CN105802610B - Fluorine ion fluorescent probe and application - Google Patents
Fluorine ion fluorescent probe and application Download PDFInfo
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- CN105802610B CN105802610B CN201610230778.0A CN201610230778A CN105802610B CN 105802610 B CN105802610 B CN 105802610B CN 201610230778 A CN201610230778 A CN 201610230778A CN 105802610 B CN105802610 B CN 105802610B
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 112
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 38
- 239000000523 sample Substances 0.000 claims abstract description 173
- 239000000017 hydrogel Substances 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000001514 detection method Methods 0.000 claims abstract description 39
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 71
- 239000000243 solution Substances 0.000 claims description 71
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 49
- 229920001983 poloxamer Polymers 0.000 claims description 43
- 239000006185 dispersion Substances 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000002189 fluorescence spectrum Methods 0.000 claims description 8
- 229960000502 poloxamer Drugs 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- -1 fluorine ions Chemical class 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000003651 drinking water Substances 0.000 abstract description 3
- 235000020188 drinking water Nutrition 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003384 imaging method Methods 0.000 abstract description 2
- 238000006757 chemical reactions by type Methods 0.000 abstract 1
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- 238000003786 synthesis reaction Methods 0.000 description 33
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- 239000012071 phase Substances 0.000 description 26
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- 101000892862 Homo sapiens Glutamate carboxypeptidase 2 Proteins 0.000 description 20
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- 239000011775 sodium fluoride Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 150000002460 imidazoles Chemical class 0.000 description 10
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- NGDMLQSGYUCLDC-UHFFFAOYSA-N pyren-1-ylmethanol Chemical compound C1=C2C(CO)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 NGDMLQSGYUCLDC-UHFFFAOYSA-N 0.000 description 6
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 5
- 101000864780 Homo sapiens Pulmonary surfactant-associated protein A1 Proteins 0.000 description 5
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- GSENNYNYEKCQGA-UHFFFAOYSA-N dichloro-di(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(Cl)C(C)C GSENNYNYEKCQGA-UHFFFAOYSA-N 0.000 description 5
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
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- INDIALLCZKIHFF-UHFFFAOYSA-N 4-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=C(O)C=C1 INDIALLCZKIHFF-UHFFFAOYSA-N 0.000 description 1
- WRHGUECAOGOUFG-UHFFFAOYSA-N 4-(dipropylamino)phenol Chemical compound CCCN(CCC)C1=CC=C(O)C=C1 WRHGUECAOGOUFG-UHFFFAOYSA-N 0.000 description 1
- UJWHLERCFNIFNJ-UHFFFAOYSA-N 4-(ethylamino)phenol Chemical compound CCNC1=CC=C(O)C=C1 UJWHLERCFNIFNJ-UHFFFAOYSA-N 0.000 description 1
- STVPBVIJXUKAMI-UHFFFAOYSA-N 4-(propan-2-ylamino)phenol Chemical compound CC(C)NC1=CC=C(O)C=C1 STVPBVIJXUKAMI-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- GWMQUIVBSNVXKT-UHFFFAOYSA-N 4-ethyl-2-(propan-2-ylamino)phenol Chemical compound C(C)C1=CC(=C(C=C1)O)NC(C)C GWMQUIVBSNVXKT-UHFFFAOYSA-N 0.000 description 1
- KJLLGBXKDDRVCG-UHFFFAOYSA-N 4-ethyl-2-(propylamino)phenol Chemical compound CCCNC1=C(C=CC(=C1)CC)O KJLLGBXKDDRVCG-UHFFFAOYSA-N 0.000 description 1
- JBJLYPCVTAKOQQ-UHFFFAOYSA-N 4-methyl-2-(propan-2-ylamino)phenol Chemical compound C(C)(C)NC1=CC(=CC=C1O)C JBJLYPCVTAKOQQ-UHFFFAOYSA-N 0.000 description 1
- SYXQPYKKIILEIR-UHFFFAOYSA-N 4-methyl-2-(propylamino)phenol Chemical compound CCCNC1=CC(C)=CC=C1O SYXQPYKKIILEIR-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical class CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- ODOGYOCRSXUTCQ-UHFFFAOYSA-N C(C)(C)N(CCC1=CC=C(C=C1)O)C(C)C Chemical compound C(C)(C)N(CCC1=CC=C(C=C1)O)C(C)C ODOGYOCRSXUTCQ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
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- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical group CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
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- 235000011837 pasties Nutrition 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 108010048734 sclerotin Proteins 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
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- 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
-
- 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
-
- 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
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a fluorine ion fluorescent probe and application thereof, wherein the fluorine ion fluorescent probe has the following structural formula general formula:in the formula, R1、R2Each independently selected from hydrogen, methyl, ethyl, propyl or isopropyl. The fluorine ion fluorescent probe provided by the invention has high selectivity on fluorine ions, is based on an electron transfer mechanism for identifying the fluorine ions, is a reaction type probe, and has good selectivity and sensitivity. The detection limit of the method for the fluoride ion is low, and the method completely meets the detection requirement of the maximum fluoride ion concentration in safe drinking water specified by the United states Environmental Protection Agency (EPA). Moreover, the probe is loaded into the nano hydrogel, so that the nano hydrogel is better dispersed in a water phase, is convenient to detect and has potential application in biological aspects such as cell imaging and the like.
Description
Technical field
The present invention relates to fluorescence probe field.Visited more particularly, to a kind of fluorescence that fluorine ion is detected in water environment
Pin.
Background technology
Fluorine ion is minimum anion, there is special chemical property.In terms of health, suitable fluorine ion pair
There is good effect in prevention carious tooth and clinical treatment osteoporosis, therefore, fluoride salt is commonly added to drinking water and toothpaste
In, but the fluoride of excess intake can cause tooth or sclerotin " fluorine poisoning " again;In terms of environment, fluorine ion is someization
Learn the important Testing index of weapon (such as sarin) residue.Therefore, it is qualitative in various fields such as environmental protection, life sciences
Quantitatively detection fluorine ion suffers from important meaning.
Due to the limitation of various complicated test environment and detection methods, the quantitative detection of fluorine ion is often in the presence of very big
Interference.Traditional potentiometry due to poor sensitivity, easily cause error and gradually by later fluoride ion selective electrode and
The methods of ion chromatography, replaces, but due to these new detection methods there are equipment it is expensive, it is complicated and cannot at any time with
The defects of ground is detected.In contrast, the fluorine ion fluorescence probe based on the design of chemical sensor principle then has convenient, fast
The advantages that victory, high sensitivity.
The signal reports group of fluorescence probe is usually organic fluorescent dye, and there are the problem of poorly water-soluble.In order to solve
This problem, the present invention load to fluorescence probe in nano-hydrogel, it has been distributed in water phase.Nano-hydrogel is to receive
The hydrogel nanoparticles of meter ruler cun, have the tridimensional network formed by crosslinked macromolecular chain.Tridimensional network makes
Obtain nano-hydrogel probe molecule can be stably wrapped in its nano-space, so as to play compatibilization.The present invention will
The fluorescence probe of design synthesis is loaded in nano-hydrogel, is used successfully to the detection of water phase fluorine ion, and is shown good
Selectivity and sensitivity.
