CN113817090A - Triterpyridine-based transition metal ion fluorescence chemical sensor and preparation method thereof - Google Patents
Triterpyridine-based transition metal ion fluorescence chemical sensor and preparation method thereof Download PDFInfo
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- CN113817090A CN113817090A CN202110902660.9A CN202110902660A CN113817090A CN 113817090 A CN113817090 A CN 113817090A CN 202110902660 A CN202110902660 A CN 202110902660A CN 113817090 A CN113817090 A CN 113817090A
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- Prior art keywords
- fluorene
- bromo
- dialkyl fluorene
- dialkylfluorene
- dialkyl
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Links
- 239000000126 substance Substances 0.000 title claims abstract description 35
- 229910001428 transition metal ion Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 179
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 claims abstract description 31
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920005604 random copolymer Polymers 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 41
- 238000004440 column chromatography Methods 0.000 claims description 35
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- 230000015572 biosynthetic process Effects 0.000 claims description 32
- 238000003786 synthesis reaction Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 30
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- FXSCJZNMWILAJO-UHFFFAOYSA-N 2-bromo-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(Br)C=C3CC2=C1 FXSCJZNMWILAJO-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229960001701 chloroform Drugs 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 9
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012346 acetyl chloride Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 claims description 5
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001347 alkyl bromides Chemical class 0.000 claims description 3
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 32
- 238000010521 absorption reaction Methods 0.000 description 29
- 229910021645 metal ion Inorganic materials 0.000 description 28
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
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- RXACYPFGPNTUNV-UHFFFAOYSA-N 9,9-dioctylfluorene Chemical compound C1=CC=C2C(CCCCCCCC)(CCCCCCCC)C3=CC=CC=C3C2=C1 RXACYPFGPNTUNV-UHFFFAOYSA-N 0.000 description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 13
- 238000010791 quenching Methods 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
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- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 description 7
- 239000012279 sodium borohydride Substances 0.000 description 7
- CEDQDOBRYBHPNY-UHFFFAOYSA-N 1-(9,9-dioctylfluoren-2-yl)ethanone Chemical compound C1=C(C(C)=O)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC=CC=C3C2=C1 CEDQDOBRYBHPNY-UHFFFAOYSA-N 0.000 description 6
- HBLWOORKIQFPAI-UHFFFAOYSA-N 2-bromo-7-ethenyl-9,9-dioctylfluorene Chemical compound BrC1=CC=2C(C3=CC(=CC=C3C=2C=C1)C=C)(CCCCCCCC)CCCCCCCC HBLWOORKIQFPAI-UHFFFAOYSA-N 0.000 description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
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- AKYHKWQPZHDOBW-UHFFFAOYSA-N (5-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol Chemical compound OS(O)(=O)=O.C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 AKYHKWQPZHDOBW-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/26—Nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
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- 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"
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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- 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
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- 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"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention relates to a terpyridine-based transition metal ion fluorescence chemical sensor and a preparation method thereof, belonging to the technical field of transition metal ion fluorescence chemical sensors. The structural formula of the terpyridine-based transition metal ion fluorescence chemical sensor is shown in the specification
Wherein Ar is a hydrophilic monomer; n is the number of repeating units, and n is 0-6; r is an alkyl chain, and the number of C atoms is 6-30; x, y and z are relative of three monomersThe proportion is x + y + z is 100 percent, wherein x is 0.2-10 percent, and z is 0.2-10 percent; adding a conjugated alkene monomer taking 9, 9-dialkyl fluorene as a structural unit, 4- (4'-2,2':6', 2' -terpyridine) styrene, a hydrophilic monomer and azobisisobutyronitrile into 1, 4-dioxane, stirring and reacting for 6-10 hours at the temperature of 75-85 ℃, and placing in dichloromethane for settling to obtain a random copolymer, namely the terpyridine-based transition metal ion fluorescence chemical sensor; the structural formula of the conjugated alkene monomer taking 9, 9-dialkyl fluorene as a structural unit is shown in the specification
Description
Technical Field
The invention relates to a terpyridine-based transition metal ion fluorescence chemical sensor and a preparation method thereof, belonging to the technical field of transition metal ion fluorescence chemical sensors.
Background
Transition metal ions are widely present in the environment and in living organisms, some ions being Fe2+、Zn2+Have very important function on life process, and some ions such as Cd2+And the like have toxic action. In addition, the nature of action of many ions also depends on their specific concentration. Therefore, rapid, accurate and convenient detection of these ions is an important issue in the fields of environmental monitoring, industrial production, biomedicine, food safety, and the like.
The traditional chemical titration method has the defects of low monitoring speed, poor data repeatability, large influence of environmental factors, high operation requirement, limited detection lower limit concentration and the like; in addition, most of application scenes of some organic/polymer chemical sensors are organic solvents, so that the organic/polymer chemical sensors cannot be applied to a water medium system, and direct application of the organic/polymer chemical sensors in the life process and the environmental field is greatly limited.
Therefore, the development of the high-efficiency fluorescence sensor in the water system has important significance.
Disclosure of Invention
Aiming at the problems of the existing transition metal ion fluorescence chemical sensor, the invention provides a terpyridine-based transition metal ion fluorescence chemical sensor and a preparation method thereof, namely, a hydrophilic monomer is taken as a main monomer, and a fluorescence conjugated monomer fluorene derivative and 4- (4'-2,2':6', 2' -terpyridine) styrene (TPY) are introduced to synthesize a hydrophilic copolymer, namely, the polymer metal ion fluorescence chemical sensor.
A terpyridine-based transition metal ion fluorescence chemical sensor has a structural formula as follows:
wherein Ar is a hydrophilic monomer; n is the number of repeating units, and n is 0-6; r is an alkyl chain, and the number of C atoms is 6-30; x, y and z are relative proportions of the three monomers, wherein x + y + z is 100%, x is 0.2-10%, and z is 0.2-10%; the hydrophilic monomer is acrylic acid, methacrylic acid, acrylamide or methacrylamide.
The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor comprises the following specific steps:
adding a conjugated alkene monomer taking 9, 9-dialkyl fluorene as a structural unit, 4- (4'-2,2':6', 2' -terpyridine) styrene, a hydrophilic monomer and azobisisobutyronitrile into 1, 4-dioxane, stirring and reacting for 6-10 hours at the temperature of 75-85 ℃, and placing in dichloromethane for settling to obtain a random copolymer, namely the terpyridine-based transition metal ion fluorescence chemical sensor;
wherein the hydrophilic monomer is acrylic acid, methacrylic acid, acrylamide or methacrylamide;
the structural formula of the conjugated alkene monomer taking 9, 9-dialkyl fluorene as a structural unit is shown in the specification
Wherein n is the number of repeating units, and n is 0-6;
r is an alkyl chain, and the number of C atoms is 6-30.
