JP6215900B2 - Compound detection method and detection apparatus - Google Patents
Compound detection method and detection apparatus Download PDFInfo
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Description
本発明は、主に食品等に含有される微量の化合物を検出する方法及びその化合物の検出に用いる装置に関する。 The present invention relates to a method for detecting a small amount of a compound contained mainly in food or the like and an apparatus used for detecting the compound.
従来から、食品の安全性を担保するために、公定法と呼ばれる機器分析による残留農薬検出方法が定められているが、ＧＣ−ＭＳのような高度な機器を用いるため検査コストが大きくなり、小規模な団体や個人で活用することは難しい。 Conventionally, in order to ensure food safety, a method for detecting residual agricultural chemicals by instrumental analysis called the official method has been established. However, since advanced equipment such as GC-MS is used, the inspection cost increases, and It is difficult to use in large groups and individuals.
これに対して、残留農薬の簡易検査方法として、コリンエステラーゼ活性阻害法やイムノアッセイ法が実用化され、簡易検査市場は急拡大している。しかしながら、コリンエステラーゼ活性阻害法は生体物質による誤検出という問題があり、また、イムノアッセイ法は対象となる農薬の範囲が狭いという課題がある。 In contrast, cholinesterase activity inhibition methods and immunoassay methods have been put to practical use as simple inspection methods for residual pesticides, and the simple inspection market is rapidly expanding. However, the cholinesterase activity inhibition method has a problem of false detection by a biological substance, and the immunoassay method has a problem that the range of target agricultural chemicals is narrow.
一方、希土類錯体を用いる化合物の分析方法、検出方法として、ＮＭＲシフト試薬を用いた方法、蛍光標識法が報告されている。しかしながら、ＮＭＲシフト試薬は管理にコストがかかるＮＭＲ装置が必須であり、また、蛍光標識法に用いられる希土類錯体は、構造が複雑で普及していないのが現状である。 On the other hand, methods using NMR shift reagents and fluorescent labeling methods have been reported as methods for analyzing and detecting compounds using rare earth complexes. However, the NMR shift reagent requires an NMR apparatus that is expensive to manage, and the rare earth complex used in the fluorescent labeling method has a complicated structure and is not widely used.
本発明は、例えば食品中に微量に混入する農薬などの有害な化合物を簡易的に検出する方法及びその検出装置を提供することを目的とする。 An object of the present invention is to provide a method and a detection apparatus for simply detecting harmful compounds such as agricultural chemicals mixed in a small amount in food.
本実施形態に係る化合物の検出方法は、被試験物に含まれるリン−酸素二重結合、硫黄―酸素二重結合、炭素―酸素二重結合、又は窒素原子の非共有電子対を有し、少なくともリン−酸素二重結合を有する化合物を抽出する抽出工程と、この抽出工程で抽出された上記化合物を、希土類錯体を構成する希土類イオンと接触させることにより上記希土類イオンと反応させる反応工程と、この反応工程における反応により引き起こされる発光強度、発光寿命、及び発光スペクトル形状の遷移のいずれかを検出することにより上記化合物を検出する検出工程とを有することを特徴とする。 Detection method of the compound according to the present embodiment, phosphorus is included in the DUT - oxygen double bond, sulfur - oxygen double bond, a carbon - oxygen double bond, or have a non-covalent electron pair of the nitrogen atom, at least phosphorus - an extraction step of extracting a compound that have a oxygen double bond, the compounds extracted in the extraction step, a reaction step of reacting with the rare earth ions by contact with the rare earth ions constituting the rare earth complex And a detection step of detecting the compound by detecting any one of emission intensity, emission lifetime, and emission spectrum shape transition caused by the reaction in this reaction step.
また、本実施形態に係る化合物の検出方法は、希土類錯体が溶媒に溶解してなる検査液中に被試験物を投入し、上記被試験物に含まれるリン−酸素二重結合、硫黄―酸素二重結合、炭素―酸素二重結合、又は窒素原子の非共有電子対を有し、少なくともリン−酸素二重結合を有する化合物を、上記希土類錯体を構成する希土類イオンと接触させることにより上記希土類イオンと反応させる反応工程と、この反応工程における反応により引き起こされる上記希土類錯体の発光強度、発光寿命、又は発光スペクトル形状の遷移のいずれかを検出することにより上記化合物を検出する検出工程を有することを特徴とする。 Further, the compound detection method according to the present embodiment is such that a test object is put into a test solution in which a rare earth complex is dissolved in a solvent, and a phosphorus-oxygen double bond, sulfur-oxygen contained in the test object. double bond, a carbon - oxygen double bond, or have a non-covalent electron pair of the nitrogen atom, at least phosphorus - compounds that have a oxygen double bond, said by contact with the rare earth ions constituting the rare earth complex A reaction step of reacting with rare earth ions, and a detection step of detecting the compound by detecting any of the emission intensity, emission lifetime, or emission spectrum shape transition of the rare earth complex caused by the reaction in the reaction step It is characterized by that.
また、本実施形態に係る化合物の検出装置は、被試験物に含まれる化合物と接触させた希土類錯体の発光強度、発光寿命、及び発光スペクトル形状から選択される少なくとも一つの発光物性を検出する検出部と、リン−酸素二重結合、硫黄―酸素二重結合、炭素―酸素二重結合、及び窒素原子の非共有電子対を有する標的化合物の少なくとも一種が１モル当量以上配位した上記希土類錯体の上記発光物性を予め記憶させた記憶部と、上記検出部による検出情報と上記記憶部による記憶情報を比較して上記標的化合物の有無を判定する判定部を有し、上記記憶部の希土類錯体が下記一般式（I）に示す構造であるか、又は下記一般式（II）に示す構造を配位子に有することを特徴とする。 In addition, the compound detection apparatus according to this embodiment detects at least one luminescent property selected from the emission intensity, emission lifetime, and emission spectrum shape of the rare earth complex in contact with the compound contained in the test object. And a rare earth complex in which at least one of a target compound having a phosphorus-oxygen double bond, a sulfur-oxygen double bond, a carbon-oxygen double bond, and an unshared electron pair of a nitrogen atom is coordinated at least 1 molar equivalent A storage unit in which the light emitting physical properties of the storage unit are stored in advance, a determination unit that compares the detection information by the detection unit and the storage information by the storage unit to determine the presence or absence of the target compound, and the rare earth complex of the storage unit Is a structure represented by the following general formula (I), or has a structure represented by the following general formula (II) in the ligand.
