（例えばメチルシリコン
ポリマー）と架橋剤（例えばテトラメチルジビニルシロ
キサン）を例えば１０：１の割合（ｖｔ／ｗｔの濃度比
）で溶解させ、例えばメチルシリコンの１％溶液でなる
溶解液とする。該溶解液（溶剤）を、例えば内径５０μ
ｍ長さ５ｍのフユーズドシリカキャピラリー内に例えば
窒素圧を利用して封入する。次に、該キャピラリーの一
端に盲栓をした状態で他端より、一定温度（例えば１５
０℃）の例えば窒素パージされている恒温槽内にゆっく
りと送り込み、該恒温槽内でゆっくりと巻き取る。この
ような＠き取り操作の間に、上記架橋剤による架橋反応
が行なわれると共に上記溶剤が揮発する。上述のような
巻き取り操作が終了したら、上記キャピラリーの一端に
ある盲栓をはずすと共に、該キャピラリー（カラム）内
に例えばＨｅガスを流しながら恒温槽を所定温度（例え
ば２５０℃）に上げて一定時間（例えば４時間）エージ
ングを行なう。その後、恒温槽のヒータをオフにし、該
恒温槽の温度が室温になるまで上記キャピラリー（カラ
ム）内に例えばＨｅガスを流す。このようにして本発明
に係るキャピラリーカラムが完成する。An oligomer made of a vinylsilane copolymer or polystyrene is prepared. Thereafter, the oligomer (for example, methyl silicone polymer) and the crosslinking agent (for example, tetramethyldivinylsiloxane) are dissolved in a solvent consisting of, for example, dichloromethane at a ratio of, for example, 10:1 (vt/wt concentration ratio). The solution is a 1% solution. The dissolving solution (solvent) is, for example,
The sample is sealed in a fused silica capillary with a length of 5 m using, for example, nitrogen pressure. Next, with a blind stopper attached to one end of the capillary, the capillary is heated to a constant temperature (for example, 15°C) from the other end.
The film is slowly fed into a constant temperature bath that is purged with nitrogen, for example, at a temperature of 0° C., and slowly wound up in the constant temperature bath. During such @sweeping operation, the crosslinking reaction by the crosslinking agent takes place and the solvent evaporates. When the winding operation as described above is completed, remove the blind stopper at one end of the capillary, and raise the thermostat to a predetermined temperature (e.g., 250°C) while flowing He gas, for example, into the capillary (column) to keep it constant. Aging is performed for a period of time (for example, 4 hours). Thereafter, the heater of the constant temperature bath is turned off, and He gas, for example, is allowed to flow into the capillary (column) until the temperature of the constant temperature bath reaches room temperature. In this way, the capillary column according to the present invention is completed.
第２図は本発明に係るキャピラリーカラムを装着した界
面動電クロマトグラフ装置の構成説明図である。この図
において、送液ポンプ２が駆動すると、槽ｌａ内の＆１
衝液が（例えば、５０ ｍ ｍｏｌ／ Ｑのラウリル硫
幽ソーダ、 ０．１ ｍｏｌ ／ ｌのＮａＨｚＰＯ４
゜および０．０５ ｍｏｌ／ ｌのＮａ２Ｂ４Ｏ７の混
合溶液）容器３の入口３ａに導びかれ、オーバーフロー
した緩衝液が出口３ｂから再び槽ｌａ内に戻されると共
に出口３ｃから送出される緩衝液が、第１切換弁４の第
１および第２接続口４ａ、４ｂを経由してスプリット５
に導びかれる。該スプリットで分流された緩衝液の一方
は、第２切換弁６の第１および第２接続口６ａ、６ｂを
経由して槽ｌａ内に戻され、他方は、キャピラリーカラ
ムおよび紫外線検出器８を経由して槽ｌｂ内に導びかれ
る。また、スプリット５と第２切換弁６の第１接続ロ６
ａを結ぶ管路はチューブ状電極を兼ねており、該チュー
ブ電極にプラス側が接続され槽Ｉｂ内の緩衝液に浸漬さ
れた電極９にマイナス側が接続されるようにして高圧電
源（例えば１６ ｋＶ）が配設され、該高圧電源によっ
てキャピラリーチューブ７の両端に高電圧が印加される
ようになっている。紫外線検出器８で検出された信号は
、例えば記録計のような表示装置１１に導びかれ該表示
装置１１の出力が例えば積分器１２に導びかれるような
構成になっていることが多く、第１切換弁４．スプリッ
タ５．キャピラリーカラム７、紫外線検出器８゜槽１ｂ
、および高圧電源１０が、恒温槽１３内に収容され例え
ば４０℃に保たれている。FIG. 2 is an explanatory diagram of the configuration of an electrokinetic chromatography apparatus equipped with a capillary column according to the present invention. In this figure, when the liquid feeding pump 2 is driven, &1 in the tank la
If the buffer solution is (e.g. 50 mmol/Q lauryl sulfate soda, 0.1 mol/l NaHzPO4
A mixed solution of Na2B4O7 and 0.05 mol/l) is introduced into the inlet 3a of the container 3, and the overflowing buffer is returned to the tank la from the outlet 3b, while the buffer sent out from the outlet 3c is Split 5 via first and second connection ports 4a and 4b of first switching valve 4
