CN105891164A - Method for perimidinium anion receptor selective fluorescent identification and color discrimination of fluoride ions - Google Patents
Method for perimidinium anion receptor selective fluorescent identification and color discrimination of fluoride ions Download PDFInfo
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Abstract
The invention provides a method for perimidinium anion receptor selective fluorescent identification and color discrimination of fluoride ions. After fluoride ions are added into a DMSO solution of a perimidinium anion receptor, a fluorescence emission spectrum is obviously improved based on no fluorescence, and simultaneously, the yellow solution is changed into a colorless solution so that direct naked eye identification is realized. The method has the advantages of detection timeliness, operation easiness, high sensitivity and use of simple detection devices. The perimidinium anion receptor in a DMSO-water mixed solution still realizes effective selective recognition of fluorine ions in a DMSO-water mixed solution and has a fluorine ion water phase recognition application prospect.
Description
Technical field
The invention belongs to detection technique field, relate to fluorescence identifying method and the colorimetric recognition methods of fluorion, be specifically related to one
UtilizePyridine anion receptor selectivity fluorescence identifying and the method than colour discrimination fluorion, andPyridine anion receptor exists
Application in aqueous phase Fluoride recognition.
Background technology
Fluorion is widely present in nature, and appropriate fluorion has the biggest at holding dental health and treatment osteoporosis
Effect.But the fluorion of excess excretes owing to being difficult to, serious stomach can be caused dirty and nephropathy etc..Fluorine and fluoride
Have a wide range of applications in fields such as Chemical Manufacture, medical science, military affairs as important chemical substance, such as special plastic, toothpaste
Production etc. with military chemistry weapon.The fluoride waste meeting using fluorine-containing chemical or production to produce containing Fluorine contained chemicals in production is tight
Heavily contaminated environment also jeopardizes human survival safety.Therefore, identification and detection to fluorion are a job the most necessary.Existing
Have Fluoride recognition method traditional in technology, including electrode method,19F nuclear magnetic resonance etc., but these methods generally need
Want expensive instrument and equipment and to detect process loaded down with trivial details, relatively costly.Wherein19F nuclear magnetic resonance analysis is difficult to accurately detection
Micro-molar concentration fluorion.Additionally, electrode method and19F nuclear magnetic resonance detection fluorion cannot be applied in bioassay.
Summary of the invention
The present invention proposes a kind of selectivity fluorescence and the method than colour discrimination fluorion, utilizesPyridine anion receptor selects
Property fluorescence identifying and than the fluorion in colour discrimination testing sample.The present invention utilizesPyridine anion receptor can be with selectivity fluorescence
Identify and ratio two kinds of detection methods of colour discrimination, detect fluorion in real time, simply, delicately.Pyridine receptor is as a kind of chemistry
Sensor, is easily accessible biological cell and is combined with fluorion, has answering by the fluorion in bioluminescence image checking cell
Use prospect.
The present invention utilizesThe method of pyridine anion receptor selectivity fluorescence identifying fluorion,Pyridine anion receptor
DMSO or DMSO: H2O=9: 1 solution unstressed configuration, after adding fluorion, solution fluorescence is remarkably reinforced, such that it is able to the fastest
Promptly by test solution fluorescence emission spectrum discrimination fluorion.The basic unstressed configuration of pyridine anion receptor solution, this feature carries
Supply the testing conditions of zero background, greatly reduced mushing error, improve the accuracy of Fluorine Ion Determination.Measure and add difference
Concentration fluoride solution fluorescence intensity, draws and adds fluorinion concentration and the standard curve of fluorescence intensity.Then can be by detection
Testing sample fluorescence intensity, learns fluorinion concentration with standard curve contrast.The inventive method is applicable to Accurate Determining low dose fluoride
Ion.
The present invention utilizesThe method of pyridine anion receptor selectivity fluorescence identifying fluorion, is containingPyridine anion receptor
DMSO solution or DMSO: H2In O=9: 1 solution, add testing sample, if detecting the Fluorescence Increasing of described solution, then
Show in this testing sample containing fluorion；
Wherein, describedShown in the structure of pyridine anion receptor such as formula (A):
Wherein, describedPyridine anion receptor concentration in DMSO solution is 5.0 × 10-6Mol/L～5.0 × 10-3
mol/L；Described testing sample concentration in DMSO solution is 0～1.0 × 10-1mol/L；The fluorescence emission spectrum of described solution
It is obviously enhanced.
