KR101879726B1 - A novel coumarin derivative, composition for detecting cyanide ion comprising the same and method for detecting cyanide ion using the same - Google Patents

A novel coumarin derivative, composition for detecting cyanide ion comprising the same and method for detecting cyanide ion using the same Download PDF

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KR101879726B1
KR101879726B1 KR1020170100463A KR20170100463A KR101879726B1 KR 101879726 B1 KR101879726 B1 KR 101879726B1 KR 1020170100463 A KR1020170100463 A KR 1020170100463A KR 20170100463 A KR20170100463 A KR 20170100463A KR 101879726 B1 KR101879726 B1 KR 101879726B1
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cyanide
compound
ethynyl
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최명석
세사세나 레디 투푸
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건국대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/10—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring unsubstituted
    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/52—Use of compounds or compositions for colorimetric, spectrophotometric or fluorometric investigation, e.g. use of reagent paper and including single- and multilayer analytical elements

Abstract

The present invention provides a novel dicyanovinyl coumarin compound, a composition for detecting cyanide containing the same, and a method for detecting cyanide using the same. The dicyanovinyl coumarin compound, the composition for detecting cyanide containing the same, and the method for detecting cyanide using the same of the present invention can be usefully used as a detecting technique for confirming human safety in a field of cyanide detection. The method for detecting cyanide comprises a step for measuring a light having a wavelength range of 360-380 nm.

Description

신규한 쿠마린 유도체, 이를 포함하는 시안 이온 검출용 조성물 및 이를 이용한 시안 이온 검출 방법{A novel coumarin derivative, composition for detecting cyanide ion comprising the same and method for detecting cyanide ion using the same}TECHNICAL FIELD The present invention relates to a novel coumarin derivative, a composition for detecting cyanide containing the same, and a method for detecting cyanide using the coumarin derivative, a composition for detecting cyanide ion,

본 발명은 시안 이온 검출용으로 사용되는 쿠마린 유도체에 관한 것으로, 더욱 상세하게는 신규한 디시아노비닐쿠마린 화합물, 이를 포함하는 시안 이온 검출용 조성물 및 이를 이용한 시안 이온 검출 방법에 관한 것이다.More particularly, the present invention relates to a novel dicyanovinyl coumarin compound, a composition for detecting cyanide containing the same, and a method for detecting cyanide using the same.

음이온을 검출하는 선택적이고 민감한 화학센서의 발전은 약품, 일상 생활 및 환경에서의 다양한 역할 때문에 상당히 주목받아 왔다. 여러 종류의 화학센서 중에 비색 측정법을 기초로 한 음이온과 양이온의 화학센서는 간단하고, 가역성이 낮으며, 분석을 빠르게 수행할 수 있는 등의 많은 이점을 갖고 있다. 그러므로 비색 측정 센서는 추가적인 고가의 장비없이 색 변화를 육안상으로 검출할 수 있으므로 최근 많은 주목을 받고 있다.The development of selective and sensitive chemical sensors for detecting anions has received considerable attention due to their varied roles in drugs, daily life and the environment. Among various chemical sensors, anionic and cationic chemical sensors based on colorimetry are simple, have low reversibility, and have many advantages such as quick analysis. Therefore, the colorimetric sensor has attracted a great deal of attention recently because it can visually detect the color change without any additional expensive equipment.

시안 이온(CN-)은 반응성이 가장 빠르며, 치명적인 독극물로 알려져 있다. 상기 독성은 시안 이온이 시토크롬c 산화효소의 철 이온과 결합하는 경향 때문에 생기는 것이며, 전자 전달을 방해하여 저산소증을 일으킨다. 또한, 여러 연구에서 시안 이온이 화재관련 사망에서 중요한 요소로 작용한다고 발표되기도 하였다. 그러나, 이러한 독성에도 불구하고 시안 이온은 전기 도금, 플라스틱 제조, 금과 은의 추출, 무두질 및 야금 등과 같은 많은 화학적 과정에서 다양하게 사용된다. 그러므로 시안 이온을 선택적이고 민감하게 검출하는 방법을 개발하는 것이 요구되는 실정이다.Cyanide (CN - ) is the most reactive and is known as a deadly poison. This toxicity is caused by the tendency of cyanide to bind to the iron ion of cytochrome c oxidase, which interferes with electron transport and causes hypoxia. In addition, several studies have reported that cyanide is an important factor in fire related deaths. Despite this toxicity, however, cyanide is widely used in many chemical processes such as electroplating, plastic manufacturing, gold and silver extraction, tanning and metallurgy. Therefore, it is required to develop a method for selectively and sensitively detecting cyanide ions.

쿠마린(coumarin)은 다양한 종류의 식물 원료에서 발견되는 천연 화합물 군을 지칭하는 것으로서, 기능성 물질로 광범위하게 연구되고 있다. 일례로서, 쿠마린 유도체는 레이저 염료로 널리 사용되며 다양한 센서 응용에 활용되고 있으며, 최근 금속 이온을 검출하는 센서의 발색단과 형광체로 자주 사용되고 있다. 그러므로 이를 이용하여 신규한 화학센서의 개발을 위한 노력이 요구되는 상황이다.Coumarin refers to a group of natural compounds found in various types of botanical raw materials and has been extensively studied as functional materials. As an example, coumarin derivatives are widely used as laser dyes and are used in various sensor applications. Recently, they have been frequently used as chromophores and phosphors for detecting metal ions. Therefore, efforts are needed to develop new chemical sensors by using them.

대한민국 특허등록 제10-1599188호 (2016년02월24일)Korean Patent Registration No. 10-1599188 (February 24, 2016) 대한민국 특허공개 제10-2016-0015725호 (2016년02월15일)Korean Patent Publication No. 10-2016-0015725 (Feb. 15, 2016) 대한민국 특허공개 제10-2010-0127042호 (2010년12월03일)Korean Patent Publication No. 10-2010-0127042 (December 03, 2010) 대한민국 특허공개 제10-2016-0038129호 (2016년04월07일)Korean Patent Publication No. 10-2016-0038129 (April 07, 2016)

본 발명의 발명자들은 인체 안전성 확인 검출에 이용할 수 있는 시안 이온 검출 기술에 대하여 연구하던 중, 디시아노비닐 쿠마린 유도체가 시안 이온에 대해 높은 선택성을 나타내고, 시안 이온 검출 감도도 우수하다는 것을 확인하였다.The inventors of the present invention have investigated cyanide ion detection technology that can be used for human safety confirmation detection, and confirmed that the dicyanovinyl coumarin derivative exhibits high selectivity for cyan ions and excellent cyan ion detection sensitivity.

