CN104230814B - A kind of fluorescence identifying fluorine ion sensing device and preparation thereof and application - Google Patents
A kind of fluorescence identifying fluorine ion sensing device and preparation thereof and application Download PDFInfo
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- CN104230814B CN104230814B CN201410491431.2A CN201410491431A CN104230814B CN 104230814 B CN104230814 B CN 104230814B CN 201410491431 A CN201410491431 A CN 201410491431A CN 104230814 B CN104230814 B CN 104230814B
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Abstract
The invention provides the sensor of a kind of high selectivity fluorescence identifying fluorion, belong to Anionic recognition field.This sensor is with p-phthalic acid and o-phenylenediamine as substrate; polyphosphoric acids is catalyst, and phosphoric acid is dehydrant, under nitrogen protection; reaction 5 ~ 6h is stirred at 160 ~ 200 DEG C; product is poured in distilled water, with alkali liquor regulation pH value to 8 ~ 9, and sucking filtration; washing; it is dried, recrystallization, obtains khaki target product.Experiment shows, in the DMSO solution of sensor molecule；It is separately added into F‑、Cl‑、Br‑、I‑、AcO‑、H2PO4 ‑、HSO4 ‑、ClO4 ‑And SCN‑DMSO solution, find only F‑Addition make solution send significant blue-fluorescence under uviol lamp.Therefore, this sensor can be used for F‑Fluorescence quickly detect, and this identification process is not disturbed by other anion.Applying for the ease of reality, the present invention has also made fluorion Test paper based on this sensor.
Description
Technical field
The invention belongs to Anionic recognition field, relate to a kind of fluorine ion sensing device, particularly relate to the sensor of a kind of high selectivity fluorescence identifying fluorion；The present invention also relates to the synthesis of this fluorine ion sensing device and the application in identifying fluorion.
Background technology
Fluorine is widely present in soil, Natural Water, animals and plants.In natural environment, fluorine is mainly presented in fluorite, and its main component is the fluoro things such as aluminium fluoride, calcium fluoride, sodium fluoride, calcium monofluorophosphate., and in the food that we are drunk simultaneously, great majority all contain a certain amount of fluorine.Owing to fluorine is one of trace element of needed by human, the aspects such as the metabolism at formation dental enamel, skeletal tissue and calcium phosphorus all play a part can not be substituted, so appropriate fluorine is to maintain skeleton and tooth development requisite, but human body is the most sensitive to Oil repellent, differing the least from the amount meeting human body and too much causing fluorine needs to fluorine poisoning, therefore fluorine is to much narrower than other trace element of the safety range of human body.Owing to fluoride is soluble in water, it forms fluorion in water, so dissolution after groundwater erosion, causes the fluoride pollution of surface water and subsoil water, and fluorion is also one of Main Anions in Atmospheric precipitation simultaneously.At present, the whole world still has a lot of people to drink high-fluorine water, and endemic fluorosis event gradually causes the attention of countries in the world.
The health of people in fluorosis serious harm, and the detection method of research fluorine suffers from practical practical value to fluoride pollution and scientific experiments, and the detection of fluorion gets more and more people's extensive concerning, and constantly inquires into its detection method.Wherein the chemical sensitisation method by colorimetric or fluorescence molecule is the most noticeable.
Summary of the invention
It is an object of the invention to provide the sensor of a kind of fluorescence identifying fluorion；
It is a further object of the present invention to provide the preparation method of this fluorescence identifying fluorine ion sensing device a kind of；
It is a further aim of the invention provide the application in detection fluorion of this fluorescence identifying fluorine ion sensing device.
One, the preparation of fluorine ion sensing device
The structure of fluorine ion sensing device of the present invention is as follows:
The preparation method of above-mentioned fluorine ion sensing device, is that polyphosphoric acids is catalyst with p-phthalic acid and o-phenylenediamine as substrate; phosphoric acid is dehydrant; under nitrogen protection, stirring reaction 5 ~ 6h at 160 ~ 200 DEG C, it is blackish green for making reaction solution; product is poured in distilled water; with alkali liquor regulation pH value to 8 ~ 9, sucking filtration, washing; it is dried, obtains the thick product of light green solid；Again with DMF and water recrystallization, obtain khaki target product.
The mol ratio of substrate p-phthalic acid and o-phenylenediamine is 1:2 ~ 1:2.5；The consumption of polyphosphoric acids be p-phthalic acid, the 2.0 ~ 2.5% of o-phenylenediamine mole total amount, the consumption of phosphoric acid be p-phthalic acid, the 15 ~ 20% of o-phenylenediamine mole total amount.
