CN111303202A - 一种用于检测氟离子的探针及其制备方法 - Google Patents
一种用于检测氟离子的探针及其制备方法 Download PDFInfo
- Publication number
- CN111303202A CN111303202A CN202010227758.4A CN202010227758A CN111303202A CN 111303202 A CN111303202 A CN 111303202A CN 202010227758 A CN202010227758 A CN 202010227758A CN 111303202 A CN111303202 A CN 111303202A
- Authority
- CN
- China
- Prior art keywords
- probe
- preparation
- formula
- solution
- probe molecule
- 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.)
- Pending
Links
- 239000000523 sample Substances 0.000 title claims abstract description 62
- -1 fluorine ions Chemical class 0.000 title claims abstract description 33
- 239000011737 fluorine Substances 0.000 title claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000005046 Chlorosilane Substances 0.000 claims description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 14
- 239000003960 organic solvent Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 231100000167 toxic agent Toxicity 0.000 description 5
- 239000003440 toxic substance Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 206010016818 Fluorosis Diseases 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 208000004042 dental fluorosis Diseases 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000001917 fluorescence detection Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GRXKLBBBQUKJJZ-UHFFFAOYSA-N Soman Chemical compound CC(C)(C)C(C)OP(C)(F)=O GRXKLBBBQUKJJZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 208000002925 dental caries Diseases 0.000 description 2
- 230000035622 drinking Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000002064 Dental Plaque Diseases 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 208000007101 Muscle Cramp Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 208000006735 Periostitis Diseases 0.000 description 1
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- 206010070863 Toxicity to various agents Diseases 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 206010016256 fatigue Diseases 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000002581 neurotoxin Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 210000003460 periosteum Anatomy 0.000 description 1
- 230000002062 proliferating effect Effects 0.000 description 1
- 208000018299 prostration Diseases 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- RWXVMOBDVOAUHW-UHFFFAOYSA-N tert-butyl-chloro-diethylsilane Chemical compound CC[Si](Cl)(CC)C(C)(C)C RWXVMOBDVOAUHW-UHFFFAOYSA-N 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000004916 vomit Anatomy 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium 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
