CN105651743A - Method for selective fluorescence recognition and colorimetric recognition of fluorine ions by using perimidine onium anion receptor - Google Patents
Method for selective fluorescence recognition and colorimetric recognition of fluorine ions by using perimidine onium anion receptor Download PDFInfo
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Abstract
The present invention provides a method for selective fluorescence recognition and colorimetric recognition of fluorine ions by using a perimidine onium anion receptor. According to the present invention, the fluorescence emission spectrum of the perimidine onium anion receptor is significantly enhanced on the basis of the zero fluorescence after fluorine ions are added to a DMSO solution while the color of the solution is colorless from the yellow color so as to achieve the naked eye recognition; the method has advantages of real-time detection, easy operation, high sensitivity, simple detection equipment, and the like; and the perimidine onium anion receptor can achieve the effective selective recognition of the fluorine ions in the mixed solution of DMSO and water, such that the perimidine onium anion receptor shows the water phase fluorine ion recognition application prospects.
Description
Technical field
The invention belongs to detection technique field, relate to selectivity fluorescence identifying method and the colorimetric recognition methods of fluorion, be specifically related to a kind of utilizationPyridine anion receptor selectivity fluorescence identifying and the method than colour discrimination fluorion, andThe application in aqueous phase Fluoride recognition of the pyridine anion receptor.
Background technology
Fluorion is widely present in nature, and appropriate fluorion has great role at maintenance dental health and treatment osteoporosis. But excessive fluorion 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, the such as production etc. of special plastic, toothpaste and military chemistry weapon. Production uses fluorine-containing chemical or produces the fluoride waste meeting serious environment pollution of fluorinated chemical product generation and jeopardize human survival safety. Therefore, to the identification of fluorion with detection be a very necessary job. Fluoride recognition method traditional in prior art, including electrode method,19FNMR nuclear magnetic resonance, NMR etc., but these methods generally need the instrument and equipment of costliness and the process that detects loaded down with trivial details, relatively costly. Wherein19FNMR nuclear magnetic resonance spectroscopy is difficult to accurately detection micro-molar concentration fluorion. Additionally, electrode method and19FNMR magnetic resonance detection fluorion cannot be applied in bioassay.
Summary of the invention
The present invention proposes a kind of selectivity fluorescence identifying and the method than colour discrimination fluorion, utilizesPyridine anion receptor identifies the fluorion in testing sample. The present invention utilizesPyridine anion receptor can selectivity fluorescence identifying and ratio two kinds of detection methods of colour discrimination, detect fluorion in real time, simply, delicately.Pyridine receptor is as a kind of chemical sensor, it is easy to enters biological cell and is combined with fluorion, has the application prospect by the fluorion in bioluminescence image checking cell.
The present invention utilizesThe method of pyridine anion receptor selectivity fluorescence identifying fluorion,DMSO or DMSO: H of pyridine anion receptor2O=9: 1 solution unstressed configuration, after adding fluorion, solution fluorescence is remarkably reinforced, such that it is able to quickly and easily by test solution fluorescence emission spectrum discrimination fluorion.The basic unstressed configuration of pyridine anion receptor solution, this feature provides the testing conditions of zero background, greatly reduces mushing error, improves the accuracy of Fluorine Ion Determination.Measure and add variable concentrations fluoride solution fluorescence intensity, draw the standard curve adding fluorinion concentration and fluorescence intensity. Then can pass through to detect testing sample fluorescence intensity, learn fluorinion concentration with standard curve contrast. The method is applicable to Accurate Determining low dose fluoride ion.
The present invention utilizesThe method of pyridine anion receptor selectivity fluorescence identifying fluorion, is containingThe DMSO solution of pyridine anion receptor or DMSO: H2In O=9: 1 solution, adding testing sample, if detecting the Fluorescence Increasing of described solution, then showing in this testing sample containing fluorion;
Wherein, described inShown in the structure of pyridine anion receptor such as formula (I):
Formula (I).
Wherein, described inPyridine anion receptor concentration in DMSO solution is 5.0 �� 10-6Mol/L��5.0 �� 10-3Mol/L; Described testing sample concentration in DMSO solution is 0��1.0 �� 10-1Mol/L; The fluorescence emission spectrum of described solution is obviously enhanced.