The sign data of above-mentioned synthetic product are as follows:
1H NMR (DMSO–d6, 400 MHz) δ: 13.58(s, 2H, N-H); δ: 7.29–7.75 (d, 8H, Ar–H); IR (KBr)v: 3391.15 cm-1(NH),
1627.35 cm-1(CH=N); MS/(EI): m/z: 311.5 (L+H+)+;
Anal. calcd for C20H14N4,C 77.40, H 4.55, N
18.05; found C 77.48, H 4.51, N 18.01。
Two, the sensor recognition performance to fluorion
1, sensor is to F-Fluorescence identifying
The sensor molecule (being called for short M) is dissolved in DMSO and is configured to bulk solution (c=2.0 × 10-5Mol/L)；It is separately added into the F of 50 times of equivalents-、Cl-、Br-、I-、AcO-、H2PO4 -、HSO4 -、ClO4 -And SCN-DMSO solution.Find, only F-Addition make bulk solution send significant blue-fluorescence under uviol lamp.In corresponding fluorescence spectrum, only F-Addition make bulk solution maximum fluorescence emission peak (λ ex=380nm) occur at 458nm and create red shift (see figure 1).Therefore, sensor M can be used for F-Fluorescence quickly detect.
2, sensor identification F-Interference free performance
From the point of view of the receptor of ion identification, interference free performance is a very important index.In order to study sensor molecule M to F-The interference free performance identified, we have done following anti-interference test: by the F of 50 times of equivalents-Join M(c=2.0 × 10-5Mol/L), in DMSO solution, solution colour is decorporated.Again by the Cl of equivalent-、 Br-、I-、 AcO-、H2PO4 -、HSO4 -、ClO4 -、SCN-Solution is added separately in above-mentioned system, and now solution fluorescence color no longer changes, this with only add F-Time phenomenon identical.Choose in fluorescence spectrum fluorescence intensity data at 458 nm and do block diagram (see figure 2).It is clear that other anion is to F from Fig. 2-Identification do not interfere with.Therefore, sensor molecule M can be with single selective identification F-, and other anion is had good anti-interference.
3, sensor is to F-Fluorescence titration
For probing into sensor molecule M further to F-Recognition mechanism, We conducted fluorescence emission spectrum titration experiments (see Fig. 3,4).Pipette 2.5mL sensor M(c=2.0 × 10-5Mol/L) DMSO solution, in quartz cell, is gradually added into F by accumulation sample-adding method-, along with F-Addition, appearance maximum fluorescence emission peak at 458m is also gradually increasing.Nuclear-magnetism titration spectrogram shows: when adding 0.5 times of F in main body M-Time, occurring in that a round peak at 10.98ppm, this is F-Seize the proton of N-H on receptor M imidazoles on one side, cause the cloud density of receptor M to increase, another side not with F-The N-H peak of effect moves to High-Field.When continuing to add 2 times of F in receptor M-Time, the N-H peak of 10.98ppm to low field movement to 13.52ppm, this phenomenon be due to two N-H protons in main body all with define hydrogen bond.When adding 4 times of F to main body-Time, occur in that HF at 15.67ppm- 2Peak, these two N-H that can illustrate on receptor M imidazoles there occurs deprotonation；High resolution mass spectrum and infrared spectrum prove the recognition mechanism of its hydrogen bond deprotonation the most very well.Therefore, we to sensor molecule M to F-Recognition mechanism inquire into as follows: F-With the H proton on main body M imidazole ring with hydrogen bond formation effect, then there is deprotonation process so that it is electron density changes, and results in bright blue fluorescence.
4, sensor molecule is to F-The mensuration of fluorescence lowest detectable limit
According to 3sB/ S method [Analytical Methods Committee.
Recommendations for the definition, estimation and use of the detection limit.Analyst.
1987,112,199-204], M is calculated to F-The minimum detectability of fluorescence spectrum can reach 8.543 × 10-6 mol/L.Therefore this sensor molecule F-Detection there is higher sensitivity.
Three,
F-
The preparation of Test paper and application
1、F-The preparation of Test paper: first soak filter paper with dilute hydrochloric acid, then be washed till neutral and vacuum drying with distilled water, be cut into and be about 4cm, the filter paper of wide about 1cm；Then will be containing host molecule M(0.01M) solution loadings on this filter paper, be finally vacuum dried, standby.
2、F-The application of Test paper: Test paper this under uviol lamp, there is no fluorescence, on reagent paper, only drip F-Time, reagent paper is bright blue fluorescence, and the addition Test paper of other anion does not all have fluorescence to produce.Therefore, this reagent paper can the detection F of rapid sensitive-。
Accompanying drawing explanation
Fig. 1 is main body M (c=2.0 × 10-5Mol/L), in DMSO solution, different anions F is added-、Cl-、Br-、I-、AcO-、H2PO4 -、HSO4 -、ClO4 -And SCN-(c =1.0×10-3Mol/L) fluorescence spectrum figure.