Wherein, describedPyridine anion receptor is at DMSO: H2Concentration in O=9: 1 solution is 5.0 × 10-6Mol/L～5.0
×10-3mol/L；Described testing sample is at DMSO: H2Concentration in O=9: 1 solution is 5 × 10-4Mol/L～5.0 × 10-1
mol/L；The fluorescence emission spectrum of described solution is obviously enhanced.
The present invention utilizesThe method of pyridine anion receptor selectivity ratios colour discrimination fluorion,Pyridine anion receptor
DMSO or DMSO: H2O=9: 1 solution is yellow, and after adding fluorion, solution is gradually become colourless by yellow.The inventive method
The biggest actual application value can be had than colour discrimination fluorion, this particularity in chemical sensor identification simple ion with bore hole.
By in same concentration same volumePyridine solution adds variable concentrations fluorion, the standard color range solution of configuration, can examine with colorimetric
Survey fluorinion concentration in testing sample.The inventive method simple and fast, it is not necessary to any precision equipment.Can be widely used in fluorine from
During the simple identification of son, its simplicity has been greatly reduced the technology requirement to operator.
The present invention utilizesThe method of pyridine anion receptor selectivity ratios colour discrimination fluorion, is containingPyridine anion receptor
DMSO solution or DMSO: H2In O=9: 1 solution, add testing sample, if the color from yellow of described solution becomes nothing
Color, then show in this testing sample containing fluorion；Wherein, describedShown in the structure of pyridine anion receptor such as formula (A):
Wherein, describedPyridine anion receptor concentration in DMSO solution is 5.0 × 10-5Mol/L～5.0 × 10-2mol/L；
Described testing sample concentration in DMSO solution is 0～1.0mol/L；The color from yellow of described solution becomes colorless.
Wherein, describedPyridine anion receptor is at DMSO: H2Concentration in O=9: 1 solution is 5.0 × 10-5Mol/L～5.0 ×
10-2mol/L；Described testing sample is at DMSO: H2Concentration in O=9: 1 solution is 5.0 × 10-3Mol/L～5.0mol/L；Institute
The color from yellow stating solution becomes colorless.
In the present invention, formula (A)Synthetic route and the crystal structure of pyridine anion receptor are as follows:
In the present invention, formula (A)The sign of pyridine anion receptor molecule includes following:
Nuclear-magnetism characterizes:
1H NMR (400MHz, DMSO-d6) δ 5.40 (s, 4H), 6.94 (d, J=8.0Hz, 2H), 7.43 (m, 8H), 7.56 (d,
J=8.0Hz, 2H), 7.72 (d, J=8.0Hz, 4H), 10.05 (s, 1H).
13C NMR (100MHz, DMSO-d6) δ 154.67,134.21,132.79,131.47,128.90,128.42,128.10,
127.46,123.78,121.33,108.98,54.64.
Elemental analysis: host molecule C25H21ClN2Theoretical value: C, 78.01；H, 5.50；N, 7.28. measured value: C, 77.97；
H, 5.46；N, 7.01..
HR MS C25H21N2 +(M-Cl), theoretical value: 349.1699, measured value: 349.1693..
In a specific embodiment, described formula (A)Pyridine anion receptor according to customary preparation methods is: at N2Protect
Protect down, 100mL two-mouth bottle add sodium hydride (60%, 0.32g, 8mmol),Pyridine (0.6728g, 4mmol), molten
Benzyl chloride (2.0253g, 16mmol) is added after 30mL acetonitrile, stirring 10min.24h is reacted under room temperature.It is filtered to remove after 24h
Precipitation, filtrate is transferred in clean 100mL flask, 85 DEG C of heated and stirred reaction 24h, produces yellow solid, and after filtration, solid is used
Acetonitrile washs 5 times, and product is vacuum dried at 50 DEG C, obtains receptor 0.7664g, and yield is 50.0%.
Selectivity fluorescence of the present invention and the method than colour discrimination fluorion, its identification includes:The DMSO of pyridine anion receptor
Adding fluorion in solution, there is obvious Fluorescence Increasing in unstressed configuration receptor solution, it is possible to achieve fluorescence identifying fluorion；?Pyridine
Adding fluorion in the DMSO solution of anion receptor, solution colour is become colorless by yellow, it is possible to achieve bore hole colorimetric is known
Other fluorion；?DMSO: H of pyridine anion receptor2Adding fluorion in O=9: 1 solution, unstressed configuration receptor solution goes out
Now obvious Fluorescence Increasing, solution colour is become colorless by yellow, it is possible to achieve aqueous phase fluorescence and ratio colour discrimination fluorion.