Wherein, described inPyridine anion receptor is DMSO: H2Concentration in O=9: 1 solution is 5.0 �� 10-6Mol/L��5.0 �� 10-3Mol/L; Described testing sample is DMSO: H2Concentration in O=9: 1 solution is 5 �� 10-4Mol/L��5.0 �� 10-1Mol/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,DMSO or DMSO: H of pyridine anion receptor2O=9: 1 solution is yellow, and after adding fluorion, solution is gradually become colourless by yellow. The method can bore hole than colour discrimination fluorion, this particularity has very big actual application value in chemical sensor identification simple ion. By in same concentration same volumePyridine solution adds variable concentrations fluorion, the standard color range solution of configuration, it is possible to fluorinion concentration in colorimetric detection testing sample. The method simple and fast, it is not necessary to any precision equipment. Can being widely used in the simple and easy identification process of fluorion, 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 containingThe DMSO solution of pyridine anion receptor or DMSO: H2In O=9: 1 solution, add testing sample, if the color from yellow of described solution becomes colorless, then show in this testing sample containing fluorion; Wherein, described inShown in the structure of pyridine anion receptor such as formula (I):
Formula (I).
Wherein, described inPyridine 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, described inPyridine anion receptor is DMSO: H2Concentration in O=9: 1 solution is 5.0 �� 10-5Mol/L��5.0 �� 10-2Mol/L; Described testing sample is DMSO: H2Concentration in O=9: 1 solution is 5.0 �� 10-3Mol/L��5.0mol/L; The color from yellow of described solution becomes colorless.
In the present invention,Synthetic route and the crystal structure of pyridine anion receptor are as follows:
In the present invention,The sign of pyridine anion receptor molecule includes following:
Nuclear-magnetism characterizes:
1HNMR (500MHz, DMSO-d6) �� 0.96 (t, J=10.0Hz, 6H), 1.42-1.47 (m, 4H), 1.77 (t, J=10.0Hz, 4H), 3.99 (t, J=10.0Hz, 4H), 7.12 (d, J=10.0Hz, 2H), 7.51 (t, J=10.0Hz, 2H), 7.61 (d, J=10.0Hz, 2H), 9.08 (s, 1H).
13CNMR (125MHz, DMSO-d6) �� 153.20,135.01,132.18,128.87,124.04,121.79,108.38,51.55,28.28,19.47,14.04.
HRMS characterizes: C19H25N2 +(M-Br), requires281.2012, found281.2031.
In a specific embodiment, described inPyridine anion receptor conventionally preparation method is: at N2Under protection, 100mL two-mouth bottle adds sodium hydride (60%, 0.32g, 8mmol),Pyridine (0.6728g, 4mmol), is dissolved in 30mL acetonitrile, adds n-butyl bromide (2.1925g, 16mmol) after stirring 10min.24h is reacted under room temperature. Being filtered to remove precipitation after 24h, filtrate is transferred in clean 100mL flask, 85 DEG C of heated and stirred reaction 24h, produces yellow solid, and solid washed with acetonitrile 5 times after filtration, product is vacuum drying at 50 DEG C, obtains receptor 1.1380g, and yield is 79.0%.
The present invention utilizesThe method of pyridine anion receptor selectivity fluorescence identifying fluorion 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, the concentration being gradually added into fluorion is0��100 times of pyridine anion receptor concentration. Solution fluorescence intensity of emission spectra strengthens, explanationPyridine anion receptor can fluorescence identifying fluorion. MeasurePyridine anion receptor solution adds the Fluorescence Increasing process of fluoride solution, draws the relation curve adding fluorinion concentration and solution fluorescence intensity, as standard curve.
When whether there is fluorion and fluorinion concentration in detecting testing sample, certain densityDMSO or DMSO: H of pyridine anion receptor2O=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 for standard curve, the solution fluorescence intensity according to the testing sample recorded, so that it is determined that the fluorinion concentration in testing sample.
Selectivity fluorescence of the present invention and the method than colour discrimination fluorion, its recognition method includes:Adding fluorion in the DMSO solution of pyridine anion receptor, there is obvious Fluorescence Increasing in unstressed configuration receptor solution, it is possible to achieve fluorescence identifying fluorion; ?Adding fluorion in the DMSO solution of pyridine anion receptor, solution colour is become colorless by yellow, it is possible to achieve bore hole is than colour discrimination fluorion; ?DMSO: H of pyridine anion receptor2Adding fluorion in O=9: 1 solution, there is obvious Fluorescence Increasing in unstressed configuration receptor solution, and solution colour is become colorless by yellow, it may be achieved aqueous phase fluorescence and ratio colour discrimination fluorion.
