WO2016117001A1 - Unité de détection de séparation, et chromatographe en phase liquide équipé de ladite unité de détection - Google Patents

Unité de détection de séparation, et chromatographe en phase liquide équipé de ladite unité de détection Download PDF

Info

Publication number
WO2016117001A1
WO2016117001A1 PCT/JP2015/051203 JP2015051203W WO2016117001A1 WO 2016117001 A1 WO2016117001 A1 WO 2016117001A1 JP 2015051203 W JP2015051203 W JP 2015051203W WO 2016117001 A1 WO2016117001 A1 WO 2016117001A1
Authority
WO
WIPO (PCT)
Prior art keywords
column
detection unit
sample
light
liquid
Prior art date
Application number
PCT/JP2015/051203
Other languages
English (en)
Japanese (ja)
Inventor
悠佑 長井
Original Assignee
株式会社島津製作所
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 株式会社島津製作所 filed Critical 株式会社島津製作所
Priority to PCT/JP2015/051203 priority Critical patent/WO2016117001A1/fr
Publication of WO2016117001A1 publication Critical patent/WO2016117001A1/fr

Links

Images

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
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/74—Optical detectors

Definitions

  • the present invention relates to a separation detection unit for separating and detecting a sample for each component and a liquid chromatograph including the separation detection unit.
  • a liquid chromatograph is a liquid feeding device that feeds a mobile phase, an analysis flow channel through which the mobile phase flows, an automatic sample injection device (auto sampler) that introduces a sample into the analysis flow channel, and an analysis column that separates the sample into components. And a detector that detects sample components separated by the analytical column.
  • the liquid feeding device, the autosampler, the analysis column, and the detector are configured as independent units, and the analysis flow path is configured by connecting these units with a pipe.
  • the separation characteristic of the analytical column since the separation characteristic of the analytical column has temperature dependence, it is housed in a column oven having a temperature control function in order to keep the temperature of the analytical column constant, and is configured as a column oven unit.
  • the detector is composed of a sample cell, a light source, an optical system that extracts light of the measurement wavelength from the light emitted from the light source and guides it to the sample cell, a detector that detects the light from the sample cell, etc. Are housed in a common housing and configured as a detection unit.
  • an object of the present invention is to reduce the dead volume from the analysis column to the sample cell and suppress the diffusion of the sample components separated by the analysis column.
  • An embodiment of a separation detection unit includes an analysis column that separates a sample into components, a detection unit that detects a sample component separated by the analysis column, and a column that accommodates the analysis column and the detection unit therein. And an oven.
  • the detection unit includes a liquid storage unit that stores the liquid from the analysis column, an inlet unit that is connected to one end of the analysis column and allows the liquid from the analysis column to flow into the liquid storage unit, and an outlet unit that allows the liquid in the liquid storage unit to flow out.
  • the column oven has an inlet port leading to the other end of the analytical column and an outlet port leading to the outlet of the sample cell.
  • One embodiment of a liquid chromatograph introduces a sample into a liquid-feeding unit that feeds a mobile phase, and a liquid-feeding unit that is connected to the liquid-feeding unit through a pipe and flows through the mobile phase from the liquid-feeding unit.
  • An automatic sample injection device a separation column connected to the automatic sample injection device through a pipe and separating the sample introduced by the automatic sample injection device for each component, and a detection unit for detecting the sample component separated by the separation column And the separation detection unit.
  • the detection unit includes a light source unit having an LED or an LD that irradiates light to the sample cell without going through the spectrometer, so that the spectrometer is unnecessary.
  • the entire detection unit is reduced in size, and the detection unit is also housed in a column oven that houses the analysis column.
  • the pipe connecting the analysis column and the sample cell can be shortened, the dead volume from the analysis column to the sample cell can be reduced, and a decrease in detection sensitivity due to diffusion of the sample component can be suppressed.
  • the sample component can be detected with high sensitivity.
  • the light source unit may include a plurality of LEDs or LDs that emit light in different wavelength ranges. If it does so, switching of a measurement wavelength can be easily performed by switching light emission and extinction of those LED or LD.
  • a plurality of analysis columns and a plurality of detection units corresponding to each analysis column may be accommodated in the column oven. By doing so, it is possible to separate samples and detect separated sample components in a plurality of analytical columns without preparing a plurality of column oven units and detection units corresponding to those column oven units.
  • One end of the analytical column and the inlet of the sample cell may be connected without a pipe. By doing so, the dead volume between the analysis column and the sample cell is further reduced, and a decrease in detection sensitivity due to sample diffusion can be further suppressed.
  • the liquid chromatograph of this embodiment includes a liquid feeding unit 2, an autosampler 4, a separation detection unit 6 and a control unit 8.
  • the liquid feeding unit 2 has an outlet port 10 for connecting a pipe, and the outlet port 10 is connected to the inlet port 12 of the autosampler 4 via the pipe 20.
  • the autosampler 4 has an outlet port 14 in addition to the inlet port 12, and the outlet port 14 is connected to the inlet port 16 of the separation detection unit 6 through a pipe 22.
  • the separation detection unit 6 also has an outlet port 18 in addition to the inlet port 16, and the outlet port 18 leads to the drain.
  • the liquid feeding unit 2 includes a liquid feeding pump 24 for feeding the mobile phase.
  • the mobile phase fed by the liquid feed pump 24 is introduced from the outlet port 10 to the autosampler 4 through the pipe 20.
  • the autosampler 4 introduces the sample into the flow path of the mobile phase supplied from the liquid feeding unit 2.
  • the introduced sample is introduced into the separation detection unit 6 through the pipe 22 together with the mobile phase.
  • the separation detection unit 6 includes an analysis column 28 that separates the sample for each component, and a detection unit 30 that detects the sample component separated by the analysis column 28.
  • the sample introduced into the flow path through which the mobile phase flows in the autosampler 4 is introduced into the analysis column 28 together with the mobile phase and separated for each component.
  • the sample components separated in the analysis column 28 are sequentially introduced into a sample cell provided in the detection unit 30 and detected.
  • the sample component that has passed through the detection unit 30 is discharged from the outlet port 18 to the drain together with the mobile phase.
  • the operations of the liquid feeding unit 2, the autosampler 4 and the separation detection unit 6 are controlled by a common control unit 8. Further, the detection signal obtained by the detection unit 30 of the separation detection unit 6 is taken into the control unit 6, and the components contained in the sample are specified and quantified.