Further, when n is 1-6, the preparation method of the conjugated alkene monomer with 9, 9-dialkyl fluorene as a structural unit comprises the following steps
(1) Synthesis of 2-bromofluorene: dropwise adding the bromine/trichloromethane mixed solution into the fluorene/catalyst/trichloromethane mixed solution at the temperature of-5-10 ℃ in a dark nitrogen atmosphere, stirring for reacting for 3-5 h, washing, filtering, drying, and recrystallizing in DCM-methanol to obtain 2-bromofluorene;
(2) synthesis of 2-bromo-9, 9-dialkylfluorene: under the conditions of light protection and nitrogen atmosphere, adding alkyl bromide and tetrabutylammonium bromide into a 2-bromofluorene/toluene mixed solution, stirring and reacting for 20-30 h at the temperature of 65-80 ℃, neutralizing with dilute hydrochloric acid in sequence, extracting with DCM, and purifying by column chromatography to obtain 2-bromo-9, 9-dialkylfluorene;
(3) synthesis of 2-bromo-7-acetyl-9, 9-dialkylfluorene: adding acetyl chloride and a catalyst into a 2-bromo-9, 9-dialkylfluorene/dichloromethane or a 2-bromo-9, 9-dialkylfluorene/chloroform mixed solution in a nitrogen atmosphere, stirring and reacting at the temperature of-5-10 ℃ for 3-5 h, washing, filtering, drying, and purifying by column chromatography to obtain 2-bromo-7-acetyl-9, 9-dialkylfluorene;
(4) synthesis of 2-bromo-7- (1-hydroxy) ethyl-9, 9-dialkylfluorene: adding strong base into the mixed solution of 2-bromo-7-acetyl-9, 9-dialkyl fluorene/absolute ethyl alcohol under the condition of nitrogen atmosphere and temperature of-5-10 ℃, uniformly mixing, heating to 20-30 ℃, stirring for reaction for 0.5-1.5 h, and recrystallizing to obtain 2-bromo-7- (1-hydroxy) ethyl-9, 9-dialkyl fluorene;
(5) synthesis of 2-bromo-7-vinyl-9, 9-dialkylfluorene: heating the 2-bromo-7- (1-hydroxy) ethyl-9, 9-dialkyl fluorene/toluene mixed solution to reflux, adding a catalyst, stirring, refluxing, reacting for 10-30 min, and purifying by column chromatography to obtain 2-bromo-7-vinyl-9, 9-dialkyl fluorene;
(6) synthesizing conjugated alkene monomers with 9, 9-dialkyl fluorene as a structural unit: adding an alkaline solution into a 2-bromo-7-vinyl-9, 9-dialkyl fluorene/monoboronic ester group substituted alkyl fluorene oligomer derivative/tetrahydrofuran mixed solution, adding a catalyst in a nitrogen atmosphere, reacting for 18-24 hours at a temperature of 60-85 ℃ in a dark place, and purifying by column chromatography to obtain a conjugated alkene monomer with 9, 9-dialkyl fluorene as a structural unit; wherein the structural formula of the oligomer derivative of the alkyl fluorene substituted by the single borate group is shown in the specification
Wherein n is the number of repeating units, and n is 0-5;
r is an alkyl chain, and the number of C atoms is 6-30.
Furthermore, when n is 1-6, the molar ratio of bromine to fluorene in the step (1) is 0.95-1.05: 1.0, the catalyst is ferric chloride, the adding amount of the catalyst is 2-3% of the molar amount of fluorene, and the detergent is NaHSO3An aqueous solution and dichloromethane; the molar ratio of alkyl bromide to 2-bromofluorene in the step (2) is 2.1-3.0: 1.0, the addition amount of tetrabutylammonium bromide is 6-15% of the molar amount of 2-bromofluorene, and the mobile phase of column chromatography is petroleum ether; the molar ratio of acetyl chloride to 2-bromo-9, 9-dialkyl fluorene in the step (3) is 1.2-2.0: 1.0, the catalyst is aluminum chloride, the molar ratio of 2-bromo-9, 9-dialkyl fluorene to aluminum chloride is 1 (1.5-3), the detergent is water and DCM, and the mobile phase of column chromatography is petroleum ether and ethyl acetate; the alkali in the step (4) is sodium borohydride, and the molar ratio of the sodium borohydride to the 2-bromo-7-acetyl-9, 9-dialkyl fluorene is 2.5-1.8: 1; the catalyst in the step (5) is toluenesulfonic acid, the molar ratio of the toluenesulfonic acid to the 2-bromo-7- (1-hydroxy) ethyl-9, 9-dialkyl fluorene is 1 (8-15), and a column chromatography mobile phase is petroleum ether or n-hexane; the molar ratio of the 2-bromo-7-vinyl-9, 9-dialkyl fluorene and the 2-pinacol borate-9, 9-dialkyl fluorene in the step (6) is 0.80-1.2: 1.0, and the catalyst is Pd (PPh)3)4Or Pd (dppf) Cl2The molar ratio of the catalyst to the 2-bromo-7-vinyl-9, 9-dialkyl fluorene is 1 (6-25), the alkaline solution is a potassium carbonate or sodium carbonate solution, and the molar ratio of the alkali in the alkaline solution to the 2-bromo-7-vinyl-9, 9-dialkyl fluorene is (15-40) to 1;
furthermore, when n is 1-6, the preparation method of the conjugated alkene monomer with 9, 9-dialkyl fluorene as the structural unit in the step (6) comprises the step of preparing the alkyl fluorene oligomer derivative substituted by the monoboronic ester group
1) Synthesis of 2-pinacol boronate-9, 9-dialkylfluorene: adding pinacol diboron and potassium ethoxide into a 2-bromo-9, 9-dialkyl fluorene/dimethyl sulfoxide mixed solution, and adding Pd (dppf) Cl in a nitrogen atmosphere2Uniformly mixing, heating to 80-95 ℃, and stirring in the darkPerforming column chromatography purification for 20-36 h to obtain 2-pinacol borate-9, 9-dialkyl fluorene, namely, the oligomer derivative of alkyl fluorene substituted by monoborate group with n being 0;
2) synthesis of 2-pinacol boronate- (9, 9-dialkylfluorene) n-mer: adding pinacol diboron and potassium ethoxide into a mixed solution of 2-bromo- (9, 9-alkyl) fluorene (n-1) polymer/dimethyl sulfoxide, and adding Pd (dppf) Cl in the nitrogen atmosphere2Uniformly mixing, heating to 80-95 ℃, stirring and reacting for 20-36 h under the condition of keeping out of the sun, and purifying by column chromatography to obtain a 2-pinacol borate- (9, 9-dialkyl fluorene) n polymer;
furthermore, the molar ratio of the pinacol diboron ester and the 2-bromo-9, 9-dialkyl fluorene in the step 1) is 1.5-3.0: 1.0, and the catalyst is Pd (dppf) Cl2Or Pd (PPh)3)4The molar ratio of the catalyst to the 2-bromo-9, 9-dialkyl fluorene is 0.02-0.05: 1.0, and the mobile phase of column chromatography is petroleum ether and ethyl acetate; step 2), the molar ratio of the pinacol diboron to the 2-bromo- (9, 9-alkyl) fluorene (n-1) polymer is 1.5-3.0: 1.0, and the catalyst is Pd (dppf) Cl2Or Pd (PPh)3)4The molar ratio of the catalyst to the 2-bromo-fluorene (n-1) polymer is 0.02-0.05: 1.0, and the mobile phase of column chromatography is petroleum ether and ethyl acetate;
