CN112079861A - 一种荧光淬灭检测氟离子的分子探针及其制备方法 - Google Patents
一种荧光淬灭检测氟离子的分子探针及其制备方法 Download PDFInfo
- Publication number
- CN112079861A CN112079861A CN202011088674.3A CN202011088674A CN112079861A CN 112079861 A CN112079861 A CN 112079861A CN 202011088674 A CN202011088674 A CN 202011088674A CN 112079861 A CN112079861 A CN 112079861A
- Authority
- CN
- China
- Prior art keywords
- molecular probe
- compound
- reaction
- fluorine ions
- probe
- 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.)
- Granted
Links
- -1 fluorine ions Chemical class 0.000 title claims abstract description 31
- 239000003068 molecular probe Substances 0.000 title claims abstract description 31
- 239000011737 fluorine Substances 0.000 title claims abstract description 25
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 25
- 238000010791 quenching Methods 0.000 title claims abstract description 14
- 230000000171 quenching effect Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XFVZSRRZZNLWBW-UHFFFAOYSA-N 4-(Diethylamino)salicylaldehyde Chemical compound CCN(CC)C1=CC=C(C=O)C(O)=C1 XFVZSRRZZNLWBW-UHFFFAOYSA-N 0.000 claims abstract description 6
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000523 sample Substances 0.000 abstract description 14
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 150000001450 anions Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 239000008055 phosphate buffer solution Substances 0.000 description 6
- 239000007850 fluorescent dye Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 238000000954 titration curve Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 208000004042 dental fluorosis Diseases 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000009911 Urinary Calculi Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 208000017169 kidney disease Diseases 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 208000025636 skeletal fluorosis Diseases 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 208000018556 stomach disease Diseases 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
-
- 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
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
本发明公开了一种荧光猝灭检测氟离子的分子探针及其制备方法。所述荧光分子探针以4‑(二乙氨基)‑2‑羟基苯甲醛为原料,引入叔丁基二甲基氯硅烷,再与丙二腈缩合而成。合成简便,反应条件温和。该探针分子光学性能稳定,合成产率高;对氟离子检测灵敏度高,检测下限低,响应范围为宽,检测限极低,检测范围宽,选择性好,对常见的阳离子,干扰性阴离子无响应;并且适合裸眼检测。该荧光分子探针在生物化学,环境科学等领域具有实际的应用价值。
Description
技术领域
本发明涉及的是化学分析检测技术领域,具体涉及一种荧光淬灭检测氟离子分子探针及其制备方法。
背景技术
氟化物阴离子因其在人类活动的许多领域中的重要性而在其对健康和环境的影响方面受到重视,因此在科学界得到了广泛的关注。尽管过去在系统研究中忽略了氟化物,但氟化物现已成为阴离子识别领域的热门目标。F-具有强烈的亲核特性,作为最小的卤化物,它具有最高的电荷密度,然而,由于其离子半径与K+的离子半径大致相同,因此不能认为其尺寸最小。所有这些都使得氟化物以氢键(HB)配偶体。近几年发表的大量科学报告,在极性和水性介质中寻求与氟化物建立有效和特异性的相互作用。
