WO2020039478A1 - Détecteur destiné à une chromatographie - Google Patents

Détecteur destiné à une chromatographie Download PDF

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Publication number
WO2020039478A1
WO2020039478A1 PCT/JP2018/030660 JP2018030660W WO2020039478A1 WO 2020039478 A1 WO2020039478 A1 WO 2020039478A1 JP 2018030660 W JP2018030660 W JP 2018030660W WO 2020039478 A1 WO2020039478 A1 WO 2020039478A1
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WO
WIPO (PCT)
Prior art keywords
light
measurement
emitting element
measurement light
solid state
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Application number
PCT/JP2018/030660
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English (en)
Japanese (ja)
Inventor
悠佑 長井
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株式会社島津製作所
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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 JP2020537910A priority Critical patent/JP7136209B2/ja
Priority to PCT/JP2018/030660 priority patent/WO2020039478A1/fr
Publication of WO2020039478A1 publication Critical patent/WO2020039478A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length

Definitions

  • the present invention relates to a detector for chromatography such as a differential refractive index detector and an absorbance detector.
  • a differential refractive index detector is known as a detector for liquid chromatography.
  • the differential refractive index detector irradiates measurement light through a slit to a flow cell having a sample cell and a reference cell separated by a partition, and forms a slit image of the measurement light passing through the flow cell on a light receiving element.
  • a change in the refractive index difference between the sample solution flowing through the sample cell and the reference solution flowing through the reference cell is detected (see Patent Document 1).
  • the differential refractive index detector detects a change in the refractive index based on the amount of displacement of the slit image formed on the light receiving element. Even if the actual position is unchanged, the fluctuation of the light amount of the light source is erroneously detected as the displacement of the slit image, and is output as a change in the refractive index.
  • the temperature control of the optical system and the high accuracy (low noise) of the light source are performed so that the refractive index change is not erroneously detected due to a change in an element other than the element that should be recognized as a refractive index change. Measures such as the use of a drive power supply have been taken.
  • Such a variation in the amount of light in the light emitting surface of the solid state light emitting element is not only when the solid state light emitting element is used as a light source of a differential refractive index detector, but also when it is used as a light source of a detector such as an absorbance detector. Has a negative effect.
  • an object of the present invention is to enable a solid-state light emitting element to be used as a light source for a detector having a stable light amount.
  • the chromatography detector according to the present invention is a solid-state light-emitting element that emits measurement light, a flow cell disposed on the optical path of the measurement light, and a detection unit for detecting the measurement light that has passed through the flow cell, A light-quantity variation reducing element provided between the solid-state light-emitting element and the detection unit and configured to reduce the influence of light-quantity variation in the peripheral region of the light beam of the measurement light emitted from the solid-state light-emitting element.
  • an aperture light shielding plate for guiding only the central region of the light beam of the measurement light emitted from the solid state light emitting element to the flow cell can be used.
  • the aperture light-shielding plate may be one that shields 50% or more of light on the peripheral edge side of the luminous flux of the measurement light emitted from the solid-state light-emitting element and extracts only the central region.
  • the first lens that collects the measurement light from the solid state light emitting element and irradiates the aperture light shielding plate, and collects the measurement light that has passed through the aperture light shielding plate and irradiates the light to the flow cell.
  • a second lens that collects the measurement light from the solid state light emitting element and irradiates the aperture light shielding plate, and collects the measurement light that has passed through the aperture light shielding plate and irradiates the light to the flow cell.
  • a second lens that collects the measurement light from the solid state light emitting element and irradiates the aperture light shielding plate, and collects the measurement light that has passed through the aperture light shielding plate and irradiates the light to the flow cell.
  • a mask that covers the peripheral area of the light emitting surface of the solid state light emitting element and blocks light emitted from the peripheral area may be used as the light quantity variation reducing element.