further, when n is 0, the preparation method of the conjugated alkene monomer with 9, 9-dialkyl fluorene as a structural unit comprises the following steps
(1) Synthesis of 9, 9-dialkylfluorene: dropwise adding n-butyllithium into a fluorene/THF system at the temperature of-78 to-50 ℃ in a nitrogen atmosphere to obtain a mixture A, dropwise adding a 1-bromoalkane/THF solution into the mixture A, reacting at room temperature for 20-36 hours under nitrogen, extracting with ethyl acetate, and purifying by column chromatography to obtain 9, 9-dialkyl fluorene;
(2) synthesis of 2-acetyl-9, 9-dialkylfluorene: adding acetyl chloride and a catalyst into a 9, 9-dialkyl fluorene/dichloromethane or a 9, 9-dialkyl fluorene/trichloromethane mixed solution in a nitrogen atmosphere, stirring and reacting for 3-5 h at the temperature of-5-10 ℃, washing, filtering, drying, and purifying by column chromatography to obtain 2-acetyl-9, 9-dialkyl fluorene;
(3) synthesis of 2-ethanol-9, 9-dialkyl fluorene: adding strong base into the mixed solution of 2-acetyl-9, 9-dialkyl fluorene and absolute ethyl alcohol under the condition of nitrogen atmosphere and temperature of-5-10 ℃, uniformly mixing, heating to 20-30 ℃, stirring for reaction for 0.5-1.5 h, and recrystallizing to obtain 2-ethanol-based-9, 9-dialkyl fluorene;
(4) synthesis of 2-vinyl-9, 9-dialkylfluorene: heating the 2-ethanol-based-9, 9-dialkyl fluorene/toluene mixed solution to reflux, adding a catalyst, stirring, refluxing and reacting for 10-30 min, and purifying by column chromatography to obtain 2-vinyl-9, 9-dialkyl fluorene;
furthermore, when n is 0, the molar ratio of n-butyllithium to fluorene in the step (1) in the preparation method of the conjugated alkene monomer with 9, 9-dialkyl fluorene as a structural unit is 2.2-4.0: 1, and the molar ratio of 1-bromoalkane to fluorene is 2.2-3.5: 1; the molar ratio of acetyl chloride to 9, 9-dioctylfluorene in the step (2) is 1.2-2.0: 1.0, the catalyst is aluminum chloride, the molar ratio of 9, 9-dioctylfluorene to aluminum chloride is 1 (1.5-3), the detergent is water and DCM, and the mobile phase of column chromatography is petroleum ether and ethyl acetate; the alkali in the step (3) is sodium borohydride, and the molar ratio of the sodium borohydride to the 2-acetyl-9, 9-dioctyl fluorene is 2.5-1.8: 1; the catalyst in the step (4) is toluenesulfonic acid, the molar ratio of the toluenesulfonic acid to the 2-ethanol-based-9, 9-dioctyl fluorene is 1 (8-15), and the column chromatography mobile phase is petroleum ether or n-hexane.
The invention has the beneficial effects that:
(1) according to the invention, the fluorescent conjugated vinyl monomer and the hydrophilic monomer are subjected to free radical copolymerization, so that the final polymer is endowed with the property of high-efficiency fluorescence emission in a water system by a conventional copolymerization method;
(2) the terpyridine derivative alkene monomer unit with wide coordination with transition metal ions is introduced into the polymer, so that an action point capable of performing coordination with the transition metal is provided for the copolymer;
(3) the polymer sensor designed by the invention can be applied to an aqueous medium, and the high-efficiency detection of transition metal ions is realized;
(4) copolymer obtained by design of the invention is Fe2+、Zn2+Has higher spectral selectivity and can carry out fluorescence spectrum detection on the fluorescent dye quantitatively.
Drawings
FIG. 1 shows a conjugated olefin monomer VOF having 9, 9-dialkylfluorene as a structural unit in examples 1 and 21And VOF2An infrared spectrum of (1);
FIG. 2 is the random copolymer PATF of example 1 and example 21And PATF2-1 infrared spectrum;
FIG. 3 is a drawing of a monomer TPY1H nuclear magnetic spectrum;
FIG. 4 is the UV-VIS absorption spectrum of example 4;
FIG. 5 is fluorescence emission spectrum of example 4;
FIG. 6 is the example 5 Polymer PATF1Color and fluorescence change pattern when reacting with different metal ions;
FIG. 7 is the example 5 Polymer PATF2-1 color and fluorescence change profiles with different metal ions;
FIG. 8 is the example 5 Polymer PATF2-1 uv-vis absorption spectrum of the interaction with different metal ions;
FIG. 9 is the example 5 Polymer PATF2-1 fluorescence emission spectra with different metal ions;
FIG. 10 is the example 5 Polymer PATF2-1 and Fe2+Quantitative fluorescence quenching response map of (1);
FIG. 11 is the example 5 Polymer PATF2-1 with Zn2+Quantitative fluorescence enhancement response map of (1).
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: the structural formula of the transition metal ion fluorescence chemical sensor based on terpyridine is shown in the specification
The structural formula of the conjugated alkene monomer taking 9, 9-dioctyl fluorene as a structural unit is shown in the specification
The synthetic route of the transition metal ion fluorescence chemical sensor based on terpyridine is
x is 0.5 and y is 5.0. z is 94.5;
the preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor comprises the following specific steps:
adding a conjugated olefin monomer taking 9, 9-dioctyl fluorene as a structural unit, 4- (4'-2,2':6', 2' -terpyridine) styrene, acrylic acid and azobisisobutyronitrile into 1, 4-dioxane, stirring and reacting for 8 hours at the temperature of 80 ℃, and placing in dichloromethane for settling to obtain a random copolymer, namely the terpyridine-based transition metal ion fluorescence chemical sensor; wherein the mol ratio of the conjugated olefin monomer taking 9, 9-dioctyl fluorene as a structural unit, 4- (4'-2,2':6', 2' -terpyridine) styrene and acrylic acid is 0.5:5.0: 94.5; the adding amount of the azodiisobutyronitrile is 0.5-2% of the mass of the monomer;
random copolymer (PATF)1) The infrared spectrum of (A) is shown in FIG. 2: 3130cm-1Nearby absorption is υOH，2930cm-1Nearby absorption is υCH，1716cm-1Is upsilonC＝O，1453cm-1Near absorption is δCH，1530cm-1Nearby absorption is upsilon on benzene ringC＝CV on pyridine heterocycleC＝NAbsorption was at 1595cm-1Nearby;
of monomeric TPY1The H nuclear magnetic spectrum is shown in FIG. 3:
1H NMR(500MHz,CDCl3):δ(ppm)8.75-8.67(6H,m),7.91-7.88(4H,m),7.56(2H,m),7.37-7.36(2H,m),6.76-6.81(1H,q),5.86(1H,d),5.34(1H,d).