-
- 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
- C07F7/20—Purification, separation
-
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (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)
Abstract
本发明公开了一种用于检测氟离子的探针及其制备方法。本发明探针的分子结构如式(I)所示：
其中，所述R1、R3分别地选自C1‑C3的烷基，所述R2选自C4‑C6的烷基。本发明的探针制备方法简单，制备得到的探针能够实现有机溶剂中对氟离子的快速检测，且检测选择性高。
Description
技术领域
本发明属于氟离子检测技术领域，特别是涉及一种用于检测氟离子的探针及其制备方法。
背景技术
神经性毒剂中的沙林、梭曼等G类毒剂在分子结构中含有磷-氟键，在水解条件(尤其是碱性)下，这些毒剂的磷-氟键会发生断裂，氟会以氟离子释放出来。所以，对于氟离子的识别与定量检测，能对G类毒剂的存在提供判断，为对该类毒剂进行防护和处理提供依据。
此外，氟是人体必须的微量元素之一，是维持骨和牙齿生长的必需物质，因此氟化物常被用来预防龋齿和治疗骨质疏松。氟离子广泛地存在于自然水体中，在河流、湖泊等地表水的含量通常为百分之几至十分之几毫克/升，而在地下水中氟的含量则在1毫克/升左右。当水中的氟含量超过1毫克/升时不宜饮用，长期饮用会患斑齿症，但若饮用水中氟离子含量过低，则又会得龋齿病。据考证，满足人体需要的氟离子的量和由于氟过多而导致氟中毒的量之间相差不大，所以严格掌握氟的摄入量十分重要，否则易造成氟中毒。严重的慢性氟中毒患者，可有骨骼的增殖性变化，骨膜、韧带等均可钙化，产生腰腿和全身关节症状。急性中毒症状为恶心、呕吐、腹泻等，血钙与氟结合，形成不溶性的氟化钙，弓健肌痉挛、虚脱和呼吸困难，以至死亡。所以，一定要建立氟的安全供给量，我国生活饮用水氟化物最高允许浓度为1.0mg/L。所以，鉴于氟离子在生物学、医学、食品科学以及环境科学中都具有重要的作用，氟离子的检测显得尤为重要。
然而，目前通过定氟对沙林、梭曼等神经性毒剂的检测方法是利用氟离子与对甲胺基偶氮苯砷酸锆的显色反应实现，其对沙林的灵敏度仅为50μg/mL。所以，该方法具有较大的局限性。
此外，对环境中氟离子所用的方法中最常用的是分光光度法(比色法)和氟离子选择性电极法。在比色法中，光度计光源的非单色性，溶液对光的散射等干扰因素的存在，都会使测量结果偏离Lambert-Beer定律，直接影响测量精度，而离子选择电极易于污染，零点和满刻度需要经常调整标定，使用维护成本高。并且，这两种方法的最低检测限都只能达到50μg/L，因此使其应用受到一定程度的限制。
发明内容
本发明的目的是弥补现有技术的不足，提供一种用于检测氟离子的探针及其制备方法。本发明的探针制备方法简单，制备得到的探针能够实现有机溶剂中对氟离子的快速检测，且检测选择性高。
为了达到上述的目的，本发明采取以下技术方案：
一种用于检测氟离子的探针，所述探针的分子结构如式(I)所示：
其中，所述R1、R3分别地选自C1-C3的烷基，所述R2选自C4-C6的烷基。
优选的，所述式(I)中R1、R3分别地选自甲基，所述R2为叔丁基。
一种用于检测氟离子的探针的制备方法，包括如下步骤：
(1)探针分子中间体的合成
水杨醛与2-氨基硫代苯酚溶于乙醇溶液中，在室温下滴入双氧水和盐酸混合溶液，在室温下进行反应12-20小时，得到所述探针分子中间体；
(2)探针分子的合成
将分子结构如式(II)所示的氯硅烷的吡啶溶液逐滴加入至探针分子中间体的吡啶溶液中，加热搅拌，温度控制在65-70℃，反应12-24h后得到探针分子；
优选的，所述式(I)中R1、R3分别地选自甲基，所述R2为叔丁基。
优选的，所述步骤(1)中水杨醛、2-氨基硫代苯酚、双氧水、盐酸的摩尔比为1:1:6:1.5。
优选的，所述步骤(1)中双氧水的质量浓度为30％，所述盐酸溶液的质量浓度为37％。
优选的，所述步骤(1)中反应结束后还包括抽滤、洗涤和重结晶的步骤。
优选的，所述步骤(1)中的洗涤的溶剂是无水乙醇。
优选的，所述步骤(2)中所述探针分子中间体与式(II)所示的氯硅烷的摩尔比为5:6。
优选的，所述步骤(2)中反应结束后还包括后处理步骤，所述后处理步骤包括萃取、洗涤和柱分离步骤。
本发明具有以下技术特点：
1)本发明提供的用于检测氟离子的探针当遇到氟离子时，探针分子发生脱除硅反应，在激发光的照射下，产生强荧光，整个检测体系出现良好的OFF-ON或者荧光光谱的波长发生显著的变化，从而完成对氟离子的检测。
2)本发明提供的用于检测氟离子的探针，在氟离子的作用下，有机硅化合物发生脱硅化(硅的氟加成)反应，反应产物在激发光的作用下，发生分子内质子转移，分子结构发生显著变化，反应具有专一性，因此，对氟离子具有很高的选择性。
3)本发明提供的用于检测氟离子的探针在有机体系种能快速的实现对氟离子的检测，几分钟内检测的荧光能达到最大值。
附图说明
图1探针分子对特定浓度氟离子的荧光强度随时间的变化。
图2探针分子对不同浓度氟离子的荧光检测。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例的技术方案进行清楚、完整的描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本发明的保护范围。
除非另作定义，本公开所使用的技术术语或者科学术语应当为本发明所属领域内有一般技能的人士所理解的通常意义。