The present invention utilizesThe method of pyridine anion receptor selectivity ratios colour discrimination fluorion 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, the concentration being gradually added into fluorion is0��100 times of pyridine anion receptor concentration. Solution colour is become colorless by yellow, explanationPyridine anion receptor can bore hole than colour discrimination fluorion. Take containing equal-volume with concentrationDMSO or DMSO: H of pyridine anion receptor2Identical one group of color comparison tube of O=9: 1 solution, is separately added into different amounts of fluorion, is made into the standard color range of color alternation gradually.
When whether there is fluorion and fluorinion concentration in detecting testing sample, certain densityDMSO or DMSO: H of pyridine anion receptor2O=9: 1 solution adds testing sample, with reference to the various criterion color range that different fluorinion concentrations are corresponding, can according to the color of testing sample, visually find out the standard color range that color and luster is the most close, the normal concentration of the institute's fluoride ion according to its correspondence, so that it is determined that the fluorinion concentration in testing sample.
In the present inventionPyridine anion receptor can pass through fluorescence identifying and than two kinds of recognition mechanism identification fluorions of colour discrimination. The invention allows forPyridine anion receptor is at DMSO solution or DMSO: H2The application of selectivity fluorescence identifying fluorion in O=9: 1 solution. The invention allows forPyridine anion receptor is at DMSO solution or DMSO: H2The application of selectivity ratios colour discrimination fluorion in O=9: 1 solution.
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, it is respectively included in the 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 (I):
Formula (I)
By nuclear magnetic resonance research course of reaction, and designing corresponding confirmatory experiment, the present invention proposesThe reaction mechanism of pyridine anion receptor identification fluorion, as shown in Figure 9. The process of identification fluorion of the present invention is: fluorion has extremely strong electronegativity and 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 and solution colour is become colorless by yellow. Compound 7a is unstable, it is easy to decomposes and produces compound 8a and 9a. The compound produced in this mechanism all has corresponding experimental data to be proved.
The present invention proposes a kind of new selectivity fluorescence identifying, method than colour discrimination fluorion. Fluorion has that minimum ionic radius, the highest electric charge be close and Lewis base character, in the inventive method, will have lewis acid characterPyridine anion receptor, as novel fluorophor and binding site, utilizesPyridine anion receptor and fluorion selective binding, it is achieved that to the selectivity fluorescence of fluorion and compare colour discrimination. Especially because colorimetric recognition methods, therefore can realize the bore hole identification of fluorion, identify fluorion quickly such that it is able to simple and easy without precision checking equipment when. The instrument and equipment implementing the inventive method has simple feature. The present invention presentsThe application prospect in Fluoride recognition field of pyridine anion receptor. The present invention utilizes efficientlyPyridine 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,19FNMR nuclear magnetic resonance, NMR, has instrument simple, and real-time easily operates, sensitivity advantages of higher. The present invention is capable of the fluorescence of fluorion and the two ways identification of colorimetric. Wherein, fluorescence identifying due toThe almost completely free fluorescence of pyridine anion receptor solution, zero detection background, it is possible to be greatly reduced detection error. Bore hole identification then can be realized, it is possible to simpler identify fluorion quickly by colorimetric. The present invention can realize fluorescence and ratio colour discrimination fluorion in moisture DMSO solution, it is seen that the present invention identifies that in aqueous phase fluorion has a good application prospect.
Accompanying drawing explanation
Fig. 1 isIn pyridine anion receptor DMSO solution (5.0 �� 10-6Mol/L) 1.0 �� 10 are added-4The fluorescence emission spectrogram of mol/L different anions.
Fig. 2 isIn pyridine anion receptor DMSO solution (5.0 �� 10-6Mol/L) fluorion (0-1.0 �� 10 are added-4Mol/L) fluorescence emission spectrogram.
Fig. 3 isIn pyridine anion receptor DMSO solution (5.0 �� 10-6Mol/L) fluorion (0-1.0 �� 10 are added-4Mol/L), fluorinion concentration and solution are at the standard curve of 400nm place fluorescence intensity.