The content of the invention
It is an object of the present invention to provide a kind of fluorine ion fluorescence probe.
It is another object of the present invention to provide a kind of answering for fluorine ion of fluorine ion fluorescence probe in water phase is detected
With.
To reach above-mentioned first purpose, the present invention uses following technical proposals:
A kind of fluorine ion fluorescence probe, has following structural formula general formula:
In formula, R1、R2It is independently selected from hydrogen, methyl, ethyl, propyl group or isopropyl.
Fluorine ion fluorescence probe with structure above general formula is prepared by the following method:
A) bibliography (Chem.Eur.J., 2010,16,9154-9163 or Chem.Mater., 2002,14,2369-
2377) synthesis material compound 1- pyrene methanol, synthetic route are as follows:
Pyrene, N- methyl formyl anilines, phosphorus oxychloride are dissolved in o-dichlorohenzene, 1h is reacted at 100 DEG C, it is purified, obtain
To 1- pyrene formaldehydes.
The 1- pyrene formaldehydes of synthesis are dissolved in tetrahydrofuran again, sodium borohydride reduction is added, obtains 1- pyrene methanol.
B) fluorine ion fluorescent probe molecule is synthesized, synthetic route is as follows:
Under nitrogen protection, diisopropyl dichlorosilane, imidazoles, the amino-phenol with different substituents are first dissolved in four
In hydrogen furans, reacted at 40 DEG C, after the reaction completely of the amino-phenol with different substituents, add 1- pyrenes methanol and imidazoles,
Then reacted at 40 DEG C.Through column chromatography for separation, fluorine ion fluorescent probe molecule is obtained.
In above-mentioned formula, R1、R2It is independently selected from hydrogen, methyl, ethyl, propyl group or isopropyl.
To reach above-mentioned second purpose, the present invention uses following technical proposals:
The application of fluorine ion of the above-mentioned fluorine ion fluorescence probe in water phase is detected, including following detecting step:
1) fluorine ion fluorescent probe molecule is loaded in nano-hydrogel, obtains Aqueous dispersions system;
2) test limit of various concentrations fluorine ion fluorescent probe molecule is determined;
3) working curve of fluorine ion fluorescent probe molecule detection fluorine ion is drawn by fluorescence spectrum;
4) concentration of fluorine ion in target solution is measured.
Preferably, it is described to load to fluorine ion fluorescent probe molecule in nano-hydrogel in step 1), obtain water phase point
Granular media system concretely comprises the following steps:
1. prepare the tetrahydrofuran solution of fluorine ion fluorescent probe molecule;
2. preparation of nano water-setting glue solution;
3. 1. solution that step is prepared is added in 2. aqueous solution that step is prepared, Aqueous dispersions system is obtained.
Preferably, (propylene oxide is total to the Poloxamer that the nano-hydrogel is activated by carbonyl dimidazoles with ethylene oxide
Polymers) and branched polyethylenimine (PEI) crosslinking obtain.
Further, the Poloxamer is triblock polyether macromolecule, is among it polyethylene glycol block, both ends are
Polyethylene glycol block.
Preferably, the number-average molecular weight M of the PoloxamernFor 4400 or 5800;The branched polyethylenimine molecule
Middle primary amine:Secondary amine:Tertiary amine=1:2:1, number-average molecular weight MnFor 1000,1200 or 1800, the branched polyethylenimine can city
Purchase is sold to obtain.
Preferably, the poloxamer of the carbonyl dimidazoles activation and the mass ratio of polyethyleneimine are 3:1-10:1.
Specifically, bibliography (Gene Therapy, 2000,7,126-138 and MolecularPharmaceutics,
2005,2,449-461), the synthetic route of the nano-hydrogel (Poloxamer-cl-PEI) is as follows:
Wherein, in the building-up process of above-mentioned nano-hydrogel,
When a=10, b=68, the trade name Pluronic L121 (M of Poloxamern=4400), corresponding nanometer water
Gel is denoted as Pluronic L121-cl-PEI;
When a=39, b=69, the trade name Pluronic P123 (M of Poloxamern=5800), corresponding nanometer water
Gel is denoted as Pluronic L123-cl-PEI;
The number-average molecular weight M of side chain PEInFor 1000,1200,1800, corresponding nano-hydrogel is denoted as Poloxamer-
cl-PEI(1K)、Poloxamer-cl-PEI(1.2K)、Poloxamer-cl-PEI(1.8K);
The mass ratio of the Poloxamer and side chain PEI of carbonyl dimidazoles activation are 3:1-10:1, corresponding nano-hydrogel
It is denoted as Poloxamer-cl-PEI (mass ratio), such as Poloxamer-cl-PEI (3:1).
Most of probe molecules are not soluble in water in the prior art, can only detect the fluorine ion in organic solution, it is impossible to be used in
The detection of water phase fluorine ion.The present invention utilizes the compatibilization of nano-hydrogel, and fluorine ion fluorescence probe is loaded to nanometer water
In gel, prevent probe molecule not soluble in water from assembling in water, so that probe molecule not soluble in water is scattered in water phase
To achieve the purpose that to detect fluorine ion in water.
The branched polyethylenimine (PEI) of nano-hydrogel can partly lead to as a kind of cationic polymer in the present invention
Cross electrostatic interaction and be effectively enriched with negatively charged analyte (fluorine ion);Another part Poloxamer be by polyethylene glycol-
Three sections of copolymers of polypropylene glycol-polyethylene glycol composition, can be self-assembled into micella in water, and energy carrying probe molecule is distributed to
In water phase.
Identification of the fluorescence probe provided by the invention to fluorine ion is based on electronics metastasis, and is visited for response type fluorescence
Pin, has good selectivity.The fluorescence probe and fluorine ion action principle are as shown in Figure 1:With silane by 1- pyrenes methanol and band
After the amino-phenol for there are different substituents connects, to be partially quenched since there are the fluorescence of electronic transfer process, 1- pyrene methanol,
Fluorescent weakening;After adding fluorine ion, fluorine ion selectively cutting silicon oxygen bond, has blocked electronic transfer process, 1- pyrene methanol it is glimmering
Light recovers.