本发明用于检测氟离子的探针的合成路线如下所示：
本发明具体实施方式中用于检测氟离子的探针的制备方法，包括如下步骤：
(1)探针分子中间体的合成
水杨醛与2-氨基硫代苯酚溶于乙醇溶液中，在室温下滴入双氧水和盐酸混合溶液，在室温下进行反应12-20小时，得到所述探针分子中间体；
(2)探针分子的合成
将分子结构如式(II)所示的氯硅烷的吡啶溶液逐滴加入至探针分子中间体的吡啶溶液中，加热搅拌，温度控制在65-70℃，反应12-24h后得到探针分子；
实施例1R1、R3为甲基，R2为叔丁基的探针分子的制备方法
包括如下步骤：
(1)探针分子P1中间体的合成
称取2.44g(20mmol)水杨醛与2.50g(20mmol)2-氨基硫代苯酚溶于20ml乙醇中，在室温下滴入10ml(120mmol)的30％H2O2和2ml(30mmol)37％HCl混合溶液，室温反应12小时，用布氏漏斗和水泵进行抽滤，滤除沉淀，用无水乙醇洗涤几次后，在旋转蒸发仪上旋干重结晶，得探针中间体2.77g，产品收率为61.0％。
(2)探针分子P1的合成
称取探针分子P1中间体A1.135g(5mmol)，加入35ml吡啶，再称取0.9g(6mmol)的叔丁基二甲基氯硅烷溶于20ml吡啶中，然后逐滴加入至探针分子P1中间体中。加热搅拌，温度控制在65-70℃。TLC监测反应进程。反应12h后，在旋转蒸发仪上旋干，加入50ml乙酸乙酯和50ml水萃取，滤去水层，先后用水20ml洗涤两次，20ml10％柠檬酸洗涤两次，20ml饱和碳酸氢钠洗涤两次，20ml饱和食盐水洗涤两次，20ml水洗涤两次后加入无水硫酸镁干燥过夜；次日用旋转蒸发仪减压旋干后得到淡黄色粘稠液体，用油泵抽滤两小时，称重得粗品0.812g。
用薄层硅胶色谱分析。用乙酸乙酯装填碱性氧化铝柱对粗品进行柱分离，先用石油醚作为流动相，滤去副产物或反应物，在用石油醚：乙酸乙酯1:1作为流动相，滤得产品。过柱后在旋转蒸发仪上旋干，并用油泵抽滤，得到淡黄色硅醚化的探针分子P1为0.711g，产率分别为35.3％。
实施例2R1、R3为乙基，R2为叔丁基的探针分子的的制备方法
包括如下步骤：
(1)探针分子P2中间体的合成
称取2.44g(20mmol)水杨醛与2.50g(20mmol)2-氨基硫代苯酚溶于20ml乙醇中，在室温下滴入10ml(120mmol)的30％H2O2和2ml(30mmol)37％HCl混合溶液，室温反应15小时，用布氏漏斗和水泵进行抽滤，滤除沉淀，用无水乙醇洗涤几次后，在旋转蒸发仪上旋干重结晶，得探针中间体2.83g，产品收率为59.5％。
(2)探针分子P2的合成
称取探针分子中间体A1.135g(5mmol)，加入35ml吡啶，再称取1.1g(6mmol)的叔丁基二乙基氯硅烷溶于20ml吡啶中，然后逐滴加入至探针分子P1中间体中。加热搅拌，温度控制在65-70℃。TLC监测反应进程。反应20h后，在旋转蒸发仪上旋干，加入50ml乙酸乙酯和50ml水萃取，滤去水层，先后用水20ml洗涤两次，20ml10％柠檬酸洗涤两次，20ml饱和碳酸氢钠洗涤两次，20ml饱和食盐水洗涤两次，20ml水洗涤两次后加入无水硫酸镁干燥过夜；次日用旋转蒸发仪减压旋干后得到淡黄色粘稠液体，用油泵抽滤两小时，称重得粗品0.953g。
用薄层硅胶色谱分析。用乙酸乙酯装填碱性氧化铝柱对粗品进行柱分离，先用石油醚作为流动相，滤去副产物或反应物，在用石油醚：乙酸乙酯1:1作为流动相，滤得产品。过柱后在旋转蒸发仪上旋干，并用油泵抽滤，得到淡黄色硅醚化的探针分子P2为0.796g，产率分别为36.2％。
(二)荧光检测波长的确定
称取1.605mg探针分子P1，溶于5mL乙腈中，配制浓度为1mmol/L的探针分子stock溶液，备用。
将1mol/L的四丁基氟化铵的四氢呋喃溶液稀释成1mmol/L的氟离子溶液。
荧光光谱是在10mm宽度的石英荧光池中加入2.0mL的目标溶液，测量过程中引入的氟离子溶液体积之和不超过100uL，以尽量减少体积变化对荧光性质造成的影响。所有荧光光谱均在室温测得。通过预实验，我们确定了探针分子P1体系检测氟离子的荧光激发波长为361nm，激发光与发射光的狭缝宽度均为5nm。
(三)探针分子P1对THF中氟离子的检测
首先测试P1浓度为200μM，氟离子浓度为200μM条件下，荧光强度随时间变化的情况。检测结果如图1所示。从图1可以看出探针分子P1在THF有机体系能快速的实现对氟离子的检测，两分钟内检测的荧光能达到最大值。
随后，P1采用的浓度为200μM，氟离子浓度为0μM、5μM、10μM、20μM、50μM、100μM、200μM。在每次加入氟离子并震荡后于阴暗处放置五分钟，测量荧光发射光谱(激发波长为361nm)。检测结果如图2所示。从图2可以看出探针分子P1在THF有机体系能对20μM(0.38mg/L)以上浓度的氟离子实现荧光检出。
以上实施例的说明只是用于帮助理解本发明方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求保护范围内。
Claims (10)
1.一种用于检测氟离子的探针，其特征在于，所述探针的分子结构如式(I)所示：
其中，所述R1、R3分别地选自C1-C3的烷基，所述R2选自C4-C6的烷基。
2.根据权利要求1所述的探针，其特征在于，所述式(I)中R1、R3分别地选自甲基，所述R2为叔丁基。
3.一种用于检测氟离子的探针的制备方法，其特征在于，包括如下步骤：
(1)探针分子中间体的合成
水杨醛与2-氨基硫代苯酚溶于乙醇溶液中，在室温下滴入双氧水和盐酸混合溶液，在室温下进行反应12-20小时，得到所述探针分子中间体；
(2)探针分子的合成
将分子结构如式(II)所示的氯硅烷的吡啶溶液逐滴加入至探针分子中间体的吡啶溶液中，加热搅拌，温度控制在65-70℃，反应12-24h后得到探针分子；
4.根据权利要求3所述的制备方法，其特征在于，所述式(I)中R1、R3分别地选自甲基，所述R2为叔丁基。