氟离子(F-)是人体必不可少的微量元素,因为低浓度的F-已被证明对龋病的预防和骨质疏松症的临床治疗有效。F-的主要来源是食物和地下水的摄入量。然而,过量摄入F-可引起胃部和肾脏疾病,例如牙齿和骨骼氟中毒,尿路结石,甚至死亡。此外,地方性氟中毒广泛存在,影响数百万人。考虑到环境问题,氟离子化学传感器可以对氟离子进行定性定量的测定,对环境保护和人类健康具有重要的意义。
在目前用于F-检测的方法中,离子选择性电极和离子色谱法的标准Willard-Winter方法常用于F-分析,他们通常需要复杂的程序和昂贵的仪器。因此,开发出高选择性,敏感性和快速性的F-检测方法变得非常重要。荧光探针是用于测试各种分析物的新兴方法,因为它们可用于具有最小干扰,以及高灵敏度和选择性。
发明内容
根据上述现有技术存在的问题,本发明的目的之一是提供一种合成简单、反应条件温和、成本低廉的荧光探针的合成方法;目的之二是提供一种选择性好,灵敏度高,能够可视化监测及荧光淬灭检测氟离子的荧光探针。
为了实现上述目的,本发明采用以下技术方案:
一种荧光猝灭检测氟离子的分子探针,其结构式为:
所述分子探针以4-(二乙氨基)-2-羟基苯甲醛衍生物为荧光团,叔丁基二甲基氯硅烷醚为氟离子识别基团的化合物。
所述快速检测氟离子的新型分子探针的制备方法,具体采用以下工艺路线:
所述快速检测氟离子的新型分子探针的制备方法,具体包括以下步骤:
(1)将化合物I(4-(二乙氨基)-2-羟基苯甲醛)溶于DMF中,加入咪唑后室温下搅拌,之后将叔丁基二甲基氯硅烷加入到上述反应液中搅拌,反应完成后,加入去离子水淬灭反应,用二氯甲烷萃取,将所得有机相用无水硫酸钠干燥,减压蒸馏除去溶剂,得到红色混合物,纯化制得黄色固体,即为化合物II;
(2)将上述化合物II和丙二腈溶于DMF中,加入无水碳酸钠,在室温下搅拌;反应完成后,加入去离子水淬灭反应,用二氯甲烷萃取,所得有机相用无水硫酸钠干燥,减压蒸馏除去溶剂,纯化制得黄色固体化合物III,即为荧光分子探针。该荧光分子探针具有很强的荧光性。
本发明的荧光分子探针使用方法没有特殊限制。通常可以将探针分子溶解在合适的有机溶剂中,如,四氢呋喃(THF)或1,4-二氧六环,室温下进行测试。
本发明的荧光分子探针对氟离子的检测原理如下式所示:探针具有PET机制,在未加入F-时,PET被抑制,因此具有强烈的荧光,当加入F-时,PET被打开,生成氧负离子基团,以及硅氟键,从而荧光淬灭。探针在未加入F-前为无色液体,当加入F-后,变为黄色液体,荧光由蓝色变为绿色。
与现有技术相比,本发明制备的荧光分子探针具有很强的荧光性,探针具有PET机制实现对氟离子的快速、可视化检测。该探针分子光学性能稳定,合成产率高;对氟离子检测灵敏度高,检测限极低,检测范围宽,选择性好,对常见的阳离子,干扰性阴离子无响应;并且适合裸眼检测。该荧光分子探针在生物化学,环境科学等领域具有实际的应用价值。
附图说明
图1为本发明探针在有机体系下,加入不同浓度的氟离子的荧光发射光谱图。
图2为本发明探针在有机体系下,加入不同干扰离子的荧光发射光谱图。
图3为本发明探针在有机体系下,加入一定浓度的氟离子,响应时间的变化图。
图4为本发明探针在PBS缓冲体系下,加入不同浓度的氟离子荧光发射光谱图。
图5为本发明探针在PBS缓冲体系下,加入不同浓度的氟离子的浓度线性方程,R2=0.9937。
图6为本发明探针在PBS缓冲体系下,加入干扰离子,荧光发射光谱图。
具体实施方式
以下结合附图和具体实施例对本发明的进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。
实施例1:
(1)化合物2的制备
在单颈圆底烧瓶中,加入化合物I(4-(二乙氨基)-2-羟基苯甲醛)和咪唑和DMF,室温搅拌。将叔丁基二甲基氯烷加入到上述反应体系中,搅拌反应完全,加入去离子水淬灭反应。然后用二氯甲烷萃取、分离得到有机相,再用无水硫酸钠干燥,蒸馏除去溶剂,得到红色固体混合物,用硅胶柱层析分离纯化,得黄色固体,为化合物II。(产率63%)
(2)分子荧光探针的制备
在单颈烧瓶中,将化合物II和丙二腈溶于DMF中,加入无水Na2CO3,室温反应。将反应液倒入水中,用二氯甲烷萃取,再用去离子水洗涤,分离得到有机相用无水硫酸钠干燥,蒸馏除去溶剂,得到固体混合物,用硅胶柱层析分离纯化,得黄色固体,化合物III,即为分子荧光探针。(产率45%)
化合物III核磁检测结果如下所示:
1H NMR(400MHz,CDCl3),δ7.97(s,1Η),7.32-7.30(d,1H),6.65-6.63(d,1H),6.47(s,1H),3.44-3.50(m,4H),1.57(s,9H),1.25-1.27(t,6H),1.23(s,6H)。
实施例2:裸眼识别检测氟离子荧光分子探针的应用
分别将实施例1制备的分子探针溶于THF溶液和THF溶液+PBS混合溶液中,加入不同的阴离子(磷酸二氢根、溴离子、硫酸氢根、碳酸根、碘离子、氯离子、硝酸根等)以及阳离子(铁离子、汞离子、锌离子、钾离子、钙离子、铜离子等)溶液,测试荧光发射光谱变化。
图1-图3表明,在荧光发射光谱中荧光分子探针对氟离子具有很高的灵敏度。在有机体系中(THF溶液),加入氟离子后,荧光发射由460nm红移到480nm,荧光强度淬灭,溶液颜色发生显著变化(淡黄色变为黄色),荧光由蓝色变为绿色,可以用裸眼检测;同时在紫外灯下照射下,荧光分子探针在加入氟离子后荧光淬灭。并且不受阴离子的影响,且探针对氟离子具有很好的选择性。在缓冲体系中,加入氟离子后,荧光发射由480nm红移到486nm,荧光强度淬灭。两种体系中都具有荧光淬灭性,且荧光强度变化与氟离子浓度呈线性关系,适用于氟离子的检测。
所述荧光分子探针用于有机体系中氟离子含量的测定,具体方法如下:
将所述分子探针加入有机溶剂中,如THF,1,4二氧六环,DMF,DMSO等,得到分子探针母液,然后配置不同氟离子浓度的标准溶液。向标准溶液中加入母液,放置1分钟后,在激发波长420nm,发射波长为460nm处分别测定不同氟离子浓度时的荧光强度,做成滴定曲线,拟合460nm处荧光强度与氟离子浓度的函数关系。再向待测氟离子溶液中加入等量的母液,将荧光强度带入上述滴定曲线,得到待测氟离子含量。
所述荧光分子探针用于缓冲体系中氟离子含量的测定,具体方法如下:
将所述分子探针加入有机溶剂中,如THF,1,4二氧六环,DMF,DMSO等,用THF:PBS=1:9(pH=7.4)的混合缓冲溶液配制探针分子母液。然后配置不同氟离子浓度的标准溶液。向标准溶液中加入母液,放置1分钟后,在激发波长440nm,发射波长为480nm处分别测定不同氟离子浓度时的荧光强度,做成滴定曲线,拟合480nm处荧光强度与氟离子浓度的函数关系。再向待测氟离子溶液中加入等量的母液,将荧光强度带入上述滴定曲线,得到待测氟离子含量。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。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 (3)
3.根据权利要求2所述荧光猝灭检测氟离子的分子探针的制备方法,其特征在于,具体包括以下步骤:
(1)将化合物I(4-(二乙氨基)-2-羟基苯甲醛)溶于DMF中,加入咪唑后室温下搅拌,之后将叔丁基二甲基氯硅烷加入到上述反应液中搅拌,反应完成后,加入去离子水淬灭反应,用二氯甲烷萃取,将所得有机相用无水硫酸钠干燥,减压蒸馏除去溶剂,得到红色混合物,纯化制得黄色固体,即为化合物II;
(2)将上述化合物II和丙二腈溶于DMF中,加入无水碳酸钠,在室温下搅拌;反应完成后,加入去离子水淬灭反应,用二氯甲烷萃取,所得有机相用无水硫酸钠干燥,减压蒸馏除去溶剂,纯化制得黄色固体化合物III,即为荧光分子探针。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011088674.3A CN112079861B (zh) | 2020-10-13 | 2020-10-13 | 一种荧光淬灭检测氟离子的分子探针及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011088674.3A CN112079861B (zh) | 2020-10-13 | 2020-10-13 | 一种荧光淬灭检测氟离子的分子探针及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112079861A true CN112079861A (zh) | 2020-12-15 |
CN112079861B CN112079861B (zh) | 2023-03-21 |
Family
ID=73730221
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011088674.3A Active CN112079861B (zh) | 2020-10-13 | 2020-10-13 | 一种荧光淬灭检测氟离子的分子探针及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112079861B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113461686A (zh) * | 2021-08-17 | 2021-10-01 | 中国农业大学 | 荧光探针及其制备方法和应用、荧光探针溶液 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100292479A1 (en) * | 2007-10-26 | 2010-11-18 | Nihon Medi-Physics Co., Ltd. | Novel compound having affinity for amyloid |
CN103923479A (zh) * | 2014-04-18 | 2014-07-16 | 大连理工大学 | 久洛尼定母核的氟离子荧光染料及其应用 |
CN104230814A (zh) * | 2014-09-23 | 2014-12-24 | 西北师范大学 | 一种荧光识别氟离子传感器及其制备和应用 |
CN104418874A (zh) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | 一种水溶液中检测氟离子荧光分子探针及其合成与应用 |
CN104418875A (zh) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | 一种检测氟离子荧光分子探针及其合成与应用 |
CN104610955A (zh) * | 2014-05-16 | 2015-05-13 | 中南大学 | 一种比率型同时检测氟离子和亚硫酸根荧光分子探针的合成及应用 |
-
2020
- 2020-10-13 CN CN202011088674.3A patent/CN112079861B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100292479A1 (en) * | 2007-10-26 | 2010-11-18 | Nihon Medi-Physics Co., Ltd. | Novel compound having affinity for amyloid |
CN104418874A (zh) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | 一种水溶液中检测氟离子荧光分子探针及其合成与应用 |