Specifically, fluorine ion fluorescence probe is applied to comprising the following steps that for the fluorine ion in detection water phase:
S1:Prepare the tetrahydrofuran solution that fluorine ion fluorescent probe molecule concentration is 0.1-5.0mM;
S2:Compound concentration is the nano-hydrogel aqueous solution of 1.0-3.0g/L;
S3:Take in the solution prepared in the step S2 for the 10mL that the solution prepared in the step S1 of 1-100 μ L is added to, obtain
To fluorine ion fluorescence probe Aqueous dispersions system;
S4:A series of fluorine ion fluorescence probe Aqueous dispersions systems of 3ml are taken, are separately added into 10-30 μ L concentration as 10-2M's
F-、Br-、Cl-、SO4 2-、NO3 -、HSO4 -、AcO-、H2PO4 -Aqueous solution, place 10-60 minutes after, measure respectively at 377nm
Fluorescence intensity, thus verify fluorescence probe to the selectivity of fluorine ion;
S5:A series of Aqueous dispersions system of fluorine ion fluorescence probes of 3mL is taken, is separately added into 10-30 μ L various concentrations
Fluorine ion (0,40,80,120,160,200 μM), after placing 10-60 minutes, measures the fluorescence intensity at 377nm respectively, by
This determines the test limit of each fluorescence probe;
S6:A series of Aqueous dispersions system of fluorine ion fluorescence probes of 3mL is taken, is separately added into 10-30 μ L various concentrations
Fluorine ion (0,0.4,0.8,1.2,1.6,2.0mM), after placing 10-60 minutes, according to fluorescence intensity and the pass of fluorinion concentration
System makes working curve;
S7:The unknown aqueous solution of 0.5-1.5mL is added to 0.5-1.5mL concentration to dissipate for 2-100 μM of fluorescence probe moisture
In system, measure and calculate the fluorescence intensity at 377nm, according to working curve, calculate the dense of fluorine ion in unknown solution
Degree.
As do not illustrated, raw material use herein can be obtained by commercially available purchase.
Beneficial effects of the present invention are as follows:
1st, detection method provided by the invention is completely suitable for water environment.
2nd, high selectivity of the probe molecule provided by the invention to fluorine ion.It is former that detection of the compound to fluorine ion is based on silicon
The idiosyncrasy of son and fluorine atom, is not disturbed be subject to other anion, especially eliminates AcO-And H2PO4-Interference.
3rd, detection method provided by the invention is low to the test limit of fluorine ion, can meet Environmental Protection Agency (EPA) completely
The testing requirements of maximum fluorinion concentration 4ppm (i.e. 211 μM) in defined safe drinking water.
4th, the nano-hydrogel that the present invention uses has good water solubility and biocompatibility, and therefore, the present invention provides
The method loaded to probe in nano-hydrogel so that probe in water phase disperse it is preferable, easy to detect, there is cell
The potential application of the biology aspect such as imaging.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the testing principle schematic diagram of fluorine ion in fluorescence probe detection water phase of the present invention.
Fig. 2 show in the embodiment of the present invention 16 nano-hydrogel Pluronic L121-cl-PEI (1K, 3:1) in D2O
In1H NMR (400MHz) collection of illustrative plates.
Fig. 3 shows the nano-hydrogel Pluronic L121-cl-PEI of the 1.5g/L prepared in the embodiment of the present invention 16
(1K,3:1) grain size distribution of solution.
Fig. 4 shows the nano-hydrogel Pluronic L121-cl-PEI of the 1.5g/L prepared in the embodiment of the present invention 16
(1K,3:1) the particle diameter distribution Zeta potential distribution map of solution.
Fig. 5 is shown in the embodiment of the present invention 16, and under 345nm excitations, PSDA fluorescence probe Aqueous dispersions systems are molten
Fluorescence intensity in the aqueous solution containing different anions.
Fig. 6 is shown in the embodiment of the present invention 16, and under 345nm excitations, PSDA fluorescence probe Aqueous dispersions systems are molten
Fluorescence spectra in various concentrations sodium fluoride aqueous solution.
Fig. 7 is shown in the embodiment of the present invention 16, and under 345nm excitations, PSDA fluorescence probe Aqueous dispersions systems are molten
After in various concentrations sodium fluoride aqueous solution, using fluorescence intensity at 377nm as ordinate, concentration of sodium fluoride is fitted for abscissa
The working curve arrived.
Fig. 8 is shown in the embodiment of the present invention 17, and under 345nm excitations, PSDM fluorescence probe Aqueous dispersions systems are molten
Fluorescence intensity in the aqueous solution containing different anions.
Fig. 9 is shown in the embodiment of the present invention 17, and under 345nm excitations, PSDM fluorescence probe Aqueous dispersions systems are molten
Fluorescence spectra in various concentrations sodium fluoride aqueous solution.
Figure 10 is shown in the embodiment of the present invention 17, and under 345nm excitations, PSDM fluorescence probe Aqueous dispersions systems are molten
After in various concentrations sodium fluoride aqueous solution, using fluorescence intensity at 377nm as ordinate, concentration of sodium fluoride is fitted for abscissa
The working curve arrived.
Figure 11 is shown in the embodiment of the present invention 18, and under 345nm excitations, PSMA fluorescence probe Aqueous dispersions systems are molten
Fluorescence intensity in the aqueous solution containing different anions.
Figure 12 is shown in the embodiment of the present invention 18, and under 345nm excitations, PSMA fluorescence probe Aqueous dispersions systems are molten
Fluorescence spectra in various concentrations sodium fluoride aqueous solution.
Figure 13 is shown in the embodiment of the present invention 18, and under 345nm excitations, PSMA fluorescence probe Aqueous dispersions systems are molten
After in various concentrations sodium fluoride aqueous solution, using fluorescence intensity at 377nm as ordinate, concentration of sodium fluoride is fitted for abscissa
The working curve arrived.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar component is indicated with identical reference numeral in attached drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1:Synthesis (the R of the fluorescence probe of PSDA fluorescence probes1=R2=H)
First, synthesis material compound 1- pyrene methanol:
1) synthesis of 1- pyrene formaldehydes
By pyrene (10.1g, 0.05mol), N- methyl formyl anilines (12.4mL, 0.1mol), phosphorus oxychloride (8mL,
0.09mol) it is dissolved in o-dichlorohenzene, heating stirring, temperature rises to 100 DEG C in 20 minutes, and question response liquid in the pasty state, stops anti-
Should.Prepare the sodium acetate aqueous solution of saturation.After the cooling of question response mixture, the sodium acetate aqueous solution prepared is added, water vapour steams
Evaporate, when cut is almost clarified, stopping is distilled.After liquid cooling in bottle, filter, with the salt acid elution of 100mL 6N, Ran Houyong
380mL water washings, crude product are recrystallized with glacial acetic acid, and methanol washing, obtains 1- pyrene formaldehyde 9.2g, yield 80%.
2) synthesis of 1- pyrenes methanol
By 1- pyrene formaldehydes (2.3g, 0.01mol), dissolved with 12mL tetrahydrofurans.Under ice bath add sodium borohydride (0.40g,
0.010mol), after question response temperature lowers, it is stirred at room temperature 75 minutes, stops reaction, adds 22mL water, 24mL second thereto
Ether.Water layer is extracted 3 times with 10mL ether, is merged organic phase, is dried with anhydrous magnesium sulfate.Filtering, is spin-dried for, crude product toluene weight
Crystallization, obtains faint yellow solid 1.5g, yield 74%.121-123 DEG C of fusing point (123-124 DEG C of document).1H NMR (400MHz,
CDCl3), δ (ppm):8.18-7.99 (m, 9H), 5.37 (s, 2H), 1.91 (s, 1H).