また、本実施形態に係る化合物の検出装置は、被試験物に含まれる化合物と接触させた希土類錯体の発光強度、発光寿命、及び発光スペクトル形状から選択される少なくとも一つの発光物性を検出する検出部と、リン−酸素二重結合、硫黄―酸素二重結合、炭素―酸素二重結合、及び窒素原子の非共有電子対を有する標的化合物の少なくとも一種が１モル当量以上配位した上記希土類錯体を有する標準発光シートと、上記検出部による検出情報と標準発光シートで検出される発光を比較して上記標的化合物の有無を判定する判定部を有し、上記標準発光シートの希土類錯体が上記一般式（I）に示す構造であるか、又は上記一般式（II）に示す構造を配位子に有することを特徴とする。 In addition, the compound detection apparatus according to this embodiment detects at least one luminescent property selected from the emission intensity, emission lifetime, and emission spectrum shape of the rare earth complex in contact with the compound contained in the test object. And a rare earth complex in which at least one of a target compound having a phosphorus-oxygen double bond, a sulfur-oxygen double bond, a carbon-oxygen double bond, and an unshared electron pair of a nitrogen atom is coordinated at least 1 molar equivalent A standard light-emitting sheet, and a determination unit that determines the presence or absence of the target compound by comparing information detected by the detection unit and light emission detected by the standard light-emitting sheet. The ligand has a structure represented by the formula (I) or a structure represented by the above general formula (II).
また、本実施形態に係る化合物の検出装置は、６配位の希土類錯体が媒体に溶解または分散してなる部位を具備する、リン−酸素二重結合、硫黄―酸素二重結合、炭素―酸素二重結合、又は窒素原子の非共有電子対を有する化合物の検出装置であって、上記希土類錯体の発光強度、発光寿命、及び分岐比から選択される発光物性の二つ以上の変移で以って上記化合物の有無を検出することを特徴とする。 In addition, the compound detection apparatus according to the present embodiment includes a phosphorus-oxygen double bond, a sulfur-oxygen double bond, a carbon-oxygen having a site in which a hexacoordinate rare earth complex is dissolved or dispersed in a medium. An apparatus for detecting a compound having a double bond or a non-shared electron pair of a nitrogen atom, comprising two or more transitions of luminescent properties selected from the emission intensity, emission lifetime, and branching ratio of the rare earth complex. The presence or absence of the compound is detected.
例えば農薬は、分子に生理活性を付与する必要上、リン−酸素二重結合（P=O）、硫黄―酸素二重結合（S=O）、炭素―酸素二重結合（C=O）、や窒素原子（N）上の非共有電子対を分子構造中に有する化合物が多い。これらの部位は、強いルイス塩基性であるため、ルイス酸性である希土類イオンに配位する。即ち、多くの農薬は、希土類蛍光錯体（以下、「希土類錯体」とも言う。）に配位して、その発光物性が変化する。 For example, pesticides need to impart physiological activity to molecules, so phosphorus-oxygen double bonds (P = O), sulfur-oxygen double bonds (S = O), carbon-oxygen double bonds (C = O), There are many compounds that have unshared electron pairs on the nitrogen atom (N) in the molecular structure. Since these sites are strongly Lewis basic, they coordinate to rare earth ions that are Lewis acidic. That is, many pesticides coordinate with rare earth fluorescent complexes (hereinafter also referred to as “rare earth complexes”), and their luminescent properties change.
本発明者らは、鋭意検討を続けた結果、上記の発想に至り、上記化合物の検出方法を見出すに至った。
以下、本実施形態に係る化合物の検出方法について図面を参照して詳細に説明する。
As a result of continuing intensive studies, the present inventors have come up with the above idea and found out a method for detecting the above compound.
Hereinafter, the compound detection method according to the present embodiment will be described in detail with reference to the drawings.
図1は、本実施形態に係る化合物の検出方法の基本原理を示す概念図である。
図1に示すように、希土類錯体1は、第1の配位子2と希土類イオン3を含む錯体である。標的化合物（残留農薬）4は、リン−酸素二重結合（P=O）、硫黄―酸素二重結合（S=O）、炭素―酸素二重結合（C=O）や窒素原子（N）上の非共有電子対を有する化合物である。リン−酸素二重結合（P=O）、硫黄―酸素二重結合（S=O）、炭素―酸素二重結合（C=O）や窒素原子（N）上の非共有電子対は、上記のとおり強いルイス塩基性部位である。このため、これらの部位を有する標的化合物4は、第2の配位子としてルイス酸性である希土類イオン3に新たに配位する。希土類錯体1から標的化合物4が配位した希土類錯体5が生じることで発光強度、発光寿命、発光スペクトル形状が変化する。本実施形態では、これらの発光物性の変化を検出することにより標的化合物（残留農薬）4の有無を簡便に判定できる。
FIG. 1 is a conceptual diagram showing the basic principle of the compound detection method according to the present embodiment.
As shown in FIG. 1, the rare earth complex 1 is a complex including a first ligand 2 and a rare earth ion 3. Target compounds (residual agricultural chemicals) 4 are phosphorus-oxygen double bonds (P = O), sulfur-oxygen double bonds (S = O), carbon-oxygen double bonds (C = O) and nitrogen atoms (N). It is a compound having the above unshared electron pair. Unshared electron pairs on phosphorus-oxygen double bonds (P = O), sulfur-oxygen double bonds (S = O), carbon-oxygen double bonds (C = O) and nitrogen atoms (N) It is a strong Lewis basic site. Therefore, the target compound 4 having these sites newly coordinates to the rare earth ion 3 that is Lewis acidic as the second ligand. The rare earth complex 5 in which the target compound 4 is coordinated from the rare earth complex 1 changes the emission intensity, emission lifetime, and emission spectrum shape. In the present embodiment, the presence or absence of the target compound (residual agricultural chemical) 4 can be easily determined by detecting these changes in luminescent properties.
また、本実施形態に係る化合物の検出方法は、コリンエステラーゼ活性阻害法との比較において、標的化合物（残留農薬）の検出にかかる時間が少なく検出感度に優れ、かつコリンエステラーゼ活性阻害法では判定できない種類の残留農薬の検出にも有利である。 In addition, the method for detecting a compound according to the present embodiment is a kind of method that is less time consuming to detect a target compound (residual pesticide), has better detection sensitivity, and cannot be determined by the cholinesterase activity inhibition method compared to the cholinesterase activity inhibition method It is also advantageous for detection of residual pesticides.