the molecular weight of the random copolymer PATF1 was 2.93X 105g/mol；
The synthetic route of the conjugated alkene monomer taking 9, 9-dioctyl fluorene as a structural unit is as follows:
the preparation method of the conjugated alkene monomer with 9, 9-dioctyl fluorene as the structural unit comprises
(1) Synthesis of 9, 9-dioctylfluorene (Compound 8): dropwise adding n-butyllithium into a fluorene/THF system under the nitrogen atmosphere at-78 ℃ to obtain a mixture A, dropwise adding a 1-bromooctane/THF solution into the mixture A, reacting at room temperature for 24 hours under nitrogen, extracting with ethyl acetate, and purifying by column chromatography to obtain 9, 9-dioctyl fluorene; wherein the molar ratio of n-butyllithium to fluorene is 3:1, and the molar ratio of 1-bromooctane to fluorene is 2.3: 1;
(2) synthesis of 2-acetyl-9, 9-dioctylfluorene (Compound 9): adding acetyl chloride and a catalyst into a 9, 9-dioctylfluorene/dichloromethane or a 9, 9-dioctylfluorene/chloroform mixed solution in a nitrogen atmosphere, stirring and reacting for 4 hours at the temperature of 0 ℃, washing, filtering, drying, and purifying by column chromatography to obtain 2-acetyl-9, 9-dioctylfluorene; wherein the molar ratio of acetyl chloride to 9, 9-dioctylfluorene is 1.5:1.0, the catalyst is aluminum chloride, the molar ratio of 9, 9-dioctylfluorene to aluminum chloride is 1:2, the detergent is water and DCM, and the mobile phase of column chromatography is petroleum ether and ethyl acetate;
(3) synthesis of 2-Ethanol-9, 9-Dioctylfluorene (Compound 10): adding strong base into the mixed solution of 2-acetyl-9, 9-dioctyl fluorene/absolute ethyl alcohol under the condition of nitrogen atmosphere and 0 ℃, uniformly mixing, heating to the temperature of 25 ℃, stirring for reacting for 1.0h, and recrystallizing to obtain 2-ethanol-based-9, 9-dioctyl fluorene; wherein the strong base is sodium borohydride, and the molar ratio of the sodium borohydride to the 2-acetyl-9, 9-dioctyl fluorene is 2.0: 1;
(4) 2-vinyl-9, 9-dioctylfluorene (compound VOF)1) Is/are as followsSynthesizing: heating the 2-ethanol-9, 9-dioctyl fluorene/toluene mixed solution to reflux, adding a catalyst, stirring, refluxing, reacting for 20min, and purifying by column chromatography to obtain 2-vinyl-9, 9-dioctyl fluorene (see figure 1); wherein the catalyst is toluenesulfonic acid, the molar ratio of the toluenesulfonic acid to the 2-ethanol-based-9, 9-dioctyl fluorene is 1:10, and the column chromatography mobile phase is petroleum ether;
as can be seen from fig. 1: 3060cm-1Absorption v＝CH，2920cm-1And 2854cm-1Near absorption vCHAnd furthermore 1370cm-1-1460cm-1Range and 827cm-1Near absorption is δCH. V in the molecular StructureC＝CAbsorption was at 1623cm-1-1570cm-1Nearby, the rest of the framework vibration absorption peaks are weak because the molecules have certain symmetry. Omega＝CHAbsorption of (2) is at 988cm-1Near, and ω＝CH2Absorption of (2) is located at 892cm-1Near, free VOF1And VOF2The molecular structure of the compound contains long alkyl chain in (CH)2)nIn the structure of CH2Has an in-plane rocking vibration absorption peak at 738cm-1Nearby;
VOF of the present embodiment1Is/are as follows1H nuclear magnetic spectrum:1H NMR(500MHz,CDCl3):δ(ppm)7.68-7.63(2H,m),7.40-7.28(5H,m),6.81(1H,m),5.82(1H,d,J＝8.8Hz),5.27(1H,d,J＝5.4Hz),1.95(4H,t,J＝6.0Hz),1.26-1.04(20H,m),0.81(6H,t,J＝7.1Hz),0.62(4H,m).
VOF of the present embodiment1Is/are as follows13C nuclear magnetic spectrum:13C NMR(100MHz,CDCl3):δ(ppm)151.1,151.0,141.1,140.8,137.5,136.5,129.1,128.2,127.0,126.7,125.2,122.9,120.5,119.7,112.9,55.0,40.4,31.8,30.0,29.3,23.7,22.6,14.1.MS(ESI+,CH3CN):m/z 418.27(M+H)+.
EXAMPLE 2 vinyl-9, 9-Dioctylfluorene VOF1The yield of (a) was 73%.
Example 2: the structural formula of the transition metal ion fluorescence chemical sensor based on terpyridine is shown in the specification
the structural formula of the conjugated alkene monomer taking 9, 9-dialkyl fluorene as a structural unit is shown in the specification
Is named as 7-vinyl-9, 9,9',9' -dioctyl- [2,2']Bifluorene, noted as Compound VOF2；
The synthetic route of the transition metal ion fluorescence chemical sensor based on terpyridine is
The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor comprises the following specific steps:
adding conjugated olefin monomer with 9, 9-dialkyl fluorene as structural unit, 4- (4'-2,2':6', 2' -terpyridine) styrene, acrylic acid and azobisisobutyronitrile into 1, 4-dioxane, stirring and reacting at 80 deg.C for 8h, and settling in dichloromethane to obtain random copolymer (PATF)2-1) transition metal ion fluorescence chemical sensors based on terpyridine; wherein the mol ratio of the conjugated olefin monomer taking 9, 9-dialkyl fluorene as a structural unit, 4- (4'-2,2':6', 2' -terpyridine) styrene and acrylic acid is 0.5:5.0: 94.5; the adding amount of the azodiisobutyronitrile is 0.5-1% of the mass of the monomer;
random copolymer (PATF)2The IR spectrum of-1) is shown in FIG. 2: 3130cm-1Nearby absorption is υOH，2930cm-1Nearby absorption is υCH，1716cm-1Is upsilonC＝O，1453cm-1Near absorption is δCH，1530cm-1Nearby absorption is upsilon on benzene ringC＝CV on pyridine heterocycleC＝NAbsorption was at 1595cm-1Nearby;
random copolymer PATF2-1 molecular weight 2.25X 105g/mol；
The synthetic route of the conjugated alkene monomer taking 9, 9-dialkyl fluorene as a structural unit is as follows:
the synthesis of conjugated olefin monomer with 9, 9-dialkyl fluorene as structural unit includes the following steps:
(1) synthesis of 2-bromofluorene (Compound 2): under the conditions of light shielding, nitrogen atmosphere and 0 ℃ of temperature, dissolving bromine (7.67mL, 0.15mol) in anhydrous trichloromethane solution (50mL) to obtain bromine/trichloromethane mixed solution, dropwise adding the bromine/trichloromethane mixed solution into fluorene/ferric chloride/trichloromethane mixed solution, stirring and reacting for 3 hours, wherein 0.65g of ferric chloride, 25.00g of fluorene (0.15 mol) and CHCl are contained in the fluorene/ferric chloride/trichloromethane mixed solution3300mL, the reaction system is subjected to NaHSO3The aqueous solution was washed to light yellow with Dichloromethane (DCM), filtered and spun dry, and recrystallized from DCM-methanol to give 33.83g of a light yellow crystalline solid (92%); fluorene is denoted as compound 1;
the nuclear magnetic resonance hydrogen spectrum of the light yellow crystalline solid is
1H NMR(500MHz,CDCl3):δ(ppm)7.76(1H,d,J＝7.5Hz),7.68(1H,s),7.65(2H,d,J＝7.5Hz),7.54(2H,d,J＝7.4Hz),7.51(2H,d,J＝8Hz),7.38(2H,d,J＝7.4Hz),7.32(2H,d,J＝7.3Hz),3.89(2H,s).