2nd, PSDA fluorescence probes are synthesized:
Appropriate tetrahydrofuran is added in three-necked flask, under conditions of nitrogen is passed through, with syringe to reaction system
Middle addition diisopropyl dichlorosilane (0.8mL, 0.004mol), then by dry imidazoles (0.41g, 0.006mol) and to ammonia
Base phenol (0.44g, 0.004mol) is dissolved in tetrahydrofuran solvent, is slowly added dropwise with syringe into reaction system.Contact plate detects
Reaction, after para-aminophenol react, by 1- pyrenes methanol (0.92g, 0.004mol) and dry imidazoles (0.30g,
0.005mol) it is dissolved in tetrahydrofuran solvent, is slowly added dropwise with syringe into reaction system, reacts 8h at room temperature.By reaction solution
It is spin-dried for, uses CH2Cl2Column chromatography for separation is carried out as eluent, obtains 0.72g PSDA fluorescence probes, yield 40%.1H NMR
(400MHz,CDCl3), δ (ppm):8.29-7.99 (m, 9H), 6.82-6.79 (m, 2H), 6.59-6.53 (m, 2H), 5.66 (s,
2H), 3.91 (s, 2H), 1.30-1.21 (m, 2H), 1.14-1.11 (m, 12H).MS(MALDI-TOF):m/z:calc.453.2
[M]+, found:453.4[M]+。
Embodiment 2:Synthesis (the R of PSDM fluorescence probes1=R2=CH3)
Synthesize PSDM fluorescence probes:
Appropriate tetrahydrofuran is added in three-necked flask, under conditions of nitrogen is passed through, with syringe to reaction system
Middle addition diisopropyl dichlorosilane (1.8mL, 0.01mol), then by dry imidazoles (0.68g, 0.01mol) and 4- diformazans
Amino-phenol (1.37g, 0.01mol) is dissolved in tetrahydrofuran solvent, is slowly added dropwise with syringe into reaction system.Contact plate detects
Reaction, after 4-DMAP has reacted, by the 1- pyrenes methanol obtained by the preparation method in embodiment 1 (2.32g,
0.01mol) it is dissolved in tetrahydrofuran solvent with dry imidazoles (0.68g, 0.01mol), is slowly added dropwise with syringe into reaction
System, reacts 8h at room temperature.Reaction solution is spin-dried for, uses petroleum ether:Ethyl acetate=9:1 carries out column chromatography as eluent divides
From obtaining 1.44g PSDM fluorescence probes, yield 30%.1HNMR(400MHz,CDCl3), δ (ppm):(8.29-7.99 m, 9H),
6.74 (d, 2H), 6.60 (d, 2H), 5.66 (s, 2H), 2.83 (s, 6H), 1.33-1.22 (m, 2H), 1.15-1.12 (m, 12H).
HRMS(ESI-TOF):m/z:calc.481.2437[M]+found:482.2507[M+H]+。
Embodiment 3:Synthesis (the R of PSMA fluorescence probes1=H, R2=CH3)
Synthesize PSMA fluorescence probes:
Now appropriate tetrahydrofuran is added in three-necked flask, under conditions of nitrogen is passed through, with syringe to reactant
Diisopropyl dichlorosilane (1.8mL, 0.01mol) is added in system, then by dry imidazoles (0.68g, 0.01mol) and 4- first
Base amino-phenol (1.23g, 0.01mol) is dissolved in tetrahydrofuran solvent, is slowly added dropwise with syringe into reaction system.Contact plate is examined
Survey reaction, after 4- methylaminophenols have reacted, by the 1- pyrenes methanol obtained by the preparation method in embodiment 1 (2.32g,
0.01mol) it is dissolved in tetrahydrofuran solvent with dry imidazoles (0.68g, 0.01mol), is slowly added dropwise with syringe into reaction
System, reacts 8h at room temperature.Reaction solution is spin-dried for, uses petroleum ether:Ethyl acetate=9:1 carries out column chromatography as eluent divides
From obtaining 2.11g PSMA fluorescence probes, yield 45%.1HNMR(400MHz,CDCl3), δ (ppm):(8.29-7.99 m, 9H),
6.59-6.53 (m, 2H), 6.60 (s, 2H), 5.66 (s, 2H), 3.81 (s, H), 2.83 (s, 3H), 1.33-1.22 (m, 2H),
1.15-1.12(m,12H).HRMS(ESI-TOF):m/z:calc.467.2281[M]+, found:467.2292[M+H]+。
Embodiment 4:Synthesis (the R of PSMP fluorescence probes1=CH3, R2=CH2CH2CH3)
Synthesize PSMP fluorescence probes:
First appropriate tetrahydrofuran is added in three-necked flask, under conditions of nitrogen is passed through, with syringe to reactant
Diisopropyl dichlorosilane (1.8mL, 0.01mol) is added in system, then by dry imidazoles (0.68g, 0.01mol) and 4- first
Base propylcarbamic phenol (1.65g, 0.01mol) is dissolved in tetrahydrofuran solvent, is slowly added dropwise with syringe into reaction system.Point
Plate detection reaction, after 4- methylpropylamino phenol reactants are complete, the 1- pyrene methanol that will be obtained by the preparation method in embodiment 1
(2.32g, 0.01mol) and dry imidazoles (0.68g, 0.01mol) are dissolved in tetrahydrofuran solvent, are slowly added dropwise with syringe
Into reaction system, 8h is reacted at room temperature.Reaction solution is spin-dried for, uses petroleum ether:Ethyl acetate=9:1 as eluent progress column layer
Analysis separation, obtains 1.51g PSMP fluorescence probes, yield 30%.1HNMR (400MHz, CDCl3), δ (ppm):8.29-7.99(m,
9H), 6.74 (d, 2H), 6.60 (d, 2H), 5.66 (s, 2H), 3.71 (t, 2H), 2.80 (s, 3H), 1.51-1.45 (m, 2H),
1.33-1.22 (m, 2H), 1.15-1.12 (m, 12H), 0.87 (t, 3H).HRMS(ESI-TOF):m/z:calc.509.2750
[M]+, found:510.2755[M+H]+。
Embodiment 5:Synthesis (the R of PSEA fluorescence probes1=H, R2=CH2CH3)
With embodiment 1, difference lies in change para-aminophenol into 4- ethylamino phenol, remaining condition is constant, is prepared into
It is as a result similar to Example 1 to PSEA fluorescence probes.
Embodiment 6:Synthesis (the R of PSPA fluorescence probes1=H, R2=CH2CH2CH3)
With embodiment 1, difference lies in:Change para-aminophenol into 4- propylcarbamic phenol, remaining condition is constant, is prepared into
It is as a result similar to Example 1 to PSPA fluorescence probes.
Embodiment 7:Synthesis (the R of PSIA fluorescence probes1=H, R2=CH2(CH3)2)
With embodiment 1, difference lies in:Change para-aminophenol into 4- isopropylamino phenol, remaining condition is constant, prepares
PSIA fluorescence probes are obtained, it is as a result similar to Example 1.