따라서, 본 발명은 디시아노비닐쿠마린 화합물, 이를 포함하는 시안 이온 검출용 조성물 및 이를 이용한 시안 이온 검출 방법을 제공하는 것을 목적으로 한다.Accordingly, it is an object of the present invention to provide a dicyanovinyl coumarin compound, a composition for detecting cyanide containing the same, and a method for detecting cyanide using the same.

본 발명의 일 측면에 따라, 하기 화학식 4로 표시되는 화합물이 제공된다.According to one aspect of the present invention, there is provided a compound represented by the following general formula (4).

[화학식 4][Chemical Formula 4]

Figure 112017076480153-pat00001
Figure 112017076480153-pat00001

일 구현예에서, 상기 화합물은 하기 화학식 4a 내지 화학식 4c로 표시되는 화합물 중 하나이다.In one embodiment, the compound is one of the compounds represented by the following formulas (4a) to (4c).

[화학식 4a][Chemical Formula 4a]

Figure 112017076480153-pat00002
Figure 112017076480153-pat00002

[화학식 4b](4b)

Figure 112017076480153-pat00003
Figure 112017076480153-pat00003

[화학식 4c][Chemical Formula 4c]

Figure 112017076480153-pat00004
Figure 112017076480153-pat00004

본 발명의 다른 측면에 따라, (i) 브로모페놀을 말산과 반응시켜 브로모쿠마린을 얻는 단계; (ⅱ) 단계(i)에서 얻은 브로모쿠마린을 4-에티닐벤즈알데히드와 반응시켜 4-((2-옥소-2H-크로메닐)에티닐)벤즈알데히드를 얻는 단계; 및 (ⅲ) 단계(ⅱ)에서 얻은 4-((2-옥소-2H-크로메닐)에티닐)벤즈알데히드를 말론니트릴과 반응시키는 단계를 포함하는 상기 화합물의 제조방법이 제공된다.According to another aspect of the present invention, there is provided a method for producing bromocoumarin comprising: (i) reacting bromophenol with malic acid to obtain bromocoumarin; (Ii) reacting the bromocoumarin obtained in step (i) with 4-ethynylbenzaldehyde to obtain 4 - ((2-oxo- 2H -chromenyl) ethynyl) benzaldehyde; And (iii) reacting the 4 - ((2-oxo- 2H -chromenyl) ethynyl) benzaldehyde obtained in step (ii) with malononitrile.

본 발명의 또 다른 측면에 따라, 상기 화합물을 포함하는 시안 이온 검출용 조성물이 제공된다.According to another aspect of the present invention, there is provided a composition for detecting cyanide which comprises the above compound.

일 구현예에서, 상기 시안 이온 검출용 조성물은 테트라히드로푸란을 용매로 포함할 수 있다.In one embodiment, the composition for detecting cyanide may comprise tetrahydrofuran as a solvent.

본 발명의 또 다른 측면에 따라, 상기 화합물을 검체와 반응시키는 단계를 포함하는 시안 이온 검출 방법이 제공된다.According to another aspect of the present invention, there is provided a cyanide detection method comprising reacting the compound with a sample.

일 구현예에서, 상기 시안 이온 검출 방법에서는 테트라히드로푸란을 용매로 사용할 수 있으며, 방출되는 형광을 파장 범위 360 - 380 nm에서 측정하는 단계를 추가로 포함할 수 있다.In one embodiment, the cyanide detection method may use tetrahydrofuran as a solvent, and may further include measuring the emitted fluorescence in the wavelength range of 360 to 380 nm.

본 발명의 또 다른 측면에 따라, 상기 화합물을 사용하는 시안 이온 검출 장치가 제공된다.According to another aspect of the present invention, there is provided a cyanide ion detection apparatus using the above compound.

일 구현예에서, 상기 시안 이온 검출 장치는 테트라히드로푸란을 용매로 사용할 수 있으며, 방출되는 형광을 파장 범위 360 - 380 nm에서 측정할 수 있다.In one embodiment, the cyanide ion detector can use tetrahydrofuran as a solvent, and the emitted fluorescence can be measured in the wavelength range of 360 to 380 nm.

본 발명에 의해, 7-치환 디시아노비닐 쿠마린이 다른 음이온(F-, Cl-, Br-, I-, HSO4 -, OCl4 - 및 NO2 -)을 첨가했을 경우보다 CN- 이온 존재 하에서 보다 우수한 형광을 나타내어, CN- 이온에 대해 높은 선택성이 있는 것으로 확인되었고, 그 검출 한계는 WHO 기준인 1.9 x 10-6 M(in Liquid system)보다 낮은 1.14 x 10-8 M로 측정되어, 인체 안전성 확인 검출에 이용 가능할 정도로 시안 이온 검출 감도가 우수하다는 것이 밝혀졌다.According to the present invention, the 7-substituted-dicyano-vinyl-coumarin other anion (F -, Cl -, Br -, I -, HSO 4 -, OCl 4 - and NO 2 -) - under ions if added to more CN than shown excellent fluorescence, CN - was found to be highly selective for the ion, the detection limit is measured at 1.14 x lower than the wHO standard of 1.9 x 10 -6 M (in Liquid system) 10 -8 M, the body It has been found that cyan ion detection sensitivity is excellent enough to be used for safety confirmation detection.

따라서, 본 발명의 디시아노비닐쿠마린 화합물, 이를 포함하는 시안 이온 검출용 조성물 및 이를 이용한 시안 이온 검출 방법은 시안 이온 검출 분야에서 인체 안전성 확인 검출 기술로 유용하게 사용될 수 있다.Accordingly, the dicyanovinyl coumarin compound of the present invention, the composition for detecting cyanide containing the same, and the method for detecting cyanide using the same, can be effectively used as a human safety confirmation detection technique in the field of cyanide detection.