図2は、本実施形態に係る化合物の検出方法とコリンエステラーゼ活性阻害法の基本原理の違いを示す図である。
図2に示すように、例えば有機リン系の農薬である5価の有機リン化合物は、酸素原子(O)、置換基Rx、Ry、及びRzを頂点とする四面体構造である。そして、P=O基はリン原子P（＋）、酸素原子O（‐）と大きく分極している。
FIG. 2 is a diagram showing the difference in basic principles between the compound detection method and the cholinesterase activity inhibition method according to this embodiment.
As shown in FIG. 2, for example, a pentavalent organophosphorus compound that is an organophosphorus pesticide has a tetrahedral structure with oxygen atoms (O), substituents Rx, Ry, and Rz as vertices. The P═O group is greatly polarized with a phosphorus atom P (+) and an oxygen atom O (−).
従来法であるコリンエステラーゼ活性阻害法では、大きく分極したリン原子Pへの求核攻撃が反応の起点となる（図中、矢印a）。しかしながら、リン原子Pは、四面体の内部に位置しているため、リン原子P上への求核攻撃は、置換基Rx、Ry、及びRzの立体障害の影響を大きく受ける。このため、コリンエステラーゼ活性阻害法では検出できない農薬が多く、また、反応に多くの時間を要する。 In the conventional cholinesterase activity inhibition method, the nucleophilic attack on the highly polarized phosphorus atom P is the starting point of the reaction (arrow a in the figure). However, since the phosphorus atom P is located inside the tetrahedron, the nucleophilic attack on the phosphorus atom P is greatly affected by the steric hindrance of the substituents Rx, Ry, and Rz. For this reason, there are many agricultural chemicals that cannot be detected by the cholinesterase activity inhibition method, and the reaction takes a long time.
これに対して、本実施形態では、ルイス塩基性の高いP=Oの酸素原子Oにルイス酸性である希土類イオン（ユーロピウムイオン（Eu3+））が配位する（図中b）。希土類イオンが配位する酸素原子Oは、四面体の頂点にあり、置換基Rx、Ry、及びRzの立体障害の影響を受けないため、反応が短時間で起こり、かつ感度が大きい。 On the other hand, in the present embodiment, Lewis acidic rare earth ions (europium ions (Eu3 +)) are coordinated to oxygen atom O of P = O having high Lewis basicity (b in the figure). The oxygen atom O to which the rare earth ions coordinate is located at the apex of the tetrahedron and is not affected by the steric hindrance of the substituents Rx, Ry, and Rz. Therefore, the reaction takes place in a short time and the sensitivity is high.
また、窒素化合物も窒素原子上の非共有電子対と、３つの置換基を頂点とする四面体構造であり、四面体の頂点にある非共有電子対は、３つの置換基の立体障害の影響を受けずに希土類イオンと配位する。本実施形態では、窒素原子上の非共有電子対が希土類イオンに配位することによる発光物性の変化についても、短時間、かつ高感度に検出することができる。 Nitrogen compounds also have a tetrahedral structure with a vertices at the top of three substituents and an unshared electron pair on the nitrogen atom. The lone pair at the top of the tetrahedron is affected by the steric hindrance of the three substituents. Coordinate with rare earth ions In the present embodiment, a change in luminescent properties due to coordination of an unshared electron pair on a nitrogen atom to a rare earth ion can be detected in a short time with high sensitivity.
本実施形態に係る化合物の検出方法は、以下の工程を有する。
（1）抽出工程（第１の工程）
抽出工程は、被試験物に含まれるリン−酸素二重結合（P=O）、硫黄―酸素二重結合（S=O）、炭素―酸素二重結合（C=O）、又は窒素原子（N）の非共有電子対を有する化合物（以下、「標的化合物」とも言う。）を溶媒に抽出する工程である。被試験物は、本実施形態に係る化合物の検出方法に供される試料であり、例えば食品、食品の洗浄水、食品の粉砕物、食品からの抽出物、飲料水、農業用水、井戸水、河川水、土壌等を挙げることができる。
The compound detection method according to this embodiment includes the following steps.
(1) Extraction process (first process)
The extraction process involves phosphorus-oxygen double bonds (P = O), sulfur-oxygen double bonds (S = O), carbon-oxygen double bonds (C = O), or nitrogen atoms ( N) a step of extracting a compound having an unshared electron pair (hereinafter also referred to as “target compound”) into a solvent. The test object is a sample used in the method for detecting a compound according to the present embodiment. For example, food, food washing water, food pulverized product, food extract, drinking water, agricultural water, well water, river Water, soil, etc. can be mentioned.
標的化合物の抽出に用いる溶媒は、標的化合物を溶解できる溶媒を選択する。また、標的化合物の官能基のルイス塩基性が溶媒のルイス塩基性より強い場合には検出感度に支障はないが、溶媒のルイス塩基性より弱い場合には溶媒が希土類イオンと標的化合物の反応を阻害し、発光強度の変化が小さくなり検出感度が低下する。このため、後述の反応工程において希土類錯体を構成する希土類イオンと実質的に反応しない溶媒を選択することが好ましい。ここで「実質的に反応しない」とは、仮に溶媒と希土類イオンとが反応したとしても標的化合物の検出に悪影響を及ぼさない程度にしか反応しないことをいう。 As the solvent used for extraction of the target compound, a solvent capable of dissolving the target compound is selected. In addition, when the Lewis basicity of the functional group of the target compound is stronger than the Lewis basicity of the solvent, there is no problem in detection sensitivity, but when the Lewis group is weaker than the Lewis basicity of the solvent, the solvent reacts with the rare earth ions and the target compound. This hinders the change in emission intensity and decreases the detection sensitivity. For this reason, it is preferable to select a solvent that does not substantially react with the rare earth ions constituting the rare earth complex in the reaction step described later. Here, “substantially does not react” means that even if the solvent reacts with rare earth ions, it reacts only to the extent that it does not adversely affect the detection of the target compound.
このような溶媒としては、例えばヘキサン等のアルカン、ハロゲンで置換されたハロアルカン、不飽和炭化水素、ベンゼン、トルエン、キシレン等の芳香族系溶媒、酢酸エチル、アセトン、アセトニトリル、エタノール、メタノール、プロパノール等のアルコール系溶媒、ジエチルエーテル等のエーテル系溶媒、ジエチレングリコール等のグリコール系溶媒等を挙げることができる。 Examples of such solvents include alkanes such as hexane, halogen-substituted haloalkanes, unsaturated hydrocarbons, aromatic solvents such as benzene, toluene, and xylene, ethyl acetate, acetone, acetonitrile, ethanol, methanol, propanol, and the like. Alcohol solvents, ether solvents such as diethyl ether, glycol solvents such as diethylene glycol, and the like.
