JP2009168478A - Photometer - Google Patents

Photometer Download PDF

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JP2009168478A
JP2009168478A JP2008003805A JP2008003805A JP2009168478A JP 2009168478 A JP2009168478 A JP 2009168478A JP 2008003805 A JP2008003805 A JP 2008003805A JP 2008003805 A JP2008003805 A JP 2008003805A JP 2009168478 A JP2009168478 A JP 2009168478A
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light
led
photometer
light source
wavelength
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Shinsuke Kaida
晋介 皆田
Kouji Tsutsuda
恒治 筒田
Go Nishitarumi
剛 西垂水
Masato Ito
正人 伊藤
Kantaro Maruoka
幹太郎 丸岡
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Hitachi High Tech Corp
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Hitachi High Technologies Corp
Hitachi High Tech Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To improve quantifying precision in analysis while analyzing at a short waiting time by suppressing drift of the base line caused by light quantity change of a light source. <P>SOLUTION: In a chromatograph including a light source 19, a sample cell 18 where light flux radiated from the light source is made incident, a detection element 21 detecting absorbance of the light passing through the cell, a photocurrent/voltage conversion circuit converting the signal of the detection element into voltage, and a light quantity correcting circuit correcting the light quantity of the light source, a plurality of light emitting diodes having at least one or more peak wavelength are used for the light source. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は光度計に関し、例えば、クロマトグラフ装置用光度計，アミノ酸分析装置用光度計に関する。   The present invention relates to a photometer, for example, a photometer for a chromatograph apparatus and a photometer for an amino acid analyzer.

従来例えば、クロマトグラフ装置用光度計の光源としてフィラメントにタングステンを使用し不活性ガスを充填したタングステンランプもしくは不活性ガスに微量のハロゲンを充填したハロゲンランプが多く用いられている。上記ランプ光を試料に照射し、特定のクロマトグラフ測定用波長における吸収された光量を検出することで、任意の試料量等を検出することができる。すなわち、入射した光量と通過した光量を比較することにより試料量等を検出するものである。関連技術として特許文献１に記載されたものがある。   Conventionally, for example, a tungsten lamp in which tungsten is used for a filament and an inert gas is filled as a light source of a photometer for a chromatograph apparatus, or a halogen lamp in which an inert gas is filled with a small amount of halogen is often used. By irradiating the sample with the lamp light and detecting the amount of light absorbed at a specific chromatographic measurement wavelength, an arbitrary sample amount or the like can be detected. That is, the amount of sample is detected by comparing the amount of incident light and the amount of light that has passed through. There exists a thing described in patent document 1 as related technology.

特開平３−２２６６３２号公報JP-A-3-226632

上記従来技術のタングステンランプは、発光が安定しないと吸光度を正確に測定できないという課題がある。また、ランプ内に蒸発した金属が付着するため長時間使用すると光量が低下する。さらに、ランプ装着時に皮脂等の有機物で表面を汚すと、高温時に付着物が分解し、石英ガラスを破損する等取り扱いが難しいという課題がある。   The conventional tungsten lamp has a problem that the absorbance cannot be measured accurately unless the light emission is stable. In addition, since the evaporated metal adheres to the inside of the lamp, the amount of light decreases when used for a long time. Further, if the surface is soiled with organic substances such as sebum when the lamp is mounted, there is a problem that the deposits are decomposed at a high temperature, and the quartz glass is damaged, which makes it difficult to handle.

本発明の一つの目的は、発熱が少なく長期間光量及び波長変化が少ないＬＥＤを用いたクロマトグラフ装置用の光度計を提供することにある。   One object of the present invention is to provide a photometer for a chromatographic apparatus using an LED that generates little heat and has a small amount of light and a small change in wavelength for a long period of time.

本発明の一つの特徴は、クロマトグラフ用光源をタングステンランプよりも安定な光源であるＬＥＤに変更することである。   One feature of the present invention is that the chromatographic light source is changed to an LED that is a more stable light source than a tungsten lamp.

本発明の他の特徴は、光源の光量変化によるベースラインのドリフトを抑制し、待ち時間の少ない分析を行うと共に、分析の定量精度を向上させることである。   Another feature of the present invention is to suppress baseline drift due to a change in the amount of light from the light source, to perform analysis with less waiting time, and to improve the quantitative accuracy of the analysis.