Therefore, the light yellow crystalline solid is 2-bromofluorene;
(2) synthesis of 2-bromo-9, 9-dioctylfluorene (Compound 3): under the conditions of light protection and nitrogen atmosphere, adding 1-bromooctane and tetrabutylammonium bromide into a 2-bromofluorene/toluene mixed solution, stirring and reacting for 20 hours at the temperature of 65 ℃, neutralizing with dilute hydrochloric acid and extracting with DCM sequentially, drying, filtering, distilling under reduced pressure to remove redundant toluene and 1-bromooctane, and purifying by column chromatography (the mobile phase is petroleum ether) to obtain 24.00g of oily product (87%); wherein the mass of the 2-bromofluorene is 14.77g, namely 0.06mol, the toluene solution is 100mL, the tetrabutylammonium bromide is 2.00g, and the 1-bromooctane is 26 mL;
the NMR spectrum of the oily product is
1H NMR(500MHz,CDCl3):δ(ppm)7.71(1H,d,J＝7.3Hz),7.68(1H,s),7.56(1H,d,J＝8.1Hz),7.43(2H,t,J＝8.4Hz),7.36(2H,m),1.97(4H,t,J＝7.2Hz),1.19(24H,m),0.85(6H,t,J＝7.8Hz).
So the oily product is 2-bromo-9, 9-dioctylfluorene;
(3) synthesis of 2-bromo-7-acetyl-9, 9-dioctylfluorene (Compound 4): dissolving 2-bromo-9, 9-dioctylfluorene (3.07g, 6.60mmol) in DCM solution to obtain 2-bromo-7-acetyl-9, 9-dioctylfluorene/DCM mixed solution, adding acetyl chloride (0.70mL, 9.90mmol) and anhydrous aluminum trichloride (1.76g, 13.20mmol) to the 2-bromo-7-acetyl-9, 9-dioctylfluorene/DCM mixed solution under nitrogen atmosphere at 0 ℃ and stirring at 0 ℃ for reaction for 3h, quenching the dark blue suspension with ice water to light yellow, washing with water and DCM, filtering and evaporating the solvent, and purifying by column chromatography (mobile phase is petroleum ether and ethyl acetate, petroleum ether: ethyl acetate: 10:1) to obtain light yellow solid (3.03g, 90%);
the nuclear magnetic resonance hydrogen spectrum of the light yellow solid is
1H NMR(500MHz,CDCl3):δ(ppm)7.97(2H,t,J＝5.6Hz),7.73(1H,d,J＝7.8Hz),7.60(1H,d,J＝8.7Hz),7.50(2H,d,J＝6.6Hz),2.66(3H,s),1.96(4H,m),1.26-1.05(24H,m),0.81(6H,t,J＝7.2Hz).
Therefore, the light yellow solid is 2-bromo-7-acetyl-9, 9-dioctyl fluorene;
(4) synthesis of 2-bromo-7-ethanolyl-9, 9-dioctylfluorene (Compound 5): under the conditions of nitrogen atmosphere and 0 ℃ temperature, adding sodium borohydride (0.22g, 5.70mmol) into a 2-bromo-7-acetyl-9, 9-dioctyl fluorene/absolute ethyl alcohol mixed solution, uniformly mixing, heating to 20 ℃, stirring for reaction for 1.0h, removing absolute ethyl alcohol in a system, extracting with DCM, and recrystallizing to obtain white crystals (1.23g, 86%); wherein the mass of the 2-bromo-7-acetyl-9, 9-dioctyl fluorene is 1.45g, namely 2.80mmol, and the absolute ethyl alcohol is 80 mL;
the nuclear magnetic resonance hydrogen spectrum of the white crystal is
1H NMR(500MHz,CDCl3):δ(ppm)7.63(1H,d,J＝8.2Hz),7.54(1H,d,J＝8.2Hz),7.44(2H,s),7.33(2H,m),4.99(1H,m),1.93(4H,m),1.72(1H,m),1.57-1.53(4H,m),1.22-1.04(20H,m),0.82(6H,t,J＝8.7Hz).
So that the white crystal is 2-bromo-7-ethanol-9, 9-dioctyl fluorene;
(5) synthesis of 2-bromo-7-vinyl-9, 9-dioctylfluorene (Compound 6): dissolving 2-bromo-7-ethanol-based-9, 9-dioctyl fluorene (1.024g, 2.00mmol) in toluene (25mL) to obtain a 2-bromo-7-ethanol-based-9, 9-dioctyl fluorene/toluene mixed solution, heating the 2-bromo-7-ethanol-based-9, 9-dioctyl fluorene/toluene mixed solution to boiling reflux, continuously evaporating toluene for 5min at a distillation head, adding a catalyst of toluenesulfonic acid (0.035g, 0.20mmol) and stirring for reflux reaction for 10min, quenching a reaction system by using ice water, washing the reaction system by using saline water and DCM, drying, filtering and spin-drying the solvent, and purifying by column chromatography (the mobile phase is petroleum ether) to obtain a transparent oily product (0.90g, 92%);
the NMR spectrum of the transparent oily product is
1H NMR(500MHz,CDCl3):δ(ppm)7.64(1H,d,J＝7.9Hz),7.57(1H,d,J＝8.6Hz),7.49(2H,m),7.44(1H,d,J＝7.8Hz),7.38(1H,s),6.84(1H,m),5.86(1H,d,J＝8.8Hz),5.32(1H,d,J＝5.4Hz),1.98(4H,t,J＝9.7Hz),1.30-1.09(24H,m),0.85(6H,t,J＝7.2Hz).
So that the transparent oily product is 2-bromo-7-vinyl-9, 9-dioctyl fluorene;
(6) synthesis of 2-p-pinacol boronate-9, 9-dioctylfluorene (Compound 7): dissolving 2-bromo-9, 9-dioctylfluorene (14.05g, 0.03mol) in dimethyl sulfoxide (DMSO) to obtain a 2-bromo-9, 9-dialkylfluorene/dimethyl sulfoxide mixed solution, adding pinacol diborate (15.23g, 0.06mol) and potassium ethoxide (8.83g, 0.09mol) into the 2-bromo-9, 9-dialkylfluorene/dimethyl sulfoxide mixed solution, and adding Pd (dppf) Cl under nitrogen atmosphere2(0.53g, 0.73mmol) are mixed uniformly, the temperature is raised to 80 ℃, the mixture is stirred and reacted for 20 hours under the condition of keeping out of the light, after DCM extraction, drying, filtering and spin-drying of the solvent, and the product is purified by column chromatography (the mobile phase is petroleum ether and ethyl acetate, and the petroleum ether is 10:1) to obtain a transparent oily product (12.05g, 78%);
the NMR spectrum of the transparent oily product is
1H NMR(500MHz,CDCl3):δ(ppm)7.79(1H,d,J＝7.8Hz),7.73-7.68(3H,m),7.32-7.31(3H,m),1.96(4H,t,J＝5.6Hz),1.39(12H,s),1.23-1.01(24H,m),0.81(6H,t,J＝7.1Hz).
