JP3286731B2 - Zinc ion fluorescent sensor - Google Patents
Zinc ion fluorescent sensorInfo
- Publication number
- JP3286731B2 JP3286731B2 JP25640199A JP25640199A JP3286731B2 JP 3286731 B2 JP3286731 B2 JP 3286731B2 JP 25640199 A JP25640199 A JP 25640199A JP 25640199 A JP25640199 A JP 25640199A JP 3286731 B2 JP3286731 B2 JP 3286731B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorescent sensor
- zinc ion
- ion fluorescent
- ions
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、亜鉛イオン蛍光セ
ンサーに関するものである。[0001] The present invention relates to a zinc ion fluorescent sensor.
【０００２】[0002]
【従来の技術】生体系或いは環境中の微量金属成分の検
知には高感度な蛍光センサーが有効と考えられている。
従来、金属イオン蛍光センサーとしては、Ｎａ+やＫ+等
のアルカリ金属イオンや、Ｍｇ2+、Ｃａ2+等のアルカリ
土類金属イオンに対するものは広く知られているが、亜
鉛、銅、ニッケル、コバルト等遷移金属イオンの蛍光セ
ンサーについては未だ例は多くない。生体系において
は、亜鉛イオン含有のタンパク質が多数存在することか
ら、微量亜鉛イオンの検知は重要である。これまで知ら
れているその蛍光センサーでは亜鉛イオンと作用する部
分と発光部とが別であり、構造が複雑で合成上難しい
か、あるいは選択性、感度等の点で改善の余地が多い。2. Description of the Related Art A highly sensitive fluorescent sensor is considered to be effective for detecting trace metal components in a biological system or environment.
Conventionally, as a metal ion fluorescent sensor, those for alkali metal ions such as Na + and K + and alkaline earth metal ions such as Mg 2+ and Ca 2+ are widely known, but zinc, copper, nickel There are not many examples of fluorescent sensors for transition metal ions such as cobalt and the like. In biological systems, detection of trace amounts of zinc ions is important because there are many zinc ion-containing proteins. The fluorescent sensor known so far has a portion that interacts with zinc ions and a light emitting portion, and has a complicated structure and is difficult to synthesize, or there is much room for improvement in selectivity and sensitivity.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、亜鉛イオン
に対して選択的にかつ高感度で応答し、しかも、構造が
単純で合成が容易な亜鉛イオン蛍光センサーを提供する
ことをその課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a zinc ion fluorescent sensor which responds selectively and with high sensitivity to zinc ions, has a simple structure and is easy to synthesize. I do.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、下記式（１）で表さ
れるピリジルピラゾリン誘導体からなる亜鉛イオン蛍光
センサーが提供される。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, there is provided a zinc ion fluorescent sensor comprising a pyridyl pyrazoline derivative represented by the following formula (1).
【化２】 Embedded image
【０００５】[0005]
【発明の実施の形態】本発明で用いる前記式（１）で表
されるピリジルピラゾリン誘導体（１−フェニル−３−
（２'−ピリジル）−５−（４'−シアノフェニル）−２
−ピラゾリン（以下、単にＰｙ−ＣＮとも略記する）
は、下記式（２）で表されるカルコン（chalcome）化合
物（ｐ−シアノスチリル−２−ピリジルケトン）とフェ
ニルヒドラジンとを反応させることによって製造するこ
とができる。BEST MODE FOR CARRYING OUT THE INVENTION The pyridyl pyrazoline derivative (1-phenyl-3-) represented by the above formula (1) used in the present invention is used.
(2′-pyridyl) -5- (4′-cyanophenyl) -2
-Pyrazoline (hereinafter abbreviated simply as Py-CN)
Can be produced by reacting a chalcone compound (p-cyanostyryl-2-pyridyl ketone) represented by the following formula (2) with phenylhydrazine.
【化３】 前記反応は、エタノール、プロパノール、ブタノール、
酢酸、プロピオン酸等の有機溶媒中で実施され、その反
応温度は６０〜１５０℃、好ましくは８０〜１１０℃で
ある。Embedded image The reaction comprises ethanol, propanol, butanol,
The reaction is performed in an organic solvent such as acetic acid or propionic acid, and the reaction temperature is 60 to 150 ° C, preferably 80 to 110 ° C.
【０００６】[0006]
【発明の効果】本発明によるＰｙ−ＣＮは、溶液に含ま
れる亜鉛イオン（Ｚｎ2+）と作用して、強い蛍光を発す
る。この場合、励起波長４００ｎｍで観測される蛍光の
波長は５００〜７００ｎｍ、特に５５０〜６００ｎｍで
ある。このＰｙ−ＣＮは、亜鉛イオンに対して選択的に
作用し、リチウムイオン（Ｌｉ+）や、マグネシウムイ
オン（Ｍｇ2+）、カルシウムイオン（Ｃａ2+）、ニッケ
ルイオン（Ｎｉ2+）、コバルトイオン（Ｃｏ 2+）、銅イ
オン（Ｃｕ2+）等の金属イオンに対しては強く作用しな
い。従って、本発明の亜鉛イオン蛍光センサーは、溶液
中で各種金属イオンのうち特に亜鉛イオンに対して選択
的かつ高感度で応答するものである。本発明の亜鉛イオ
ン蛍光センサーは、溶液中の亜鉛イオンの選択的検知の
用途に供することができる。The Py-CN according to the present invention is contained in a solution.