本発明のその他の特徴は、光源と、前記光源から放出された高速が入射する試料用セルと、前記セルを通過した光の吸光度を検出する検知素子と、前記検知素子の信号を電圧に変換する光電流電圧変換回路と、前記光源の光量を補正するための光量補正回路を有するクロマトグラフ装置において、光源に少なくとも１つ以上のピーク波長を持つ複数個の発光ダイオードを用いることである。   Other features of the present invention include a light source, a sample cell incident at a high speed emitted from the light source, a detection element that detects the absorbance of light that has passed through the cell, and a signal from the detection element is converted into a voltage. In a chromatographic apparatus having a photocurrent-voltage conversion circuit that performs the above and a light amount correction circuit for correcting the light amount of the light source, a plurality of light emitting diodes having at least one peak wavelength are used as the light source.

本発明の一つの態様によれば、光源の光量の変化を抑制し、定量精度を向上することができる。   According to one aspect of the present invention, it is possible to suppress a change in the light amount of the light source and improve the quantitative accuracy.

また、本発明の他の態様によれば、ＬＥＤは従来光源（例えば、タングステンランプ）よりも、効率が良く熱放出が少ないことから、冷却系の簡略化が可能となり、装置の小型化、低コスト化が図れる。   In addition, according to another aspect of the present invention, the LED has higher efficiency and less heat emission than a conventional light source (for example, a tungsten lamp), so that the cooling system can be simplified, and the apparatus can be reduced in size and size. Cost can be reduced.

また、本発明のその他の態様によれば、従来光源（例えば、タングステンランプ）の寿命に比べ、ＬＥＤの寿命は長く、保守コストの低減が可能である。   Moreover, according to the other aspect of this invention, compared with the lifetime of the conventional light source (for example, tungsten lamp), the lifetime of LED is long and maintenance cost can be reduced.

さらに、本発明の更に他の態様によれば、必要なピーク波長を有するＬＥＤのみを点灯させることで消費電力の低減ができる。本発明の前記した複数の特徴及び更に他の特徴については、以下の記述により説明される。   Furthermore, according to still another aspect of the present invention, power consumption can be reduced by lighting only LEDs having a necessary peak wavelength. The above-described features and further features of the present invention will be described in the following description.

本発明の実施例について、図を用いて説明する。   Embodiments of the present invention will be described with reference to the drawings.

図１はクロマトグラフ用光源の一例の説明図である。クロマトグラフ用光源は、熱伝導アレイ２０上に複数のＬＥＤ光源１９を配置している。ＬＥＤ光源１９は平面状の熱伝導アレイ２０を用いず、同一平面以外に配置しても構わない。アレイ中心部にはＬＥＤ光をフローセルに入射するための光通過口４０がある。複数（図１では、１６個）のＬＥＤ光源１９は、光通過口４０を中心として放射状に配置されている。しかし、複数のＬＥＤ光源１９は、測定対象や測定目的に応じて、縦横の行列状に配置しても良い。また、図１では平面状の熱伝導アレイ２０を示したが、後述の図２のように、熱伝導アレイ２０自体がロート状又はパラボラアンテナ名状の断面形状を有しても良い。これにより、複数のＬＥＤ光源１９の光量密度を向上させることができ、幅広い測定に対応できる。熱伝導アレイ２０自体は熱伝導効率が高い材質を使うことが、ＬＥＤ光源１９の冷却のために望ましい。   FIG. 1 is an explanatory diagram of an example of a chromatographic light source. In the chromatographic light source, a plurality of LED light sources 19 are arranged on the heat conducting array 20. The LED light source 19 may be arranged on the same plane without using the planar heat conducting array 20. At the center of the array is a light passage opening 40 for allowing LED light to enter the flow cell. A plurality (16 in FIG. 1) of LED light sources 19 are arranged radially with the light passage opening 40 as the center. However, the plurality of LED light sources 19 may be arranged in rows and columns depending on the measurement object and measurement purpose. Further, although the planar heat conducting array 20 is shown in FIG. 1, the heat conducting array 20 itself may have a funnel-shaped or parabolic antenna-shaped cross-sectional shape as shown in FIG. Thereby, the light quantity density of the some LED light source 19 can be improved, and it can respond to a wide measurement. It is desirable for the cooling of the LED light source 19 that the heat conducting array 20 itself is made of a material having high heat conducting efficiency.