本実施形態に係る検出方法で対象となる標的化合物は、本実施形態に係る基本原理から、P＝O、S＝O、C＝O、又は窒素原子（N）の非共有電子対を分子構造中に有する化合物である。特にP＝O、S＝Oの部分的双極子モーメントが5.4以上、或いはP＝O、又はS＝Oの酸素原子の遮蔽率が27%未満の化合物については、高感度に検出することができる。 From the basic principle according to the present embodiment, the target compound targeted by the detection method according to the present embodiment has a molecular structure of P = O, S = O, C = O, or a lone pair of nitrogen atoms (N). It is a compound contained in it. In particular, a compound with a partial dipole moment of P = O and S = O of 5.4 or more, or a compound with a P = O or S = O oxygen atom shielding ratio of less than 27% can be detected with high sensitivity. .
このような標的化合物としては、具体的には、例えばプロフェノホス、ホスチアゼート、エディフェンホス、ジクロルボス等の有機リン系の農薬等、メチオカルブスルホン等のカーバメート系の農薬等を挙げることができる。 Specific examples of such a target compound include organophosphorus pesticides such as profenofos, phosphiazates, edifenphos, and dichlorophos, and carbamate pesticides such as methiocarbsulfone.
（2）反応工程（第2の工程）
反応工程は、上記（1）抽出工程にて上記溶媒に抽出された標的化合物を、希土類錯体を構成する希土類イオンと接触させることにより上記希土類イオンと反応させる工程である。反応工程では、希土類錯体がアルコール系、酢酸エステル系、フッ素系アルカンから選択される何れかの溶媒に溶解した溶液（検査液）に、上記（1）抽出工程にて得られた標的化合物の抽出溶液を添加し、必要に応じて加熱、撹拌等を行うことで希土類イオンと標的化合物を反応させる。
(2) Reaction process (second process)
The reaction step is a step of allowing the target compound extracted in the solvent in the (1) extraction step to react with the rare earth ion by contacting with the rare earth ion constituting the rare earth complex. In the reaction step, extraction of the target compound obtained in the above (1) extraction step is performed in a solution (test solution) in which the rare earth complex is dissolved in any solvent selected from alcohol-based, acetate-based, and fluorine-based alkanes. The solution is added, and the rare earth ions and the target compound are reacted by heating, stirring, and the like as necessary.
検査液における希土類錯体の濃度は、2mg/l以上400mg/l以下の範囲であることが望ましい。上記濃度範囲を逸脱すると、例えば低濃度側の場合は標的化合物と反応しても発光強度の変化が目視確認できなくなり、検出に測定装置が必要となる。一方、高濃度側の場合は、標的化合物のモル量に対して希土類錯体のモル量が大過剰となり、発光強度の変化が目視確認できなくなる。 The concentration of the rare earth complex in the test solution is preferably in the range of 2 mg / l to 400 mg / l. When deviating from the above concentration range, for example, in the case of a low concentration side, even if it reacts with the target compound, a change in emission intensity cannot be visually confirmed, and a measuring device is required for detection. On the other hand, in the case of a high concentration side, the molar amount of the rare earth complex is excessively large with respect to the molar amount of the target compound, and the change in emission intensity cannot be visually confirmed.
本実施形態で用いる希土類錯体は、6配位のものが望ましい。希土類錯体は、6配位と8配位が安定であり、6配位の錯体を検出用に用いて８配位まで標的化合物を配位させて発光物性の変化を検出する。また、本実施形態で用いる希土類錯体は、単独で用いても良いし、2種以上を混合して用いてもよい。 The rare earth complex used in this embodiment is preferably a six-coordinate one. The rare earth complex is stable in 6-coordinate and 8-coordinate, and a change in luminescent properties is detected by coordinating the target compound up to 8-coordinate using the 6-coordinate complex for detection. In addition, the rare earth complex used in the present embodiment may be used alone or in combination of two or more.
6配位の希土類錯体を構成する希土類イオンは、発光強度が高い錯体が得られるユーロピウムイオン（Eu3+）が望ましい。
また、6配位の希土類錯体を構成する配位子は、βジケトン骨格を有する配位子であることが望ましい。また、希土類錯体の発光強度を大きく保つことができるため、βジケトン骨格に接続する置換基の少なくとも一つはフルオロアルキル基、特にパーフルオロアルキル基であることが望ましい。さらに、もう一方の置換基を芳香族基とすると、配位子による光吸収強度が増大するため、さらに大きな発光強度が得られるため望ましい。
The rare earth ions constituting the six-coordinate rare earth complex are preferably europium ions (Eu3 +) from which a complex with high emission intensity can be obtained.
The ligand constituting the 6-coordinate rare earth complex is preferably a ligand having a β-diketone skeleton. In addition, since the emission intensity of the rare earth complex can be kept high, it is desirable that at least one of the substituents connected to the β-diketone skeleton is a fluoroalkyl group, particularly a perfluoroalkyl group. Furthermore, when the other substituent is an aromatic group, the light absorption intensity by the ligand is increased, and therefore, it is desirable because a larger light emission intensity can be obtained.
上記した観点から、下記化学式（1）で示される錯体、又は下記化学式（2）で示される錯体が望ましい。これらの錯体に標的化合物が作用した場合、発光物性の変化が顕著となる。 From the above viewpoint, a complex represented by the following chemical formula (1) or a complex represented by the following chemical formula (2) is desirable. When the target compound acts on these complexes, the change in luminescent physical properties becomes significant.
また、他の態様として、上記（1）抽出工程を介さず、被試験物を希土類錯体が溶媒に溶解してなる検査液中に投入し、被試験物に含まれる標的化合物と希土類イオンを接触させて反応させても良い。また或いは、希土類錯体を媒体に吸着させた形態とし、この検査媒体を被試験物、その洗浄液、又はその粉砕体と接触させ、標的化合物と希土類イオンを接触させて反応させても良い。希土類錯体を吸着させる媒体としては、例えばアクリル系ポリマー、フッ素系ポリマー、セルロース繊維等のポリマー、紙、布、フィルタ、スポンジ等を挙げることができる。 As another embodiment, without passing through the extraction step (1), the test sample is put into a test solution in which a rare earth complex is dissolved in a solvent, and the target compound and the rare earth ions contained in the test sample are contacted. You may make it react. Alternatively, a form in which a rare earth complex is adsorbed on a medium may be used, and this test medium may be brought into contact with a test object, its washing liquid, or its pulverized body, and the target compound and rare earth ions may be brought into contact with each other to be reacted. Examples of the medium for adsorbing the rare earth complex include polymers such as acrylic polymers, fluorine polymers, and cellulose fibers, paper, cloth, filters, sponges, and the like.