So that the transparent oily product is 2-p-pinacol borate-9, 9-dioctyl fluorene;
(7) 7-vinyl-9, 9,9',9' -dioctyl- [2,2']Bifluorene (VOF)2) Synthesizing: adding 2-bromo-7-vinyl-9, 9-dioctylfluorene (1.17g, 2.40mmol) and 2-p-pinacol boronate-9, 9-dioctylfluorene (1.35g, 2.60mmol) into a THF (100mL) solution to obtain a 2-bromo-7-vinyl-9, 9-dioctylfluorene/2-p-pinacol boronate-9, 9-dioctylfluorene/THF mixed solution, adding an aqueous sodium carbonate solution (1.6M, 35mL) into a 2-bromo-7-vinyl-9, 9-dioctylfluorene/2-p-pinacol boronate-9, 9-dioctylfluorene/THF mixed solution, and rapidly adding a catalyst Pd (dppf) Cl under a nitrogen atmosphere2(0.26g, 0.36mmol) and refluxing reaction for 20h under the conditions of keeping out of the sun and at the temperature of 75 ℃, extracting by DCM, drying, filtering, evaporating the solvent, and purifying by column chromatography (the mobile phase is petroleum ether) to obtain the target product;
nuclear magnetic resonance hydrogen spectrum of target product:
1H NMR(500MHz,CDCl3):δ(ppm)7.78-7.73(3H,m),7.67(1H,d,J＝7.7Hz),7.64(2H,d,J＝7.9Hz),7.60(2H,s),7.43(1H,d,J＝7.9Hz),7.39(1H,s),7.37-7.30(3H,m),6.86-6.80(1H,m),5.84(1H,d,J＝8.8Hz),5.28(1H,d,J＝5.4Hz),2.03(8H,t,J＝7.7Hz),1.25-1.08(48H,m),0.80(12H,t,J＝7.2Hz).
nuclear magnetic resonance carbon spectrum of target product:
13C NMR(100MHz,CDCl3):δ(ppm)151.8,151.5,151.4,151.0,140.8,140.5,140.4,140.3,140.0,137.5,136.5,129.0,128.8,128.2,127.2,127.0,126.8,126.1,126.0,125.3,123.0,121.5,121.4,120.6,119.9,119.7,113.0,55.17,55.14,31.8,30.0,29.2,23.8,22.6,14.0.MS(ESI+,CH3CN):m/z 827.69(M+Na)+.
infrared pattern of target productAs can be seen from the spectrum in FIG. 1, 3060cm-1 is the C-H stretching vibration peak on the unsaturated carbon, 2920cm-1、2854cm-1Is a saturated C-H stretching vibration peak, 1623cm-1Is C ═ C stretching vibration peak, 1457cm-1892-738 cm as C-H deformation vibration peak-1Is the C-H deformation vibration peak of aromatic ring;
so that the target product is 7-vinyl-9, 9,9',9' -dioctyl- [2,2']Bifluorene (VOF)2)。
Example 3: the structural formula of the terpyridine-based transition metal ion fluorescence chemical sensor is shown in the specification
the preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor comprises the following specific steps:
adding conjugated olefin monomer with 9, 9-dialkyl fluorene as structural unit, 4- (4'-2,2':6', 2' -terpyridine) styrene, acrylic acid and azobisisobutyronitrile into 1, 4-dioxane, stirring and reacting at 80 deg.C for 8h, and settling in dichloromethane to obtain random copolymer (PATF)2-1) transition metal ion fluorescence chemical sensors based on terpyridine; wherein the mol ratio of the conjugated olefin monomer taking 9, 9-dialkyl fluorene as a structural unit, 4- (4'-2,2':6', 2' -terpyridine) styrene and acrylic acid is 0.5:1.5: 98.0; the addition amount of the azodiisobutyronitrile is 0.8 percent of the mass of the monomer;
random copolymer PATF2-2 molecular weight 2.56X 105g/mol；
In this example, the conjugated ethylenic monomers having a 9, 9-dialkylfluorene as a structural unit were 7-vinyl-9, 9,9',9' -dioctyl- [2,2']Bifluorene (VOF)2)。
Comparative example 1: adding 4- (4'-2,2':6', 2' -terpyridine) styrene, acrylic acid and azobisisobutyronitrile to 1, 4-dioxane, reactingStirring and reacting for 8h at the temperature of 80 ℃, and settling in dichloromethane to obtain a random copolymer which is marked as PAT; wherein the mol ratio of 4- (4'-2,2':6', 2' -terpyridine) styrene to acrylic acid is 5.0: 95.0; the addition amount of the azodiisobutyronitrile is 0.8 percent of the mass of the monomer; the molecular weight of the random copolymer PAT was 3.78X 105g/mol。
Comparative example 2: conjugated olefin monomer (VOF) with 9, 9-dialkyl fluorene as structural unit2) Adding acrylic acid and azobisisobutyronitrile into 1, 4-dioxane, stirring at 80 deg.C for 8 hr, and settling in dichloromethane to obtain random copolymer, named as PAF2(ii) a Wherein, the mol ratio of the conjugated alkene monomer taking 9, 9-dialkyl fluorene as a structural unit to the acrylic acid is 0.5: 99.5; the addition amount of the azodiisobutyronitrile is 0.8 percent of the mass of the monomer; random copolymer PAF2Molecular weight of 3.12X 105g/mol。
Example 4: random copolymer PATF of example 11Example 2 random copolymer PATF2Random copolymer PAT of comparative example 1 and random copolymer PAF of comparative example 22The photophysical property characterization of (a);
the polymer skeleton structure mainly comprises hydrophilic monomer acrylic acid, so that the polymer skeleton structure has good solubility in a water system, and the copolymer is prepared into a solution with the concentration of 2.5g/L to characterize the ultraviolet-visible absorption spectrum and the fluorescence emission spectrum of the copolymer;
the ultraviolet-visible absorption spectrum of the polymer is shown in FIG. 4, the polymer PAT shows a strong absorption peak near 284nm, and the polymer PAF2The main absorption peak appears only at 335nm, the benzene ring in the TPY is used as a weak electron-donating group caused by pi-pi transition of a strong conjugated unit TPY contained in the polymer, and the polymer solution has a weak absorption shoulder peak at 335nm due to an intramolecular charge transfer process (ICT) of bipyridyl heterocycle with electroabsorptivity; PATF1-1 and PATF2Absorption spectrum-1 it can be seen that the intensity of the weak absorption peak at 335nm, which occurs after addition of the VOF moiety to the polymer backbone, increases with increasing degree of conjugation of the VOF moiety, due to the introduction of VOF groups enhancing the Intramolecular Charge Transfer (ICT), and in aqueous polymer solutionsThe hydrophobic interaction of the VOF groups makes them close to each other, the stacking action aggravates the absorption phenomenon by affecting the distribution of the electron cloud;
the fluorescence emission spectrum is shown in FIG. 5, the emission peak of the polymer PAT is located near 365nm, and the peak shape is broad and slow, and is caused by the intramolecular charge transfer process (ICT) of the TPY part; polymer PATF1-1 and PATF2-1 fluorescence emission peaks around 378nm and 400nm, respectively, red-shifted by 13nm and 35nm with respect to PAT due to the addition of VOF increasing the conjugation of the polymer and the red-shifted degree increases with increasing conjugation, and the polymer PATF1-1 and PATF2The peak shape of the fluorescence emission peak of-1 becomes wider and slower, and the introduction of the conjugated group enhances the ICT process; while the polymer PAF does not contain TPY groups2The emission peak of (2) is located in the vicinity of 400nm, and the peak type is relatively sharp.