次に、図２を用いてクロマトグラフ用光源を使用した検出系を説明する。ある特定波長に吸光度を持つ任意の物質を測定する場合、異なる波長特性を有する複数のＬＥＤ光源１９の中からその特定波長にピークを有する１つ又は複数のＬＥＤ光源１９を点灯させる。点灯したＬＥＤ光源１９から放出した光（以下、ＬＥＤ光とも称する。）は、可動式ミラー４１により反射し、熱伝導アレイ２０の光通過口４０を通過する。可動式ミラー４１の角度を変更することで、任意のＬＥＤを点灯させた場合でも、同一光軸４２でフローセル１８にＬＥＤ光を入射することが可能である。ＬＥＤ光は試料用のフローセル１８に入射し、入射した光はフローセル１８内に流れる物質（試料、又は、試料を希釈又は濃縮したもの）により吸収され減光する。吸収を受け減光した光は、検知素子２１により光強度を電流に変換し、光電流電圧変換回路２２（図２には図示せず、図３参照）で電圧に変換される。光電流電圧変換回路２２で変換された電圧は、吸光度として出力する。検知素子２１としては、シリコンホトセル等を用いることができる。   Next, a detection system using a chromatographic light source will be described with reference to FIG. When measuring an arbitrary substance having absorbance at a specific wavelength, one or a plurality of LED light sources 19 having a peak at the specific wavelength are turned on among the plurality of LED light sources 19 having different wavelength characteristics. Light emitted from the lit LED light source 19 (hereinafter also referred to as LED light) is reflected by the movable mirror 41 and passes through the light passage port 40 of the heat conducting array 20. By changing the angle of the movable mirror 41, it is possible to make the LED light incident on the flow cell 18 with the same optical axis 42 even when any LED is lit. The LED light is incident on the flow cell 18 for the sample, and the incident light is absorbed and attenuated by a substance (sample or a diluted or concentrated sample) flowing in the flow cell 18. The light that has been absorbed and dimmed is converted into current by the detection element 21 and converted into voltage by the photocurrent-voltage conversion circuit 22 (not shown in FIG. 2, see FIG. 3). The voltage converted by the photocurrent voltage conversion circuit 22 is output as absorbance. As the detection element 21, a silicon photocell or the like can be used.

可動式ミラー４１の代わりに可動式グレーティングを用いることが可能である。可動式グレーティングやプリズムと言った光学素子を用いることで、ピーク強度をより先鋭化してフローセル１８に入射することが可能である。また、ピーク強度の先鋭化の方法として、任意のバンドパスフィルタを光軸上に配置してもよい。また、複数のＬＥＤのうち全てを点灯させてもよいまた、複数のＬＥＤのうち一部分を点灯させてもよい。   Instead of the movable mirror 41, a movable grating can be used. By using an optical element such as a movable grating or a prism, the peak intensity can be made sharper and incident on the flow cell 18. As a method for sharpening the peak intensity, an arbitrary band pass filter may be arranged on the optical axis. Further, all of the plurality of LEDs may be turned on, or a part of the plurality of LEDs may be turned on.

図３は、３個のＬＥＤを使用した、３ＬＥＤ式アミノ酸分析装置の検出器（光度計）の説明図である。平板形状の熱伝導アレイ２０上に配置された３個のＬＥＤ光源１９として、それぞれ、アミノ酸分析用波長４４０ｎｍ，５７０ｎｍを持つ独立したＬＥＤと、リファレンス波長の７００ｎｍを使用する。ＬＥＤ光源１９より放出された光は、分析対象である試料用のフローセル１８に照射される。フローセル１８に対して光軸を直角に入射するため、ＬＥＤの数だけフローセル１８を用いた。入射した光はフローセル１８内に流れる試薬により発色したアミノ酸試料により、波長４４０ｎｍ，５７０ｎｍ付近の光が吸収を受け減光する。吸収を受け減光した光は、複数（図３では３個）の検知素子２１により光強度を電流に変換し、光電流電圧変換回路２２で電圧に変換される。光電流電圧変換回路２２で変換された電圧は、吸光度のデータとして出力する。このフローセル１８の入射口間隔（図３ではｄ１，ｄ２）から、吸光度のデータの時間ズレを補正することでアミノ酸分析が可能となる。   FIG. 3 is an explanatory diagram of a detector (photometer) of a 3LED type amino acid analyzer using three LEDs. As the three LED light sources 19 arranged on the plate-shaped heat conduction array 20, independent LEDs having amino acid analysis wavelengths of 440 nm and 570 nm and a reference wavelength of 700 nm are used, respectively. The light emitted from the LED light source 19 is irradiated to the sample flow cell 18 to be analyzed. Since the optical axis is incident at a right angle with respect to the flow cell 18, the flow cells 18 corresponding to the number of LEDs are used. The incident light is attenuated by absorption of light in the vicinity of wavelengths of 440 nm and 570 nm by the amino acid sample colored by the reagent flowing in the flow cell 18. The light that has been absorbed and dimmed is converted into current by a plurality of (three in FIG. 3) sensing elements 21 and converted into voltage by the photocurrent-voltage conversion circuit 22. The voltage converted by the photocurrent / voltage conversion circuit 22 is output as absorbance data. The amino acid analysis can be performed by correcting the time shift of the absorbance data from the entrance opening interval (d1, d2 in FIG. 3) of the flow cell 18.