5.根据权利要求3所述的制备方法，其特征在于，所述步骤(1)中水杨醛、2-氨基硫代苯酚、双氧水、盐酸的摩尔比为1:1:6:1.5。
6.根据权利要求3所述的制备方法，其特征在于，所述步骤(1)中双氧水的质量浓度为30％，所述盐酸溶液的质量浓度为37％。
7.根据权利要求3所述的制备方法，其特征在于，所述步骤(1)中反应结束后还包括抽滤、洗涤和重结晶的步骤。
8.根据权利要求3所述的制备方法，其特征在于，所述步骤(1)中的洗涤的溶剂是无水乙醇。
9.根据权利要求3所述的制备方法，其特征在于，所述步骤(2)中所述探针分子中间体与式(II)所示的氯硅烷的摩尔比为5:6。
10.根据权利要求3所述的制备方法，其特征在于，所述步骤(2)中反应结束还包括后处理步骤，所述后处理步骤包括萃取、洗涤和柱分离步骤。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010227758.4A CN111303202A (zh) | 2020-03-27 | 2020-03-27 | 一种用于检测氟离子的探针及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010227758.4A CN111303202A (zh) | 2020-03-27 | 2020-03-27 | 一种用于检测氟离子的探针及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111303202A true CN111303202A (zh) | 2020-06-19 |
Family
ID=71157337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010227758.4A Pending CN111303202A (zh) | 2020-03-27 | 2020-03-27 | 一种用于检测氟离子的探针及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111303202A (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620904A (zh) * | 2020-06-30 | 2020-09-04 | 莆田学院 | 基于羟基脱保护反应的喹啉偶氮衍生物传感器及其制备与应用 |
| WO2022104414A1 (en) * | 2020-11-17 | 2022-05-27 | The University Of Queensland | Detection method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250134A (zh) * | 2010-05-21 | 2011-11-23 | 中国科学院化学研究所 | 一种识别氟离子的荧光探针及其制备方法和用途 |
| CN104449677A (zh) * | 2014-12-29 | 2015-03-25 | 大连理工常熟研究院有限公司 | 一种用于识别氟离子的特异性荧光探针及其应用 |
| 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 |
-
2020
- 2020-03-27 CN CN202010227758.4A patent/CN111303202A/zh active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250134A (zh) * | 2010-05-21 | 2011-11-23 | 中国科学院化学研究所 | 一种识别氟离子的荧光探针及其制备方法和用途 |
| 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 |
| CN104449677A (zh) * | 2014-12-29 | 2015-03-25 | 大连理工常熟研究院有限公司 | 一种用于识别氟离子的特异性荧光探针及其应用 |
Non-Patent Citations (1)
| Title |
|---|
| CHENGFENG WU ET AL.,: "Separately enhanced dual emissions of the amphiphilic derivative of 2-(20-hydroxylphenyl) benzothiazole by supramolecular complexation", 《SOFT MATTER》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620904A (zh) * | 2020-06-30 | 2020-09-04 | 莆田学院 | 基于羟基脱保护反应的喹啉偶氮衍生物传感器及其制备与应用 |
| CN111620904B (zh) * | 2020-06-30 | 2023-02-24 | 福建省海凝环保科技有限公司 | 基于羟基脱保护反应的喹啉偶氮衍生物传感器及其制备与应用 |
| WO2022104414A1 (en) * | 2020-11-17 | 2022-05-27 | The University Of Queensland | Detection method |
| EP4247823A4 (en) * | 2020-11-17 | 2024-10-23 | The Univ Of Queensland | PROOFING PROCEDURES |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gai et al. | Organosilicon compounds as fluorescent chemosensors for fluoride anion recognition | |