The present invention utilizesThe method of pyridine anion receptor selectivity fluorescence identifying is: be 5.0 × 10 in concentration-6Mol/L～5.0
×10-3Mol/L'sDMSO or DMSO: H of pyridine anion receptor2In O=9: 1 solution, be gradually added into fluorion,
Chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate
4-butyl ammonium, concentration is0～20 times of pyridine anion receptor concentration.When adding fluorion, solution fluorescence emission spectrum is strong
Degree strengthens the most obvious, explanationPyridine anion receptor can fluorescence identifying fluorion.MeasurePyridine anion receptor solution
Add the Fluorescence Increasing process of fluoride solution, draw and add fluorinion concentration and the relation curve of solution fluorescence intensity, as mark
Directrix curve.
When whether there is fluorion and fluorinion concentration in detecting testing sample, certain densityPyridine anion receptor
DMSO or DMSO: H2O=9: 1 solution adds testing sample, measures the solution fluorescence intensity adding testing sample.With
The relation curve of fluorinion concentration and solution fluorescence intensity is standard curve, according to the solution fluorescence intensity of the testing sample recorded,
So that it is determined that the fluorinion concentration in testing sample.
The present invention utilizesThe method of pyridine anion receptor selectivity ratios colour discrimination is: be 5.0 × 10 in concentration-5Mol/L～5.0
×10-2Mol/L'sDMSO or DMSO: H of pyridine anion receptor2In O=9: 1 solution, be gradually added into fluorion,
Chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate
4-butyl ammonium, concentration is0～20 times of pyridine anion receptor concentration.When adding fluorion, solution colour is become from yellow
Colourless, explanationPyridine anion receptor can bore hole than colour discrimination fluorion.Take containing equal-volume with concentrationPyridine cloudy from
DMSO or DMSO: H of sub-receptor2Identical one group of color comparison tube of O=9: 1 solution, be separately added into different amounts of fluorine from
Son, is made into the standard color range of color gradually alternation.
When whether there is fluorion and fluorinion concentration in detecting testing sample, certain densityPyridine anion receptor
DMSO or DMSO: H2O=9: 1 solution adds testing sample, with reference to the different marks corresponding by different fluorinion concentrations
Quasi-color range, can according to detection sample color, visually find out the standard color range that color and luster is the most close, by its correspondence institute fluorine-containing from
The normal concentration of son, determines fluorinion concentration in testing sample.
In the present inventionPyridine anion receptor can be by fluorescence identifying with than two kinds of recognition mechanism identification fluorions of colour discrimination.This
Bright also proposedPyridine anion receptor is at DMSO solution or DMSO: H2Selectivity fluorescence identifying fluorion in O=9: 1 solution
Application.The invention allows forPyridine anion receptor is at DMSO solution or DMSO: H2Selectivity ratios in O=9: 1 solution
The application of colour discrimination fluorion.
Further, the invention allows forThe application in aqueous phase Fluoride recognition of the pyridine anion receptor, i.e.Pyridine
Anion receptor is still capable of the effective selectivity identification of fluorion in the mixed solution of DMSO and water, and it includes respectively
Application in aqueous phase fluorion fluorescence identifying, at aqueous phase fluorion than the application in colour discrimination.
DescribedShown in pyridine anion receptor such as formula (A):
The present invention passes through nuclear magnetic resonance research course of reaction, and designs corresponding confirmatory experiment, it is proposed thatPyridine anion receptor
Identify the reaction mechanism of fluorion, as shown in Figure 9.The process of identification fluorion of the present invention is: fluorion has extremely strong electronegativity
With deprotonation ability, withPyridine C (2)-H acts on, and causesPyridine anion receptor deprotonation, forms carbene compound.
Carbene compound reacts with water, generates fluorescent chemicals 7a.The generation of noval chemical compound 7a, result in the obvious Fluorescence Increasing of solution
Become colorless by yellow with solution colour.Compound 7a is unstable, easily decomposes and produces compound 8a and 9a.This mechanism produces
Compound all there is corresponding experimental data proved.
