CN115141185B - 一种香豆素-吡唑衍生物荧光探针及其制备方法和应用 - Google Patents
一种香豆素-吡唑衍生物荧光探针及其制备方法和应用 Download PDFInfo
- Publication number
- CN115141185B CN115141185B CN202210821205.0A CN202210821205A CN115141185B CN 115141185 B CN115141185 B CN 115141185B CN 202210821205 A CN202210821205 A CN 202210821205A CN 115141185 B CN115141185 B CN 115141185B
- Authority
- CN
- China
- Prior art keywords
- coumarin
- fluorescent probe
- phosgene
- pyrazole derivative
- derivative fluorescent
- 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.)
- Active
Links
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 12
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 59
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000001514 detection method Methods 0.000 claims abstract description 21
- 238000012360 testing method Methods 0.000 claims abstract description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000523 sample Substances 0.000 claims description 12
- 238000003958 fumigation Methods 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000012491 analyte Substances 0.000 claims description 2
- OSTKEWCVGRYJIB-UHFFFAOYSA-N 1-(4-hydroxy-2-oxochromen-3-yl)butane-1,3-dione Chemical compound C1=CC=C2OC(=O)C(C(=O)CC(=O)C)=C(O)C2=C1 OSTKEWCVGRYJIB-UHFFFAOYSA-N 0.000 abstract description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010992 reflux Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000000967 suction filtration Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 7
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000003217 pyrazoles Chemical class 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 150000004775 coumarins Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000011897 real-time detection Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 2
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical group OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 208000004756 Respiratory Insufficiency Diseases 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- BOGSOFADOWIECK-UHFFFAOYSA-N [N].C=1C=NNC=1 Chemical compound [N].C=1C=NNC=1 BOGSOFADOWIECK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013462 industrial intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 208000005333 pulmonary edema Diseases 0.000 description 1