| Guo et al. | Near‐Infrared Cell‐Permeable Hg2+‐Selective ratiometric fluorescent chemodosimeters and fast indicator paper for MeHg+ based on tricarbocyanines | |
| Trombly et al. | Fractionation and analysis of fluorescent products of lipid peroxidation | |
| Santos et al. | New coumarin–corrole and–porphyrin conjugate multifunctional probes for anionic or cationic interactions: Synthesis, spectroscopy, and solid supported studies | |
| Zhou et al. | The 8-silyloxyquinoline scaffold as a versatile platform for the sensitive detection of aqueous fluoride | |
| CN111303202A (zh) | 一种用于检测氟离子的探针及其制备方法 | |
| Yang et al. | Phenothiazine–aminothiourea–Hg (II) ensemble-based fluorescence turn-on toward iodide in aqueous media and imaging application in live cells | |
| Guo et al. | Highly efficient and selective detection of sulfur ions and picric acid through salamo-Cd (II) coordination polymer chemosensor | |
| Wang et al. | Dual binding site assisted chromogenic and fluorogenic discrimination of fluoride and cyanide by boryl functionalized BODIPY | |
| Zhang et al. | A turn-on fluorescence probe for the selective and sensitive detection of fluoride ions | |
| Keşan et al. | Azaindole-BODIPYs: Synthesis, fluorescent recognition of hydrogen sulfate anion and biological evaluation | |
| Li et al. | Development of carbazole-based fluorescent probe for highly sensitive application in fluoride ion detection | |
| Panda et al. | An efficient PET-based probe for detection and discrimination of Zn2+ and Cd2+ in near-aqueous media and live-cell imaging | |
| CN104845611B (zh) | 一种新型氟离子比率荧光探针及应用 | |
| Kádár et al. | Spectrophotometric determination of the dissociation constants of crown ethers with grafted acridone unit in methanol based on Benesi-Hildebrand evaluation | |
| Chakraborty et al. | Cu (II) complexes of a bio-compatible aminoguanidine Schiff base: Histidine sensing and DNA-binding studies | |
| CN110373181A (zh) | 一种检测氟离子的荧光探针 | |
| CN110655510B (zh) | 一种靶向脂滴的亚硫酸盐比率荧光探针及其应用 | |
| Beltyukova et al. | Use of sensitized luminescence of lanthanides in analysis of drugs | |
| CN110878100B (zh) | 一种可裸眼识别的氰根离子探针及其制备方法和在含水体系中检测氰根离子的应用 | |
| Cugnasca et al. | Precision detection of cyanide, fluoride, and hydroxide ions using a new tetraseleno-BODIPY fluorescent sensor | |
| CN111423467A (zh) | 一种检测氟离子用荧光探针及其制备方法和应用 | |
| CN110894193B (zh) | 一种新型荧光探针的合成及在检测半胱氨酸中的应用 | |
| CN111548304A (zh) | 一种基于三苯胺的衍生物及制备方法与应用 | |
| CN110389117A (zh) | 凹土-硫代香豆素功能杂化材料及其制备方法和应用 |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200619 |