図４は、１個のＬＥＤを使用した、１ＬＥＤ式アミノ酸分析装置の検出器（光度計）の説明図である。この場合、ＬＥＤ光源１９はシングルチップ型、もしくはマルチチップ型ＬＥＤを用いる。   FIG. 4 is an explanatory diagram of a detector (photometer) of a 1 LED type amino acid analyzer using one LED. In this case, the LED light source 19 uses a single chip type or a multichip type LED.

シングルチップ型とは、青色もしくは紫外ＬＥＤのチップにより、蛍光体を励起させるＬＥＤである。すなわち、単一樹脂内に青色もしくは紫外ＬＥＤを有し、ＬＥＤ内に蛍光体が充填されることで４４０ｎｍ，５７０ｎｍ，７００ｎｍの波長を発するものをシングルチップ型ＬＥＤという。シングルチップ型ＬＥＤでアミノ酸分析装置光源を構成した場合、図４に示すようにフローセル１８の入射口は一つで良い。フローセル通過光をグレーティングやプリズム等の分光素子２３を使用して各波長に分離し、複数の検知素子２１にそれぞれ入射すると、３ＬＥＤ光源式同様の測定が可能となる。   The single chip type is an LED that excites a phosphor with a blue or ultraviolet LED chip. That is, a single chip type LED having a blue or ultraviolet LED in a single resin and emitting a wavelength of 440 nm, 570 nm, or 700 nm when the LED is filled with a phosphor. When the amino acid analyzer light source is composed of a single chip LED, the flow cell 18 may have only one entrance as shown in FIG. When the light passing through the flow cell is separated into wavelengths by using a spectroscopic element 23 such as a grating or a prism, and enters each of the plurality of detection elements 21, the same measurement as that of the 3LED light source type can be performed.

マルチチップ型とは、光の３原色である赤・緑・青のＬＥＤのチップや補色となる２色のＬＥＤを一つの発光源とするＬＥＤである。すなわち、単一樹脂内に赤・青・緑の３ＬＥＤチップに備え、４４０ｎｍ，５７０ｎｍ，７００ｎｍの波長を発するものをマルチチップ型ＬＥＤという。ハロゲンランプのフィラメントサイズが２.１×４.０であるから、フィラメントサイズと同等の領域内に上記３ＬＥＤを配置することでハロゲンランプ同等の点光源と見做してアミノ酸分析を行うことができる。これは、ハロゲンランプ以外の光源のフィラメントサイズと同等の領域内に上記３ＬＥＤを配置することで当該光源と同等の点光源と見做すことができる。   The multi-chip type is an LED having one light emission source of red, green, and blue LED chips that are the three primary colors of light and two-color LEDs that are complementary colors. That is, a multi-chip type LED that emits wavelengths of 440 nm, 570 nm, and 700 nm in a single resin and is provided in three LED chips of red, blue, and green. Since the filament size of the halogen lamp is 2.1 × 4.0, amino acid analysis can be performed by considering the point light source equivalent to the halogen lamp by arranging the 3 LEDs in an area equivalent to the filament size. . This can be regarded as a point light source equivalent to the light source by arranging the 3 LEDs in a region equivalent to the filament size of the light source other than the halogen lamp.