  • the control unit 8 is realized by a computer such as a general-purpose personal computer or a dedicated system controller.
  • the separation detection unit 6 has a heat insulating column oven 32.
  • An inlet port 16 and an outlet port 18 for connecting a pipe end to the outer side surface of the column oven 32 are provided.
  • An analysis column 28 and a detection unit 30 are accommodated in an internal space 34 of the column oven 32.
  • the column oven 32 has, for example, a width dimension of about 250 mm, a height dimension of about 350 mm, and a depth dimension of about 100 mm.
  • the size of the analytical column 28 is, for example, about 8 mm in outer diameter and about 150 mm in length.
  • the analysis column 28 is arranged in the vertical direction so that the inlet 28a is on the lower side and the outlet 28b is on the upper side.
  • the analysis column 28 is held by a column holder 36 made of a metal having good thermal conductivity.
  • a heater is embedded in the column holder 36 (not shown), and the temperature of the analysis column 28 is controlled to a preset temperature by increasing or decreasing the output of the heater.
  • An inlet 28 a of the analysis column 28 is connected to the inlet port 16 via a piping tube 38, and an outlet 28 b of the analysis column 28 is connected to an inlet 42 a of the sample cell 42 of the detection unit 30 via a piping tube 40.
  • a direct temperature control method is adopted in which the temperature is controlled by directly heating the analytical column 28 by the column holder 36 in which the heater is embedded.
  • a heater and a fan are used instead of this. Therefore, an indirect temperature control method for adjusting the temperature of the entire internal space 34 of the column oven 32 may be adopted.
  • the detection unit 30 is provided above the analysis column 28.
  • the detection unit 30 includes a sample cell 42, a light emitting element 44, and a detection element 46.
  • the sample cell 42 is made of a light transmissive material.
  • the sample cell 42 has a size of, for example, about 35 mm ⁇ 40 mm ⁇ 80 mm.
  • the inlet portion 42 a of the sample cell 42 is connected to the outlet 28 b of the analytical column 28 via the piping tube 40, and the outlet portion 42 b is connected to the outlet port 18 via the piping tube 48.
  • the length of the piping tube 40 is 60 mm or less.
  • the inlet 42a of the sample cell 42a and the outlet 28b of the analysis column 28 may be directly connected without a pipe.
  • the light-emitting element 44 is an LED or an LD, and forms a light source unit that irradiates the sample cell 42 with light having a measurement wavelength.
  • the light emitting element 44 is disposed on the side of the sample cell 42 so as to emit light toward the sample cell 42.
  • Examples of the LED used as the light emitting element 44 include a LED having a diameter of about 8 mm, a length of about 8 mm, and a half width of 15 nm or less.
  • Examples of the LD used as the light emitting element 44 include those having a diameter of about 8 mm, a length of about 8 mm, and a half width of 5 nm or less.
  • the detection element 46 is, for example, a photodiode, and is arranged on the opposite side of the light source unit 44 with the sample cell 42 interposed therebetween.
  • a condensing lens for condensing the light emitted from the light emitting element 44 may be disposed between the light emitting element 44 and the sample cell 42.
  • the light emitting diode or laser diode used as the light emitting element 44 has a very small half-value width of several nanometers to several tens of nanometers. Therefore, the light emitted from the light emitting element 44 irradiates the sample cell 42 without passing through the spectroscope. Is done.
  • a spectroscope such as a diffraction grating for extracting light in a specific wavelength range from light emitted from the light emitting element 44 is not necessary.
  • a spectroscope such as a diffraction grating is provided, a large space of about 100 mm ⁇ 150 mm ⁇ 150 mm is required.
  • the entire size of the detection unit 30 is reduced, It can be accommodated in the same column oven 32 as the analytical column 28. Since the analysis column 28 and the sample cell 42 are accommodated in the same column oven 32, the piping connecting the analysis column 28 and the sample cell 42 can be shortened. Thereby, the dead volume from the analysis column 28 to the sample cell 42 can be reduced, and the diffusion of the sample component from the analysis column 28 to the sample cell 42 can be suppressed to improve the detection sensitivity.
  • the light-emitting element composed of a light-emitting diode or a laser diode is small, as shown in FIG. 3, a plurality of light-emitting elements are arranged side by side and arranged on the side of the sample cell 42, thereby allowing light of a plurality of wavelengths to be emitted.
  • the detection unit 30a that can be used for measurement can be configured.
  • two light emitting elements 44a and 44b having different emission wavelength ranges are arranged on the side of the sample cell 42 to constitute a light source unit. In such a case, an optical system such as a half mirror or a spectroscope is not necessary.
  • a detection element 50 such as a photodiode that detects a part of light from the light emitting element 44 as reference light may be provided. If it does so, the change of the emitted light amount of a light emitting diode or a laser diode can be detected with reference light, and the detection signal obtained by the detection element 46 can be corrected based on it.
  • FIG. 1 Another embodiment of the separation detection unit is shown in FIG. 1
  • each analytical column 28 has different separation characteristics.
  • the number of combinations of the analysis column 28 and the detection units 30 corresponding to the analysis column 28 may be two, or four or more.
  • the detection unit 30 does not have an optical system such as a spectroscope, the size of a combination of the analysis column 28 and the detection unit 30 can be reduced, and a plurality of the combinations can be reduced to the size of the column oven 32a. It can be accommodated in the common column oven 32a without increasing the size so as to form one separation detection unit 6a.
  • the mobile phase flowing from the inlet port 16 is branched between the inlet port 16 and the inlet 28a of each analytical column 28, and between the outlet port 18 and the outlet portion 42b of each sample cell 42, so that each analytical column 28 A branch flow channel portion 52 is provided for connecting the mobile phase flowing out from the outlet portion 42 b of each sample cell 42 to the common outlet port 18, connected to the inlet 28 a.
  • the inlet 28 a of each analysis column 28 is connected to the common inlet port 16, and the outlet 42 b of each sample cell 42 is connected to the common outlet port 18.
  • the sample introduced in the autosampler 4 flows into the separation detection unit 6a from the inlet port 16 and is divided into three flow paths by the branch flow path section 52 and introduced into each analysis column 28.
  • the sample that flows together with the mobile phase is separated for each component in a plurality of analysis columns 28 having different separation characteristics, and is detected by a detection unit 30 corresponding to each analysis column 28. Thereby, one sample can be separated and analyzed by a plurality of analysis columns 28 having different separation specificities.
  • the detector 30a in the embodiment of FIG. 3 or the detector 30b in the embodiment of FIG. 4 may be used.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