도 1은 CDCl3 중 4b 화합물의 1H NMR 스펙트럼이다.
도 2는 CDCl3 중 4b 화합물의 13C NMR 스펙트럼이다.
도 3은 4b 화합물의 질량분석(Mass) 스펙트럼이다.
도 4는 3b 화합물의 질량분석 스펙트럼이다.
도 5는 CDCl3에서 4b 화합물 및 4b 화합물 + TBACN의 1H NMR 스펙트럼이다.
도 6은 밀도 함수 이론(Density Functional Theory, DFT)의 B3LYP 수준을 이용하여 계산된, DCV 쿠마린 화합물인 4a, 4b 및 4c의 경계 분자 궤도(frontier molecular orbital, HOMO 에서 LUMO) 및 최적화된 구조이다.
도 7은 366 nm에서 4b 화합물 및 THF 용매 중의 다양한 음이온 존재 하에서의 4b 화합물의 형광 반응 결과이다.
도 8은 THF 중 4b 화합물의 형광 방출 스펙트럼(λex = 365 nm)에 대한 다양한 음이온의 영향을 나타낸 것이다.
도 9는 THF 용매 중 TBACN을 이용한 4b의 형광 적정 스펙트럼(λex = 365 nm)이다.
도 10은 THF 중 4c 화합물의 형광 방출 스펙트럼(λex = 365 nm)에 대한 다양한 음이온의 영향을 나타낸 것이다.
도 11은 THF 중 4a 화합물의 형광 방출 스펙트럼(λex = 365 nm)에 대한 다양한 음이온의 영향을 나타낸 것이다. 1 is a 1 H NMR spectrum of a 4b compound in CDCl 3 .
2 is a 13 C NMR spectrum of a compound 4b in CDCl 3 .
3 is a mass spectrometry of the 4b compound.
4 is a mass spectrometry spectrum of the compound 3b.
5 is a 1 H NMR spectrum of a 4b compound and a 4b compound + TBACN in CDCl 3 .
Figure 6 is a frontier molecular orbital (LUMO in HOMO) and optimized structure of DCV coumarin compounds 4a, 4b and 4c, calculated using the B3LYP level of the Density Functional Theory (DFT).
Figure 7 shows the fluorescence results of the 4b compound at 366 nm and the 4b compound in the presence of various anions in THF solvent.
8 shows the effect of various anions on the fluorescence emission spectrum (? Ex = 365 nm) of the 4b compound in THF.
9 is a fluorescence titration spectrum (lambda ex = 365 nm) of 4b using TBACN in THF solvent.
10 shows the effect of various anions on the fluorescence emission spectrum (λ ex = 365 nm) of the 4c compound in THF.
Fig. 11 shows the effect of various anions on the fluorescence emission spectrum (? Ex = 365 nm) of the compound 4a in THF.

본 발명은 하기 화학식 4로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the following formula (4).

[화학식 4][Chemical Formula 4]

Figure 112017076480153-pat00005
Figure 112017076480153-pat00005

일 구현예에서, 상기 화합물은 하기 화학식 4a 내지 화학식 4c로 표시되는 화합물 중 하나이다.In one embodiment, the compound is one of the compounds represented by the following formulas (4a) to (4c).

[화학식 4a][Chemical Formula 4a]

Figure 112017076480153-pat00006
Figure 112017076480153-pat00006

[화학식 4b](4b)

Figure 112017076480153-pat00007
Figure 112017076480153-pat00007

[화학식 4c][Chemical Formula 4c]

Figure 112017076480153-pat00008
Figure 112017076480153-pat00008

또한, 본 발명은 (i) 브로모페놀을 말산과 반응시켜 브로모쿠마린을 얻는 단계; (ⅱ) 단계(i)에서 얻은 브로모쿠마린을 4-에티닐벤즈알데히드와 반응시켜 4-((2-옥소-2H-크로메닐)에티닐)벤즈알데히드를 얻는 단계; 및 (ⅲ) 단계(ⅱ)에서 얻은 4-((2-옥소-2H-크로메닐)에티닐)벤즈알데히드를 말론니트릴과 반응시키는 단계를 포함하는 상기 화합물의 제조방법을 제공한다.The present invention also relates to a method for producing bromocoumarin, comprising the steps of: (i) reacting bromophenol with malic acid to obtain bromocoumarin; (Ii) reacting the bromocoumarin obtained in step (i) with 4-ethynylbenzaldehyde to obtain 4 - ((2-oxo- 2H -chromenyl) ethynyl) benzaldehyde; And (iii) reacting the 4 - ((2-oxo- 2H -chromenyl) ethynyl) benzaldehyde obtained in step (ii) with malononitrile.

상기 제조방법은 크뇌페나겔(Knoevenagel) 축합 반응에 의해 수행되며, 각 단계는 하기 반응식 1과 같이 요약된다.The preparation process is carried out by the Knoevenagel condensation reaction, and each step is summarized as shown in the following reaction formula (1).

[반응식 1][Reaction Scheme 1]

Figure 112017076480153-pat00009
Figure 112017076480153-pat00009

상기 단계(i)은 브로모페놀[1a, 1b, 1c]을 말산과 반응시켜 브로모쿠마린[2a, 2b, 2c]을 얻는 단계이다. 상기 단계는 통상적으로 사용되는 축합(condensation) 반응 조건 하에서 수행될 수 있으며, 예를 들어, H2SO4 존재 하, 120 ℃에서 6 시간 반응시켜 브로모쿠마린을 얻을 수 있다.Step (i) is a step of reacting bromophenol [1a, 1b, 1c] with malic acid to obtain bromocoumarin [2a, 2b, 2c]. The above step can be carried out under commonly used condensation reaction conditions. For example, bromocoumarin can be obtained by reacting in the presence of H 2 SO 4 at 120 ° C for 6 hours.