Embodiment 8:Synthesis (the R of PSME fluorescence probes1=CH3, R2=CH2CH3)
With embodiment 1, difference lies in:Change para-aminophenol into 4- methylethylamine phenol, remaining condition is constant, system
It is standby to obtain PSME fluorescence probes, it is as a result similar to Example 1.
Embodiment 9:Synthesis (the R of PSMI fluorescence probes1=CH3, R2=CH2(CH3)2)
With embodiment 1, difference lies in:Changing para-aminophenol into 4- methylisopropylamino phenol, remaining condition is constant,
PSMI fluorescence probes are prepared, it is as a result similar to Example 1.
Embodiment 10:Synthesis (the R of PSDE fluorescence probes1=CH2CH3, R2=CH2CH3)
With embodiment 1, difference lies in:Change para-aminophenol into 4- diethylamino phenol, remaining condition is constant, prepares
PSDE fluorescence probes are obtained, it is as a result similar to Example 1.
Embodiment 11:Synthesis (the R of PSEP fluorescence probes1=CH2CH3, R2=CH2CH2CH3)
With embodiment 1, difference lies in:Change para-aminophenol into 4- ethylpropylamino phenol, remaining condition is constant, system
It is standby to obtain PSEP fluorescence probes, it is as a result similar to Example 1.
Embodiment 12:Synthesis (the R of PSEI fluorescence probes1=CH2CH3, R2=CH2(CH3)2)
With embodiment 1, difference lies in:Changing para-aminophenol into 4- ethylisopropylamino phenol, remaining condition is constant,
PSEI fluorescence probes are prepared, it is as a result similar to Example 1.
Embodiment 13:Synthesis (the R of PSDP fluorescence probes1=CH2CH2CH3, R2=CH2CH2CH3)
With embodiment 1, difference lies in:Change para-aminophenol into 4- dipropylamino phenol, remaining condition is constant, prepares
PSDP fluorescence probes are obtained, it is as a result similar to Example 1.
Embodiment 14:Synthesis (the R of PSPI fluorescence probes1=CH2CH2CH3, R2=CH2(CH3)2)
With embodiment 1, difference lies in:Changing para-aminophenol into 4- propyl iso-propyl amino-phenols, remaining condition is constant,
PSPI fluorescence probes are prepared, it is as a result similar to Example 1.
Embodiment 15:Synthesis (the R of PSDI fluorescence probes1=CH2(CH3)2, R2=CH2(CH3)2)
With embodiment 1, difference lies in:Change para-aminophenol into 4- diisopropylaminoethyl phenol, remaining condition is constant, system
It is standby to obtain PSDI fluorescence probes, it is as a result similar to Example 1.
Embodiment 16:Application of the PSDA fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic L121-cl-PEI (1K, 3:1) synthesis:
1st, Pluronic L121 are activated
(13.2g, 0.003mol) Pluronic P123 are weighed in the there-necked flask of 500mL, it is molten with 150mL anhydrous acetonitriles
Solution, adds carbonyl dimidazoles (2.43g, 0.015mol) under conditions of nitrogen is passed through, and oil bath is warming up to 40 DEG C, reacts 17h.Instead
After answering, add 150mL deionized waters and reaction is quenched, be put into the bag filter that molecular cut off is 2000, at 4 DEG C,
Dialysis 4h is carried out in 10% ethanol solution, then changes dialysis solution, dialyse 4h at 4 DEG C again.By the reaction solution in bag filter
It is spin-dried at 25 DEG C, it is spare.
2nd, the larger branched polyethylenimine (PEI, 1K) of molecular weight is removed
Weigh PEI (4.0g, 0.0004mol) to be dissolved in the deionized water of about 30mL, it is 25000 to be put into molecular cut off
In bag filter, dialyse 48h in deionized water.The component that the molecular weight for giving to come in beaker is less than 25000 is collected, is spin-dried for.
3rd, synthesize nano-hydrogel Pluronic L121-cl-PEI (1K, 3:1)
The Pluronic L121 of 3.0g carbonyl dimidazoles activation are weighed, are dissolved in the dichloromethane of 25mL.Weigh purifying
Side chain PEI (1.0g, 0.0001mol), is dissolved in 250mL deionized waters.Under ultrasound condition, by carbonyl dimidazoles activation
The dichloromethane solution of Pluronic L121 is added dropwise in the aqueous solution of side chain PEI (1K) dropwise, after being added dropwise, is then surpassed
Sound 10min, then removes dichloromethane with Rotary Evaporators.It is stirred overnight under the conditions of 25 DEG C.With 12000RPM centrifugations very
Clock, removes the gel of big sheet.Finally with the bag filter that molecular cut off is 10000, under the conditions of 25 DEG C, containing 10% ethanol
0.025% ammonia spirit in dialyse 24h.Solution in bag filter is freeze-dried, obtains nano-hydrogel Pluronic
L121-cl-PEI(1K,3:1)。
Fig. 2 show nano-hydrogel Pluronic L121-cl-PEI (1K, 3:1) in D2In O1H NMR(400MHz)
Collection of illustrative plates.
2nd, the preparation of PSDA fluorescence probes Aqueous dispersions system
1st, the nano-hydrogel solution of 1.5g/L is prepared
Weigh 62.5mg Pluronic L121-cl-PEI (1K, 3:1) molecule adds ultra-pure water in 25mL volumetric flasks
Constant volume, prepares the nano-hydrogel solution of 1.5g/L.Then, its particle diameter and Zeta potential are tested with dynamic light scattering, its Z is equal
Particle diameter is 127.0nm, Zeta potential 4.16mV.
Fig. 3 show the 1.5g/L of preparation Pluronic L121-cl-PEI (1K, 3:1) grain of nano-hydrogel solution
Footpath is distributed.
Fig. 4 show the 1.5g/L of preparation Pluronic L121-cl-PEI (1K, 3:1) nano-hydrogel solution
Zeta potential is distributed.
2nd, the tetrahydrofuran solution of the PSDA fluorescence probes of 1mM is prepared
4.5mg probe molecules PSDA is weighed in 10mL volumetric flasks, the THF constant volumes steamed again is added, prepares the PSDA's of 1mM
Tetrahydrofuran solution.
3rd, the PSDA fluorescent probe molecule Aqueous dispersions systems using nano-hydrogel as carrier are prepared
Take in 10mL 1 that prepared nano-hydrogel solution is in 10mL volumetric flasks, under ultrasound condition, with micro note
Emitter adds the tetrahydrofuran solution of the PSDA of the 100 prepared 1mM of μ L thereto, and ultrasonic 5min, prepares PSDA fluorescence probes
Aqueous dispersions system.
3rd, the measure of PSDA fluorescence probes selectivity
A series of Aqueous dispersions system of PSDA fluorescence probes of 3ml is taken, is separately added into 30 μ L concentration as 1.0 × 10-2M's
F-、Cl-、Br-、NO3 -、SO4 2-、HSO4 -、H2PO4 -、AcO-Aqueous solution, after placing 30 minutes, is excited down, with fluorescence light with 345nm
Spectrometer measures the fluorescence intensity (as shown in Figure 5) at 377nm respectively.In addition to fluorine ion, other ions do not cause 377nm
Locate the significant change of fluorescence intensity, PSDA fluorescent probe molecules have selectivity well.