- -1 pyrazole Schiff base Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 201000004193 respiratory failure Diseases 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
本发明属于有机合成领域，涉及荧光探针的制备，具体涉及一种香豆素‑吡唑衍生物荧光探针及其制备方法和应用。将3‑乙酰乙酰‑4‑羟基香豆素和水合肼溶于有机溶剂中，回流搅拌，反应结束后冷却静置至室温，抽滤、水洗、重结晶得到香豆素‑吡唑衍生物荧光探针。本发明制备的香豆素‑吡唑衍生物荧光探针在乙腈体系中能选择性的与光气作用，表现为溶液蓝色荧光显著减弱；同时还可以将荧光探针附着在滤纸上制备成试纸条实现对气态光气的方便检测。本发明制备的荧光探针可以灵敏地检测溶液中的光气和气态光气，具有广泛的潜在应用价值。
Description
技术领域
本发明属于有机合成领域，涉及荧光探针的制备，具体涉及一种香豆素-吡唑衍生物荧光探针及其制备方法和应用。
背景技术
光气（COCl2）又名碳酰氯，是一种无色的剧毒气体，接触光气会导致肺水肿、呼吸衰竭，甚至会导致生物体死亡。但是，光气又是一种重要的工业中间体，可用于生产农药、染料和药品，—旦发生泄露，将会对公共生命财产安全造成重大威胁。因此，用于光气检测的选择性和敏感性工具的开发愈发显得重要。
近年来，荧光分子探针技术由于具有灵敏度高、操作简单、成本低等特点，已经成为检测重要金属离子、阴离子和小分子的重要手段。但现有光气荧光探针报道不多，且绝大多数基于邻苯二胺、乙二胺、乙醇胺、3-1H-咪唑-亚胺香豆素或2-羟基/氨基苯基-1H-咪唑等结构作为光气的识别位点。与咪唑类似，吡唑衍生物具有易于酰化的活性氨基
现有技术中有将吡唑衍生物应用于其他物质的检测，如专利CN110964516A制备了吡唑类Schiff碱荧光探针用于环境中Al3+检测，探针中具有席夫碱C=N双键和吡唑氮杂环两类化合物，其含有多个孤对电子的N原子易与金属离子形成配位键。基于此，测定不同金属离子存在下荧光探针的荧光发射光谱，结果表明，荧光探针对Al3+具有明显的荧光响应和选择性，Al3+的最低检出限为4.18×10-8mol/L。但却少有报道利用吡唑衍生物制备荧光探针并检测光气。
发明内容
针对上述技术问题，本发明提出一种香豆素-吡唑衍生物荧光探针及其制备方法和应用。本发明考虑到香豆素衍生物优异的光化学和光物理特性，以含吡唑的香豆素衍生物为荧光团，合成了一种高灵敏度、高选择性的光气荧光探针。本发明涉及的探针具有羟基-吡唑结构，在检测溶液和气态光气时均表现优异的选择性和灵敏度，可实现实时检测。
本发明的主要目的在于提供一种可用于乙腈溶液和气体中针对光气的灵敏度高、选择性好的香豆素-吡唑衍生物荧光探针；另一目的是提供该荧光探针的制备方法和应用。
为了达到上述目的，本发明的技术方案是这样实现的：
一种香豆素-吡唑衍生物荧光探针，所述的香豆素-吡唑衍生物荧光探针的结构式如下所示：。
进一步，所述的香豆素-吡唑衍生物荧光探针的制备方法，步骤如下：
（1）将3-乙酰乙酰-4-羟基香豆素和水合肼溶解于有机溶剂中，回流搅拌，得反应液；
（2）将步骤（1）所得的反应液冷却至室温后，于饱和食盐水中减压抽滤，所得固体用水洗涤后，乙醇重结晶，得到香豆素-吡唑衍生物荧光探针。
进一步，所述步骤（1）中3-乙酰乙酰-4-羟基香豆素的结构式如下所示：。
进一步，所述步骤（1）中3-乙酰乙酰-4-羟基香豆素和水合肼的摩尔比为1：（0.6-0.8），所述有机溶剂为无水乙醇。
进一步，所述步骤（1）中回流搅拌的温度为78℃，回流搅拌的时间为1-3h。
进一步，香豆素-吡唑衍生物荧光探针的制备方法为：将3-乙酰乙酰-4-羟基香豆素（0.32g，1.3mmol）溶于15mL无水乙醇中，加入水合肼（50μL，0.79mmol），80℃下回流搅拌1-3h，冷却静置至室温，倒入饱和食盐水中，减压抽滤，所得固体用水洗涤得到所述香豆素-吡唑衍生物荧光探针。
进一步，所述的香豆素-吡唑衍生物荧光探针在乙腈体系中选择性检测光气的应用。
进一步，所述的应用步骤如下：
配制香豆素-吡唑衍生物荧光探针的乙腈溶液，然后加入三乙胺和待测物溶液，通过荧光光谱仪记录荧光信号，代入线性方程计算待测溶液中光气的浓度。