The present invention proposes a kind of new selectivity fluorescence identifying, method than colour discrimination fluorion.Fluorion has the ion of minimum
Radius, the highest electric charge be close and Lewis base character, in the present invention, will have lewis acid characterPyridine anion receptor
As novel fluorophor and binding site, utilizePyridine anion receptor and fluorion selective binding, it is achieved that to fluorine
The selectivity fluorescence of ion and compare colour discrimination.Especially because colorimetric recognition methods, the bore hole identification of fluorion therefore can be realized,
Such that it is able to simply identify fluorion quickly under conditions of without precision checking equipment.Implement the instrument and equipment tool of the inventive method
There is simple feature.The present invention presentsThe application prospect in Fluoride recognition field of pyridine anion receptor.The present invention is high
Effect ground utilizesPyridine anion receptor identification fluorion, has detection real-time, simple to operation, sensitivity advantages of higher.
Beneficial effect of the present invention also includes: the method for the present invention compares traditional Fluoride recognition mode, as electrode method,19F NMR
Nuclear magnetic resonance, NMR, has instrument simple, and real-time easily operates, sensitivity advantages of higher.The present invention is capable of the glimmering of fluorion
The two ways identification of light and colorimetric.Wherein, fluorescence identifying due toThe almost completely free fluorescence of pyridine anion receptor solution, zero
Detection background, can be greatly reduced detection error.Bore hole identification then can be realized, it is possible to simpler know quickly by colorimetric
Other fluorion.The present invention can realize fluorescence and ratio colour discrimination fluorion in aqueous DMSO solution, it is seen that the present invention is at aqueous phase
Middle identification fluorion has a good application prospect.
Accompanying drawing explanation
Fig. 1 isIn pyridine anion receptor DMSO solution (5.0 × 10-6Mol/L) 2.5 × 10 are added-5Mol/L different anions
Fluorescence emission spectrogram.
Fig. 2 isIn pyridine anion receptor DMSO solution (5.0 × 10-6Mol/L) fluorion (0-2.5 × 10 are added-5Mol/L) glimmering
Optical emission spectroscopy figure.
Fig. 3 isIn pyridine anion receptor DMSO solution (5.0 × 10-6Mol/L) fluorion (0-2.5 × 10 are added-5Mol/L), fluorine
Ion concentration and solution is the standard curve of fluorescence intensity at 400nm.
Fig. 4 isIn pyridine anion receptor DMSO solution (5.0 × 10-5Mol/L) 1.5 × 10 are added-4Mol/L different anions
Uv absorption spectra.
Fig. 5 isPyridine anion receptor DMSO: H2In O=9: 1 solution (5.0 × 10-6Mol/L) 1.0 × 10 are added-4Mol/L is not
Fluorescence emission spectrogram with anion.
Fig. 6 isPyridine anion receptor DMSO: H2In O=9: 1 solution (5.0 × 10-6Mol/L) fluorion (0-1.0 × 10 are added-4
Mol/L) fluorescence emission spectrogram.
Fig. 7 isPyridine anion receptor DMSO: H2In O=9: 1 solution (5.0 × 10-6Mol/L) fluorion (0-1.0 × 10 are added-4
Mol/L), fluorinion concentration and the solution standard curve of fluorescence intensity at 400nm.
Fig. 8 isPyridine anion receptor DMSO: H2In O=9: 1 solution (5.0 × 10-5Mol/L) 5.0 × 10 are added-4mol/L
The uv absorption spectra of different anions.
Fig. 9 is the mechanism schematic diagram of identification fluorion of the present invention.
Detailed description of the invention
In conjunction with specific examples below and accompanying drawing, the present invention is described in further detail, and the protection content of the present invention is not limited to
In following example.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change and advantage
All it is included in the present invention, and with appending claims as protection domain.Implement the process of the present invention, condition, examination
Agent, experimental technique etc., outside the lower content mentioned specially, be universal knowledege and the common knowledge of this area, the present invention
Content is not particularly limited.In each embodimentShown in pyridine anion receptor such as formula (A).
Embodiment 1: fluorion in fluorescence identifying DMSO solution
Pipette 1mL respectivelyThe DMSO solution (5.0 × 10 of pyridine anion receptor-5Mol/L) in a series of 10mL volumetric flasks,
It is separately added into 0.5mL fluorion, chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, biphosphate
Radical ion, the DMSO solution (5.0 × 10 of 4-butyl ammonium of perchlorate-4Mol/L), it is diluted to scale with DMSO.