L'invention concerne une unité de détection de séparation qui comporte : une colonne d'analyse pour séparer un échantillon en ses composants respectifs ; une unité de détection pour détecter les composants de l'échantillon séparés par la colonne d'analyse ; et un four de colonne, dans lequel la colonne d'analyse et l'unité de détection sont contenus. L'unité de détection comporte : une cellule d'échantillon pourvue d'une partie réception de liquide destinée à recevoir un liquide provenant de la colonne d'analyse, une partie d'entrée qui est reliée à une extrémité de la colonne d'analyse, et par laquelle le liquide provenant de la colonne d'analyse de liquide s'écoule dans la partie réception de liquide, et une partie de sortie par laquelle sort le liquide se situant dans la partie réception de liquide ; une unité source lumineuse équipée d'une diode électroluminescente ou d'une diode laser pour exposer la cellule d'échantillon à une lumière sans que la lumière ne traverse un diviseur de faisceau ; et un élément de détection pour détecter soit la lumière émise par l'unité source lumineuse et qui a traversé la cellule d'échantillon, soit la lumière émise par l'échantillon dans la cellule d'échantillon, ladite lumière ayant été excitée par la lumière provenant de l'unité source lumineuse. Le four de colonne comporte : un orifice d'entrée qui mène à une autre extrémité de la colonne d'analyse ; et un orifice de sortie qui mène à la partie de sortie de la cellule d'échantillon.
PCT/JP2015/051203 2015-01-19 2015-01-19 Unité de détection de séparation, et chromatographe en phase liquide équipé de ladite unité de détection WO2016117001A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2015/051203 WO2016117001A1 (fr) 2015-01-19 2015-01-19 Unité de détection de séparation, et chromatographe en phase liquide équipé de ladite unité de détection