进一步，所述的香豆素-吡唑衍生物荧光探针溶液的浓度为1×10-5mol/L，乙腈体积为2mL，三乙胺浓度为5×10-4mol/L，待测物浓度为1×10-4mol/L，线性方程为Y=1079.71x+10921.59，线性检测范围为2-9×10-6mol/L，光气的检出限为4.78×10-9mol/L。
进一步，所述的香豆素-吡唑衍生物荧光探针在气态光气检测中的应用。
进一步，所述的应用步骤如下：
a. 将香豆素-吡唑衍生物荧光探针溶于乙腈溶液中，配制成1×10-3mol/L的探针溶液；
b. 将滤纸在步骤a所得的探针溶液中浸泡3s后取出自然风干，即可得到负载香豆素-吡唑衍生物荧光探针的光气试纸条；
c. 将步骤b中所得的光气试纸条暴露于待测气体的环境中熏蒸2min，在365nm紫外灯下检测，通过颜色变化对比定性或半定量检测气态光气。
本发明具有以下有益效果：
1、本发明制备的香豆素-吡唑衍生物荧光探针，原料易得，合成和后处理方法简单。利用本发明方法制备的香豆素-吡唑衍生物荧光探针的产率为84%。
2、本发明制备的香豆素-吡唑衍生物荧光探针在多种常见酰氯中，对光气表现出较高的荧光识别性能。探针的羟基和吡唑氮可以同时被光气酰化，该反应选择性好，灵敏度高。在乙腈溶液中，能选择性的识别光气，而不被其他常见的酰氯和分析物干扰。光气浓度与探针检测体系荧光强度F437呈良好的线性关系，线性检测范围为2-9×10-6mol/L，光气的检出限为4.78×10-9mol/L。
3、本发明制备的香豆素-吡唑衍生物荧光探针可以容易地附着在滤纸上用于检测气态光气。将试纸条浸泡于含荧光探针的乙腈溶液中3s后取出，暴露于不同量光气熏蒸2min后，即可在365nm紫外灯下观察到光气使试纸条蓝色荧光减弱，因此本发明制备的香豆素-吡唑衍生物荧光探针具有响应快速高效的优点，可以实现对光气的实时检测及半定量检测，具有广泛的潜在应用价值。
4、将试纸条浸泡于含荧光探针的乙腈溶液中3s后取出，暴露于光气和其他分析物中2min后，即可在365nm紫外灯下观察到仅有光气使试纸条蓝色荧光猝灭，因此可以用于对气态光气的定性检测，同样具有响应快速高效的优点。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例1制得的香豆素-吡唑衍生物荧光探针的1H-NMR谱图。
图2为本发明实施例1制得的香豆素-吡唑衍生物荧光探针的13C-NMR谱图。
图3为本发明实施例1制得的香豆素-吡唑衍生物荧光探针的质谱谱图。
图4为本发明实施例1制得的香豆素-吡唑衍生物荧光探针（1×10-5mol/L）在乙腈溶液（含5×10-4mol/L三乙胺）中选择性识别光气的荧光光谱图（激发波长为350 nm）。
图5为本发明实施例1制得的香豆素-吡唑衍生物荧光探针（1×10-5mol/L）在乙腈溶液（含5×10-4mol/L三乙胺）中滴定不同浓度三光气（理论上可产生3倍三光气）的荧光光谱图，插图表示437nm处荧光强度随光气浓度的线性变化趋势图（激发波长为350 nm）。
图6为本发明实施例1制备的负载香豆素-吡唑衍生物荧光探针的试纸条在暴露于3ppm光气和其他分析物时，在365nm紫外灯下的荧光响应照片；（1）空白，（2）光气，（3）对甲苯磺酰氯，（4）过氧化二苯甲酰，（5）草酰氯，（6）氯乙酰氯，（7）硫酰氯，（8）苯磺酰氯，（9）丙烯酰氯，（10）三氯氧磷，（11）氯化亚砜，（12）乙酰氯。
图7为本发明实施例1制备的负载香豆素-吡唑衍生物荧光探针的试纸条在暴露于不同量的光气熏蒸时，在365nm紫外灯下的荧光响应照片。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本实施例为香豆素-吡唑衍生物荧光探针的制备方法，步骤如下：
将3-乙酰乙酰-4-羟基香豆素（0.32g，1.3mmol）溶于15mL无水乙醇中，加入水合肼（50μL，0.79mmol），78℃下回流搅拌1h，冷却静置至室温，倒入饱和食盐水中，减压抽滤，所得固体用水洗涤得到所述香豆素-吡唑衍生物荧光探针。目标产物的产率为84%。
产物鉴定
1H-NMR(400 MHz, Acetonitrile-d3): δ (ppm) 8.01 (dd, J = 7.8, 1.4 Hz,1H), 7.59-7.49 (m, 1H), 7.34 - 7.23 (m, 2H), 6.75 (s, 1H), 2.29 (s, 3H)。具体核磁共振氢图谱见图1。
13C-NMR(101 MHz, Acetonitrile-d3): δ (ppm) 153.50, 132.04, 125.03,123.87, 116.60, 103.11. 具体核磁共振碳图谱见图2。
质谱ESI-MS: m/z = 243.0767 for [M+H]+。具体质谱谱图见图3。
实施例2
本实施例为香豆素-吡唑衍生物荧光探针的制备方法，步骤如下：