Now, in solutionPyridine acceptor density is 5.0 × 10-6Mol/L, anion in solution (respectively fluorion, chloride ion,
Bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate) concentration is 2.5 × 10-5
Mol/L, i.e. the anion concentration in each solution is 5 times of acceptor density, stands overnight after mix homogeneously.With concentration for 5.0 × 10-6
Mol/L'sThe DMSO solution (not adding anion) of pyridine anion receptor is as comparison.Under the conditions of 25 DEG C, 353nm
For excitation wavelength, measure the fluorescence emission spectrum of each solution.
The comparison of the acceptor fluorescence intensity change before and after addition anion as shown in Figure 1, shows: after adding fluorion,Pyridine
Anion receptor solution fluorescence emission spectrum at 400nm is obviously enhanced.And add other aniones (e.g., chloride ion,
Bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions or perchlorate),Pyridine
The fluorescence emission spectrum change at 400nm of the anion receptor solution is less or almost unchanged.ExplanationPyridine anion receptor
Can in DMSO solution Selective recognition fluorion.
Embodiment 2: content of fluoride ion in fluoroscopic examination DMSO solution
Taking concentration is 5.0 × 10-6Mol/L'sThe DMSO solution 2mL of pyridine anion receptor, being gradually added into concentration is 5.0
×10-3Mol/L fluorion 0-10 μ L, in ie in solution, fluorinion concentration gradually increases to 2.5 × 10 from 0mol/L--5mol/L(
5 times of pyridine acceptor density).MeasurePyridine anion receptor solution adds the Fluorescence Increasing mistake of variable concentrations fluoride solution
Journey.As in figure 2 it is shown, along with the increase of addition fluorinion concentration, solution fluorescence emission spectrum at 400nm is remarkably reinforced.Take
Solution fluorescence intensity at 400nm, draws and adds the relation curve of solution fluorescence intensity at fluorinion concentration and 400nm, such as Fig. 3
Shown in, i.e. fluorion and the standard curve of solution fluorescence intensity.
Taking 2 μ L liquid to be measured, adding 2mL concentration is 5.0 × 10-6Mol/L'sIn the DMSO solution of pyridine anion receptor,
Measure the fluorescence emission spectral intensity of solution.According to fluorescence intensity, according to fluorinion concentration and the standard curve of solution fluorescence intensity
Correspondence checks in fluorinion concentration, can be by being calculated the content of fluorion in liquid to be measured.
According to fluorinion concentration and the standard curve of solution fluorescence intensity, detection method, lowest detection line is up to 1.0
×10-6Mol/L, detecting optimal interval is 1.0 × 10-6mol/L-2.5×10-5Mol/L, can detect low dose fluoride with sensitivity
Ion.Additionally, due toThe almost completely free fluorescence of pyridine anion receptor solution, zero detection background, detection can be greatly reduced
Error.
Embodiment 3: than fluorion in colour discrimination DMSO solution
Pipette 1mL respectivelyThe DMSO solution (5.0 × 10 of pyridine anion receptor-4Mol/L) in a series of 10mL volumetric flasks,
It is separately added into 0.3mL fluorion, chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, biphosphate
Radical ion, the DMSO solution (5.0 × 10 of 4-butyl ammonium of perchlorate-3Mol/L), it is diluted to scale with DMSO.
Now, in the solution,Pyridine anion receptor concentration is 5.0 × 10-5Mol/L, anion (respectively fluorion, chloride ion,
Bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate) concentration is 1.5 × 10-4
Mol/L, i.e. the anion concentration in solution is 3 times of acceptor density, stands overnight after mix homogeneously.With concentration for 5.0 × 10-5
Mol/L'sThe DMSO solution (not adding anion) of pyridine anion receptor is as comparison.Measure each under the conditions of 25 DEG C
The ultra-violet absorption spectrum of solution.
As shown in Figure 4, add the receptor ultraviolet change before and after anion find by comparing: after adding fluorion,Pyridine is cloudy
Ion receptor solution has the newest absworption peak to produce at 353nm；Ultra-violet absorption spectrum at 400nm substantially weakens.And
Add other aniones (chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions,
Perchlorate) after,Pyridine anion receptor solution new absworption peak at 353nm generates less or generates without new absworption peak；
It is less or almost unchanged that absworption peak at 400nm weakens change.ExplanationPyridine anion receptor can pass through uv absorption
Spectrum is Selective recognition fluorion in DMSO solution.