be guided by. One of the buffer solutions separated by the split is returned into the tank la via the first and second connection ports 6a and 6b of the second switching valve 6, and the other is returned via the capillary column and the ultraviolet detector 8. and guided into tank lb. Also, the first connecting hole 6 between the split 5 and the second switching valve 6
The conduit connecting the tubes a also serves as a tube-shaped electrode, and the positive side is connected to the tube electrode, and the negative side is connected to the electrode 9 immersed in the buffer solution in tank Ib. is provided, and a high voltage is applied to both ends of the capillary tube 7 by the high voltage power supply. The signal detected by the ultraviolet detector 8 is often guided to a display device 11, such as a recorder, and the output of the display device 11 is guided to, for example, an integrator 12. First switching valve4. Splitter 5. Capillary column 7, UV detector 8° tank 1b
, and high-voltage power supply 10 are housed in a constant temperature bath 13 and maintained at, for example, 40°C.
ところで本１ｉｌ１１発明に係るキャピラリーカラムの
ような内面コーティングカラムは、カラムの内壁面にイ
オン性の末端基がなく、界面動電クロマトグラフに不可
欠となっている電気浸透流がカラム担体では発生しない
。しかし、界面動電クロマトグラフは、１ｌｌｉ液中に
イオン性の界面活性剤（例えばラウリル巖ソーダ）を含
んでおり、該界面活性剤が上記コーティングのポリマ一
層に疎水性吸着してイオン性界面活性剤の薄膜を形成し
ている。By the way, internally coated columns such as the capillary column according to the present invention do not have ionic end groups on the inner wall surface of the column, and electroosmotic flow, which is essential for electrokinetic chromatography, does not occur in the column carrier. However, in electrokinetic chromatographs, the 1lli liquid contains an ionic surfactant (e.g. lauryl soda), and the surfactant is hydrophobically adsorbed to the polymer layer of the coating to activate the ionic surface. Forms a thin film of agent.
このような界面活性剤＜ｒａ膜）は表面にイオン性の末
端基を有しており、該末端基によって上記電気ｉ’１ｆ
ｆｌ流が発生するようになっている。一方、前記オリゴ
マーがメチルシリコンポリマーの場合、上記界面活性剤
の吸着量は多くなっており上記内面コーティングを施こ
さない通常のキャピラリーカラムに比し大きな電気浸透
流を発生させる。このことは、前記オリゴマーがフェニ
ルシリコンやフェニルシアノシリコンでも同様であるが
、前記オリゴマーがポリエチレングリコーン茗しくはヒ
ドロキシアルキレンオキシド含有シリコンの場合には上
記電気浸透流は小さくなる。また、上記内面コーティン
グ層とキャピラリーカラム内に導入された試料は相互作
用を及ぼしあい、例えば、前記オリゴマーたるメチルシ
リコンやフェニルシリコンは疎水性吸着を示し、親水性
のコーティング層は水素結合等の相互作用を示す。この
ように、上記内面コーティング層の物質を変更すると、
上記電気浸透流だけでなく試料との間の相互作用も変化
するようになる。従って、本発明に係るキャピラリーカ
ラムは、再現性が向上する以外に種々の内面コーティン
グ層をもつカラムを製造できるようになる。Such a surfactant <ra membrane) has an ionic terminal group on its surface, and the terminal group allows the above-mentioned electric i'1f
fl flow is generated. On the other hand, when the oligomer is a methyl silicone polymer, the amount of the surfactant adsorbed is large and a larger electroosmotic flow is generated than in a normal capillary column without the inner surface coating. This is true even if the oligomer is phenyl silicon or phenyl cyano silicon, but when the oligomer is polyethylene glycone or silicon containing hydroxyalkylene oxide, the electroosmotic flow becomes smaller. In addition, the inner surface coating layer and the sample introduced into the capillary column interact with each other; for example, the oligomers methyl silicon and phenyl silicon exhibit hydrophobic adsorption, and the hydrophilic coating layer exhibits interactions such as hydrogen bonding. shows. In this way, when the substance of the inner coating layer is changed,
Not only the electroosmotic flow but also the interaction with the sample will change. Therefore, the capillary column according to the present invention not only improves reproducibility but also allows columns with various inner coating layers to be manufactured.
再び第１図に戻って説明する０例えば、メタノール、フ
ェノール、０−クレゾール、０−クロロフェノール、ｍ
−クロロフェノール、２．６−キシレノール、２．４−
キシレノール、およびスダン■を各々一定量ずつ含む試
料（以下「標準液」という）をシリンジ１４から第１切
換弁４の計量管４ｇに注入する。その後、第１切換弁４
をオンにしその内部流路を実線接続状態から破線接続状
態に切換えると、計量管４ｇ内の標準液が＆１衝液に搬
送されてスプリッタ５に至り標準液の一部がスプリット
され、その後、キャピラリーカラム７に入る。至り、こ
こで、高圧電源１０から高電圧が印加されると、キャピ
ラリカラム７内でクロマトグラフィツクに分離されての
ち、紫外線検出器８でその紫外線吸光度が検出される。Returning to Figure 1 again, 0 For example, methanol, phenol, 0-cresol, 0-chlorophenol, m
-chlorophenol, 2.6-xylenol, 2.4-
A sample (hereinafter referred to as "standard solution") containing fixed amounts of xylenol and Sudan (2) is injected from the syringe 14 into the measuring tube 4g of the first switching valve 4. After that, the first switching valve 4
is turned on and its internal flow path is switched from the solid line connection state to the broken line connection state, the standard solution in the measuring tube 4g is transported to the &1 buffer solution, reaches the splitter 5, and a part of the standard solution is split, and then a part of the standard solution is split into the capillary column 7. to go into. When a high voltage is applied from the high-voltage power supply 10, the particles are chromatographically separated in the capillary column 7, and then their ultraviolet absorbance is detected by the ultraviolet detector 8.
該検出器８で検出された信号は表示装置１１に送出され
、第２図のようなりロマトグラムを与える。このクロマ
トグラムから明らかなように標準液中の各成分は、上記
キャピラリーカラム７で良好に分１ｌ１１されているこ
とが分る。The signal detected by the detector 8 is sent to a display device 11, giving a romatogram as shown in FIG. As is clear from this chromatogram, each component in the standard solution was well separated by the capillary column 7.
第３図は、上記標準液中のフェノールに注目しながらキ
ャピラリーカラム７の分離特性（フェノールの溶出時間
）の再現性を調べたグラフである。FIG. 3 is a graph showing the reproducibility of the separation characteristics (phenol elution time) of the capillary column 7, focusing on phenol in the standard solution.
即ち、上述のような内面処理が施こされていない従来の
キャピラリーカラムや本発明に係るキャピラリーカラム
を上記キャピラリーカラム７として用いた界面動電クロ
マトグラフ装置（第１図参Ｉｌｌ）を使用し、上記試料
中のフェノールについて溶出時間Ｔが時間（即ち、注入
回数ｎ）とともにどのように変化するかを調べたもので
あり、曲線イ。That is, using an electrokinetic chromatography apparatus (see Ill in FIG. 1) using a conventional capillary column that has not been subjected to the inner surface treatment as described above or a capillary column according to the present invention as the capillary column 7, This study investigated how the elution time T changes with time (i.e., the number of injections n) for the phenol shown in curve A.
口は従来のキャピラリーカラムを用い日を興にして調べ
た実験結果であり、曲線ハは本発明に係るキャピラリー
カラムを用い曲線イと同一の日に調べた実験結果である
。二のグラフから明らかなように、従来のキャピラリー
カラムを用いると測定開始当初に被測定成分の溶出時間
変動が大きく、該変動を安定させるには数回（６〜７回
）測定を繰り返さなければないが、本発明に係るキャピ
ラリーカラムを用いれば測定開始当初から被測定成分の
溶出時間変動がほとんどなく正確な測定ができるように
なる。尚、下表１は上記標準液中のフェノール、ｍ−ク
ロロフェノール、および２，４−キシレノールに着目し
、従来のキャピラリーカラムと本発明に係るキャピラリ
ーカラムについて分離特性の再現性（即ち、相対標準編
差を示すＣ。Curve C is the result of an experiment conducted on the same day as curve A, using a capillary column according to the present invention, using a conventional capillary column. As is clear from the second graph, when using a conventional capillary column, there is a large variation in the elution time of the analyte at the beginning of the measurement, and it is necessary to repeat the measurement several times (6 to 7 times) to stabilize the variation. However, if the capillary column according to the present invention is used, there will be almost no fluctuation in the elution time of the component to be measured from the beginning of the measurement, and accurate measurement will be possible. Table 1 below focuses on phenol, m-chlorophenol, and 2,4-xylenol in the standard solution, and shows the reproducibility of separation characteristics (i.e., relative standard deviation) for the conventional capillary column and the capillary column according to the present invention. C.
−ｅｆｆｉｃｉｅｎｔ Ｖａｌｕｅ値であり、その単位
は％である）を比較した実験結果を示すものである。下
表１から、本発明に係るキャピラリーカラムを用いれば
、上述のフェノールのみならずｍ−クロロフェノールや
２，４−キシレノールについても分離特性の再現性が向
上することが分る。-efficient Value, whose unit is %). From Table 1 below, it can be seen that when the capillary column according to the present invention is used, the reproducibility of separation characteristics is improved not only for the above-mentioned phenol but also for m-chlorophenol and 2,4-xylenol.
尚、本発明は上述の実施例に限定されることなく種々の
変形が可能であり例えば次のようにしてもよいものとす
る。即ち、前記オリゴマーとしてカルボキシル基やアル
キルアミノ基を有する化合物を用いると結果的に電気浸
透流をもたせることが可能となり、界面動電クロマトや
浸透流を利用するキャピラリーゾーン電気泳動に使用で
きるようになる。また、前記オリゴマーとして含弗素シ
リコン化合物を使用すれば、テフロン内面コーティング
のキャピラリーカラムの代用となるうえ速達電気泳動法
にも適用できることとなり、等速電気泳動法で用いられ
ていた従来のカラムより内径を極小さくできるようにな
る。It should be noted that the present invention is not limited to the above-described embodiments, and can be modified in various ways, for example, as follows. That is, when a compound having a carboxyl group or an alkylamino group is used as the oligomer, it becomes possible to have electroosmotic flow, and it becomes possible to use it for electrokinetic chromatography and capillary zone electrophoresis that utilizes osmotic flow. . In addition, if a fluorine-containing silicon compound is used as the oligomer, it can be used as a substitute for a capillary column with a Teflon inner surface coating, and can also be applied to express electrophoresis, with an inner diameter smaller than that of conventional columns used in isotachophoresis. It can be made extremely small.
〈発明の効果〉
以上詳しく説明したような本発明によれば、内壁面へ試
料や緩衝液などからの不純物等が吸着し難くて寿命が長
く、且つ、分離特性の再現性も優れたキャピラリーカラ
ムが実現する。また、測定開始当初から溶出時間の変動
がほとんどなく、試料中の被測定成分を安定的（再現性
よく）に測定できるうえ、上記不純物等の吸着に起因す
る測定結果への悪影響も回避できる。更に、内壁面にコ
ーティングする物質を変えて分離特性を大幅に変化させ
ることも可能である。<Effects of the Invention> According to the present invention as described in detail above, a capillary column is provided which has a long service life because it is difficult for impurities from samples, buffer solutions, etc. to be adsorbed to the inner wall surface, and has excellent reproducibility of separation characteristics. Realize. Furthermore, there is almost no variation in the elution time from the beginning of the measurement, and the component to be measured in the sample can be measured stably (with good reproducibility), and the adverse effects on the measurement results due to the adsorption of the above-mentioned impurities can be avoided. Furthermore, it is also possible to significantly change the separation characteristics by changing the substance coated on the inner wall surface.
第１図は本発明に係るキャピラリーカラムの製法説明図
、第２図は界面動電クロマトグラフ装置の構成説明図、
第３図はクロマトグラム、第４図は分離特性の再現性を
調べた結果を示すグラフである。
Ｉａ、 Ｉｂ・・・槽、４．６・・・切換弁、５・・・
スプリッター、７・・・キャピラリーカラム、８・・・
検出器、９・・・電極、１０・・・高圧電源、１１・・
・表示装置。
第４図FIG. 1 is an explanatory diagram of the manufacturing method of a capillary column according to the present invention, FIG. 2 is an explanatory diagram of the configuration of an electrokinetic chromatography device,
FIG. 3 is a chromatogram, and FIG. 4 is a graph showing the results of examining the reproducibility of separation characteristics. Ia, Ib...Tank, 4.6...Switching valve, 5...
Splitter, 7... Capillary column, 8...
Detector, 9... Electrode, 10... High voltage power supply, 11...
・Display device. Figure 4
Claims (4)
ピラリーカラムにおいて、内部にメチルシリコン系シリ
コンポリマー溶液と架橋剤溶液とを封入して架橋反応を
行なわせ前記内壁面に一定膜厚を有する高分子膜をコー
ティングさせたことを特徴とするキャピラリーカラム。(1) In a capillary column used in an electrokinetic chromatography device, etc., a methylsilicon-based silicone polymer solution and a crosslinking agent solution are sealed inside to perform a crosslinking reaction, and a polymer having a constant film thickness on the inner wall surface is formed. A capillary column characterized by being coated with a membrane.
ルシリコン、メチルシアノフェニルシリコン、若しくは
メチルフェニルシリコンでなる特許請求範囲第（１）項
記載のキャピラリーカラム。(2) The capillary column according to claim (1), wherein the methylsilicon-based silicone polymer is methylsilicon, methylcyanophenylsilicon, or methylphenylsilicon.
ずれかの値でなる特許請求範囲第（１）項記載のキャピ
ラリーカラム。(3) The capillary column according to claim (1), wherein the constant film thickness has a value between 0.05 and 2.00 μm.
第（１）項記載のキャピラリーカラム。(4) The capillary column according to claim (1), wherein the crosslinking agent is divinylsilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62044768A JPS63210766A (en) | 1987-02-27 | 1987-02-27 | Capillary column |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62044768A JPS63210766A (en) | 1987-02-27 | 1987-02-27 | Capillary column |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63210766A true JPS63210766A (en) | 1988-09-01 |
Family
ID=12700598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62044768A Pending JPS63210766A (en) | 1987-02-27 | 1987-02-27 | Capillary column |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63210766A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997537A (en) * | 1986-10-21 | 1991-03-05 | Northeastern University | High performance microcapillary gel electrophoresis |
| JPH05180819A (en) * | 1991-12-26 | 1993-07-23 | Shimadzu Corp | Column filler for gas chromatograph |
| JP2003526781A (en) * | 2000-03-05 | 2003-09-09 | スリーエム イノベイティブ プロパティズ カンパニー | Fluid treatment device with diamond-like film |
| WO2008013222A1 (en) * | 2006-07-26 | 2008-01-31 | Keio University | Capillary with its internal wall modified, and process for producing the same |
-
1987
- 1987-02-27 JP JP62044768A patent/JPS63210766A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997537A (en) * | 1986-10-21 | 1991-03-05 | Northeastern University | High performance microcapillary gel electrophoresis |
| JPH05180819A (en) * | 1991-12-26 | 1993-07-23 | Shimadzu Corp | Column filler for gas chromatograph |
| JP2003526781A (en) * | 2000-03-05 | 2003-09-09 | スリーエム イノベイティブ プロパティズ カンパニー | Fluid treatment device with diamond-like film |
| JP4704653B2 (en) * | 2000-03-05 | 2011-06-15 | スリーエム イノベイティブ プロパティズ カンパニー | Fluid treatment apparatus having diamond-like film |
| WO2008013222A1 (en) * | 2006-07-26 | 2008-01-31 | Keio University | Capillary with its internal wall modified, and process for producing the same |
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