상기 단계(ⅱ)는 단계(i)에서 얻은 브로모쿠마린을 4-에티닐벤즈알데히드와 반응시켜 4-((2-옥소-2H-크로멘-6-일)에티닐)벤즈알데히드, 4-((2-옥소-2H-크로멘-7-일)에티닐)벤즈알데히드, 4-((2-옥소-2H-크로멘-8-일)에티닐)벤즈알데히드[3a, 3b, 3c]를 각각 얻는 단계이다. 상기 단계는 통상적으로 사용되는 소노가시라 교차 결합 반응(Sonogashira cross-coupling reaction) 조건 하에서 수행될 수 있으며, 예를 들어, 4-에티닐벤즈알데히드와 Pd(PPh3)2Cl2, CuI 존재 하에서, THF:트리에틸아민(1:1 v/v) 용매 하에서, N2 분위기 중(atm)에서, 8 시간 환류시켜 4-((2-옥소-2H-크로멘-6-일)에티닐)벤즈알데히드, 4-((2-옥소-2H-크로멘-7-일)에티닐)벤즈알데히드, 4-((2-옥소-2H-크로멘-8-일)에티닐)벤즈알데히드를 각각 얻을 수 있다.The step (ii) is a step wherein the bromocoumarin obtained in step (i) is reacted with 4-ethynylbenzaldehyde to give 4 - ((2-oxo- 2H -chromen-6-yl) ethynyl) benzaldehyde, 4- a ethynyl - (chromen-8-yl (2-oxo-2 H -2-)) benzaldehyde [3a, 3b, 3c] (2-oxo -2 H-chromen-7-yl) ethynyl) benzaldehyde, 4 Respectively. This step can be carried out under conventional Sonogashira cross coupling reaction (Sonogashira cross-coupling reaction), and the conditions used, for example, under the benzaldehyde and Pd (PPh 3) 2 Cl 2 , CuI present ethynyl 4-, THF : (2-oxo- 2H -chromen-6-yl) ethynyl) benzaldehyde (1: 1 v / v) in a N 2 atmosphere (atm) , 4 - ((2-oxo -2 H-chromen-7-yl) ethynyl) benzaldehyde, 4 - ((2-oxo -2 H-chromen-8-yl) ethynyl) benzaldehyde to obtain the respective have.

상기 단계(ⅲ)은 단계(ⅱ)에서 얻은 4-((2-옥소-2H-크로멘-6-일)에티닐)벤즈알데히드, 4-((2-옥소-2H-크로멘-7-일)에티닐)벤즈알데히드, 4-((2-옥소-2H-크로멘-8-일)에티닐)벤즈알데히드를 말론니트릴과 반응시켜 2-(4-((2-옥소-2H-크로멘-6-일)에티닐)벤질리덴)말로노니트릴, 2-(4-((2-옥소-2H-크로멘-7-일)에티닐)벤질리덴)말로노니트릴, 2-(4-((2-옥소-2H-크로멘-8-일)에티닐)벤질리덴)말로노니트릴[4a, 4b, 4c]을 각각 얻는 단계이다. 상기 단계는 통상적으로 사용되는 크뇌페나겔(Knoevenagel) 축합 반응 조건 하에서 수행될 수 있으며, 예를 들어, 4-((2-옥소-2H-크로멘-6-일)에티닐)벤즈알데히드, 4-((2-옥소-2H-크로멘-7-일)에티닐)벤즈알데히드, 4-((2-옥소-2H-크로멘-8-일)에티닐)벤즈알데히드[3a, 3b, 3c]를 말론니트릴(malonitrile), 에탄올 및 피페리딘(piperidine)과 함께 4 시간 환류시켜 2-(4-((2-옥소-2H-크로멘-6-일)에티닐)벤질리덴)말로노니트릴, 2-(4-((2-옥소-2H-크로멘-7-일)에티닐)벤질리덴)말로노니트릴, 2-(4-((2-옥소-2H-크로멘-8-일)에티닐)벤질리덴)말로노니트릴[4a, 4b, 4c]을 얻을 수 있다.It said step (ⅲ) is obtained in step 4 (ⅱ) ((2-oxo-2 H -2-ethynyl-chromen-6-yl)) benzaldehyde, 4 - ((2-oxo-2 H -2-chromen -7 -yl) ethynyl) benzaldehyde, 4 - ((2-oxo -2 H-chromen-8-yl) in an ethynyl) benzaldehyde was reacted with malonic nitrile 2- (4 - ((2-oxo-2 H -2- (2-oxo- 2H -chromen-7-yl) ethynyl) benzylidene) malononitrile, 2- (4 - ((2-oxo- 2H -chromen-8-yl) ethynyl) benzilidene) malononitrile [4a, 4b, 4c]. This step can be carried out under conventional Knoevenagel condensation reaction conditions, for example, 4 - ((2-oxo- 2H -chromen-6-yl) ethynyl) benzaldehyde, 4 - ((2-oxo -2 H-chromen-ethynyl-7-yl)) benzaldehyde, 4-benzaldehyde [3a, 3b, 3c - ((2-ethynyl -2 H-chromen-8-yl)) Was refluxed with malonitrile, ethanol and piperidine for 4 hours to obtain 2- (4 - ((2-oxo- 2H -chromen-6-yl) ethynyl) benzylidene) no nitrile, 2- (4 - ((2-oxo -2 H-chromen-7-yl) ethynyl) benzylidene) malononitrile, 2- (4 - ((2-oxo-2 H -2-chromene -8-yl) ethynyl) benzylidene) malononitrile [4a, 4b, 4c].

또한, 본 발명은 상기 화합물을 포함하는 시안 이온 검출용 조성물을 제공한다.The present invention also provides a composition for detecting cyanide which comprises the above compound.

일 구현예에서, 상기 시안 이온 검출용 조성물은 테트라히드로푸란을 용매로 포함할 수 있다.In one embodiment, the composition for detecting cyanide may comprise tetrahydrofuran as a solvent.

또한, 본 발명은 상기 화합물을 검체와 반응시키는 단계를 포함하는 시안 이온 검출 방법을 제공한다.The present invention also provides a method for detecting cyanide comprising the step of reacting the compound with a sample.