図５はダイクロイックミラーを用いた３ＬＥＤ式アミノ酸分析装置の検出器（光度計）の説明図である。ダイクロイックミラーは特定の波長の光を反射し、その他の波長の光を透過する特性を有する。アミノ酸分析装置はフローセルに入射する光の光軸を合わせる必要がある。図５に示す、ダイクロイックミラー１（２５）は５００ｎｍ、ダイクロイックミラー２（２６）は６５０ｎｍを閾値とする特性を有する。ＬＥＤ１（２７）は４４０ｎｍのＬＥＤであり、ダイクロイックミラー１（２５）裏面から入射する。ＬＥＤ２（２８）からの５７０ｎｍの光はダイクロイックミラー１（２５）の表面で反射する。ＬＥＤ１（２７）とＬＥＤ２（２８）の光は混光され、ダイクロイックミラー２（２６）裏面に入射する。ＬＥＤ３（２９）からの７００ｎｍの光はダイクロイックミラー２（２６）表面で反射し、混光した３ＬＥＤの光はフローセル１８に入射する。フローセル１８からの通過光は例えば、グレーティング等の分光素子２３により分光され検知素子２１に入射し、吸光度のデータとして出力される。ＬＥＤ光源の波長及びダイクロイックミラー閾値波長は、混光した光を同一光軸でフローセルに入射できれば、上記特性値でなくてもよい。また、ダイクロイックミラーの代わりにハーフミラー等で構成してもよい。   FIG. 5 is an explanatory diagram of a detector (photometer) of a 3LED amino acid analyzer using a dichroic mirror. The dichroic mirror has a characteristic of reflecting light of a specific wavelength and transmitting light of other wavelengths. The amino acid analyzer needs to align the optical axis of light incident on the flow cell. The dichroic mirror 1 (25) shown in FIG. 5 has a threshold value of 500 nm, and the dichroic mirror 2 (26) has a threshold value of 650 nm. LED1 (27) is a 440-nm LED and is incident from the back surface of the dichroic mirror 1 (25). The light of 570 nm from the LED 2 (28) is reflected by the surface of the dichroic mirror 1 (25). The lights of the LED 1 (27) and the LED 2 (28) are mixed and enter the back surface of the dichroic mirror 2 (26). The 700 nm light from the LED 3 (29) is reflected by the surface of the dichroic mirror 2 (26), and the mixed light of the 3 LEDs enters the flow cell 18. The passing light from the flow cell 18 is dispersed by, for example, a spectroscopic element 23 such as a grating, enters the detection element 21, and is output as absorbance data. The wavelength of the LED light source and the dichroic mirror threshold wavelength may not be the above-described characteristic values as long as mixed light can enter the flow cell with the same optical axis. Further, a half mirror or the like may be used instead of the dichroic mirror.

（ＬＥＤ光量の調整）
図６は光量補正回路の説明図である。図６に示すとおり、ＬＥＤ順電流制御回路はアナログ部６６とディジタル部６７から構成される。ディジタル部６７はマイコンと処理ソフトとから構成しても良い。複数のＬＥＤ光源１９には直列に可変抵抗３１が接続される。各ＬＥＤ光源１９は、定電圧源から電力が供給されて動作する。なお、ＬＥＤ光源１９は可変抵抗３１に対して直列に単一で接続しても良いし、複数個を直列に接続しても良い。また、定電圧源は各ＬＥＤ毎に独立した電源を配置しても良い。ＬＥＤ順電流制御回路はＬＥＤ光源１９の光量を測定する受光素子２４と、光電流を電圧に変換する変換部６１と、変換部６１からの電圧を示すアナログ信号をディジタル信号へ変換するＡＤＣ部６２と、基準値の信号を発生する基準値信号発生部６３と、ＡＤＣ部６２からのディジタル信号を基準値の信号と比較する比較部６４と、比較部６４での比較結果から順電流値を最適化する抵抗値を設定する抵抗値制御部６５を有する。 (Adjustment of LED light quantity)
FIG. 6 is an explanatory diagram of the light amount correction circuit. As shown in FIG. 6, the LED forward current control circuit includes an analog unit 66 and a digital unit 67. The digital unit 67 may be composed of a microcomputer and processing software. A variable resistor 31 is connected in series to the plurality of LED light sources 19. Each LED light source 19 is operated with power supplied from a constant voltage source. Note that the LED light source 19 may be connected in series to the variable resistor 31, or a plurality of LED light sources 19 may be connected in series. The constant voltage source may be provided with an independent power source for each LED. The LED forward current control circuit includes a light receiving element 24 that measures the light quantity of the LED light source 19, a conversion unit 61 that converts photocurrent into voltage, and an ADC unit 62 that converts an analog signal indicating the voltage from the conversion unit 61 into a digital signal. A reference value signal generation unit 63 for generating a reference value signal, a comparison unit 64 for comparing a digital signal from the ADC unit 62 with a reference value signal, and a forward current value from the comparison result in the comparison unit 64 is optimized. A resistance value control unit 65 for setting a resistance value to be converted.