4th, the measure of PSDA fluorescence probes test limit
The Aqueous dispersions system of 3mL PSDA fluorescence probes is taken, adds various concentrations (0-2.0 × 10-5Mol/L fluorination)
Sodium water solution, after placing 30 minutes, is excited with 345nm, measures the fluorescence intensity (fluorescence at 377nm respectively with Fluorescence Spectrometer
Spectrum is as shown in Figure 6), using the fluorescence intensity at 377nm as ordinate, concentration of sodium fluoride is mapped for abscissa, and it is straight to obtain fitting
The slope of line, utilizes test limit (limit of detection, LOD) calculation formula:LOD=3 × S.D./K (wherein, S.D.
The standard deviation that probe molecule fluorescence spectrum changes during to be not added with fluorine ion, K is straight slope) inspection of the probe is calculated
Survey is limited to 4.9 × 10-8M。
5th, the measure of the working curve of fluorescence probe detection fluorine ion
The Aqueous dispersions system of 3mL PSDA fluorescence probes is taken, adds 30 μ L various concentrations (0,4,8,12,16,20mM)
Sodium fluoride aqueous solution, after placing 30 minutes, Fluorescence Spectrometer records the change of fluorescence intensity at 377nm respectively.With glimmering at 377nm
Luminous intensity is ordinate, and concentration of sodium fluoride is mapped for abscissa, and fitting obtains the working curve of fluorescence probe detection fluorine ion (such as
Shown in Fig. 7).
6th, measure and calculate the concentration of fluorine ion in solution
The unknown aqueous solution of 1.5mL is added to Aqueous dispersions system (the PSDA fluorescence spy of 1.5mL PSDA fluorescence probes
Pin molecular concentration is 2 × 10-5M, the concentration of nano-hydrogel is 3.0g/L), measure and calculate the fluorescence intensity at 377nm,
According to working curve, the concentration for calculating fluorine ion in unknown solution is 98 μM.
Embodiment 17:Application of the PSDM fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic L121-cl-PEI (1K, 10:1) synthesis
It is similar with the step one in embodiment 16, the difference is that being to weigh the activation of 10.0g carbonyl dimidazoles in step 1 (3)
Pluronic L121, be dissolved in the dichloromethane of 83mL.
2nd, the preparation of the Aqueous dispersions system of PSDM fluorescence probes
1st, the nano-hydrogel solution of 1.5g/L is prepared
Weigh 62.5mg Pluronic L121-cl-PEI (1K, 10:1) molecule adds ultra-pure water in 25mL volumetric flasks
Constant volume, prepares the nano-hydrogel solution of 1.5g/L.
2nd, the tetrahydrofuran solution of the PSDM fluorescence probes of 1mM is prepared
4.8mg probe molecules PSDM is weighed in 10mL volumetric flasks, the THF constant volumes steamed again is added, prepares the PSDM's of 1mM
Tetrahydrofuran solution.
3rd, the Aqueous dispersions system of PSDM fluorescence probes is prepared
Take in 10mL 1 that prepared nano-hydrogel solution is in 10mL volumetric flasks, under ultrasound condition, with micro note
Emitter adds the tetrahydrofuran solution of the PSDM of the 100 prepared 1mM of μ L thereto, and ultrasonic 5min, prepares PSDM fluorescence probes
Aqueous dispersions system.
3rd, the measure of PSDM fluorescent probe molecules selectivity
A series of Aqueous dispersions system of PSDM fluorescence probes of 3ml is taken, is separately added into 30 μ L concentration as 1.0 × 10-2M's
F-、Br-、Cl-、SO4 2-、NO3 -、HSO4 -、AcO-、H2PO4 -Aqueous solution, after placing 30 minutes, is excited down, with fluorescence light with 345nm
Spectrometer measures the fluorescence intensity (as shown in Figure 8) at 377nm respectively.In addition to fluorine ion, other ions do not cause 377nm
Locate the significant change of fluorescence intensity, PSDM fluorescent probe molecules have selectivity well.
4th, the measure of PSDM fluorescent probe molecules test limit
The Aqueous dispersions system of 3mL PSDM fluorescence probes is taken, adds various concentrations (0-2.0 × 10-5Mol/L fluorination)
Sodium water solution, after placing 30 minutes, is excited with 345nm, measures the fluorescence intensity (fluorescence at 377nm respectively with Fluorescence Spectrometer
Spectrum is as shown in Figure 9), using the fluorescence intensity at 377nm as ordinate, concentration of sodium fluoride is mapped for abscissa, and it is straight to obtain fitting
The slope of line, utilizes test limit (limit of detection, LOD) calculation formula:LOD=3 × S.D./K (wherein, S.D.
The standard deviation that probe molecule fluorescence spectrum changes during to be not added with fluorine ion, K is straight slope) probe molecule is calculated
Detection be limited to 4.8 × 10-8M。
5th, the measure of the working curve of fluorescence probe detection fluorine ion
The Aqueous dispersions system of 3mL PSDM fluorescence probes is taken, adds 30 μ L various concentrations (0,4,8,12,16,20mM)
Sodium fluoride aqueous solution, after placing 30 minutes, Fluorescence Spectrometer records the change of fluorescence intensity at 377nm respectively.With glimmering at 377nm
Luminous intensity is ordinate, and concentration of sodium fluoride is mapped for abscissa, and fitting obtains the working curve of fluorescence probe detection fluorine ion (such as
Shown in Figure 10).
6th, measure and calculate the concentration of fluorine ion in solution
The unknown aqueous solution of 1.5mL is added to (PSDM fluorescence in the Aqueous dispersions system of 1.5mL PSDM fluorescence probes
Probe molecule concentration is 2 × 10-5M, the concentration of nano-hydrogel is 3.0g/L), measure and to calculate the fluorescence at 377nm strong
Degree, according to working curve, the concentration for calculating fluorine ion in unknown solution is 101 μM.
Embodiment 18:Application of the PSMA fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic L121-cl-PEI (1.2K, 3:1) synthesis
Similar with the step one in embodiment 16, different uses MnThe side chain PEI of=1.2K.
2nd, with the preparation of the Aqueous dispersions system of PSMA fluorescence probes
1st, the nano-hydrogel solution of 1.5g/L is prepared
Weigh 62.5mg Pluronic L121-cl-PEI (1.2K, 3:1) molecule adds ultrapure in 25mL volumetric flasks
Water constant volume, prepares the nano-hydrogel solution of 1.5g/L.
2nd, the tetrahydrofuran solution of the PSMA fluorescence probes of 1mM is prepared
4.7mg probe molecules PSMA is weighed in 10mL volumetric flasks, the THF constant volumes steamed again is added, prepares the PSDA's of 1mM
Tetrahydrofuran solution.