일 구현예에서, 상기 시안 이온 검출 방법에서는 테트라히드로푸란을 용매로 사용할 수 있다.In one embodiment, the cyanide detection method may use tetrahydrofuran as a solvent.

상기 시안 이온 검출 방법에 있어서, 화학식 4b의 화합물은 시안 이온 첨가시 파란색의 턴온 형광(turn-on fluorescence)을 나타낸다. 이때 방출되는 형광은 파장 범위 360 - 380 nm에서 측정할 수 있으며, 바람직하게는 356 - 366 nm에서 측정할 수 있다. 이러한 형광 반응은 디시아노비닐기가 시안 이온과 화학적으로 반응하는 기전에 의한 것으로 추정되고, 이는 디시아노비닐기의 α-탄소(α-Carbon)가 전자가 부족하여 강력한 친핵체 존재시에 마이클 부가 반응이 진행되기 쉽기 때문이다.In the above-described cyanide detection method, the compound of formula (IVb) exhibits blue turn-on fluorescence upon addition of cyanide. The emitted fluorescence can be measured in the wavelength range of 360 to 380 nm, preferably 356 to 366 nm. This fluorescence reaction is presumed to be caused by the mechanism that the dicyanovinyl group chemically reacts with the cyanide ion. This is because when the α-carbon of the dicyanovinyl group lacks electrons and the strong nucleophile exists, It is easy to proceed.

상기 파장 범위에서의 형광 반응은 시안 이온 및 플루오르화물(F-)에 대하여 나타나고, 다른 음이온(F-, Cl-, Br-, I-, HSO4 -, OCl4 - 및 NO2 -)에 대하여는 나타나지 않는다. 특히, 시안 이온에 대하여 가장 강한 형광 반응을 나타내고, 형광 반응 정도가 시안 이온 농도에 따라 증가되어, 시안 이온에 대한 선택적 정량 검출이 가능하다는 것이 확인되었다. 7-치환 디시아노비닐 쿠마린(4b)의 시안 이온에 대한 검출 한계를 측정한 결과, 1.14 x 10-8 M로 측정되었다. 이는 WHO 기준인 1.9 x 10-6 M(in Liquid system)보다 낮아서 인체 안전성 확인 검출에 이용 가능한 수치이다.Fluorescence response in the above wavelength range appears for cyanide and fluoride (F - ) and not for other anions (F - , Cl - , Br - , I - , HSO 4 - , OCl 4 - and NO 2 - ) Do not. Particularly, it has been confirmed that the most intense fluorescence reaction is exhibited with respect to cyan ions, and the degree of fluorescence reaction increases with the concentration of cyan ions, and selective quantitative detection of cyan ions is possible. The detection limit of the 7-substituted dicyanovinyl coumarin (4b) to cyanide was measured to be 1.14 x 10 -8 M. This is lower than the WHO standard of 1.9 x 10-6 M (in Liquid system), which is a figure that can be used to detect human safety.

또한, 본 발명은 상기 화합물을 사용하는 시안 이온 검출 장치를 제공한다.Further, the present invention provides a cyanide ion detection apparatus using the above compound.

일 구현예에서, 상기 시안 이온 검출 장치는 테트라히드로푸란을 용매로 사용할 수 있으며, 방출되는 형광은 파장 범위 360 - 380 nm에서 측정할 수 있다.In one embodiment, the cyanide ion detection apparatus can use tetrahydrofuran as a solvent, and the emitted fluorescence can be measured in the wavelength range of 360 to 380 nm.

이하, 본 발명을 실시예 및 시험예를 통하여 더욱 상세히 설명한다. 그러나, 하기 실시예 및 시험예는 본 발명을 예시하기 위한 것으로, 본 발명의 범위가 이에 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples and test examples. However, the following examples and test examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

실시예 1. Example 1. 디시아노비닐Dicyanovinyl 쿠마린 화합물의 합성 Synthesis of coumarin compound

(1) 합성 방법(1) Synthesis method

일련(4a, 4b, 4c)의 디시아노비닐 쿠마린(dicyanovinyl-coumarins, DCVC)을 크뇌페나겔(Knoevenagel) 축합 반응에 의해 하기 반응식 1과 같은 순서로 합성하였다.Dicyanovinyl-coumarins (DCVC) of series 4a, 4b, 4c were synthesized by the Knee-Henegel condensation reaction in the same manner as in Scheme 1 below.

[반응식 1][Reaction Scheme 1]

Figure 112017076480153-pat00010
Figure 112017076480153-pat00010

상기 반응식에서 각 단계(ⅰ, ⅱ, ⅲ)의 반응 과정은 다음과 같다.The reaction procedure of each step (i, ii, iii) in the above reaction formula is as follows.

(i) 단계(i)

브로모페놀(bromophenol)[1a, 1b, 1c]을 H2SO4 존재 하에서 말산(malic acid)과 120 ℃에서 6 시간 반응시켜 브로모쿠마린(bromocoumarin)[2a, 2b, 2c]을 합성하였다.Bromocoumarin [2a, 2b, 2c] was synthesized by reacting bromophenol [1a, 1b, 1c] with malic acid in the presence of H 2 SO 4 at 120 ° C for 6 hours.

(ⅱ) 단계(Ii)

얻어진 브로모쿠마린을 4-에티닐벤즈알데히드(4-ethynylbenzaldehyde)와 Pd(PPh3)2Cl2, CuI 존재 하에서, THF/트리에틸아민(1;1 v/v) 용매 하에서, N2 분위기 중(atm)에서, 8 시간 환류시켜 4-((2-옥소-2H-크로멘-6-일)에티닐)벤즈알데히드[4-((2-oxo-2H-chromen-6-yl)ethynyl)benzaldehyde], 4-((2-옥소-2H-크로멘-7-일)에티닐)벤즈알데히드[4-((2-oxo-2H-chromen-7-yl)ethynyl)benzaldehyde], 4-((2-옥소-2H-크로멘-8-일)에티닐)벤즈알데히드[4-((2-oxo-2H-chromen-8-yl)ethynyl)benzaldehyde] [3a, 3b, 3c]를 각각 합성하였다.Of a solvent, N 2 atmosphere (; obtained under bromo benzaldehyde (4-ethynylbenzaldehyde) and Pd (PPh 3) 2 Cl 2 , CuI ethynyl present in the parent coumarin 4-, THF / triethylamine (1 v / v 1) in atm), was refluxed for 8 hours 4 - ((2-oxo -2 H-chromen-6-yl) ethynyl) benzaldehyde [4 - ((2-oxo -2 H -chromen-6-yl) ethynyl) benzaldehyde], 4 - ((2- oxo -2 H - chromen-ethynyl-7-yl)) benzaldehyde [4 - ((2-oxo -2 H -chromen-7-yl) ethynyl) benzaldehyde], 4- for [3a, 3b, 3c] ( (2- oxo -2 H - - chromen-ethynyl-8-yl)) benzaldehyde [((2-oxo-2 H -chromen-8-yl) ethynyl) benzaldehyde 4] Respectively.