Zinc ions (Zn2+) And emits strong fluorescence
You. In this case, the fluorescence observed at an excitation wavelength of 400 nm
The wavelength is 500-700nm, especially 550-600nm
is there. This Py-CN selectively reacts with zinc ions.
Acts on lithium ions (Li+) And magnesium
ON (Mg2+), Calcium ions (Ca2+), Nicke
Luion (Ni2+), Cobalt ions (Co 2+), Copper
ON (Cu2+Does not act strongly on metal ions such as
No. Therefore, the zinc ion fluorescent sensor of the present invention
Of various metal ions, especially zinc ions
It responds accurately and with high sensitivity. The zinc ion of the present invention
Fluorescent sensors detect zinc ions in solution selectively.
Can be used for applications.
【０００７】[0007]
【実施例】以下、本発明を実施例により詳述する。 実施例１ （１）カルコン化合物（ｐ−シアノスチリル−２−ピリ
ジルケトン）の合成 １０％水酸化ナトリウム水溶液２０ｍｌに４−シアノベ
ンズアルデヒド６．５５ｇ（０．０５モル）をエタノー
ル１０ｍｌに溶かして加え０〜１０℃に冷却した。これ
に２−アセチルピリジン６．０５ｇ（０．０５モル）の
エタノール溶液１０ｍｌを攪拌しつつ加えた。さらに、
３時間程度攪拌すると淡黄色の沈殿が生成した。濾過し
た沈殿は水洗後、乾燥した。９５％エタノール中での再
結晶化により、カルコンの精製物を９．７１ｇ 収率８
３％で得た。このものは、ＭＳにより、その構造を同定
した。 ＭＳ ｍ／ｚ ２３４ （２）Ｐｙ−ＣＮの合成 前記式（２）で表されるカルコン化合物２３．４ｇ
（０．１モル）とフェニルヒドラジン１０．８ｇ（０．
１モル）をエチルアルコール−酢酸（２０ｍｌ／５ｍ
ｌ）の混合溶媒に溶かした。溶液を６時間加熱還流した
後、水１０ｍｌを加えた。冷却後、析出する生成物の結
晶を濾過した。９５％エタノール中での再結晶化によ
り、Ｐｙ−ＣＮの精製物を１６．５ｇ 収率５１％で得
た。このものは、 1ＨＮＭＲ、ＭＳ及び元素分析によ
り、その構造を同定した。1 Ｈ ＮＭＲ（ＣＤＣ１3）δ＝６．７８〜６．８３（１
Ｈ、ｍ、aromatic）７．０３〜７．０６（２Ｈ、ｍ、ar
omatic）、７．１６〜７．２９（３Ｈ、ｍ、aromati
c）、７．４５〜７．４８（２Ｈ、ｍ、aromatic）、
７．６８〜７．８１（３Ｈ、ｍ、aromatic）、８．１１
〜８．１４（１Ｈ、ｍ、aromatic）、８．５１〜８．５
３（１Ｈ、ｍ、aromatic） ＭＳ ｍ／ｚ ３２４（元素分析値（Ｃ21Ｎ4Ｈ16とし
て）） 計算値 Ｃ７７．７６、Ｈ４．９７、Ｎ１７．２７ 実測値 Ｃ７７．４３、Ｈ４．９１、Ｎ１７．５３The present invention will be described below in detail with reference to examples. Example 1 (1) Chalcone compound (p-cyanostyryl-2-pyri)
4-cyanobe in 20 ml of 10% aqueous sodium hydroxide solution
6.55 g (0.05 mol) of Nsaldehyde in ethanol
And cooled to 0-10 ° C. this
6.05 g (0.05 mol) of 2-acetylpyridine
10 ml of ethanol solution was added with stirring. further,
After stirring for about 3 hours, a pale yellow precipitate was formed. Filter
The precipitate was washed with water and dried. Re-use in 95% ethanol
By crystallization, 9.71 g of purified chalcone was obtained in a yield of 8.
Obtained at 3%. The structure is identified by MS
did. MS m / z 234 (2) Synthesis of Py-CN 23.4 g of a chalcone compound represented by the above formula (2)
(0.1 mol) and 10.8 g of phenylhydrazine (0.
1 mol) in ethyl alcohol-acetic acid (20 ml / 5 m
l). The solution was heated at reflux for 6 hours
Thereafter, 10 ml of water was added. After cooling, the product
The crystals were filtered. By recrystallization in 95% ethanol
Thus, 16.5 g of a purified product of Py-CN was obtained in a yield of 51%.