Example 5: random copolymer PATF of example 11Example 2 random copolymer PATF2Sensing and detecting transition metal ions;
preparation concentration 2.5 g. L-1Of the polymer PATF1And PATF2-1 aqueous solutions, respectively, in the polymer PATF1And PATF2-1 aqueous solution with a concentration of 1X 10-3Different type of metal ion (Fe) of M2+，Cu2+，Co2+，Sn2+，Ni2+，Zn2+，Cd2+)；
Polymer PATF1Color and fluorescence change pattern with different metal ions (see FIG. 6), Polymer PATF 21 color and fluorescence change diagram with different metal ions (see FIG. 7), two polymer solutions having different color responses to different metal ions, adding Fe2+Then all the polymer solution is changed into violet from colorless, and Co is added into the polymer solution2+Then turns brown, Cu is added2+Then becomes light blue;
addition of Zn to Polymer solutions2+And Cd2+Fluorescence enhancement phenomena can be observed, in which Zn2+The fluorescence enhancement phenomenon caused by the method is more obvious, and the fluorescence color is more biased to white(ii) a And Fe2+，Co2+，Cu2+，Sn2+And Ni2+The addition of plasma metal ions allows to observe the phenomenon of fluorescence quenching, in which Fe2+The addition of (A) results in the most intense phenomenon of fluorescence quenching, whereas Sn2 +The resulting quenching of fluorescence is not as severe as the rest of the metal ions;
concentration of 2.5 g--1PATF (A)1Solutions and PATF2-1 adding different metal ions (Fe) into the solution respectively2+，Cu2+，Co2+，Sn2+，Ni2+，Zn2+，Cd2+) Measuring the ultraviolet-visible absorption spectrum of the sample by taking pure water as a blank reference sample;
polymer PATF2-1 uv-vis absorption spectra of the action with different metal ions see fig. 8, the solution of the copolymer ligand without complexing with metal ions shows a strong absorption peak around 284nm due to the pi-pi transition of the strongly conjugated units in the polymer, including VOF and TPY; after different types of metal ions are added, slight red shift appears near 325nm, a secondary absorption peak appears at the same time, the coordination relationship between the metal ions and ligands shortens the distance of a conjugated part, so that the conjugation effect of the whole metal copolymer is enhanced, the delocalization of pi electrons can reduce the gap between an emission state and a ground state, the intensity of the secondary absorption peak at 325nm is obviously enhanced along with the addition of the metal ions, and the electron withdrawing property of a bipyridine heterocyclic ring part is increased after the metal ions are coordinated with TPY, so the intramolecular charge transfer process (ICT) between the bipyridine heterocyclic ring part and a benzene ring with weak power supply property is enhanced, so that the intensity of the secondary absorption peak is increased; addition of Fe to the polymer solution2+A new characteristic absorption peak at 570nm later, due to the metal-ligand charge transfer (MLCT) process;
polymer PATF2-1 fluorescence emission spectra of interaction with different metal ions are shown in figure 9; zn in contrast to other ions2+And Cd2+The ICT is strengthened by adding metal ions, so that the fluorescence emission peak of the polymer solution is wide and slow, wherein Zn is used2+Peak type of (1)Representatively, the coverage of the emission spectrum can explain that the polymer solution is observed by naked eyes when Zn is added2+The back color is changed from blue to white green; zn2+With Cd2+In the same group of the periodic Table of the elements and thus have similar spectral properties, but Zn2+Interactions with ligand solutions are distinguished from Cd2+A unique broad slow peak-type variation of; the interaction of other metal ions and a ligand solution can cause fluorescence quenching, and the coordination relationship between the metal ions and the ligand can change the configuration of an electron cloud, so that the fluorescence emission is influenced and even completely quenched;
polymer PATF1And PATF2-1 action of solution with metal ions photophysical data are shown in table 2;
TABLE 2 Polymer PATF1And PATF2-1 action of solution with metal ions photophysical data
Fluorescence quantum yield Φ as quinine sulfate (0.1M H)2SO4) Solution as control, PATF 21 as an example, ligand-Zn2+With ligand-Cd2+The fluorescence quantum yield of the solution is 0.318 and 0.236, the fluorescence enhancement effect is very obvious, and Fe2+、Cu2+、Co2 +、Sn2+And Ni2+The fluorescence quantum yields after interaction with the ligand solution were 0.017, 0.016, 0.055, 0.027, and 0.040, respectively, showing strong fluorescence quenching;
polymer PATF2-1 and Fe2+The quantitative fluorescence quenching response of (1) is shown in FIG. 10, low concentration of metal ion Fe2+Namely, the fluorescence quenching can be triggered, and the quenching degree and the metal ion Fe2+The concentration is in positive correlation, and the metal ion Fe with high concentration2+Can completely quench the fluorescence emission of the ligand solution;
polymer PATF2-1 with Zn2+FIG. 11 shows the quantitative fluorescence enhancement response with Zn2+The concentration is increased to cause polymerizationCompound PATF2-1 ligand solution producing fluorescence enhancement effect, copolymer PATF2Emission peak of-1 in Zn addition2+After all, a clear red shift is shown and the peak shape is broadened, i.e. the polymer PATF2-1 the emission spectrum of the solution is red-shifted from 377nm to about 475nm, which is caused by the increase of coplanarity of the fluorescence emitting group due to the enhancement of intramolecular conjugation, and the energy gap between the excited state and the ground state is also reduced, resulting in a relatively wide emission wavelength range, the degree of the fluorescence enhancement and the red shift of the spectrum and Zn2+And strong concentration dependence exists, and support is provided for quantitative detection of metal ions.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (5)
1. A transition metal ion fluorescence chemical sensor based on terpyridine is characterized in that: the structural formula is as follows:
wherein Ar is a hydrophilic monomer; n is the number of repeating units, and n is 0-6; r is an alkyl chain, and the number of C atoms is 6-30; x, y and z are relative proportions of the three monomers, wherein x + y + z is 100%, x is 0.2-10%, and z is 0.2-10%.