(ⅲ) 단계(Iii)

얻어진 4-((2-옥소-2H-크로멘-6-일)에티닐)벤즈알데히드, 4-((2-옥소-2H-크로멘-7-일)에티닐)벤즈알데히드, 4-((2-옥소-2H-크로멘-8-일)에티닐)벤즈알데히드를 말론니트릴(malonitrile), 에탄올 및 피페리딘(piperidine)과 4 시간 환류시켜 2-(4-((2-옥소-2H-크로멘-6-일)에티닐)벤질리덴)말로노니트릴[2-(4-((2-oxo-2H-chromen-6-yl)ethynyl)benzylidene)malononitrile], 2-(4-((2-옥소-2H-크로멘-7-일)에티닐)벤질리덴)말로노니트릴[2-(4-((2-oxo-2H-chromen-7-yl)ethynyl)benzylidene)malononitrile], 2-(4-((2-옥소-2H-크로멘-8-일)에티닐)벤질리덴)말로노니트릴[2-(4-((2-oxo-2H-chromen-8-yl)ethynyl)benzylidene)malononitrile] [4a, 4b, 4c]을 각각 얻었다.The resulting 4 - ((2-oxo -2 H-chromen-6-yl) ethynyl) benzaldehyde, 4 - ((2-oxo-2 H -2-ethynyl-chromen-7-yl)) benzaldehyde, 4- ( (2-oxo -2 H-chromen-8-yl) ethynyl) benzaldehyde the malonic nitrile (malonitrile), ethanol, and piperidine (by refluxing piperidine) and 4 hours 2- (4 - ((2- 2 H - chromen-6-yl) ethynyl) benzylidene) malononitrile [2- (4 - ((2 -oxo-2 H -chromen-6-yl) ethynyl) benzylidene) malononitrile], 2- ( 4 - ((2-oxo-2 H -2-ethynyl-chromen-7-yl)) benzylidene) malononitrile [2- (4 - ((2 -oxo-2 H -chromen-7-yl) ethynyl) benzylidene) malononitrile], 2- (4 - ((2- oxo -2 H - chromen-8-yl) ethynyl) benzylidene) malononitrile [2- (4 - ((2 -oxo-2 H - chromen-8-yl) ethynyl) benzylidene) malononitrile] [4a, 4b, 4c].

(2) 구조 분석(2) Structural analysis

4b 화합물의 CDCl3 중 4b 화합물의 1H NMR 스펙트럼, CDCl3 중 4b 화합물의 13C NMR 스펙트럼, 및 질량분석(Mass) 스펙트럼을 각각 도 2, 도 3 및 도 4에 나타내었다. 또한, 3b 화합물의 질량분석 스펙트럼을 도 4에 나타내었다.4b of the compounds of the CDCl 3 of compound 4b Compound 4b of the 1 H NMR spectrum, CDCl 3 for 13 C NMR spectra, and mass spectrometry (Mass) was the spectrum, respectively Figure 2, shown in Figs. The mass spectrum of the 3b compound is shown in Fig.

4a, 4b, 4c 화합물의 1H NMR 데이터 및 13C NMR 데이터는 하기와 같다.The 1 H NMR data and 13 C NMR data of the compounds 4a, 4b and 4c are as follows.

[4a][ 4a ]

수율: 68 % (0.16 g)Yield: 68% (0.16 g)

1H NMR(600 MHz, CDCl3):δ = 8.56 (s, 1H, - C=CH), 8.08 (d, J =9.35 Hz, 1H, aromatic), 8.02-7.99 (m, 3H, aromatic), 7.82-7.80 (m, 3H, aromatic), 7.48 (d, J =8.5 Hz, 1H, aromatic), 6.59 (d, J =10.2 Hz, 1H, aromatic) 1 H NMR (600 MHz, CDCl 3): δ = 8.56 (s, 1H, - C = CH), 8.08 (d, J = 9.35 Hz, 1H, aromatic), 8.02-7.99 (m, 3H, aromatic), 7.48 (d, J = 8.5 Hz, 1H, aromatic), 6.59 (d, J = 10.2 Hz, 1H, aromatic)

13C(100MHz,CDCl3):160.194, 159.55, 153.84, 143.57, 134.93, 132.32, 131.88, 131.34, 130.89, 127.60, 119.30, 117.67, 117.37, 117.35, 114.29, 113.27, 92.42, 88.87, 82.16. 13 C (100 MHz, CDCl 3 ): 160.194, 159.55, 153.84, 143.57, 134.93, 132.32, 131.88, 131.34, 130.89, 127.60, 119.30, 117.67, 117.37, 117.35, 114.29, 113.27, 92.42, 88.87, 82.16.

HRMS (EI): m/Z calculated for C21H10N2O2 322.0742 [M+], measured C21H10N2O2 322.0746 [M+].HRMS (EI): m / Z calculated for C 21 H 10 N 2 O 2 322.0742 [M +], measured C 21 H 10 N 2 O 2 322.0746 [M +].