（３）検出工程（第３の工程）
検出工程は、上記（２）反応工程にて標的化合物と希土類イオンとの反応により引き起こされる発光物性の遷移を検出することにより標的化合物を検出する工程である。検出工程では、紫外光などを照射し、標的化合物が配位した希土類錯体の発光強度、発光寿命、及び発光スペクトル形状の少なくとも１つの発光物性の遷移を検出する。
(3) Detection step (third step)
The detection step is a step of detecting the target compound by detecting the transition of the luminescent property caused by the reaction between the target compound and rare earth ions in the above (2) reaction step. In the detection step, irradiation with ultraviolet light or the like is performed, and a transition of at least one luminescent property of the emission intensity, emission lifetime, and emission spectrum shape of the rare earth complex coordinated with the target compound is detected.
発光スペクトル形状は、分岐比（branching ratio）とするのが好ましい。ここで分岐比（branching ratio）とは、希土類錯体において、電気双極子遷移と磁気双極子遷移に帰属される発光ピークの比率である。発光スペクトル形状は、電気双極子遷移に由来する発光スペクトル形状と磁気双極子遷移に由来する発光スペクトル形状とがあり、磁気双極子遷移に由来する発光スペクトル形状が常に一定であるのと異なり、電気双極子遷移に由来する発光スペクトル形状は、希土類錯体の配位環境に大きく依存する。即ち、分岐比（branching ratio）は、配位子の構造によって変化するため、分岐比（branching ratio）によって希土類錯体の配位環境をある程度特定することができる。具体的には、電気双極子遷移とはユーロピウム錯体の発光スペクトルにおける5D0→7F2であり、磁気双極子遷移とは、5D0→7F1などである。 The emission spectrum shape is preferably a branching ratio. Here, the branching ratio is the ratio of the emission peak attributed to the electric dipole transition and the magnetic dipole transition in the rare earth complex. The emission spectrum shape has an emission spectrum shape derived from an electric dipole transition and an emission spectrum shape derived from a magnetic dipole transition. Unlike the emission spectrum shape derived from a magnetic dipole transition, the electric spectrum shape is always constant. The emission spectrum shape derived from the dipole transition largely depends on the coordination environment of the rare earth complex. That is, since the branching ratio varies depending on the structure of the ligand, the coordination environment of the rare earth complex can be specified to some extent by the branching ratio. Specifically, the electric dipole transition is 5 D 0 → 7 F 2 in the emission spectrum of the europium complex, and the magnetic dipole transition is 5 D 0 → 7 F 1 or the like.
図３は、本実施形態に係る化合物の検出装置の機能構成図である。
図３に示すように、本実施形態に係る化合物の検出装置10は、被試験物に含まれる化合物と接触させた希土類錯体の発光物性を検出する検出部11と、標的化合物が1モル当量以上配位した上記希土類錯体の発光物性を予め記憶させた記憶部12と、上記検出部による検出情報と上記記憶部による記憶情報を比較して前記標的化合物の有無を判別する判定部13を有している。検出部11では、発光強度、発光寿命、及び発光スペクトル形状から選択される少なくとも一つの発光物性を検出する。
FIG. 3 is a functional configuration diagram of the compound detection apparatus according to the present embodiment.
As shown in FIG. 3, the compound detection apparatus 10 according to the present embodiment includes a detection unit 11 that detects a luminescent property of a rare earth complex brought into contact with a compound contained in a test object, and a target compound of 1 molar equivalent or more. A storage unit 12 that stores in advance the luminescent physical properties of the coordinated rare earth complex, and a determination unit 13 that compares the detection information by the detection unit and the storage information by the storage unit to determine the presence or absence of the target compound. ing. The detection unit 11 detects at least one luminescent property selected from the luminescence intensity, the luminescence lifetime, and the luminescence spectrum shape.
記憶部12では下記一般式（I）に示す構造の希土類錯体の発光物性が予め記憶される。
上記一般式（I）に示す構造を有する希土類錯体において、βジケトン骨格を有する配位子（第１の配位子）とユーロピウムイオン（Eu3+）までが検出試薬であり、有機リン配位子（第２の配位子）の部分は標的化合物である。本実施形態にて標的化合物が検出された場合は、検出試薬と標的化合物から構成される上記一般式（I）に示す錯体が必ず生成する。この錯体の発光物性である発光強度、発光寿命、及び発光スペクトル形状のすくなくとも何れかを以って標的化合物の有無を判定する。 In the rare earth complex having the structure shown in the general formula (I), a ligand having a β-diketone skeleton (first ligand) and europium ion (Eu3 +) are detection reagents, and an organophosphorus ligand ( The portion of the second ligand) is the target compound. When a target compound is detected in this embodiment, a complex represented by the above general formula (I) composed of a detection reagent and a target compound is inevitably generated. The presence or absence of the target compound is determined based on at least one of the emission intensity, emission lifetime, and emission spectrum shape, which are the emission physical properties of this complex.
本実施形態に係る化合物の検出装置は、第一の機能として定性的に標的化合物の有無を判定する。この場合、上記一般式（I）に示す希土類錯体を用いた標準発光試料が記憶部12に組み込まれる。標準発光試料は、溶液またはシートに希土類錯体を吸着させた形態であり、判定部13に設けられる光源を有する試料室にて標準発光試料に対して上記光源から紫外線が照射され、検出部11で検出された発光と標準発光試料の発光との比較がなされる。この比較により定性的に標準化合物の有無を判定する。 The compound detection apparatus according to the present embodiment qualitatively determines the presence or absence of the target compound as the first function. In this case, a standard luminescent sample using the rare earth complex represented by the general formula (I) is incorporated in the storage unit 12. The standard luminescent sample is a form in which a rare earth complex is adsorbed on a solution or sheet, and the standard luminescent sample is irradiated with ultraviolet rays from the light source in a sample chamber having a light source provided in the determination unit 13, and the detection unit 11 A comparison is made between the detected luminescence and the luminescence of the standard luminescent sample. This comparison qualitatively determines the presence or absence of a standard compound.