3rd, the Aqueous dispersions system of PSMA fluorescence probes is prepared
Take in 10mL 1 that prepared nano-hydrogel solution is in 10mL volumetric flasks, under ultrasound condition, with micro note
Emitter adds the tetrahydrofuran solution of the PSMA of the 100 prepared 1mM of μ L thereto, and ultrasonic 5min, prepares PSMA fluorescence probes
Aqueous dispersions system.
3rd, the measure of PSMA fluorescent probe molecules selectivity
A series of Aqueous dispersions system of PSMA fluorescence probes of 3ml is taken, is separately added into 30 μ L concentration as 1.0 × 10-2M's
F-、Cl-、Br-、NO3 -、SO4 2-、HSO4 -、H2PO4 -、AcO-Aqueous solution, after placing 30 minutes, is excited down, with fluorescence light with 345nm
Spectrometer measures the fluorescence intensity (as shown in figure 11) at 377nm respectively.In addition to fluorine ion, other ions do not cause
The significant change of fluorescence intensity at 377nm, PSMA fluorescent probe molecules have selectivity well.
4th, the measure of PSMA fluorescent probe molecules test limit
The Aqueous dispersions system of 3mL PSDA fluorescence probes is taken, adds various concentrations (0-2.0 × 10-5Mol/L fluorination)
Sodium water solution, after placing 30 minutes, is excited with 345nm, measures the fluorescence intensity (fluorescence at 377nm respectively with Fluorescence Spectrometer
Spectrum is as shown in figure 12), using the fluorescence intensity at 377nm as ordinate, concentration of sodium fluoride is mapped for abscissa, and it is straight to obtain fitting
The slope of line, utilizes test limit (limit of detection, LOD) calculation formula:LOD=3 × S.D./K (wherein, S.D.
The standard deviation that probe molecule fluorescence spectrum changes during to be not added with fluorine ion, K is straight slope) probe molecule is calculated
Detection be limited to 5.5 × 10-8M。
5th, the measure of the working curve of fluorescence probe detection fluorine ion
The Aqueous dispersions system of 3mL PSMA fluorescence probes is taken, adds 30 μ L various concentrations (0,4,8,12,16,20mM)
Sodium fluoride aqueous solution, after placing 30 minutes, Fluorescence Spectrometer records the change of fluorescence intensity at 377nm respectively.With glimmering at 377nm
Luminous intensity is ordinate, and concentration of sodium fluoride is mapped for abscissa, and fitting obtains the working curve of fluorescence probe detection fluorine ion (such as
Shown in Figure 13).
6th, measure and calculate the concentration of fluorine ion in solution
The unknown aqueous solution of 1.5mL is added to (PSMA fluorescence in the Aqueous dispersions system of 1.5mL PSMA fluorescence probes
Probe molecule concentration is 2 × 10-5M, the concentration of nano-hydrogel is 3.0g/L), measure and to calculate the fluorescence at 377nm strong
Degree, according to working curve, the concentration for calculating fluorine ion in unknown solution is 92 μM.
Embodiment 19:Application of the PSMP fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic L121-cl-PEI (1.2K, 10:1) synthesis
Similar with 17 step 1 of embodiment, difference lies in the number-average molecular weight of the branched polyethylenimine used is Mn=
1.2K。
2nd, three, four, five, six, with embodiment 16, difference lies in change PSDA fluorescence probes into PSMP fluorescence probes, receive
Rice hydrogel change into Pluronic L121-cl-PEI (1.2K, 10:1), remaining condition is constant, as a result close with embodiment 16,
There is PSMP fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 4.5 × 10-8M, calculates unknown solution
The concentration of middle fluorine ion is 100 μM.
Embodiment 20:Application of the PSEA fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic L121-cl-PEI (1.8K, 3:1) synthesis
Similar with the step one in embodiment 16, difference lies in the number-average molecular weight of the branched polyethylenimine used is
Mn=1.8K.
2nd, three, four, five, six, with embodiment 16, difference lies in change PSDA fluorescence probes into PSEA fluorescence probes, receive
Rice hydrogel change into Pluronic L121-cl-PEI (1.8K, 3:1), remaining condition is constant, as a result close with embodiment 16,
There is PSEA fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 4.8 × 10-8M, calculates unknown solution
The concentration of middle fluorine ion is 92 μM.
Embodiment 21:Application of the PSPA fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic L121-cl-PEI (1.8K, 10:1) synthesis
It is similar to Example 17, difference lies in the number-average molecular weight of the branched polyethylenimine used is Mn=1.8K.
2nd, three, four, five, six, with embodiment 16, difference lies in change PSDA fluorescence probes into PSPA fluorescence probes, receive
Rice hydrogel change into Pluronic L121-cl-PEI (1.8K, 10:1), remaining condition is constant, as a result close with embodiment 16,
There is PSPA fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 5.2 × 10-8M, calculates unknown solution
The concentration of middle fluorine ion is 98 μM.
Embodiment 22:Application of the PSIA fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic P123-cl-PEI (1K, 3:1) synthesis
1st, Pluronic P123 are activated
(11.6g, 0.002mol) Pluronic P123 are weighed in the there-necked flask of 250mL, it is molten with 100mL anhydrous acetonitriles
Solution, adds carbonyl dimidazoles (1.62g, 0.010mol) under conditions of nitrogen is passed through, and oil bath is warming up to 40 DEG C, reacts 17h.Instead
After answering, add 100mL deionized waters and reaction is quenched, be put into the bag filter that molecular cut off is 2000, at 4 DEG C,
Dialysis 4h is carried out in 10% ethanol solution, then changes dialysis solution, dialyse 4h at 4 DEG C again.By the reaction solution in bag filter
It is spin-dried at 25 DEG C, it is spare.
2nd, the larger branched polyethylenimine (PEI, 1K) of molecular weight is removed
Weigh PEI (4.0g, 0.0004mol) to be dissolved in the deionized water of about 30mL, it is 25000 to be put into molecular cut off
In bag filter, dialyse 48h in deionized water.The component that the molecular weight for giving to come in beaker is less than 25000 is collected, is spin-dried for.
3rd, synthesize nano-hydrogel Pluronic P123-cl-PEI (1K, 3:1)
The Pluronic P123 of 3.0g carbonyl dimidazoles activation are weighed, are dissolved in the dichloromethane of 25mL.Weigh purifying
PEI (1.0g, 0.0001mol), is dissolved in 250mL deionized waters.Under ultrasound condition, by carbonyl dimidazoles activation
The dichloromethane solution of Pluronic P123 is added dropwise in the aqueous solution of PEI (1K) dropwise, then ultrasonic after being added dropwise
10min, then removes dichloromethane with Rotary Evaporators.It is stirred overnight under the conditions of 25 DEG C.Centrifuged ten minutes with 12000rmp,
Remove the gel of big sheet.Finally with the bag filter that molecular cut off is 10000, under the conditions of 25 DEG C, containing 10% ethanol
Dialyse 24h in 0.025% ammonia spirit.Solution in bag filter is freeze-dried, obtains nano-hydrogel PluronicP123-
cl-PEI(1K,3:1)。
2nd, three, four, five, six, with embodiment 16, difference lies in change PSDA fluorescence probes into PSIA fluorescence probes, receive
Rice hydrogel change into Pluronic P123-cl-PEI (1K, 3:1), remaining condition is constant, as a result close with embodiment 16, PSIA
There is fluorescent probe molecule selectivity, the detection of the probe molecule well to be limited to 5.5 × 10-8M, calculates fluorine in unknown solution
The concentration of ion is 101 μM.