[4b] [ 4b ]

수율: 76 % (0.18 g)Yield: 76% (0.18 g)

1HNMR(400 MHz, CDCl3):δ = 7.94-7.89(m, 2H, aromatic), 7.77 (s, 1H, C=CH), 7.73-7.69 (m, 3H, aromatic), 7.52-7.44 (m, 3H, aromatic), 6.54 (d, J =9.6, 1H, aromatic). 1 HNMR (400 MHz, CDCl 3 ): δ = 7.94-7.89 (m, 2H, aromatic), 7.77 (s, 1H, C = CH), 7.73-7.69 (m, 3H, aromatic), 7.52-7.44 (m , 3H, aromatic), 6.54 (d, J = 9.6, 1H, aromatic).

13C(150MHz,CDCl3):160.12,158.36,153.76,142.60,132.67,130.77,130.66,128.83,127.93,127.80,125.69,119.86,119.39,117.50,113.53,112.44,93.04,91.3,83.4. 13 C (150 MHz, CDCl 3 ): 160.12,158.36,153.76,142.60,132.67,130.77,130.66,128.83,127.93,127.80,125.69,119.86,119.39,117.50,113.53,112.44,93.04,91.3,83.4.

HRMS (FAB+): m/Z calculated for C21H11N2O2 323.0821 [M+1], measured C21H11N2O2 322.0825 [M+1].HRMS (FAB +): m / z calculated for C 21 H 11 N 2 O 2 323.0821 [M + 1], measured C 21 H 11 N 2 O 2 322.0825 [M + 1].

[4c] [ 4c ]

수율: 85 % (0.2 g)Yield: 85% (0.2 g)

1HNMR(400MHz,DMSO-d6): δ = 8.586(s, 1H, =CH), 8.381 (d, J =9.60, 1H, aromatic), 8.03 (d, J =8.4,2H, aromatic, phenyl), 7.94 (d, J =8.4,2H, aromatic, phenyl), 7.708-7.646 (m, 2H, aromatic), 7.52 (d, J =7.6, 1H, aromatic), 6.62 (d, J =10, 1H, aromatic) 1 HNMR (400MHz, DMSO-d 6): δ = 8.586 (s, 1H, = CH), 8.381 (d, J = 9.60, 1H, aromatic), 8.03 (d, J = 8.4,2H, aromatic, phenyl) , 7.94 (d, J = 8.4,2H , aromatic, phenyl), 7.708-7.646 (m, 2H, aromatic), 7.52 (d, J = 7.6, 1H, aromatic), 6.62 (d, J = 10, 1H, aromatic)

13C(100MHz,CDCl3):160.202,159.540,153.837,141.691,132.657,132.146,131.778,130.787,128.52,127.01,120.292,119.614,118.062,117.787,114.263,113.263,94.559,89.127,82.566. 13 C (100 MHz, CDCl 3 ): 160.202,159.540,153.837,141.691,132.657, 132.146,131.778, 130.787,128.52,127.01,120.292,119.614,118.062,117.787,114.263,113.263,94.559,89.127,82.566.

Mass spectral data: m/z = 322 (M+1). Mass spectral data: m / z = 322 (M + 1).

시험예 1. Test Example 1 음이온에 대한 반응 감도Sensitivity to anions 비교 compare

테트라히드로푸란(Tetrahydrofuran, THF) 용매 중에 4b 화합물을 7.76 x 10-6 M 농도로 용해시키고 다양한 음이온(F-, Cl-, Br-, I-, HSO4 -, OCl4 - 및 NO2 -)(1 x 10-5 M, 20 μl)을 첨가하였다. 366 nm에서 각 반응계의 형광 여부를 측정하여, 그 결과를 도 7에 나타내었다. 도 7에 나타난 바와 같이, 디시아노비닐 쿠마린 4b 화합물은 다른 음이온에 비하여 플루오르화물 및 시안 이온 첨가시 파란색의 턴온 형광(turn-on fluorescence)을 나타내었다.4b compounds were dissolved in tetrahydrofuran (THF) at a concentration of 7.76 x 10-6 M and various anions (F - , Cl - , Br - , I - , HSO 4 - , OCl 4 - and NO 2 - (1 x 10-5 M, 20 [mu] l). The fluorescence of each reaction system was measured at 366 nm, and the results are shown in Fig. As shown in Fig. 7, the dicyanovinyl coumarin 4b compound exhibited blue turn-on fluorescence when fluoride and cyanide ions were added compared to other anions.

또한, THF 중 4b, 4c, 4a 각 화합물의 형광 방출 스펙트럼(λex = 365 nm)에 대한 다양한 음이온의 영향을 도 8, 도 10 및 도 11에 나타내었고, THF 용매 중 TBACN(tetrabutylammonium cyanide)을 이용한 4b의 형광 적정 스펙트럼(λex = 365 nm)을 도 9에 나타내었다.The effect of various anions on the fluorescence emission spectrum (λ ex = 365 nm) of each compound of 4b, 4c and 4a in THF is shown in FIGS. 8, 10 and 11, and TBACN (tetrabutylammonium cyanide) The fluorescence titration spectrum (? Ex = 365 nm) of 4b used is shown in Fig.

상기 도 8 내지 11에 나타난 바와 같이, 플루오르화물 및 시안 이온에 의한 형광 반응은 다른 음이온에서는 나타나지 않았으며, 시안 이온의 형광 반응 정도는 농도에 따라 증가되는 것으로 측정되었다.As shown in FIGS. 8 to 11, the fluorescence reaction by fluoride and cyanide was not observed in other anions, and the degree of fluorescence reaction of cyanide was measured to increase with concentration.

이러한 형광 반응은 디시아노비닐기가 시안 이온과 화학적으로 반응하는 기전에 의한 것으로 추정되고, 이는 디시아노비닐기의 α-탄소(α-Carbon)가 전자가 부족하여 강력한 친핵체 존재시에 마이클 부가 반응이 진행되기 쉽기 때문이다.This fluorescence reaction is presumed to be caused by the mechanism that the dicyanovinyl group chemically reacts with the cyanide ion. This is because when the α-carbon of the dicyanovinyl group lacks electrons and the strong nucleophile exists, It is easy to proceed.