将3-乙酰乙酰-4-羟基香豆素（0.28g，1.12mmol）溶于15mL无水乙醇中，加入水合肼（50μL，0.79mmol），78℃下回流搅拌2h，冷却静置至室温，倒入饱和食盐水中，减压抽滤，所得固体用水洗涤得到所述香豆素-吡唑衍生物荧光探针。
产物鉴定
1H-NMR(400 MHz, Acetonitrile-d3): δ (ppm) 8.01 (dd, J = 7.8, 1.4 Hz,1H), 7.59-7.49 (m, 1H), 7.34 - 7.23 (m, 2H), 6.75 (s, 1H), 2.29 (s, 3H)。具体核磁共振氢图谱见图1。
13C-NMR(101 MHz, Acetonitrile-d3): δ (ppm) 153.50, 132.04, 125.03,123.87, 116.60, 103.11. 具体核磁共振碳图谱见图2。
质谱ESI-MS: m/z = 243.0767 for [M+H]+。具体质谱谱图见图3。
实施例3
本实施例为香豆素-吡唑衍生物荧光探针的制备方法，步骤如下：
将3-乙酰乙酰-4-羟基香豆素（0.24g，0.99mmol）溶于15mL无水乙醇中，加入水合肼（50μL，0.79mmol），78℃下回流搅拌3h，冷却静置至室温，倒入饱和食盐水中，减压抽滤，所得固体用水洗涤得到所述香豆素-吡唑衍生物荧光探针。
产物鉴定
1H-NMR(400 MHz, Acetonitrile-d3): δ (ppm) 8.01 (dd, J = 7.8, 1.4 Hz,1H), 7.59 - 7.49 (m, 1H), 7.34 - 7.23 (m, 2H), 6.75 (s, 1H), 2.29 (s, 3H)。具体核磁共振氢图谱见图1。
13C-NMR(101 MHz, Acetonitrile-d3): δ (ppm) 153.50, 132.04, 125.03,123.87, 116.60, 103.11. 具体核磁共振碳图谱见图2。
质谱ESI-MS:m/z = 243.0767 for [M+H]+。具体质谱谱图见图3。
应用例1
香豆素-吡唑衍生物对光气的光学性质测定，步骤如下：
将上述实施例1制得的香豆素-吡唑衍生物荧光探针（1×10-5mol/L）的2mL乙腈溶液中（含5×10-4mol/L的三乙胺），再加入1×10-4mol/L常见酰氯及其他分析物（（1）空白，（2）光气，（3）对甲苯磺酰氯，（4）过氧化二苯甲酰，（5）草酰氯，（6）氯乙酰氯，（7）硫酰氯，（8）苯磺酰氯，（9）丙烯酰氯，（10）三氯氧磷，（11）氯化亚砜，（12）乙酰氯），混合均匀后采用荧光光谱仪进行分析（激发波长为350nm），所得荧光光谱图见图4。通过图4可以看出，本发明制得的香豆素-吡唑衍生物作为探针只对光气具有明显响应，荧光信号可用于光气的快速鉴别，而其它分析物无变化。
通过图5的滴定光谱计算可以得到光气检出限为4.78×10-9mol/L，荧光光谱的线性检测范围为2-9×10-6mol/L，因此本发明制得的香豆素-吡唑衍生物可用于光气荧光定量检测。
应用例2
香豆素-吡唑衍生物荧光探针用于气态光气的检测实验，步骤如下：
将上述实施例1制得的香豆素-吡唑衍生物荧光探针用乙腈溶解配置1×10-3mol/L的探针溶液。将滤纸浸泡到该溶液中3s后取出，自然风干得到负载探针的试纸条。将试纸条暴露于3ppm光气和其他分析物（（1）空白，（2）光气，（3）对甲苯磺酰氯，（4）过氧化二苯甲酰，（5）草酰氯，（6）氯乙酰氯，（7）硫酰氯，（8）苯磺酰氯，（9）丙烯酰氯，（10）三氯氧磷，（11）氯化亚砜，（12）乙酰氯）熏蒸2min后，在365nm紫外灯下可以看到仅有光气可以使试纸条蓝色荧光淬灭，具体如图6所示。故本发明实施例1制得的香豆素-吡唑衍生物可用于气态光气的定性检测。
将负载香豆素-吡唑衍生物荧光探针的试纸条暴露于不同量的光气（0ppm，0.5ppm，1ppm，1.5ppm，2ppm）熏蒸2min后，在365nm紫外灯下可以看到蓝色荧光逐渐减弱，具体如图7所示。故本发明实施例1制得的香豆素-吡唑衍生物荧光探针可以半定量检测光气浓度。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (5)
1.一种香豆素-吡唑衍生物荧光探针在乙腈体系中选择性检测光气的应用，其特征在于：所述的香豆素-吡唑衍生物荧光探针的结构式如下所示：。
2.根据权利要求1所述的应用，其特征在于，步骤如下：配制香豆素-吡唑衍生物荧光探针的乙腈溶液，然后加入三乙胺和待测物溶液，通过荧光光谱仪记录荧光信号，代入线性方程计算待测物溶液中光气的浓度。
3.权利要求2所述的应用，其特征在于：所述的香豆素-吡唑衍生物荧光探针溶液的浓度为1×10-5mol/L，乙腈体积为2mL，三乙胺浓度为5×10-4mol/L，待测物浓度为1×10-4mol/L，线性方程为Y=1079.71x+10921.59，线性检测范围为2-9×10-6mol/L，光气的检出限为4.78×10-9mol/L。