Embodiment 23:Application of the PSME fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic P123-cl-PEI (1K, 10:1) synthesis
Similar with the step one in embodiment 22, difference lies in " will weigh the activation of 3.0g carbonyl dimidazoles in step 3)
Pluronic P123, are dissolved in the dichloromethane of 25mL " it is changed to " weigh the Pluronic of 10.0g carbonyl dimidazoles activation
P123, is dissolved in the dichloromethane of 83mL ".
2nd, three, four, five, six, with embodiment 16, difference lies in change PSDA fluorescence probes into PSME fluorescence probes, receive
Rice hydrogel change into Pluronic P123-cl-PEI (1K, 10:1), remaining condition is constant, as a result close with embodiment 16,
There is PSME fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 4.9 × 10-8M, calculates unknown solution
The concentration of middle fluorine ion is 94 μM.
Embodiment 24:Application of the PSMI fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic P123-cl-PEI (1.2K, 3:1) synthesis
Similar with embodiment 22, difference lies in the number-average molecular weight of the branched polyethylenimine used is Mn=1.2K.
2nd, three, four, five, six, with embodiment 16, difference lies in change PSDA fluorescence probes into PSMI fluorescence probes, receive
Rice hydrogel change into Pluronic P123-cl-PEI (1.2K, 3:1), remaining condition is constant, as a result close with embodiment 16,
There is PSMI fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 5.2 × 10-8M, calculates unknown solution
The concentration of middle fluorine ion is 94 μM.
Embodiment 25:Application of the PSDE fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic P123-cl-PEI (1.2K, 10:1) synthesis
Similar with embodiment 23, difference lies in the number-average molecular weight of the branched polyethylenimine used is Mn=1.2K.
2nd, three, four, five, six, with embodiment 16, difference lies in change PSDA fluorescence probes into PSDE fluorescence probes, receive
Rice hydrogel change into Pluronic P123-cl-PEI (1.2K, 10:1), remaining condition is constant, as a result close with embodiment 16,
There is PSDE fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 4.8 × 10-8M, calculates unknown solution
The concentration of middle fluorine ion is 94 μM.
Embodiment 26:Application of the PSEP fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic P123-cl-PEI (1.8K, 3:1) synthesis
Similar with embodiment 22, difference lies in the number-average molecular weight of the branched polyethylenimine used is Mn=1.8K.
2nd, three, four, five, six, with embodiment 16, difference lies in change PSDA fluorescence probes into PSEP fluorescence probes, receive
Rice hydrogel change into Pluronic P123-cl-PEI (1.8K, 3:1), remaining condition is constant, as a result close with embodiment 16,
There is PSEP fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 5.2 × 10-8M, calculates unknown solution
The concentration of middle fluorine ion is 93 μM.
Embodiment 27:Application of the PSEI fluorescence probes in water phase fluorine ion is detected
First, nano-hydrogel Pluronic P123-cl-PEI (1.8K, 10:1) synthesis
Similar with embodiment 23, difference lies in the number-average molecular weight of the branched polyethylenimine used is Mn=1.8K.
2nd, three, four, five, six, with embodiment 16, difference lies in change PSDA fluorescence probes into PSEI fluorescence probes, receive
Rice hydrogel change into Pluronic P123-cl-PEI (1.8K, 10:1), remaining condition is constant, as a result close with embodiment 16,
There is PSEI fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 5.0 × 10-8M, calculates unknown solution
The concentration of middle fluorine ion is 108 μM.
Embodiment 28:Application of the PSDP fluorescence probes in water phase fluorine ion is detected
With embodiment 16, difference lies in change PSDA fluorescence probes into PSDP fluorescence probes, remaining condition is constant, as a result
Close with embodiment 16, there is PSDP fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 4.5 × 10- 8M, the concentration for calculating fluorine ion in unknown solution are 100 μM.
Embodiment 29:Application of the PSPI fluorescence probes in water phase fluorine ion is detected
With embodiment 16, change PSDA fluorescence probes into PSPI fluorescence probes, remaining condition is constant, as a result with embodiment 16
Close, there is PSPI fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 5.2 × 10-8M, calculates not
The concentration for knowing fluorine ion in solution is 93 μM.
Embodiment 30:Application of the PSDI fluorescence probes in water phase fluorine ion is detected
With embodiment 16, change PSDA fluorescence probes into PSDI fluorescence probes, remaining condition is constant, as a result with embodiment 16
Close, there is PSDI fluorescent probe molecules selectivity, the detection of the probe molecule well to be limited to 5.5 × 10-8M, calculates not
The concentration for knowing fluorine ion in solution is 98 μM.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical solution is extended out still in protection scope of the present invention.
Claims (6)
1. a kind of fluorine ion fluorescence probe, it is characterised in that the fluorine ion fluorescence probe has following structural formula general formula:
In formula, R1、R2It is independently selected from hydrogen, methyl, ethyl, propyl group or isopropyl.
2. the application of fluorine ion of the fluorine ion fluorescence probe as claimed in claim 1 in water phase is detected, it is characterised in that bag
Include following detecting step:
1) fluorine ion fluorescent probe molecule is loaded in nano-hydrogel, obtains Aqueous dispersions system;
2) test limit of various concentrations fluorine ion fluorescent probe molecule is determined;
3) working curve of fluorine ion fluorescent probe molecule detection fluorine ion is drawn by fluorescence spectrum;
4) concentration of fluorine ion in target solution is measured.
3. application according to claim 2, it is characterised in that described to bear fluorine ion fluorescent probe molecule in step 1)
It is downloaded to concretely comprising the following steps in nano-hydrogel:
1. prepare the tetrahydrofuran solution of fluorine ion fluorescent probe molecule;
2. preparation of nano water-setting glue solution;
3. 1. solution that step is prepared is added in 2. aqueous solution that step is prepared, Aqueous dispersions system is obtained.
4. the application according to Claims 2 or 3, it is characterised in that the nano-hydrogel is activated by carbonyl dimidazoles
Poloxamer and branched polyethylenimine are crosslinked to obtain.
5. application according to claim 4, it is characterised in that the number-average molecular weight M of the PoloxamernFor 4400 or
5800;The ratio of the amount of the material of primary amine, secondary amine and tertiary amine is 1 in the branched polyethylenimine molecule:2:1, number-average molecular weight
MnFor 1000,1200 or 1800.
6. application according to claim 4, it is characterised in that the poloxamer and side chain of the carbonyl dimidazoles activation
The mass ratio of polyethyleneimine is 3:1-10:1.
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