When adding fluorion, solution absworption peak at 400nm weakens, and causes solution to gradually become colourless molten from yellow solution
Liquid.The change explanation of colorPyridine anion receptor can realize the bore hole of fluorion and compare colour discrimination.The inventive method can be
Without under conditions of precision equipment, recognition detection fluorion in DMSO solution conveniently and efficiently.
Embodiment 4: content of fluoride ion in colorimetric determination DMSO solution
Taking concentration is 5.0 × 10-5Mol/L'sThe DMSO solution 10mL of pyridine anion receptor, is separately added into identical
One group of color comparison tube, be separately added into different amounts of fluorion, fluorinion concentration is respectively 0mol/L, 5.0 × 10-5Mol/L, 1.0
×10-4Mol/L, 1.5 × 10-4Mol/L, 2.0 × 10-4Mol/L, 2.5 × 10-4mol/L.Solution colour in color comparison tube is along with adding
Enter fluorinion concentration to increase, gradually become colorless from yellow, form the standard color range of color gradually alternation.
Taking 10 μ L liquid to be measured, being equipped with 10mL concentration is 5.0 × 10-5Mol/L'sAnion receptor DMSO is molten in pyridine
In the identical color comparison tube of liquid.After adding liquid to be measured, solution colour and standard sample color contrast, visually find out color and luster phase
Near standard sample, the normal concentration of fluorion in standard sample, fluorinion concentration in color comparison tube the most to be measured.By being calculated
The content of fluorion in liquid to be measured.
According to adding fluorinion concentration and the standard color range of solution colour, detection method, lowest detection line is up to 5.0
×10-5Mol/L, detecting optimal interval is 5.0 × 10-5mol/L-2.5×10-4Mol/L, can be at the bar without accurate expensive instrument
Under part, convenient and swift detection low dose fluoride ion.
Embodiment 5: fluorescence identifying DMSO: H2Fluorion in O=9: 1 solution
Pipette 1mL respectivelyThe DMSO solution (5.0 × 10 of pyridine anion receptor-5Mol/L), 1mL water is in a series of 10mL
In volumetric flask, be separately added into 2.0mL fluorion, chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion,
Dihydrogen phosphate ions, the DMSO solution (5.0 × 10 of 4-butyl ammonium of perchlorate-4Mol/L), dilute with DMSO
To scale.Now, in solutionPyridine acceptor density is 5.0 × 10-6Mol/L, anion in solution (respectively fluorion,
Chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate)
Concentration is 1.0 × 10-4Mol/L, i.e. the anion concentration in each solution is 20 times of acceptor density, places after mix homogeneously
Night.With concentration for 5.0 × 10-6Mol/L'sDMSO: H of pyridine anion receptor2O=9: 1 solution (does not adds anion)
As comparison.Under the conditions of 25 DEG C, 353nm is excitation wavelength, measures the fluorescence emission spectrum of each solution.
As it is shown in figure 5, compare the acceptor fluorescence intensity change before and after addition anion, find: after adding fluorion,Pyridine
Anion receptor solution fluorescence emission spectrum at 400nm is obviously enhanced.And add other aniones (e.g., chloride ion,
Bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate),Pyridine is cloudy
The fluorescence emission spectrum change at 400nm of the ion receptor solution is less or almost unchanged.ExplanationPyridine anion receptor can
With at DMSO: H2Selective recognition fluorion in O=9: 1 solution.
Embodiment 6: fluoroscopic examination DMSO: H2Content of fluoride ion in O=9: 1 solution
Taking concentration is 5.0 × 10-6Mol/L'sDMSO: H of pyridine anion receptor2O=9: 1 solution 2mL, is gradually added into
Concentration is 5.0 × 10-3Mol/L fluorion 0-40 μ L, in ie in solution, fluorinion concentration gradually increases to 1.0 × 10 from 0mol/L-4
mol/L(20 times of pyridine acceptor density).MeasurePyridine anion receptor solution adds the glimmering of variable concentrations fluoride solution
Light strengthens process.As shown in Figure 6, along with the increase of addition fluorinion concentration, solution fluorescence emission spectrum at 400nm is obvious
Strengthen.Take solution fluorescence intensity at 400nm, draw and add the relation curve of solution fluorescence intensity at fluorinion concentration and 400nm,
As it is shown in fig. 7, i.e. fluorion and the standard curve of solution fluorescence intensity.