  • a light diffusing plate that mixes a central region of the luminous flux of the measurement light emitted from the solid state light emitting device and a peripheral region thereof and guides the mixed light to the flow cell may be used.
  • the chromatography detector according to the present invention includes the light amount fluctuation reducing element that reduces the influence of the light amount fluctuation in the peripheral region of the light flux of the measurement light emitted from the solid state light emitting element, the light emitting surface of the solid state light emitting element has The influence of the light quantity fluctuation of the light emitted from the area is reduced.
  • the solid state light emitting device can be used as a light source for a detector having a stable light amount.
  • FIG. 11 is a diagram illustrating a further variation of the light amount variation reducing element. It is data showing a verification result on the relationship between the presence or absence of the light amount fluctuation reducing element and the stability of the detection signal of the light receiving element.
  • the differential refractive index detector includes a flow cell 2, a solid light emitting element 4, a lens 5, an aperture light shielding plate 8, a lens 10, a mirror 12, a zero glass 14, a light receiving element 16, and an arithmetic and control unit 20. It has.
  • the solid state light emitting device 4 is an LED or LD.
  • the flow cell 2 is arranged on the optical axis of the measurement light 6 emitted from the solid state light emitting device 4.
  • the flow cell 2 has a sample cell 2a and a reference cell 2b, and the cells 2a and 2b are separated by a transparent partition.
  • a lens 10 is disposed in front of the flow cell 2, and a mirror 12 that reflects the measurement light 6 transmitted through the flow cell 2 is disposed behind the lens 10.
  • a light receiving element 16 such as a photodiode is provided on the optical path of the measuring light 6a reflected by the mirror 12, and the measuring light 6a reflected by the mirror 12 and transmitted through the flow cell 2 is imaged on the light receiving element 16. .
  • a zero glass 14 for translating the image of the measuring light 6a formed on the light receiving element 16 in parallel is arranged.
  • the arithmetic processing unit 20 is connected to the light receiving element 16.
  • the measurement light 6 emitted from the solid state light emitting element 4 is condensed by the lens 5, passes through the aperture light shielding plate 8, further irradiates the flow cell 2 through the lens 10, passes through the flow cell 2, and is reflected by the mirror 12. Is done.
  • the measurement light 6 a reflected by the mirror 12 passes through the flow cell 2 again and is imaged on the light receiving element 16 by the lens 10.
  • the light receiving element 16 includes two light receiving areas 16A and 16B, and a detection signal based on the amount of light incident on each light receiving area is taken into the arithmetic processing unit 20.
  • the optical path of the measurement light 6 passing through the flow cell 2 changes, and the image of the measurement light 6a formed on the light receiving surface of the light receiving element 16 moves in a certain direction. Is displaced.
  • the light receiving areas 16A and 16B of the light receiving element 16 are arranged adjacent to each other in the direction of displacement of the image of the measurement light 6a.
  • the image of the measurement light 6a is formed on the light receiving surface of the light receiving element 16 so as to straddle the boundary between the light receiving regions 16A and 16B.
  • the refractive index difference between the sample cell 2a and the reference cell 2b changes and an image is formed on the light receiving surface of the light receiving element 16.
  • the image of the light 6a is displaced. The displacement is detected by taking the difference between the detection signal values of the light receiving areas 16A and 16B, and the difference in the refractive index between the sample cell 2a and the reference cell 2b is obtained.
  • the arithmetic processing unit 20 is realized by a computer provided in the differential refractive index detector or a dedicated or general-purpose computer connected to the differential refractive index detector.
  • the arithmetic processing unit 20 has a function of calculating the difference in the refractive index between the sample cell 2a and the reference cell 2b in the flow cell 2 based on the detection signal values of the light receiving areas 16A and 16B of the light receiving element 16.
  • an aperture light shielding plate 8 is provided between the flow cell 2 and the solid state light emitting element 4. As shown in FIG. 2, the aperture light-shielding plate 8 is provided to shield the peripheral region of the light beam of the measurement light 6 emitted from the solid-state light-emitting element 4 and passing through the lens 5 to extract only the central region. It is. That is, the aperture light shielding plate 8 constitutes a light amount variation reducing element that reduces the influence of the light amount variation by shielding the peripheral area of the light beam emitted from the solid state light emitting element 4 where the light amount variation is large.