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2015/051203 WO2016117001A1 (fr) 2015-01-19 2015-01-19 Unité de détection de séparation, et chromatographe en phase liquide équipé de ladite unité de détection

Publications (1)

Publication Number Publication Date
WO2016117001A1 true WO2016117001A1 (fr) 2016-07-28

Family

ID=56416569

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/051203 WO2016117001A1 (fr) 2015-01-19 2015-01-19 Unité de détection de séparation, et chromatographe en phase liquide équipé de ladite unité de détection

Country Status (1)

Country Link
WO (1) WO2016117001A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010026742A1 (fr) * 2008-09-02 2010-03-11 ジーエルサイエンス株式会社 Chromatographie liquide
JP3191627U (ja) * 2014-04-18 2014-07-03 株式会社島津製作所 クロマトグラフ
WO2014157282A1 (fr) * 2013-03-26 2014-10-02 積水メディカル株式会社 Dispositif de détection de l'absorbance pour l'analyse des écoulements et dispositif d'analyse des écoulements

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010026742A1 (fr) * 2008-09-02 2010-03-11 ジーエルサイエンス株式会社 Chromatographie liquide
WO2014157282A1 (fr) * 2013-03-26 2014-10-02 積水メディカル株式会社 Dispositif de détection de l'absorbance pour l'analyse des écoulements et dispositif d'analyse des écoulements
JP3191627U (ja) * 2014-04-18 2014-07-03 株式会社島津製作所 クロマトグラフ

Similar Documents

Publication Publication Date Title
US11513006B2 (en) Systems and methods for an absorbance detector with optical reference
US7928408B2 (en) Multi-channel fluorescence measuring optical system and multi-channel fluorescence sample analyzer
US11828682B2 (en) Integrated illumination-detection flow cell for liquid chromatography
US8218141B2 (en) Universal multidetection system for microplates
CN104204739B (zh) 分光测定装置
JP6394803B2 (ja) 分取クロマトグラフ
US9880093B2 (en) Optical absorption monitor system
US7532313B2 (en) Fluorescence detector and liquid chromatograph having the fluorescence detector
JP2009168478A (ja) 光度計
US20180120222A1 (en) Planar reflective ring
US20230101434A1 (en) Apparatus and Method for Measuring the Light Absorbance of a Substance in a Solution
US9448177B2 (en) Flame photometric detector
WO2016117001A1 (fr) Unité de détection de séparation, et chromatographe en phase liquide équipé de ladite unité de détection
US20180120223A1 (en) Planar reflective ring
JP2015094586A (ja) 電気泳動装置
WO2014021099A1 (fr) Analyseur chromatographique liquide
CN108955889A (zh) 用于低温透射测温的探测器
JP6269345B2 (ja) 超臨界流体を用いた成分抽出分離装置及び成分抽出分離方法
JP6477891B2 (ja) 液体クロマトグラフ用検出器
US20120006998A1 (en) Configurations of using a point light source in the context of sample separation
JP2012007930A5 (fr)
CN115931792A (zh) 一种多通道荧光定量pcr的荧光检测光路系统
KR20190014158A (ko) 광 필터를 이용한 가스 검출기
KR20190092430A (ko) 복수의 빔 경로를 갖는 분광계

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15878697

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 15878697

Country of ref document: EP

Kind code of ref document: A1