Taking 2 μ L liquid to be measured, adding 2mL concentration is 5.0 × 10-6Mol/L'sDMSO: H of pyridine anion receptor2O=9: 1
In solution, measure the fluorescence emission spectral intensity of solution.According to fluorescence intensity, according to fluorinion concentration and solution fluorescence intensity
Standard curve correspondence checks in fluorinion concentration, can be by being calculated the content of fluorion in liquid to be measured.
According to fluorinion concentration and the standard curve of solution fluorescence intensity, detection method, lowest detection line is up to 1.0
×10-6Mol/L, detecting optimal interval is 1.0 × 10-6mol/L-1.0×10-4Mol/L, can detect with sensitivity low dose fluoride from
Son.
Embodiment 7: ratio colour discrimination DMSO: H2Fluorion in O=9: 1 solution
Pipette 1mL respectivelyThe DMSO solution (5.0 × 10 of pyridine anion receptor-4Mol/L), 1mL water is in a series of 10mL
In volumetric flask, be separately added into 1.0mL fluorion, chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion,
Dihydrogen phosphate ions, the DMSO solution (5.0 × 10 of 4-butyl ammonium of perchlorate-3Mol/L), dilute with DMSO
To scale.Now, in the solution,Pyridine anion receptor concentration is 5.0 × 10-5Mol/L, anion (respectively fluorion,
Chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate)
Concentration is 5.0 × 10-4Mol/L, i.e. the anion concentration in solution is 10 times of acceptor density, stands overnight after mix homogeneously.
With concentration for 5.0 × 10-5Mol/L'sDMSO: H of pyridine anion receptor2O=9: 1 solution (not adding anion) conduct
Comparison.The ultra-violet absorption spectrum of each solution is measured under the conditions of 25 DEG C.
As shown in Figure 8, add the receptor ultraviolet change before and after anion find by comparing: after adding fluorion,Pyridine is cloudy
Ion receptor solution has the newest absworption peak to produce at 353nm；Ultra-violet absorption spectrum at 400nm substantially weakens.And
Add other aniones (chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions,
Perchlorate) after,Pyridine anion receptor solution new absworption peak at 353nm generates less or generates without new absworption peak；
It is less or almost unchanged that absworption peak at 400nm weakens change.ExplanationPyridine anion receptor can pass through uv absorption
Spectral selection identification fluorion.
When adding fluorion, solution absworption peak at 400nm weakens, and causes solution to gradually become colourless molten from yellow solution
Liquid.The change explanation of colorPyridine anion receptor can realize the bore hole of fluorion and compare colour discrimination.The inventive method can be
Under conditions of precision equipment, recognition detection fluorion conveniently and efficiently.
Embodiment 8: colorimetric determination DMSO: H2Content of fluoride ion in O=9: 1 solution
Taking concentration is 5.0 × 10-5Mol/L'sDMSO: H of pyridine anion receptor2O=9: 1 solution 10mL, is separately added into
Identical one group of color comparison tube, is separately added into different amounts of fluorion, and fluorinion concentration is respectively 0mol/L, and 1.0 × 10-4
Mol/L, 2.0 × 10-4Mol/L, 3.0 × 10-4Mol/L, 4.0 × 10-4Mol/L, 5.0 × 10-4Mol/L, 6.0 × 10-4Mol/L,
7.0×10-4Mol/L, 8.0 × 10-4Mol/L, 9.0 × 10-4Mol/L, 1.0 × 10-3mol/L.Solution colour in color comparison tube with
Addition fluorinion concentration to increase, gradually become colorless from yellow, form the standard color range of color gradually alternation.
Taking 10 μ L liquid to be measured, being equipped with 10mL concentration is 5.0 × 10-5Mol/L'sPyridine anion receptor DMSO:
H2In the identical color comparison tube of O=9: 1 solution.After adding liquid to be measured, solution colour and standard sample color contrast, visually look for
Go out the standard sample that color and luster is the most close, the normal concentration of fluorion in standard sample, fluorinion concentration in color comparison tube the most to be measured.Logical
Cross and be calculated the content of fluorion in liquid to be measured.