2. The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor in claim 1 is characterized by comprising the following specific steps:
adding a conjugated alkene monomer taking 9, 9-dialkyl fluorene as a structural unit, 4- (4'-2,2':6', 2' -terpyridine) styrene, a hydrophilic monomer and azobisisobutyronitrile into 1, 4-dioxane, stirring and reacting for 6-10 hours at the temperature of 75-85 ℃, and placing in dichloromethane for settling to obtain a random copolymer, namely the terpyridine-based transition metal ion fluorescence chemical sensor;
wherein the hydrophilic monomer is acrylic acid, methacrylic acid, acrylamide or methacrylamide;
the structural formula of the conjugated alkene monomer taking 9, 9-dialkyl fluorene as a structural unit is shown in the specification
Wherein n is the number of repeating units, and n is 0-6;
r is an alkyl chain, and the number of C atoms is 6-30.
3. The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor according to claim 2, wherein the preparation method comprises the following steps: when n is 1-6, the preparation method of the conjugated alkene monomer with 9, 9-dialkyl fluorene as the structural unit comprises
(1) Synthesis of 2-bromofluorene: dropwise adding the bromine/trichloromethane mixed solution into the fluorene/catalyst/trichloromethane mixed solution at the temperature of-5-10 ℃ in a dark nitrogen atmosphere, stirring for reacting for 3-5 h, washing, filtering, drying, and recrystallizing in DCM-methanol to obtain 2-bromofluorene;
(2) synthesis of 2-bromo-9, 9-dialkylfluorene: under the conditions of light protection and nitrogen atmosphere, adding alkyl bromide and tetrabutylammonium bromide into a 2-bromofluorene/toluene mixed solution, stirring and reacting for 20-30 h at the temperature of 65-80 ℃, neutralizing with dilute hydrochloric acid in sequence, extracting with DCM, and purifying by column chromatography to obtain 2-bromo-9, 9-dialkylfluorene;
(3) synthesis of 2-bromo-7-acetyl-9, 9-dialkylfluorene: adding acetyl chloride and a catalyst into a 2-bromo-9, 9-dialkylfluorene/dichloromethane or a 2-bromo-9, 9-dialkylfluorene/chloroform mixed solution in a nitrogen atmosphere, stirring and reacting at the temperature of-5-10 ℃ for 3-5 h, washing, filtering, drying, and purifying by column chromatography to obtain 2-bromo-7-acetyl-9, 9-dialkylfluorene;
(4) synthesis of 2-bromo-7- (1-hydroxy) ethyl-9, 9-dialkylfluorene: adding strong base into the mixed solution of 2-bromo-7-acetyl-9, 9-dialkyl fluorene/absolute ethyl alcohol under the condition of nitrogen atmosphere and temperature of-5-10 ℃, uniformly mixing, heating to 20-30 ℃, stirring for reaction for 0.5-1.5 h, and recrystallizing to obtain 2-bromo-7- (1-hydroxy) ethyl-9, 9-dialkyl fluorene;
(5) synthesis of 2-bromo-7-vinyl-9, 9-dialkylfluorene: heating the 2-bromo-7- (1-hydroxy) ethyl-9, 9-dialkyl fluorene/toluene mixed solution to reflux, adding a catalyst, stirring, refluxing, reacting for 10-30 min, and purifying by column chromatography to obtain 2-bromo-7-vinyl-9, 9-dialkyl fluorene;
(6) synthesizing conjugated alkene monomers with 9, 9-dialkyl fluorene as a structural unit: adding an alkaline solution into a 2-bromo-7-vinyl-9, 9-dialkyl fluorene/monoboronic ester group substituted alkyl fluorene oligomer derivative/tetrahydrofuran mixed solution, adding a catalyst in a nitrogen atmosphere, reacting for 18-24 hours at a temperature of 60-85 ℃ in a dark place, and purifying by column chromatography to obtain a conjugated alkene monomer with 9, 9-dialkyl fluorene as a structural unit; wherein the structural formula of the oligomer derivative of the alkyl fluorene substituted by the single borate group is shown in the specification
Wherein n is the number of repeating units, and n is 0-5;
r is an alkyl chain, and the number of C atoms is 6-30.
4. The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor, according to claim 3, is characterized in that: the preparation method of the oligomer derivative of the alkyl fluorene substituted by the single boric acid ester group in the step (6) comprises the following steps
1) Synthesis of 2-pinacol boronate-9, 9-dialkylfluorene: adding pinacol diboron and potassium ethoxide into a 2-bromo-9, 9-dialkyl fluorene/dimethyl sulfoxide mixed solution, and adding Pd (dppf) Cl in a nitrogen atmosphere2Uniformly mixing, heating to 80-95 ℃, stirring and reacting for 20-36 h under the condition of keeping out of the sun, and purifying by column chromatography to obtain 2-pinacol borate-9, 9-dialkyl fluorene, namely the monoboronate substituted by n of 0Oligomeric derivatives of alkylfluorenes;
2) synthesis of 2-pinacol boronate- (9, 9-dialkylfluorene) n-mer: adding pinacol diboron and potassium ethoxide into a 2-bromo-fluorene (n-1) polymer/dimethyl sulfoxide mixed solution, and adding Pd (dppf) Cl under a nitrogen atmosphere2Uniformly mixing, heating to 80-95 ℃, stirring and reacting for 20-36 h under the condition of keeping out of the sun, and purifying by column chromatography to obtain the 2-pinacol borate- (9, 9-dialkyl fluorene) n polymer.
5. The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor according to claim 2, wherein the preparation method comprises the following steps: when n is 0, the preparation method of the conjugated alkene monomer with 9, 9-dialkyl fluorene as the structural unit comprises
(1) Synthesis of 9, 9-dialkylfluorene: dropwise adding n-butyllithium into a fluorene/THF system at the temperature of-78 to-50 ℃ in a nitrogen atmosphere to obtain a mixture A, dropwise adding a 1-bromoalkane/THF solution into the mixture A, reacting at room temperature for 20-36 hours under nitrogen, extracting with ethyl acetate, and purifying by column chromatography to obtain 9, 9-dialkyl fluorene;
(2) synthesis of 2-acetyl-9, 9-dialkylfluorene: adding acetyl chloride and a catalyst into a 9, 9-dialkyl fluorene/dichloromethane or a 9, 9-dialkyl fluorene/trichloromethane mixed solution in a nitrogen atmosphere, stirring and reacting for 3-5 h at the temperature of-5-10 ℃, washing, filtering, drying, and purifying by column chromatography to obtain 2-acetyl-9, 9-dialkyl fluorene;
(3) synthesis of 2-ethanol-9, 9-dialkyl fluorene: adding strong base into the mixed solution of 2-acetyl-9, 9-dialkyl fluorene and absolute ethyl alcohol under the condition of nitrogen atmosphere and temperature of-5-10 ℃, uniformly mixing, heating to 20-30 ℃, stirring for reaction for 0.5-1.5 h, and recrystallizing to obtain 2-ethanol-based-9, 9-dialkyl fluorene;
(4) synthesis of 2-vinyl-9, 9-dialkylfluorene: heating the 2-ethanol-based-9, 9-dialkyl fluorene/toluene mixed solution to reflux, adding a catalyst, stirring, refluxing and reacting for 10-30 min, and purifying by column chromatography to obtain 2-vinyl-9, 9-dialkyl fluorene.
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