  • the aperture light-shielding plate 8 shields 50% or more of the luminous flux of the measurement light 6 emitted from the solid-state light-emitting element 4 on the peripheral side and extracts only the central region.
  • a slit is provided between the light source of the differential refractive index detector and the flow cell, but this slit is for extracting parallel light and extracts only the central region of the light beam whose light intensity is stable. It is not meant to be.
  • a mask 8 'made of a metal, an oxide, a dielectric, or the like may be arranged as the light amount variation reducing element. With the mask 8 ′, only the central region of the luminous flux of the measurement light 6 emitted from the solid-state light emitting element 4 can be extracted.
  • the light in the central region and the light in the peripheral region of the measurement light 6 are mixed on the optical axis of the measurement light 6 emitted from the solid-state light emitting element 4, that is, the light amount
  • a light diffusing plate 9 for making the instability uniform in the light beam may be provided.
  • the light diffusion plate 9 a microlens array having a light diffusion function (for example, LSD (lens diffusion plate: a product of Optical Solutions Co., Ltd.)) or the like can be used.
  • the light diffusing plate 9 mixes the light within the light beam of the measurement light 6 emitted from the solid state light emitting element 4 to make the instability of the light amount uniform within the light beam, thereby reducing the effect of the light amount fluctuation in the peripheral region of the light beam. Is done.
  • FIG. 5 shows data showing the results of verification of the relationship between the presence / absence of a light amount fluctuation reducing element such as an aperture light shielding plate or a light diffusion plate and the stability of the detection signal of the light receiving element 16.
  • a light amount fluctuation reducing element such as an aperture light shielding plate or a light diffusion plate
  • the aperture light-shielding plate 8 was installed on the optical axis of the measurement light 6 from the solid-state light-emitting element 4 (LED) under the condition that the refractive index difference between the sample cell 2a and the reference cell 2b did not change.
  • the fluctuation of the detection signal was monitored for each of the case where the light diffusion plate 9 (LSD) was disposed and the case where the light amount fluctuation reducing element was not disposed.
  • the aperture light shielding plate 8 used in this verification is designed to shield the peripheral side of the luminous flux of the measurement light 6 by about 70%.
  • the signal intensity of the light receiving element 16 should theoretically be constant. However, as shown in FIG. 5, when the light amount fluctuation reducing element is not provided, the signal intensity includes large noise and the signal intensity fluctuates between about 100 and 1100. When the signal intensity fluctuates in this way, it is erroneously detected as a displacement of the image of the measurement light 6a formed on the light receiving element 16, and is erroneously detected as a change in the refractive index difference between the sample cell 2a and the reference cell 2b.
  • the peripheral region of the light emitting surface of the solid state light emitting element 4 is obtained.
  • the effect of fluctuations in the amount of light emitted from the light source on the detection signal can be reduced, and the solid-state light emitting element 4 can be used as a light source for a detector having a stable amount of light.
  • the inventor also verified the relationship between the width dimension of the opening of the aperture light shielding plate 8 and the signal intensity of the light receiving element 16.
  • the verification results are as follows.
  • the smaller the opening width dimension of the aperture light shielding plate 8 the smaller the noise amount. This indicates that the amount of light is more stable toward the center of the light beam of the measurement light 6, and conversely, the fluctuation in the amount of light is larger as the light beam approaches the periphery of the light beam of the measurement light 6.
  • the light amount fluctuation reducing elements such as the aperture light shielding plate 8 and the light diffusion plate 9 are arranged on the optical axis of the measurement light 6 between the solid state light emitting element 4 and the flow cell 2.
  • the present invention is not limited to this, and a light quantity fluctuation reducing element may be arranged on the optical axis of the measurement light 6a between the flow cell 2 and the light receiving element 16.
  • the differential refractive index detector was described as an example of the detector for chromatography.
  • the present invention is similarly applied to a detector such as an absorbance detector using a solid light emitting element as a light source. Can be applied.