可変抵抗３１はディジタルポテンショメータであり、抵抗値制御部６５からの信号で抵抗値を変更することができる。可変抵抗３１は、リアルタイム制御が可能であれば、ディジタルポテンショメータでなくても構わない。可変抵抗３１の抵抗値を制御することにより、ＬＥＤ光源１９に流れる順電流を制御することができる。すなわち、ＬＥＤ光源１９の光量は順電流に依存することから、ＬＥＤの光量制御ができる。順電流を制御する方法として、光量を測定するのではなく直接ＬＥＤの順電流を測定しても良い。また、ＬＥＤの順電圧を測定しても良い。   The variable resistor 31 is a digital potentiometer, and the resistance value can be changed by a signal from the resistance value control unit 65. The variable resistor 31 may not be a digital potentiometer as long as real-time control is possible. By controlling the resistance value of the variable resistor 31, the forward current flowing through the LED light source 19 can be controlled. That is, since the light amount of the LED light source 19 depends on the forward current, the light amount of the LED can be controlled. As a method of controlling the forward current, the forward current of the LED may be directly measured instead of measuring the light amount. Further, the forward voltage of the LED may be measured.

図６のように、ＬＥＤ光源１９に複数個のＬＥＤを使用する場合、同一平面上の熱伝導アレイ２０上に配置する。これは、ＬＥＤ相互に熱伝導を行わせることで、ＬＥＤの発熱及び周囲温度による光量の変化を同期させるためである。光量変化を同期させることで、各ＬＥＤの温度依存性による光量変化を同期させることができる。同期したリファレンス信号ＬＥＤの波長７００ｎｍよりベースラインノイズを求めることで、より精密な測定が可能となる。この熱伝導アレイ２０は同一平面上でなくても良く、効率的な熱の交換が行えれば良い。例えば、ＬＥＤ同士を熱伝導性の良い金属を用いて接続してもよい。例えば、３種類のＬＥＤは互いの温度を平準化するために同一熱伝導アレイ上に設置されても良い。また、ＬＥＤの温度による光量の変化を補正するために、ＬＥＤの光量を測定してＬＥＤに流れる順電流を制御するため可変抵抗制御回路を有しても良い。また、３６５ｎｍの近紫外ＬＥＤを用いて光化学オキシダントを測定することことにより、オキシダント測定装置として機能する光度計としても良い。   When using several LED for the LED light source 19 like FIG. 6, it arrange | positions on the heat conductive array 20 on the same plane. This is to synchronize the heat generation of the LEDs and the change in the amount of light due to the ambient temperature by causing the LEDs to conduct heat. By synchronizing the light quantity changes, the light quantity changes due to the temperature dependence of each LED can be synchronized. By obtaining the baseline noise from the wavelength 700 nm of the synchronized reference signal LED, more precise measurement is possible. The heat conducting array 20 does not have to be on the same plane as long as efficient heat exchange can be performed. For example, the LEDs may be connected using a metal having good thermal conductivity. For example, the three types of LEDs may be installed on the same heat conducting array in order to level the temperature of each other. Further, in order to correct the change in the light amount due to the temperature of the LED, a variable resistance control circuit may be provided to control the forward current flowing in the LED by measuring the light amount of the LED. Moreover, it is good also as a photometer which functions as an oxidant measuring apparatus by measuring a photochemical oxidant using 365 nm near-ultraviolet LED.

ＬＥＤ光源を光度計・クロマトグラフィに使用する場合、複数の波長でピークが必要となる。従来のように、ブロードな波長帯を持つ光源だとフィルタや回折格子と言った光学素子で波長を分けることが必要である。一般的にＬＥＤは、それぞれ特定の波長にピークを持つ特徴があることからこの特徴を活かすことで上記光学素子を省略することが可能となる。   When an LED light source is used for a photometer / chromatography, peaks are required at a plurality of wavelengths. If the light source has a broad wavelength band as in the prior art, it is necessary to divide the wavelength by optical elements such as filters and diffraction gratings. In general, each LED has a characteristic having a peak at a specific wavelength. Therefore, the optical element can be omitted by utilizing this characteristic.