また、本実施形態に係る化合物の検出装置は、第２の機能として標的化合物の種類を判別する。標的化合物の種類によって発光物性の変化の態様が異なるため、この差異を基準に標的化合物の種類を割り出すことができる。この場合、予め測定された上記一般式（I）に示す希土類錯体のライブラリーが記憶部12に備えられ、検出部11にて検出された検出結果と希土類錯体のライブラリーの照合により、標的化合物の種類を判定することができる。 In addition, the compound detection apparatus according to the present embodiment determines the type of the target compound as the second function. Since the mode of change in luminescent physical properties varies depending on the type of target compound, the type of target compound can be determined based on this difference. In this case, the library of the rare earth complex represented by the general formula (I) measured in advance is provided in the storage unit 12, and the target compound is obtained by collating the detection result detected by the detection unit 11 with the library of the rare earth complex. Can be determined.
また、上記一般式（I）に示す希土類錯体において、有機リン配位子（第２の配位子）の部分が、下記一般式（II）に示すS＝O、C＝O基を有する構造を有する化合物である錯体としても良い。この場合、標的化合物は、下記一般式（II）に示すS＝O、C＝O基を有する構造を有する化合物となる。
本実施形態に係る化合物の検出方法及びその検出装置は、農薬に代表されるP＝O、S＝O、C＝OやN原子上の非共有電子対を分子構造中に有する化合物を簡便、かつ高感度に検出できるため、例えば食品中に微量に混入する農薬を検出する残留農薬検出方法及び残留農薬検出装置として有用である。 The compound detection method and the detection apparatus according to the present embodiment are simple compounds having P = O, S = O, C = O and N = unshared electron pairs on the N atom represented by agricultural chemicals in the molecular structure, Since it can be detected with high sensitivity, it is useful as a residual pesticide detection method and a residual pesticide detection apparatus for detecting pesticides mixed in a trace amount in foods, for example.
以下、実施例により本発明を更に詳細に説明する。なお、本発明は下記実施例に限定されるものではない。
［発光スペクトル］
（実施例１）
希土類錯体に化学式（1）で示される錯体を用いて、有機リン系殺虫剤であるジクロルボスと酢酸エチル中で共存させ、発光スペクトルの強度変化を観察した。実験の手順は以下の通りである。まず、メスフラスコを用いて所定濃度、所定容量の希土類錯体溶液を作成し、この一部を採取して石英セルに投入し、発光物性を測定する。次にメスフラスコの定容値を基準に100ppmになる農薬を投入し、先の石英セルの溶液を追加して定容する。この方法では、同一の溶液で発光物性の初期値と農薬添加後の値を測定するため、秤量誤差が関与しないというメリットがある。
図4にジクロルボス共存前後の発光スペクトルを示す。
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to the following Example.
[Emission spectrum]
Example 1
Using the complex represented by the chemical formula (1) as a rare earth complex, it was allowed to coexist in dichlorvos, an organophosphorus insecticide, in ethyl acetate, and the intensity change of the emission spectrum was observed. The experimental procedure is as follows. First, a rare earth complex solution having a predetermined concentration and a predetermined volume is prepared using a volumetric flask, a part thereof is collected and put into a quartz cell, and the luminescent properties are measured. Next, pesticide that becomes 100 ppm based on the constant volume value of the volumetric flask is added, and the volume of the previous quartz cell solution is added to the volume. This method has an advantage that weighing error is not involved because the initial value of the luminescent property and the value after addition of the pesticide are measured in the same solution.
Fig. 4 shows the emission spectra before and after dichlorvos coexistence.
図4は、化学式（1）で示される錯体単独の発光スペクトル、ジクロルボスを1モル当量共存させた系の発光スペクトル、及びジクロルボスを2モル当量共存させた系の発光スペクトルである。なお、図中、no.1は化学式（1）で示される錯体単独の発光スペクトル、no.2はジクロルボスを1モル当量共存させた系の発光スペクトル、及びno.3はジクロルボスを2モル当量共存させた系の発光スペクトルを示している。 FIG. 4 shows an emission spectrum of the complex alone represented by the chemical formula (1), an emission spectrum of a system in which 1 mol equivalent of dichloroboss is present, and an emission spectrum of a system in which 2 mol equivalent of dichloroboss is present. In the figure, no.1 is the emission spectrum of the complex represented by the chemical formula (1) alone, no.2 is the emission spectrum of the system in which 1 mol equivalent of dichloroboss is present, and no.3 is in the presence of 2 mol equivalent of dichlorvos. The emission spectrum of the obtained system is shown.
図4に示すように、ジクロルボスを1モル当量共存させた系（no.2）の発光強度（612nmのピーク波長で観測）は、化学式（1）で示される錯体単独（no.1）の発光強度と比較して半減していることが分かる。さらに、ジクロルボスを2モル当量共存させた系（no.3）の発光強度は、化学式（1）で示される錯体単独（no.1）の発光強度と比較して15分の1まで減衰していることが分かる。 As shown in Fig. 4, the emission intensity (observed at the peak wavelength of 612 nm) of the system in which 1 mol equivalent of dichlorovos coexists (no.2) is the emission of the complex represented by chemical formula (1) (no.1) It can be seen that it is halved compared to the strength. Furthermore, the emission intensity of the system (no.3) in which 2 mol equivalents of dichlorovos coexisted attenuated to 1/15 compared to the emission intensity of the complex represented by chemical formula (1) alone (no.1). I understand that.
（実施例2〜実施例5）
他の標的化合物と化学式（1）で示される錯体の共存前後における発光強度の変化率について評価した。なお、変化率は、化学式（1）で示される錯体単独の発光強度に対する標的化合物を共存させた系の発光強度の比率とした。
(Example 2 to Example 5)
The rate of change in luminescence intensity before and after the coexistence of other target compounds and the complex represented by chemical formula (1) was evaluated. The rate of change was the ratio of the emission intensity of the system in which the target compound coexists to the emission intensity of the complex represented by the chemical formula (1) alone.
（実施例2）
有機リン系農薬であるプロフェノホスの酢酸エチル溶液を、実施例1と同様に100ppmとなるようにして化学式（1）で示される錯体と接触させたところ、発光強度（612nmのピーク波長で観測）の変化率は24%であった。
(Example 2)
When the ethyl acetate solution of profenofos, an organophosphorus pesticide, was brought into contact with the complex represented by the chemical formula (1) so as to be 100 ppm as in Example 1, the emission intensity (observed at a peak wavelength of 612 nm) The rate of change was 24%.