4.一种香豆素-吡唑衍生物荧光探针在气态光气检测中的应用，其特征在于：所述的香豆素-吡唑衍生物荧光探针的结构式如下所示： 。
5.根据权利要求4所述的应用，其特征在于，步骤如下：
a. 将香豆素-吡唑衍生物荧光探针溶于乙腈溶液中，配制成1×10-3mol/L的探针溶液；
b. 将滤纸在步骤a所得的探针溶液中浸泡3s后取出自然风干，即可得到负载香豆素-吡唑衍生物荧光探针的光气试纸条；
c. 将步骤b中所得的光气试纸条暴露于待测气体的环境中熏蒸2min，在365nm紫外灯下检测，通过颜色变化对比定性或半定量检测气态光气。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210821205.0A CN115141185B (zh) | 2022-07-13 | 2022-07-13 | 一种香豆素-吡唑衍生物荧光探针及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210821205.0A CN115141185B (zh) | 2022-07-13 | 2022-07-13 | 一种香豆素-吡唑衍生物荧光探针及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115141185A CN115141185A (zh) | 2022-10-04 |
| CN115141185B true CN115141185B (zh) | 2023-12-29 |
Family
ID=83412480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210821205.0A Active CN115141185B (zh) | 2022-07-13 | 2022-07-13 | 一种香豆素-吡唑衍生物荧光探针及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115141185B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003390B (zh) * | 2023-02-06 | 2024-03-08 | 焦作师范高等专科学校 | 一种吲哚-苯并咪唑衍生物荧光探针及其制备方法和应用 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190109063A (ko) * | 2018-03-16 | 2019-09-25 | 경희대학교 산학협력단 | 포스겐 검출용 화합물 및 이를 포함한 센서 |
| CN111499629A (zh) * | 2020-04-14 | 2020-08-07 | 曲阜师范大学 | 一种用于检测光气的荧光探针及其制备方法和应用 |
| CN112209953A (zh) * | 2020-08-19 | 2021-01-12 | 曲阜师范大学 | 一种基于荧光能量共振转移机理的双光子探针及应用 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10640513B2 (en) * | 2016-02-24 | 2020-05-05 | Ewha University - Industry Collaboration Foundation | Compound and composition for detecting phosgene and diethyl chlorophosphate |
-
2022
- 2022-07-13 CN CN202210821205.0A patent/CN115141185B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190109063A (ko) * | 2018-03-16 | 2019-09-25 | 경희대학교 산학협력단 | 포스겐 검출용 화합물 및 이를 포함한 센서 |
| CN111499629A (zh) * | 2020-04-14 | 2020-08-07 | 曲阜师范大学 | 一种用于检测光气的荧光探针及其制备方法和应用 |
| CN112209953A (zh) * | 2020-08-19 | 2021-01-12 | 曲阜师范大学 | 一种基于荧光能量共振转移机理的双光子探针及应用 |
Non-Patent Citations (1)
| Title |
|---|