実施例１に、単一ピークを有する複数のＬＥＤから必要な波長のＬＥＤを選択し、同一光軸にてＬＥＤ光をフローセルに入射する構造について記載した。   Example 1 describes a structure in which an LED having a required wavelength is selected from a plurality of LEDs having a single peak, and LED light is incident on the flow cell along the same optical axis.

また、ＬＥＤ光源の電流制御法に関しては、可変抵抗制御を用いると、制御が容易になるという効果がある。   Further, regarding the current control method of the LED light source, the use of variable resistance control has an effect that the control becomes easy.

本発明の実施例のクロマトグラフ用ＬＥＤ光源の説明図である。It is explanatory drawing of the LED light source for chromatographs of the Example of this invention. 本発明の実施例のクロマトグラフ用検出器の説明図である。It is explanatory drawing of the detector for chromatographs of the Example of this invention. 本発明の実施例の３ＬＥＤ式アミノ酸分析装置の検出器説明図である。It is detector explanatory drawing of the 3LED type | mold amino acid analyzer of the Example of this invention. 本発明の実施例の１ＬＥＤ式アミノ酸分析装置の検出器説明図である。It is detector explanatory drawing of the 1LED type | mold amino acid analyzer of the Example of this invention. 本発明の実施例のダイクロイックミラーを用いた３ＬＥＤ式アミノ酸分析装置の検出器の説明図である。It is explanatory drawing of the detector of the 3LED type amino acid analyzer using the dichroic mirror of the Example of this invention. 本発明の実施例の光量補正回路の説明図である。It is explanatory drawing of the light quantity correction circuit of the Example of this invention.

符号の説明Explanation of symbols

１８ フローセル
１９ ＬＥＤ光源
２０ 熱伝導アレイ
２１ 検知素子
２２ 光電流電圧変換回路
２３ 分光素子
２４ 受光素子
２５ ダイクロイックミラー１
２６ ダイクロイックミラー２
２７ ＬＥＤ１
２８ ＬＥＤ２
２９ ＬＥＤ３
３１ 可変抵抗
４０ 光通過口
４１ 可動式ミラー
４２ 光軸 18 Flow Cell 19 LED Light Source 20 Thermal Conduction Array 21 Detection Element 22 Photocurrent Voltage Conversion Circuit 23 Spectroscopic Element 24 Light Receiving Element 25 Dichroic Mirror 1
26 Dichroic Mirror 2
27 LED1
28 LED2
29 LED3
31 Variable resistor 40 Light passage port 41 Movable mirror 42 Optical axis

Claims (17)