According to adding fluorinion concentration and the standard color range of solution colour, detection mode of the present invention, lowest detection line is up to 1.0
×10-4Mol/L, detecting optimal interval is 1.0 × 10-4mol/L-1.0×10-3Mol/L, can be in the condition without accurate expensive instrument
Under, conveniently detection low dose fluoride ion.
Claims (9)
1. a utilizationThe method of pyridine anion receptor selectivity fluorescence identifying fluorion, it is characterised in that containingPyridine is cloudy
The DMSO solution of ion receptor or DMSO: H2In O=9: 1 solution, add testing sample, if detecting the fluorescence of described solution
Strengthen, then show in this testing sample containing fluorion；
Wherein, describedShown in the structure of pyridine anion receptor such as formula (A):
2. the method for claim 1, it is characterised in that describedPyridine anion receptor concentration in DMSO solution
It is 5.0 × 10-6Mol/L～5.0 × 10-3mol/L；Described testing sample concentration in DMSO solution is 0～1.0 × 10-1
mol/L；The fluorescence emission spectrum of described solution strengthens.
3. the method for claim 1, it is characterised in that describedPyridine anion receptor is at DMSO: H2O=9: 1 solution
In concentration be 5.0 × 10-6Mol/L～5.0 × 10-3mol/L；Described testing sample is at DMSO: H2Dense in O=9: 1 solution
Degree is 5 × 10-4Mol/L～5.0 × 10-1mol/L；The fluorescence emission spectrum of described solution strengthens.
4. a utilizationThe method of pyridine anion receptor selectivity ratios colour discrimination fluorion, it is characterised in that containingPyridine is cloudy
The DMSO solution of ion receptor or DMSO: H2In O=9: 1 solution, add testing sample, if the color of described solution is by Huang
Color becomes colorless, then show in this testing sample containing fluorion；
Wherein, describedShown in the structure of pyridine anion receptor such as formula (A):
5. method as claimed in claim 4, it is characterised in that describedPyridine anion receptor concentration in DMSO solution
It is 5.0 × 10-5Mol/L～5.0 × 10-2mol/L；Described testing sample concentration in DMSO solution is 0～1.0mol/L；
The color from yellow of described solution becomes colorless.
6. method as claimed in claim 4, it is characterised in that describedPyridine anion receptor is at DMSO: H2O=9: 1 solution
In concentration be 5.0 × 10-5Mol/L～5.0 × 10-2mol/L；Described testing sample is at DMSO: H2Dense in O=9: 1 solution
Degree is 5.0 × 10-3Mol/L～5.0mol/L；The color from yellow of described solution becomes colorless.
7. formula (A)Pyridine anion receptor is at DMSO solution or DMSO: H2Selectivity fluorescence identifying fluorine in O=9: 1 solution
The application of ion.
8. formula (A)Pyridine anion receptor is at DMSO solution or DMSO: H2Selectivity ratios colour discrimination fluorine in O=9: 1 solution
The application of ion.
9. formula (A)Pyridine anion receptor is in the application of aqueous phase Fluoride recognition, and wherein, described application is at DMSO and water
Mixed solution in identify in testing sample whether contain fluorion.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19536403A1 (en) * | 1994-09-30 | 1996-04-04 | Basf Ag | Perimidinium salts and prepn. thereof |
| CN1815201A (en) * | 2006-02-13 | 2006-08-09 | 南京大学 | Visual colorimetric fluorine ion sensing test-paper and use thereof |
| CN101863825A (en) * | 2010-06-24 | 2010-10-20 | 华东师范大学 | Ionic liquid containing carbamido group and pyridinium main ring and preparation method thereof |
-
2014
- 2014-09-11 CN CN201410491425.7A patent/CN105891164A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19536403A1 (en) * | 1994-09-30 | 1996-04-04 | Basf Ag | Perimidinium salts and prepn. thereof |
| CN1815201A (en) * | 2006-02-13 | 2006-08-09 | 南京大学 | Visual colorimetric fluorine ion sensing test-paper and use thereof |
| CN101863825A (en) * | 2010-06-24 | 2010-10-20 | 华东师范大学 | Ionic liquid containing carbamido group and pyridinium main ring and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MEIYUN FENG等: "Selective recognition of acetate ion by perimidinium-based receptors", 《TETRAHEDRON LETTERS》 * |
| 杨海强等: "Perimidinium 荧光比色传感器识别F-离子", 《中国化学会第29届学术年会摘要集——第18分会：超分子组装与软物质材料》 * |
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