（実施例3）
有機リン系農薬であるエディフェンホスの酢酸エチル溶液を実施例1と同様に100ppmとなるようにして化学式（1）で示される錯体と接触させたところ、発光強度（612nmのピーク波長で観測）の変化率は19%であった。
(Example 3)
When an ethyl acetate solution of edifenphos, an organophosphorus pesticide, was brought into contact with the complex represented by the chemical formula (1) at 100 ppm as in Example 1, the emission intensity (observed at a peak wavelength of 612 nm) The rate of change was 19%.
（実施例4）
カーバメート系農薬であるメチオカルブスルホンの酢酸エチル溶液を実施例1と同様に100ppmとなるようにして化学式（1）で示される錯体と接触させたところ、発光強度（612nmのピーク波長で観測）の変化率は9%であった。
(Example 4)
When an ethyl acetate solution of methiocarbsulfone, which is a carbamate pesticide, was brought into contact with the complex represented by the chemical formula (1) at 100 ppm as in Example 1, the emission intensity (observed at a peak wavelength of 612 nm) The rate of change was 9%.
（実施例5）
有機リン系農薬であるホスチアゼートの酢酸エチル溶液を実施例1と同様に100ppmとなるようにして化学式（1）で示される錯体と接触させたところ、発光強度（612nmのピーク波長で観測）の変化率は16%であった。
(Example 5)
Changes in emission intensity (observed at a peak wavelength of 612 nm) when an organophosphorus pesticide ethyl acetate solution was brought into contact with the complex represented by chemical formula (1) at 100 ppm as in Example 1. The rate was 16%.
［励起スペクトル］
（実施例6）
有機リン系殺虫剤であるジクロルボス10ppmの溶液を用意し、これと化学式（1）で示される錯体を酢酸溶液中で共存させ、励起スペクトルの強度変化を観察した。図5にジクロルボス共存前後の励起スペクトルに示す。
[Excitation spectrum]
(Example 6)
A 10 ppm solution of dichlorvos, an organophosphorus insecticide, was prepared, and the complex represented by the chemical formula (1) was allowed to coexist in an acetic acid solution, and the intensity change of the excitation spectrum was observed. Figure 5 shows the excitation spectrum before and after dichlorvos coexistence.
図5は、化学式（1）で示される錯体単独の励起スペクトル、及びジクロルボスを共存させた系の励起スペクトルである。なお、図中、no.4は化学式（1）で示される錯体単独の励起スペクトル、及びno.5はジクロルボスを共存させた系の励起スペクトルを示している。
図5に示すように、ジクロルボスを共存させた系（no.5）の励起スペクトル強度は、化合物（1）単独（no.4）の励起スペクトル強度に比べ、半減していることが分かる。
FIG. 5 shows an excitation spectrum of the complex alone represented by the chemical formula (1) and an excitation spectrum of a system in which dichlorvos coexists. In the figure, no. 4 shows the excitation spectrum of the complex represented by the chemical formula (1) alone, and no. 5 shows the excitation spectrum of the system coexisting with dichloroboss.
As shown in FIG. 5, it can be seen that the excitation spectrum intensity of the system (no. 5) coexisting with dichloroboss is halved compared to the excitation spectrum intensity of the compound (1) alone (no. 4).
［発光寿命］
（実施例7）
希土類錯体に化学式（2）で示される錯体を用いて、有機リン系殺虫剤であるジクロルボスを作用させることによる発光寿命の変化を観察した。表1に観察結果を示す。
[Luminescence life]
(Example 7)
Using the complex represented by the chemical formula (2) to the rare earth complex, the change in the luminescence lifetime due to the action of dichlorvos, an organophosphorus insecticide, was observed. Table 1 shows the observation results.
表1に示すように、化学式（2）で示される錯体の発光寿命は、ジクロルボスとの相互作用により有意に変化していることが分かる。 As shown in Table 1, it can be seen that the emission lifetime of the complex represented by the chemical formula (2) changes significantly due to the interaction with dichlorvos.
［部分双極子モーメント及び遮蔽率］
上記実施例にて評価した農薬、プロフェノホス、 ホスチアゼート、エディフェンホス、ジクロルボス、メチオカルブスルホンについて、分子軌道法計算で構造最適化（MM2）を行い、P＝O、又はS＝Oの部分的双極子モーメント、及びP＝O、又はS＝Oの酸素原子の立体的な遮蔽率を計算した。表2に計算結果を示す。
[Partial dipole moment and shielding rate]
Structural optimization (MM2) was performed by molecular orbital calculation for pesticides, profenofos, phosphiazates, edifenphos, dichlorobos, and methiocarbsulfone evaluated in the above examples, and P = O or S = O partial The dipole moment and the three-dimensional shielding rate of oxygen atoms with P = O or S = O were calculated. Table 2 shows the calculation results.
ここで、P＝O、S＝Oの部分的双極子モーメントは、高い値になるほど酸素原子のルイス塩基性が高くなり、ルイス酸であるEu(III)イオンとの配位結合は大きくなる。また、P＝O、S＝Oの遮蔽率は、低いほど立体障害の影響が小さくなり、酸素原子はEu(III)イオンに配位し易くなる。
表2に示す計算結果から、本実施形態に係る検出方法で検出可能な標的化合物の部分的双極子モーメントは5.4以上、遮蔽率は27%未満という特徴が見られることが分かる。
Here, the higher the partial dipole moment of P = O and S = O, the higher the Lewis basicity of the oxygen atom, and the greater the coordination bond with the Eu (III) ion, which is a Lewis acid. Further, the lower the shielding ratio of P = O and S = O, the smaller the influence of steric hindrance, and the oxygen atoms are more easily coordinated to Eu (III) ions.
From the calculation results shown in Table 2, it can be seen that the partial dipole moment of the target compound that can be detected by the detection method according to the present embodiment is characterized by 5.4 or more and shielding rate of less than 27%.
一方、従来法であるコリンエステラーゼ活性阻害法では、プロフェノホス、エディフェンホスの検出はできないことが分かっている。コリンエステラーゼ活性阻害法における反応点であるリン原子の遮蔽率は、プロフェノホスで37.6%、エディフェンホスで40.2%であった。このように、反応点であるリン原子の遮蔽率が高いことがこれらの化合物の検出を阻害した要因と考えられる。 On the other hand, it is known that profenofos and edifenphos cannot be detected by the conventional cholinesterase activity inhibition method. The phosphorus atom shielding rate, which is the reaction point in the cholinesterase activity inhibition method, was 37.6% for profenofos and 40.2% for edifenphos. Thus, the high shielding rate of the phosphorus atom which is a reaction point is considered to be the factor which inhibited the detection of these compounds.