CN104418875A (zh) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | 一种检测氟离子荧光分子探针及其合成与应用 |
CN103923479A (zh) * | 2014-04-18 | 2014-07-16 | 大连理工大学 | 久洛尼定母核的氟离子荧光染料及其应用 |
CN104610955A (zh) * | 2014-05-16 | 2015-05-13 | 中南大学 | 一种比率型同时检测氟离子和亚硫酸根荧光分子探针的合成及应用 |
CN104230814A (zh) * | 2014-09-23 | 2014-12-24 | 西北师范大学 | 一种荧光识别氟离子传感器及其制备和应用 |
Non-Patent Citations (4)
Title |
---|
HOU, P等: "An aqueous red emitting fluorescent fluoride sensing probe exhibiting a large Stokes shift and its application in cell imaging", 《CHEMICAL COMMUNICATIONS》 * |
HU, QH等: "A near-infrared large Stokes shift probe based enhanced ICT strategy for F- detection in real samples and cell imaging", 《TETRAHEDRON》 * |
KIM, D等: "In vivo two-photon fluorescent imaging of fluoride with a desilylation-based reactive probe", 《CHEMICAL COMMUNICATIONS》 * |
刘倩等: "荧光探针检测水中F-研究", 《商洛学院学报》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113461686A (zh) * | 2021-08-17 | 2021-10-01 | 中国农业大学 | 荧光探针及其制备方法和应用、荧光探针溶液 |
Also Published As
Publication number | Publication date |
---|---|
CN112079861B (zh) | 2023-03-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1305133C (en) | Fluorogenic and chromogenic three-dimensional ionophores as selective reagents for detecting ions in biological fluids | |
CN107056769A (zh) | 一种l‑半胱氨酸荧光探针及其制备方法 | |
CN104132920B (zh) | 一种荧光猝灭测定Ag+或F-的方法 | |
CN106905310A (zh) | 一种检测次氯酸的荧光探针及其制备方法和应用 | |
CN109266331A (zh) | 一种基于半花菁结构测次氯酸根离子的近红外荧光探针、其制备方法及应用 | |
CN110372632A (zh) | 一种快速识别次氯酸根离子的荧光探针分子及其制备方法和应用 | |
CN110373181B (zh) | 一种检测氟离子的荧光探针 | |
CN111205220B (zh) | 一种荧光探针及其制备方法和应用 | |
CN112079861B (zh) | 一种荧光淬灭检测氟离子的分子探针及其制备方法 | |
CN112939956A (zh) | 一种用于检测汞离子和次氯酸根离子的荧光探针及其制备方法和应用 | |
CN116751210B (zh) | 一种检测汞离子的水溶性探针及其制备方法和应用 | |
CN109370573B (zh) | 一种二价汞离子和温度检测的荧光探针、制备方法及其应用 | |
Nakaya et al. | Sensitive fluorimetric flow injection analysis for fluoride ion with a novel reagent, 2′, 7′-dichlorofluorescein di-tert-butyldimethylsilyl ether | |
CN103497189A (zh) | 1-羟基-3,4:9,10-苝四羧酸二酰亚胺、其合成方法及在氟含量测定中的应用 | |
CN110483542A (zh) | 用于水合肼检测的v型香豆素荧光探针及其制备方法 | |
CN114380792B (zh) | “off-on”型离子检测荧光探针、离子检测试剂盒、制备方法及应用 | |
CN107831165B (zh) | 一种双通道铜离子检测试纸及其制备方法 | |
CN109053750A (zh) | 罗丹明肼希夫碱衍生物及其制备方法和应用 | |
CN108640924A (zh) | 一种不可逆罗丹明基ClO-荧光探针及其合成方法 | |
CN113061139A (zh) | 一种含氨基脲结构的六元螺环罗丹明荧光探针及其制备方法和应用 | |
CN108191760B (zh) | 用于检测Cu(Ⅱ)的荧光探针及其制备方法和应用 | |
CN106841132B (zh) | 检测样品中汞离子浓度的方法 | |
CN113702342B (zh) | 一种利用荧光转换检测溶液中汞离子的方法 | |
CN109503443A (zh) | 一种超灵敏高选择性实时分析次氯酸的荧光探针 | |
CN109608469A (zh) | 一种新型化合物及其制备方法和在检测Ti3+中的应用 |
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 |