Was. This one is 1By HNMR, MS and elemental analysis
Thus, its structure was identified.1 1 H NMR (CDC1Three) Δ = 6.78 to 6.83 (1
H, m, aromatic) 7.03 to 7.06 (2H, m, ar
omatic), 7.16-7.29 (3H, m, aromati
c), 7.45 to 7.48 (2H, m, aromatic),
7.68-7.81 (3H, m, aromatic), 8.11
-8.14 (1H, m, aromatic), 8.51-8.5
3 (1H, m, aromatic) MS m / z 324 (elemental analysis (Ctwenty oneNFourH16age
T)) Calculated values C77.76, H4.97, N17.27 Actual values C77.43, H4.91 and N17.53
【０００８】（３）金属イオンに対するＰｙ−ＣＮの作
用 Ｐｙ−ＣＮの蛍光センサーとしての性能を調べるため
に、Ｐｙ−ＣＮを含むアセトニトリル溶液にＺｎ2+を作
用させた。即ち、Ｐｙ−ＣＮを２．０×１０-5Ｍ／Ｌの
濃度で含むアセトニトリル溶液に対し、Ｚｎ2+を、金属
イオンとＰｙ−ＣＮの濃度比［Ｍ］／［Ｌ］：０．２〜
２０の範囲で添加して、その際にＰｙ−ＣＮが発する蛍
光（５６８ｎｍ）の相対強度(Ｉｆ)(ａ.ｎ.)測定した。
その結果を表１に示す。(3) Effect of Py-CN on metal ions In order to examine the performance of Py-CN as a fluorescent sensor, Zn 2+ was allowed to act on an acetonitrile solution containing Py-CN. That is, in an acetonitrile solution containing Py-CN at a concentration of 2.0 × 10 −5 M / L, Zn 2+ is added to a metal ion and Py-CN at a concentration ratio [M] / [L]: 0.2. ~
In this case, the relative intensity (If) (an) of the fluorescence (568 nm) emitted from Py-CN was measured.
Table 1 shows the results.
【０００９】[0009]
【表１】 （注） ［Ｍ］：金属イオンの濃度 ［Ｌ］：Ｐｙ−ＣＮの濃度[Table 1] (Note) [M]: Metal ion concentration [L]: Py-CN concentration
【００１０】参考例１ 実施例１の（３）において、亜鉛イオンの代りに、Ｎｉ
2+、Ｃｏ2+、Ｃｕ2+、Ｌｉ+、Ｃａ2+又はＭｇ2+を用い
た以外は同様にして実験を行なった結果を表２に示す。
それらの金属イオンの添加によるＰｙ−ＣＮの蛍光強度
の変化はＮｉ2+、Ｃａ2+、Ｃａ2+では濃度の増加ととも
に減少し、Ｚｎ2+の場合の蛍光強度の約１／５０以下
（［Ｍ］／［Ｌ］＝２０．０）であり、また、Ｌｉ+、
Ｃａ2+、Ｍｇ2+では蛍光にほとんど変化が無く非常に低
いものであった。Reference Example 1 In Example 1 (3), instead of zinc ions, Ni
Table 2 shows the results of an experiment performed in the same manner except that 2+ , Co2 + , Cu2 + , Li + , Ca2 +, or Mg2 + was used.
The change in the fluorescence intensity of Py-CN due to the addition of these metal ions decreases with increasing concentration in Ni 2+ , Ca 2+ , and Ca 2+ , and is about 1/50 or less of the fluorescence intensity in the case of Zn 2+ ( [M] / [L] = 20.0), and Li + ,
In Ca 2+ and Mg 2+ , there was almost no change in fluorescence, and the fluorescence was very low.
【００１１】[0011]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 杉原 秀樹 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 荒川 裕則 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 審査官 加々美 一恵 (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 21/78 C09K 11/07 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hideki Sugihara 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Institute of Industrial Science and Technology (72) Inventor Hironori Arakawa 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Examiner, Kazumi Kagami, National Institute for Materials Technology (58) Fields investigated (Int. Cl. 7 , DB name) G01N 21/78 C09K 11/07 CA (STN)
Claims (1)
リン誘導体からなる亜鉛イオン蛍光センサー。 【化１】 1. A zinc ion fluorescent sensor comprising a pyridyl pyrazoline derivative represented by the following formula (1). Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25640199A JP3286731B2 (en) | 1999-09-09 | 1999-09-09 | Zinc ion fluorescent sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25640199A JP3286731B2 (en) | 1999-09-09 | 1999-09-09 | Zinc ion fluorescent sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001083097A JP2001083097A (en) | 2001-03-30 |
| JP3286731B2 true JP3286731B2 (en) | 2002-05-27 |
Family
ID=17292176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25640199A Expired - Lifetime JP3286731B2 (en) | 1999-09-09 | 1999-09-09 | Zinc ion fluorescent sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3286731B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100446466B1 (en) * | 2001-08-31 | 2004-08-30 | 네오뷰코오롱 주식회사 | Organic luminescent compound, and organic electroluminescence device using the same |
-
1999
- 1999-09-09 JP JP25640199A patent/JP3286731B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001083097A (en) | 2001-03-30 |
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