［有機リン化合物の化学構造と発光物性］
希土類錯体である化学式（2）で示される錯体に、標的化合物（農薬）のモデルとして種々の有機リン化合物が配位した錯体の発光物性である発光スペクトル、励起スペクトル、発光寿命、及び分岐比（branching ratio）を評価した。
表3に評価結果を示す。
[Chemical structure and luminescent properties of organophosphorus compounds]
Emission spectra, excitation spectra, emission lifetimes, and branching ratios of complex complexes in which various organophosphorus compounds are coordinated to the complex represented by chemical formula (2), which is a rare earth complex, as a target compound (agricultural chemical) model ( The branching ratio was evaluated.
Table 3 shows the evaluation results.
表３に示すように、配位した有機リン化合物の構造の微差により発光スペクトル、励起スペクトル、発光寿命、及び分岐比（branching ratio）は鋭敏に変化していることが分かる。これら発光物性の2種類の変移を選択することにより、有機リン化合物（標的化合物）の有無だけでなく、配位した有機リン化合物（標的化合物）を絞り込むことが可能である。 As shown in Table 3, it can be seen that the emission spectrum, excitation spectrum, emission lifetime, and branching ratio change sharply due to slight differences in the structure of the coordinated organophosphorus compound. By selecting two kinds of transitions of these luminescent properties, it is possible to narrow down not only the presence or absence of an organophosphorus compound (target compound) but also the coordinated organophosphorus compound (target compound).
以上、本発明の実施形態を説明したが、本実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。この新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。本実施形態およびその変形は、発明の範囲や要旨に含まれるとともに、特許請求の範囲に記載された発明とその均等の範囲に含まれる。 As mentioned above, although embodiment of this invention was described, this embodiment is shown as an example and is not intending limiting the range of invention. The novel embodiment can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. This embodiment and its modifications are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.
1；希土類蛍光錯体
2；第1の配位子
3；希土類イオン
4；標的化合物（残留農薬、第2の配位子）
5；標的化合物が配位した希土類蛍光錯体
10；検出装置
11；検出部
12；記憶部
13；判定部
a；コリンエステラーゼ活性阻害法に係る反応の起点
b；本実施形態に係る反応の起点
1; Rare earth fluorescent complex
2; 1st ligand
3; rare earth ions
4; Target compound (residual pesticide, second ligand)
5; Rare earth fluorescent complex with coordinated target compound
10; Detection device
11; Detection unit
12; Memory
13; Judgment part
a: Origin of reaction related to cholinesterase activity inhibition method
b: Reaction start point according to this embodiment
Claims (12)
この抽出工程で抽出された前記化合物を、希土類錯体を構成する希土類イオンと接触させることにより前記希土類イオンと反応させる反応工程と、
この反応工程における反応により引き起こされる発光強度、発光寿命、及び発光スペクトル形状の遷移のいずれかを検出することにより前記化合物を検出する検出工程と、を有することを特徴とする化合物の検出方法。 Oxygen double bond, sulfur - - phosphorus contained in the DUT oxygen double bond, a carbon - oxygen double bond, or have a non-covalent electron pair of the nitrogen atom, at least phosphorus - compounds which have a oxygen double bond An extraction process for extracting
A reaction step in which the compound extracted in the extraction step is reacted with the rare earth ions by contacting with the rare earth ions constituting the rare earth complex;
And a detection step of detecting the compound by detecting any one of emission intensity, emission lifetime, and emission spectrum shape transition caused by the reaction in the reaction step.
この反応工程における反応により引き起こされる前記希土類錯体の発光強度、発光寿命、又は発光スペクトル形状の遷移のいずれかを検出することにより前記化合物を検出する検出工程と、を有することを特徴とする化合物の検出方法。 A test sample is put into a test solution in which a rare earth complex is dissolved in a solvent, and a phosphorus-oxygen double bond, sulfur-oxygen double bond, carbon-oxygen double bond, or nitrogen contained in the test sample. have a lone pair of atoms, at least phosphorus - and compounds that have a oxygen double bond, the reaction step of reacting with the rare earth ions by contact with the rare earth ions constituting the rare earth complex,
A detection step of detecting the compound by detecting any one of emission intensity, emission lifetime, or emission spectrum shape transition of the rare earth complex caused by the reaction in the reaction step. Detection method.
この抽出工程で抽出された前記化合物を、希土類錯体を構成する希土類イオンと接触させることにより前記希土類イオンと反応させる反応工程と、
この反応工程における反応により引き起こされる発光強度、発光寿命、及び発光スペクトル形状の遷移のいずれかを検出することにより前記化合物を検出する検出工程と、を有し、
前記発光スペクトル形状は、前記希土類イオンの磁気双極子遷移に基づく発光スペクトル強度と電気双極子遷移に基づく発光スペクトル強度の比率であることを特徴とする化合物の検出方法。 An extraction step of extracting a compound having a phosphorus-oxygen double bond, a sulfur-oxygen double bond, a carbon-oxygen double bond, or a nitrogen atom unshared electron pair contained in the test sample;
A reaction step in which the compound extracted in the extraction step is reacted with the rare earth ions by contacting with the rare earth ions constituting the rare earth complex;
Detecting the compound by detecting any one of emission intensity, emission lifetime, and emission spectrum shape transition caused by the reaction in the reaction step, and
The emission spectral shape, method of detecting that reduction compound be characterized by the ratio of the emission spectrum intensity based on the emission spectrum intensity and the electric dipole transitions based on magnetic dipole transition of the rare earth ion.
この反応工程における反応により引き起こされる前記希土類錯体の発光強度、発光寿命、又は発光スペクトル形状の遷移のいずれかを検出することにより前記化合物を検出する検出工程と、を有し、Detecting the compound by detecting any of the emission intensity, emission lifetime, or emission spectrum shape transition of the rare earth complex caused by the reaction in this reaction step, and
前記発光スペクトル形状は、前記希土類イオンの磁気双極子遷移に基づく発光スペクトル強度と電気双極子遷移に基づく発光スペクトル強度の比率であることを特徴とする化合物の検出方法。The compound emission method, wherein the emission spectrum shape is a ratio of an emission spectrum intensity based on a magnetic dipole transition of the rare earth ion and an emission spectrum intensity based on an electric dipole transition.
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