光源と、前記光源から放出された光束が入射する試料用セルと、前記セルを通過した光の吸光度を検出する検知素子と、前記検知素子の信号を電圧に変換する光電流電圧変換回路と、前記光源の光量を補正する光量補正回路とを有し、前記光源に少なくとも１つ以上のピーク波長を持つ発光ダイオード（以下ＬＥＤと称する。）を具備することを特徴とする光度計。   A light source, a sample cell on which a light beam emitted from the light source is incident, a detection element that detects the absorbance of light that has passed through the cell, a photocurrent-voltage conversion circuit that converts a signal of the detection element into a voltage, A photometer comprising: a light amount correction circuit for correcting a light amount of the light source; and a light emitting diode (hereinafter referred to as an LED) having at least one peak wavelength in the light source. 請求項１において、
前記セルはフローセルであり、
前記検知素子はシリコンホトセルであり、
前記光源は複数個のＬＥＤを有し、
全てのＬＥＤから放出した光を同一光軸でフローセルに入射させるための光学素子を有することを特徴とする光度計。 In claim 1,
The cell is a flow cell;
The sensing element is a silicon photocell;
The light source has a plurality of LEDs,
A photometer comprising an optical element for causing light emitted from all LEDs to enter the flow cell along the same optical axis. 請求項２において、複数個のＬＥＤはそれぞれピーク波長が異なることを特徴とする光度計。   3. The photometer according to claim 2, wherein the plurality of LEDs have different peak wavelengths. 請求項３において、任意の物質を測定する場合、その特有の吸光波長付近の発光波長を有するＬＥＤを点灯させることを特徴とする光度計。   4. The photometer according to claim 3, wherein when an arbitrary substance is measured, an LED having an emission wavelength near its specific absorption wavelength is turned on. 請求項２において、前記光学素子は、グレーティングであることを特徴とする光度計。   The photometer according to claim 2, wherein the optical element is a grating. 請求項２において、前記光学素子は、ミラーであることを特徴とする光度計。   The photometer according to claim 2, wherein the optical element is a mirror. 請求項１において、光源の発光波長が、それぞれ４４０ｎｍ，５７０ｎｍのアミノ酸分析用の波長と、７００ｎｍのリファレンス信号用の波長であり、アミノ酸分析装置用光度計として機能する光度計。   The photometer according to claim 1, wherein the light emission wavelengths of the light source are a wavelength for amino acid analysis of 440 nm and 570 nm and a wavelength for a reference signal of 700 nm, respectively, and function as a photometer for an amino acid analyzer. 請求項７において、光源からの４４０ｎｍ，５７０ｎｍ，７００ｎｍの各波長の光が、それぞれ独立したＬＥＤから発せられることを特徴とする光度計。   8. The photometer according to claim 7, wherein light having wavelengths of 440 nm, 570 nm, and 700 nm from the light source are emitted from independent LEDs. 請求項７において、３種類の光源を混光する２種類のダイクロイックミラーと、フローセル通過光を分光するグレーティングとを有し、アミノ酸を測定可能な光度計。   8. The photometer according to claim 7, comprising two types of dichroic mirrors that mix three types of light sources, and a grating that separates light passing through the flow cell, and capable of measuring amino acids. 請求項７において、単一樹脂内に青色もしくは紫外ＬＥＤを有し、ＬＥＤ内に蛍光体が充填されることで４４０ｎｍ，５７０ｎｍ，７００ｎｍの波長を発するシングルチップ型ＬＥＤを備え、フローセル透過光を分光するグレーティングを備え、各波長の吸光度を測定することを特徴とする光度計。   8. A single chip LED having a blue or ultraviolet LED in a single resin and emitting a wavelength of 440 nm, 570 nm, and 700 nm by being filled with a phosphor in the single resin, and splitting flow cell transmitted light. A photometer comprising a grating for measuring the absorbance of each wavelength. 請求項７において、単一樹脂内に赤・青・緑の３ＬＥＤチップに備え、４４０ｎｍ，５７０ｎｍ，７００ｎｍの波長を発するマルチチップ型ＬＥＤを備え、フローセル透過光を分光するグレーティングを備え、各波長の吸光度を測定することにより、アミノ酸分析装置用検出器として機能する光度計。   In Claim 7, it is equipped with 3LED chips of red, blue, and green in a single resin, a multichip LED emitting wavelengths of 440 nm, 570 nm, and 700 nm, a grating that separates flow cell transmitted light, A photometer that functions as a detector for an amino acid analyzer by measuring absorbance. 請求項７において、３種類のＬＥＤは互いの温度を平準化するために同一熱伝導アレイ上に設置されていることを特徴とする光度計。   8. The photometer according to claim 7, wherein the three kinds of LEDs are installed on the same heat conducting array in order to level the temperature of each other. 請求項１において、ＬＥＤの温度による光量の変化を補正するために、ＬＥＤの光量を測定してＬＥＤに流れる順電流を制御するため可変抵抗制御回路を有することを特徴とする光度計。   2. The photometer according to claim 1, further comprising a variable resistance control circuit for measuring a light amount of the LED and controlling a forward current flowing through the LED in order to correct a change in the light amount due to the temperature of the LED. 請求項１において、３６５ｎｍの近紫外ＬＥＤを用いて光化学オキシダントを測定することにより、オキシダント測定装置として機能する光度計。   In Claim 1, the photometer which functions as an oxidant measuring apparatus by measuring photochemical oxidant using 365 nm near-ultraviolet LED. 請求項１において、
複数個の前記ＬＥＤが配置された熱伝導アレイを有することを特徴とする光度計。 In claim 1,
A photometer comprising a heat conducting array in which a plurality of the LEDs are arranged. 請求項１ないし請求項１５のいずれか記載の光度計を有するクロマトグラフ装置。   A chromatographic apparatus comprising the photometer according to any one of claims 1 to 15. 請求項７ないし請求項１２、及び請求項１５のいずれか記載の光度計を有するアミノ酸分析装置。   An amino acid analyzer having the photometer according to any one of claims 7 to 12 and claim 15.
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