Fig. 2 is main body M (c=2.0 × 10-5Mol/L) to F- (c =1.0×10-3The anti-interference figure that mol/L) identifies (black: M adds the fluorescence intensity of other each anion, ash: add F-After add the fluorescence intensity of each anion again, 1 ~ 9 is respectively as follows: main body, F-、Cl-、Br-、I-、AcO-、H2PO4 -、HSO4 -、ClO4 -、SCN-).
Fig. 3 is main body M (c=2.0 × 10-5Mol/L), in DMSO solution, accumulation adds F-Fluorescence titration figure.
Fig. 4 is in main body M (c=2.0 × 10-5Mol/L), in DMSO solution, accumulation adds F-Time fluorescence emission spectrogram at 458nm.
Fig. 5 is for being 380nm in excitation wavelength, in DMSO solvent, and F-Between addition 20 ~ 35 equivalent, solution fluorescence intensity spectrogram at 458nm.
Detailed description of the invention
1、F-The preparation of sensor: in the three-neck flask of 250mL, adds the p-phthalic acid of 0.05mol, the o-phenylenediamine of 0.12mmol, 11mL polyphosphoric acids and 40mL phosphoric acid, at N2Protection under, return stirring 6h at 200 DEG C, reaction solution is blackish green, until solution cool down after; pour in the distilled water of 400mL, the NaOH solution of dropping 15%, it is adjusted to pH=8, generates a large amount of greenish precipitate; after solution stands overnight, sucking filtration, wash, be dried, obtain the thick product of light green solid.By thick product DMF and water recrystallization, obtain khaki product.Productivity 88% (m.p. > 300 DEG C).
2、F-The preparation of Test paper: first soak filter paper with dilute hydrochloric acid, then be washed till neutral and vacuum drying with distilled water, be cut into and be about 4cm, the filter paper of wide about 1cm；Then will be containing host molecule M(0.01M) solution loadings on this filter paper, be finally vacuum dried, standby.
3、F-Detection: Test paper this under uviol lamp, there is no fluorescence. on Test paper, drip F respectively-、Cl-、Br-、I-、AcO-、H2PO4 -、HSO4 -、ClO4 -And SCN-If reagent paper is in bright blue fluorescence under uviol lamp, then that add is F-；If reagent paper does not has fluorescence to produce under uviol lamp, then that add is not F-。
Claims (3)
1. the fluorescence identifying fluorine ion sensing device molecule application in detection fluorion, it is characterised in that: in the DMSO solution of sensor molecule, it is separately added into F-、Cl-、Br-、I-、AcO-、H2PO4 -、HSO4 -、ClO4 -And SCN-If solution sends significant blue-fluorescence under uviol lamp, then that add is F-；If solution does not has fluorescence to produce under uviol lamp, then that add is not F-；The structural formula of described sensor molecule is as follows:
。
2. fluorescence identifying fluorine ion sensing device molecule is carried on reagent paper and makes a fluorion Test paper, and the structural formula of described sensor molecule is as follows:
。
3. fluorion Test paper, for the method detecting fluorion, is to drip F on fluorion Test paper respectively as claimed in claim 2-、Cl-、Br-、I-、AcO-、H2PO4 -、HSO4 -、ClO4 -And SCN-If reagent paper is in bright blue fluorescence under uviol lamp, then that add is F-；If reagent paper does not has fluorescence to produce under uviol lamp, then that add is not F-。
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| CN107267139B (en) * | 2017-07-04 | 2020-04-17 | 华南师范大学 | Multifunctional bis (benzimidazole) naphthalene fluorescence chemical sensor and application thereof |
| CN108061728B (en) * | 2017-12-22 | 2020-06-16 | 西北师范大学 | Supermolecule sensor and application thereof in synthesizing and identifying fluoride ions and arginine by fluorescence |
| CN112079861B (en) * | 2020-10-13 | 2023-03-21 | 西北师范大学 | Molecular probe for detecting fluorine ions through fluorescence quenching and preparation method thereof |
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| CN103822916A (en) * | 2014-01-17 | 2014-05-28 | 西北师范大学 | Double-schiff-base based on naphthol, synthesis thereof and application thereof as fluorinion sensor molecular |
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| CN102604095A (en) * | 2012-03-01 | 2012-07-25 | 中国工程物理研究院激光聚变研究中心 | N-substituted polybenzimidazole amide compound and preparation method thereof |
| CN103822916A (en) * | 2014-01-17 | 2014-05-28 | 西北师范大学 | Double-schiff-base based on naphthol, synthesis thereof and application thereof as fluorinion sensor molecular |
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