| Mulwad V. V. 等.Indian Journal of Heterocyclic Chemistry.Synthesis of some 4-hydroxy-3-(3,5-disubstituted pyrazolyl)benzopyran-2-ones and pyranobenzopyrans.2001,第10卷(第04期),第241-244页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115141185A (zh) | 2022-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | A NIR ratiometric probe for hydrazine “naked eye” detection and its imaging in living cell | |
| Choi et al. | Dual signaling of hydrazine by selective deprotection of dichlorofluorescein and resorufin acetates | |
| CN111423423B (zh) | 一种比率型荧光探针在检测过氧亚硝基阴离子中的应用 | |
| CN108003869B (zh) | 一种高灵敏检测次氯酸根的荧光探针及其合成方法与应用 | |
| CN115141185B (zh) | 一种香豆素-吡唑衍生物荧光探针及其制备方法和应用 | |
| CN107011340A (zh) | 一种希夫碱荧光探针及其合成方法和应用 | |
| CN110172070B (zh) | 一种检测粘度与过氧化氢的荧光探针及其合成方法与应用 | |
| CN108088828A (zh) | 一种双柱芳烃汞离子荧光传感器及其制备和应用 | |
| Karakuş et al. | Fluorescein based three-channel probe for the selective and sensitive detection of CO32− ions in an aqueous environment and real water samples | |
| CN109021000B (zh) | 一种检测过氧化氢的荧光探针、合成方法和应用 | |
| CN106608862A (zh) | 一种长波长检测肼的荧光探针及其合成方法与应用 | |
| CN106397319A (zh) | 一种比率式检测肼的荧光探针及其合成方法与应用 | |
| Zhou et al. | A fluorescent probe based on modulation of ESIPT signaling for the highly selective detection of N2H4 and cell-imaging | |
| Zhou et al. | A novel near-infrared colorimetric and fluorescent probe based on a piperidine-substituted aza-BODIPY photosensitizer for detection of extreme acidity | |
| CN109734711B (zh) | 一种检测过硫化氢的荧光探针及其合成方法与应用 | |
| CN114394978B (zh) | 一种一氧化氮光激活荧光探针及其制备方法和应用 | |
| CN112898963B (zh) | 一种检测粘度的荧光探针及其制备方法和应用 | |
| Xue et al. | A highly selective and sensitive ratiometric fluorescent probe for hypochlorite and its application | |
| CN112521376B (zh) | 色烯-吡啶衍生物荧光探针、制备方法及应用 | |
| CN116003390B (zh) | 一种吲哚-苯并咪唑衍生物荧光探针及其制备方法和应用 | |
| CN104122243B (zh) | 一种检测微量Zn2+、F‑ 或AcO‑的荧光光谱分析法 | |
| CN111233885A (zh) | 一种检测甲醇的荧光探针及其应用 | |
| Mariappan et al. | A chemodosimeter for the detection of hydroxide using an anthraquinone-based receptor: Photophysical properties and X-ray crystallography | |
| CN115894293B (zh) | 一种检测肼的比率型近红外荧光探针及其合成方法与应用 | |
| CN113354662B (zh) | 一种上/下转换荧光探针四溴代荧光素螺环内硫酯及其制备方法与应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |