JPH01196563A - Liquid chromatography and apparatus therefor - Google Patents
Liquid chromatography and apparatus thereforInfo
- Publication number
- JPH01196563A JPH01196563A JP1965288A JP1965288A JPH01196563A JP H01196563 A JPH01196563 A JP H01196563A JP 1965288 A JP1965288 A JP 1965288A JP 1965288 A JP1965288 A JP 1965288A JP H01196563 A JPH01196563 A JP H01196563A
- Authority
- JP
- Japan
- Prior art keywords
- sample solution
- separation column
- unknown sample
- eluent
- eluate
- 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.)
- Granted
Links
- 238000004811 liquid chromatography Methods 0.000 title claims description 5
- 239000012488 sample solution Substances 0.000 claims abstract description 33
- 239000000523 sample Substances 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract 4
- 239000003480 eluent Substances 0.000 claims description 20
- 238000012544 monitoring process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 2
- 239000013074 reference sample Substances 0.000 abstract 6
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012088 reference solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- -1 sulfuric acid ions Chemical class 0.000 description 1
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は液体クロマトグラフィー及びその装置に係り、
特に試料溶液を連続的に流して標準試料と未知試料との
差を検出するのに好適な液体クロマトグラフィー及びそ
の装置に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to liquid chromatography and its apparatus,
In particular, the present invention relates to liquid chromatography and its apparatus suitable for detecting differences between a standard sample and an unknown sample by continuously flowing a sample solution.
従来のイオンクロマトグラフィーにおいては、試料は間
歇的、パルス的に加え、また、ペイカントクロマトグラ
フィーにあっては、溶離液と試料溶液を一定比率で連続
的に流して分離カラムの直前に試料溶液を含まない純水
（あるいは希薄な水酸化ナトリウム水溶液）を注入し、
試料中の目的成分の濃度に比例したシグナルを得るよう
にしていた。In conventional ion chromatography, the sample is added intermittently or in pulses, while in paycant chromatography, the eluent and sample solution are continuously flowed at a fixed ratio, and the sample solution is added just before the separation column. Inject pure water (or dilute aqueous sodium hydroxide solution) that does not contain
The aim was to obtain a signal proportional to the concentration of the target component in the sample.
なお、イオンクロマトグラフィーの分野では、次の先行
技術が発表されている。この先行技術としては、″アナ
リテイカル・ケミストリ、５６巻。In addition, in the field of ion chromatography, the following prior art has been announced. This prior art includes "Analytical Chemistry, Volume 56.
第２０７３〜２０７８頁（１９８４） （Ａｎａｌ、Ｃ
ｈｅａ＋。pp. 2073-2078 (1984) (Anal, C
hea+.
ＶｏＱ、５６．ｐｐ ２０７３〜２０７８）（１９８４
）があり、この先行技術は、イオンクロマトグラフィー
において、溶離液だけを分離カラムに連続的に流し、そ
の流れに蒸留水を注入すると、溶離液中の陰イオンがア
ブセントピークとして観察できる旨を示唆している。VoQ, 56. pp 2073-2078) (1984
), and this prior art shows that in ion chromatography, if only the eluent is continuously passed through a separation column and distilled water is injected into the flow, anions in the eluent can be observed as absent peaks. Suggests.
上記従来技術は、試料Ａと試料Ｂとの濃度差、を測定す
る場合に差が小さく、特にばらつき範囲にある場合など
の差が不明瞭であり、正確な測定が困難であるという問
題があった。The above conventional technology has the problem that when measuring the difference in concentration between sample A and sample B, the difference is small and the difference is unclear, especially when it is within the variation range, making accurate measurement difficult. Ta.
本発明の目的は、２つの試料間の濃度差を明瞭に検出す
ることができる液体クロマトグラフィー及びその装置を
提供することにある。An object of the present invention is to provide a liquid chromatography device that can clearly detect the concentration difference between two samples.
〔課題を解決するための手段〕
上記目的は、溶離液と標準試料溶液または未知試料溶液
をコントローラによって制御して所定の比率（例えば、
５０対５０）に混合してポンプを介してインジェクター
、分離カラム、検出器の順に連続的に送液し、上記分離
カラムの下流において上記検知器で溶出液中の試料成分
を連続的にモニタしながら上記溶離液と未知試料溶液ま
たは標準試料溶液を上記コントローラによって制御して
所定の比率（例えば、５０対５０）に混合してポンプを
介して上記分離カラムに間歇的に注入して上記未知試料
溶液中の試料濃度を分析することにより達成するように
した。[Means for solving the problem] The above purpose is to control the eluent and standard sample solution or unknown sample solution by a controller to maintain a predetermined ratio (for example,
The sample components in the eluate are continuously monitored by the detector downstream of the separation column. Meanwhile, the eluent and unknown sample solution or standard sample solution are mixed at a predetermined ratio (for example, 50:50) under the control of the controller and intermittently injected into the separation column via a pump to obtain the unknown sample. This was achieved by analyzing the sample concentration in the solution.
ペイカントクロマトグラフィーは、分離カラムに試料溶
液を連続的に流すと、カラム充填剤と試料溶液との間で
試料成分は平衡に達する。この定常状態において、流れ
の中に試料成分を含まない純粋な溶媒のバンドを形成し
、これが流れにしたがってカラム中に流れると、各々の
試料成分毎にこの試料成分の欠けたバンドとして移動し
、展開されていくうちにいくつかの試料成分の欠けたバ
ンドに分かれて溶出することになる。本方式では、この
作用を利用して、標準試料溶液と溶離液を分離カラムに
連続的に送液しているところにインジェクタより標準試
料溶液と濃度差の少ない未知試料溶液を間歇的に注入し
て濃度差を測定し、また、溶離液中のフタル酸水素カリ
ウムのペイカントを除去するために、電磁バルブを介し
て溶離液も展開液と同−比で送液することにより可能と
した。In paycant chromatography, when a sample solution is continuously passed through a separation column, sample components reach equilibrium between the column packing material and the sample solution. In this steady state, a band of pure solvent containing no sample components is formed in the flow, and as it flows into the column along with the flow, each sample component moves as a band lacking this sample component, As it develops, it separates into bands lacking some sample components and elutes. In this method, by utilizing this effect, an injector intermittently injects an unknown sample solution with a small concentration difference from the standard sample solution while the standard sample solution and eluent are continuously fed to the separation column. In order to measure the difference in concentration and to remove the paycant of potassium hydrogen phthalate in the eluent, the eluent was also fed at the same ratio as the developing solution through an electromagnetic valve.
以下本発明を第１図に示した実施例及び第２図。 The following is an embodiment of the present invention shown in FIG. 1 and FIG. 2.
第３図を用いて詳細に説明する。This will be explained in detail using FIG.
第１図は本発明の一実施例を示す流路図である。FIG. 1 is a flow path diagram showing one embodiment of the present invention.
第１図において、溶離液１と標準試料溶液２とがコント
ローラ１２によって制御される電磁弁３及び３′の開閉
により一定割合（例えば、５０対５０）でポンプ５によ
り吸引され、試料−溶離液混合部４で混合される。混合
された液はポンプ５によって注入部８を経て分離カラム
９に連続的に送られる。分離カラム溶出液は、検出器１
０を経て外部へ排出される。標準試料溶液２には、−船
釣に管理しようとする基準溶液（標準溶液）が送液され
る。In FIG. 1, an eluent 1 and a standard sample solution 2 are sucked by a pump 5 at a fixed ratio (for example, 50:50) by opening and closing electromagnetic valves 3 and 3' controlled by a controller 12, and the sample-eluent Mixed in the mixing section 4. The mixed liquid is continuously sent to the separation column 9 via the injection section 8 by the pump 5. The separation column eluate is sent to detector 1.
It passes through 0 and is discharged to the outside. A standard solution (standard solution) to be managed in a boat is fed to the standard sample solution 2 .
一方、測定しようとする未知試料溶液１１は、コントロ
ーラ１２により制御される電磁バルブ３及び３′の開閉
によって溶離液を５０対５０に混合され、送液ポンプ７
によって注入部８を経て間歇的に分離カラム９に注入さ
れる。なお、１３はドレンパイプである。On the other hand, the unknown sample solution 11 to be measured is mixed with an eluent at a ratio of 50:50 by opening and closing the electromagnetic valves 3 and 3' controlled by the controller 12, and
is intermittently injected into the separation column 9 via the injection section 8. Note that 13 is a drain pipe.
第２図に従来測定されているペイカントクロマトグラム
を示す。このクロマトグラムは、フッ素イオン（Ｆ−）
から硫酸イオン（Ｓ０４”−″）までを純水を注入して
測定しであるため、電導度が少なくなり、各イオンのピ
ークとして検出しである。FIG. 2 shows a conventionally measured paycant chromatogram. This chromatogram shows the fluorine ion (F-)
Since the sulfuric acid ions (S04''-'') were measured by injecting pure water, the conductivity was reduced and the peaks of each ion were detected.
第３図は本発明の装置により求めたクロマトグラムであ
る。標準試料溶液２（基準溶液）と測定しようとする未
知試料溶液１１を溶離液１とそれぞれ同一比率で混合し
て分析した場合、もし、試料溶液２と１１に差がなけれ
ば、ピークとして検出しない。第３図に示すクロマトグ
ラムのフッ素（Ｆ−）、塩素（ｃｐｔ−）、亜硝酸（Ｎ
Ｏｘ’″）は、未知試料の方が濃度が低く、シュウ素（
Ｂ ｒ” ） 。FIG. 3 is a chromatogram obtained using the apparatus of the present invention. When standard sample solution 2 (reference solution) and unknown sample solution 11 to be measured are mixed with eluent 1 in the same ratio and analyzed, if there is no difference between sample solutions 2 and 11, it will not be detected as a peak. . The chromatogram shown in Figure 3 shows fluorine (F-), chlorine (cpt-), nitrite (N
The concentration of Ox''') is lower in the unknown sample, and the concentration of Ox''') is lower in the unknown sample.
Br").
硝酸（ＮＯａ”’）は多く含まれていることを示し、硫
酸（Ｓ○４２″″）とフタル酸水素カリウムピークは、
溶離液（展開液）と未知試料に同−濃度含まれているた
め、ピークとして検出されない。この結果、従来法と比
較して濃度差を１回の測定で行えるので、迅速分析がで
きる。It shows that nitric acid (NOa"') is abundant, and the sulfuric acid (S○42") and potassium hydrogen phthalate peaks are
Since the eluent (developing solution) and the unknown sample contain the same concentration, it is not detected as a peak. As a result, compared to conventional methods, concentration differences can be determined in one measurement, allowing for rapid analysis.
以上説明した本発明によれば、標準溶液（基準溶液）と
未知試料溶液の差クロマトグラムが得られ、高感度に差
を測定できるので、迅速に品質管理ができ、また、溶離
液中に含まれるフタル酸水素カリウムのペイカントピー
クも除去でき、迅速分析が可能であるという効果がある
。According to the present invention described above, a difference chromatogram between a standard solution (reference solution) and an unknown sample solution can be obtained, and the difference can be measured with high sensitivity, so quality control can be performed quickly. It is also possible to remove the pecant peak of potassium hydrogen phthalate, which makes rapid analysis possible.
第１図は本発明の一実施例を示す流路図、第２図は従来
装置によるクロマトグラム、第３図は第１図の実施例に
よるクロマトグラムの例を示す図である。
１・・・溶離液、２・・・試料溶液（基準溶液）、３゜
３′・・・電磁弁、４・・・試料−溶離液混合部、５，
７・・・送液ポンプ、８・・・溶媒注入部、９・・・分
離カラム、１０・・・検出器、１１・・・試料溶液（未
知試料）、代理人 弁理士 小川勝男（、−１FIG. 1 is a flow path diagram showing an embodiment of the present invention, FIG. 2 is a chromatogram obtained by a conventional apparatus, and FIG. 3 is a diagram showing an example of a chromatogram obtained by the embodiment of FIG. 1... Eluent, 2... Sample solution (standard solution), 3゜3'... Solenoid valve, 4... Sample-eluent mixing section, 5,
7...Liquid pump, 8...Solvent injection part, 9...Separation column, 10...Detector, 11...Sample solution (unknown sample), Agent: Patent attorney Katsuo Ogawa (- 1
Claims (1)
比率に混合して分離カラムに連続的に送液し、前記分離
カラムの下流側において溶出液中の試料成分を連続的に
モニタしながら、前記溶離液と未知試料溶液または標準
試料溶液を所定の比率に混合したものを前記分離カラム
に間歇的に注入して前記未知試料溶液中の試料濃度を分
析することを特徴とする液体クロマトグラフィー。 ２、溶離液と標準試料溶液または未知試料溶液をコント
ローラによつて制御して所定の比率に混合してポンプを
介してインジェクター、分離カラム、検出器の順に連続
的に送液する手段と、該手段によつて送液中に前記溶離
液と未知試料溶液を前記コントローラによつて制御して
所定の比率に混合してポンプを介して前記分離カラムに
間歇的に注入する手段とを備え、前記検出器によつて前
記未知試料中の試料濃度を分析する手段を具備すること
を特徴とする液体クロマトグラフ装置。[Claims] 1. The eluent and the standard sample solution or unknown sample solution are mixed at a predetermined ratio, and the mixture is continuously fed to a separation column, and the sample components in the eluate are separated on the downstream side of the separation column. Analyzing the sample concentration in the unknown sample solution by intermittently injecting a mixture of the eluent and unknown sample solution or standard sample solution at a predetermined ratio into the separation column while continuously monitoring. Features of liquid chromatography. 2. A means for mixing an eluent and a standard sample solution or an unknown sample solution in a predetermined ratio under the control of a controller, and continuously sending the mixture through a pump in the order of the injector, separation column, and detector; means for intermittently injecting the eluent and the unknown sample solution into the separation column via a pump while controlling the eluent and the unknown sample solution at a predetermined ratio under the control of the controller; A liquid chromatograph apparatus comprising means for analyzing the sample concentration in the unknown sample using a detector.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1965288A JP2613237B2 (en) | 1988-02-01 | 1988-02-01 | Liquid chromatography and apparatus therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1965288A JP2613237B2 (en) | 1988-02-01 | 1988-02-01 | Liquid chromatography and apparatus therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01196563A true JPH01196563A (en) | 1989-08-08 |
| JP2613237B2 JP2613237B2 (en) | 1997-05-21 |
Family
ID=12005180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1965288A Expired - Fee Related JP2613237B2 (en) | 1988-02-01 | 1988-02-01 | Liquid chromatography and apparatus therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2613237B2 (en) |
-
1988
- 1988-02-01 JP JP1965288A patent/JP2613237B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2613237B2 (en) | 1997-05-21 |
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