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  • Physics & Mathematics (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)
  • Optical Measuring Cells (AREA)

Abstract

Ledit détecteur destiné à une chromatographie comprend un élément électroluminescent à semi-conducteurs permettant d'émettre une lumière de mesure, une cuve à circulation disposée sur le trajet optique de la lumière de mesure, une unité de détection permettant de détecter une lumière de mesure ayant traversé la cuve à circulation, et un élément de réduction de fluctuation d'intensité de lumière situé entre l'élément électroluminescent à semi-conducteurs et l'unité de détection et destiné à réduire l'influence de fluctuation d'intensité de lumière dans une zone périphérique du faisceau de lumière de la lumière de mesure émise à partir de l'élément électroluminescent à semi-conducteurs.
PCT/JP2018/030660 2018-08-20 2018-08-20 Détecteur destiné à une chromatographie WO2020039478A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2020537910A JP7136209B2 (ja) 2018-08-20 2018-08-20 クロマトグラフィー用検出器
PCT/JP2018/030660 WO2020039478A1 (fr) 2018-08-20 2018-08-20 Détecteur destiné à une chromatographie

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2018/030660 WO2020039478A1 (fr) 2018-08-20 2018-08-20 Détecteur destiné à une chromatographie

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WO2020039478A1 true WO2020039478A1 (fr) 2020-02-27

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4816856B1 (fr) * 1968-12-25 1973-05-25
JPS6453132A (en) * 1987-08-24 1989-03-01 Fujitsu Ltd Particle detecting device
JPH04168347A (ja) * 1990-10-31 1992-06-16 Shimamura Keiki Seisakusho:Yugen 液体クロマトグラフィー用示差屈折率検出装置
JPH07318489A (ja) * 1994-05-20 1995-12-08 Shimamura Keiki Seisakusho:Kk 液体クロマトグラフィー用示差屈折率検出装置
JP2002296181A (ja) * 2001-03-30 2002-10-09 Jasco Corp 示差屈折率計
US20030206290A1 (en) * 2002-05-06 2003-11-06 Leica Microsystems Inc. Optical configuration and method for differential refractive index measurements
JP2004170218A (ja) * 2002-11-19 2004-06-17 Atago:Kk 屈折計

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2566124Y2 (ja) * 1992-06-01 1998-03-25 有限会社島村計器製作所 液体クロマトグラフィー用示差屈折率検出装置
JP3032485B2 (ja) * 1997-05-29 2000-04-17 ホーチキ株式会社 光電式煙感知器の投光装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4816856B1 (fr) * 1968-12-25 1973-05-25
JPS6453132A (en) * 1987-08-24 1989-03-01 Fujitsu Ltd Particle detecting device
JPH04168347A (ja) * 1990-10-31 1992-06-16 Shimamura Keiki Seisakusho:Yugen 液体クロマトグラフィー用示差屈折率検出装置
JPH07318489A (ja) * 1994-05-20 1995-12-08 Shimamura Keiki Seisakusho:Kk 液体クロマトグラフィー用示差屈折率検出装置
JP2002296181A (ja) * 2001-03-30 2002-10-09 Jasco Corp 示差屈折率計
US20030206290A1 (en) * 2002-05-06 2003-11-06 Leica Microsystems Inc. Optical configuration and method for differential refractive index measurements
JP2004170218A (ja) * 2002-11-19 2004-06-17 Atago:Kk 屈折計

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JPWO2020039478A1 (ja) 2021-08-10

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