상기 반응에 의하여, 7-치환 디시아노비닐 쿠마린(7-substituted dicyanovinyl-coumarin, 4b)은 다른 음이온(F-, Cl-, Br-, I-, OCl4 -, HSO4 - 및 NO2 -)을 첨가했을 경우보다 CN- 이온의 존재 하에서 보다 우수한 형광을 나타내어, CN- 이온에 대해 높은 선택성이 있는 것으로 확인되었다.By this reaction, 7-substituted dicyanovinyl-coumarin (4b) can be reacted with other anions (F - , Cl - , Br - , I - , OCl 4 - , HSO 4 - and NO 2 - Was found to be superior to CN - ion in the presence of CN - ion.

시험예 2. 4b 화합물의 검출 한계 측정Test Example 2. Measurement of detection limit of 4b compound

4b 화합물의 검출한계(limit of detection, LOD)는 다음 식에 의해 계산하였다.The limit of detection (LOD) of 4b compounds was calculated by the following equation.

[계산식 1][Equation 1]

Figure 112017076480153-pat00011
Figure 112017076480153-pat00011

(s: 공시료 측정의 표준편차,

Figure 112017076480153-pat00012
: 시안화물 농도 대 형광 강도 사이의 기울기)(s: standard deviation of blanket measurement,
Figure 112017076480153-pat00012
: Slope between cyanide concentration versus fluorescence intensity)

첨가된 CN- 이온에 의한 4b 화합물의 형광 강도의 증가는 0.23 μM - 2.26 μM 범위에서 선형 관계(R2=0.994)를 따른다. 상기와 같이 실험한 결과, 7-치환 디시아노비닐 쿠마린의 CN- 이온에 대한 검출 한계는 1.14 x 10-8 M로 측정되었다. 이는 WHO 기준인 1.9 x 10-6 M(in Liquid system)보다 낮아서 인체 안전성 확인 검출에 이용 가능하며, 쿠마린 유도체 4b가 다른 유도체 4a 및 4c보다 시안 이온 검출 감도가 우수한 것으로 측정되었다.The increase in fluorescence intensity of the 4b compound by the added CN - ion follows a linear relationship (R 2 = 0.994) in the range of 0.23 μM - 2.26 μM. As a result, the detection limit of the 7-substituted dicyanovinyl coumarin to CN - ion was 1.14 x 10 -8 M. It is lower than the WHO standard of 1.9 x 10-6 M (in Liquid system) and can be used for human safety confirmation detection, and coumarin derivative 4b is measured to be superior in sensitivity to cyanide detection than other derivatives 4a and 4c.

Claims (11)

하기 화학식 4로 표시되는 화합물:
[화학식 4]
Figure 112017076480153-pat00013
.
A compound represented by the following formula (4):
[Chemical Formula 4]
Figure 112017076480153-pat00013
.
제1항에 있어서, 상기 화합물이 하기 화학식 4a 내지 화학식 4c로 표시되는 화합물 중 하나인 것을 특징으로 하는 화합물:
[화학식 4a]
Figure 112017076480153-pat00014

[화학식 4b]
Figure 112017076480153-pat00015

[화학식 4c]
Figure 112017076480153-pat00016
.
The compound according to claim 1, wherein said compound is one of the compounds represented by the following formulas (4a) to (4c):
[Chemical Formula 4a]
Figure 112017076480153-pat00014

(4b)
Figure 112017076480153-pat00015

[Chemical Formula 4c]
Figure 112017076480153-pat00016
.
(i) 브로모페놀을 말산과 반응시켜 브로모쿠마린을 얻는 단계;
(ⅱ) 단계(i)에서 얻은 브로모쿠마린을 4-에티닐벤즈알데히드와 반응시켜 4-((2-옥소-2H-크로메닐)에티닐)벤즈알데히드를 얻는 단계; 및
(ⅲ) 단계(ⅱ)에서 얻은 4-((2-옥소-2H-크로메닐)에티닐)벤즈알데히드를 말론니트릴과 반응시키는 단계
를 포함하는 제1항 또는 제2항의 화합물의 제조방법.
(i) reacting bromophenol with malic acid to obtain bromocoumarin;
(Ii) reacting the bromocoumarin obtained in step (i) with 4-ethynylbenzaldehyde to obtain 4 - ((2-oxo- 2H -chromenyl) ethynyl) benzaldehyde; And
(Iii) reacting the 4 - ((2-oxo- 2H -chromenyl) ethynyl) benzaldehyde obtained in step (ii) with malononitrile
Lt; RTI ID = 0.0 > 1, < / RTI >
제1항 또는 제2항의 화합물을 포함하는 시안 이온 검출용 조성물.
A composition for detecting cyanide comprising the compound of claim 1 or 2.
제4항에 있어서, 테트라히드로푸란을 용매로 포함하는 것을 특징으로 하는 시안 이온 검출용 조성물.
5. The composition for detecting cyanide according to claim 4, which comprises tetrahydrofuran as a solvent.
제1항 또는 제2항의 화합물을 검체와 반응시키는 단계를 포함하는 시안 이온 검출 방법.
A method for detecting cyanide comprising the step of reacting a compound of claim 1 or 2 with a sample.
제6항에 있어서, 테트라히드로푸란을 용매로 사용하는 것을 특징으로 하는 시안 이온 검출 방법.
7. The cyanide detection method according to claim 6, wherein tetrahydrofuran is used as a solvent.
제6항에 있어서, 방출되는 형광을 파장 범위 360 - 380 nm에서 측정하는 단계를 추가로 포함하는 것을 특징으로 하는 시안 이온 검출 방법.
7. The method of claim 6, further comprising the step of measuring emitted fluorescence in a wavelength range of 360 to 380 nm.
제1항 또는 제2항의 화합물을 사용하는 시안 이온 검출 장치.
A cyanide ion detection apparatus using the compound of claim 1 or 2.
제9항에 있어서, 테트라히드로푸란을 용매로 사용하는 것을 특징으로 하는 시안 이온 검출 장치.
10. The cyanide ion detection apparatus according to claim 9, wherein tetrahydrofuran is used as a solvent.
제9항에 있어서, 방출되는 형광을 파장 범위 360 - 380 nm에서 측정하는 것을 특징으로 하는 시안 이온 검출 장치.
The cyan ion detection apparatus according to claim 9, wherein the emitted fluorescence is measured in a wavelength range of 360 to 380 nm.
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