Fig. 4 isIn pyridine anion receptor DMSO solution (5.0 �� 10-5Mol/L) 5.0 �� 10 are added-4The uv absorption spectra of mol/L different anions.
Fig. 5 isPyridine anion receptor DMSO: H2In O=9: 1 solution (5.0 �� 10-6Mol/L) 5.0 �� 10 are added-4The fluorescence emission spectrogram of mol/L different anions.
Fig. 6 isPyridine anion receptor DMSO: H2In O=9: 1 solution (5.0 �� 10-6Mol/L) fluorion (0-5.0 �� 10 are added-4Mol/L) fluorescence emission spectrogram.
Fig. 7 isPyridine anion receptor DMSO: H2In O=9: 1 solution (5.0 �� 10-6Mol/L) fluorion (0-5.0 �� 10 are added-4Mol/L), fluorinion concentration and solution are at the standard curve of 400nm place fluorescence intensity.
Fig. 8 isPyridine anion receptor DMSO: H2In O=9: 1 solution (5.0 �� 10-5Mol/L) 1.0 �� 10 are added-3The uv absorption spectra of mol/L 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 protected content of the present invention is not limited to 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 be all included in the present invention, and with appending claims for protection domain. Implementing the process of the present invention, condition, reagent, experimental technique etc., outside the lower content mentioned specially, be the universal knowledege of this area and known general knowledge, the present invention is not particularly limited content. In each embodimentShown in pyridine anion receptor such as formula (I).
Formula (I)
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 the DMSO solution (5.0 �� 10 of the 4-butyl ammonium of 2.0mL fluorion, chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, 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 1.0 �� 10-4Mol/L, i.e. the anion concentration in each solution is 20 times of acceptor density, places overnight after mix homogeneously. With concentration for 5.0 �� 10-6Mol/L'sThe DMSO solution (not adding anion) of pyridine anion receptor is as comparison. Under 25 DEG C of conditions, 357nm is excitation wavelength, measures the fluorescence emission spectrum of each solution.
As it is shown in figure 1, compare the acceptor fluorescence intensity change added before and after anion, it has been found that: after adding fluorion,The pyridine anion receptor solution fluorescence emission spectrum at 400nm place is obviously enhanced. And add other aniones (e.g., chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate),The fluorescence emission spectrum change at 400nm place of the pyridine anion receptor solution is less or almost constant. 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 0-40 �� L, in ie in solution, fluorinion concentration increases to 1.0 �� 10 from 0mol/L gradually--4mol/L(20 times of pyridine acceptor density).MeasurePyridine anion receptor solution adds the Fluorescence Increasing process of variable concentrations fluoride solution. As in figure 2 it is shown, along with the increase adding fluorinion concentration, solution is remarkably reinforced at 400nm place fluorescence emission spectrum. Take 400nm place solution fluorescence intensity, draw the relation curve adding fluorinion concentration and 400nm place solution fluorescence intensity, as it is shown on figure 3, be the standard curve of fluorion and solution fluorescence intensity.
Taking 2 �� 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, check in fluorinion concentration according to fluorinion concentration is corresponding with the standard curve of solution fluorescence intensity, the content of fluorion in liquid to be measured can be obtained by calculating.
Standard curve according to fluorinion concentration and solution fluorescence intensity is it can be seen that detection method, and lowest detection line is up to 5.0 �� 10-6Mol/L, the best interval of detection is 5.0 �� 10-6mol/L-1.0��10-4Mol/L, can detect low dose fluoride ion with sensitivity. Additionally, due toThe almost completely free fluorescence of pyridine anion receptor solution, zero detection background, it is possible to be greatly reduced detection 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 the DMSO solution (5.0 �� 10 of the 4-butyl ammonium of 0.5mL fluorion, chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, 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 2.5 �� 10-4Mol/L, i.e. the anion concentration in solution is 5 times of acceptor density, places overnight after mix homogeneously. With concentration for 5.0 �� 10-5Mol/L'sThe DMSO solution (not adding anion) of pyridine anion receptor is as comparison. The ultra-violet absorption spectrum of each solution is measured under 25 DEG C of conditions.
As shown in Figure 4, find by comparing the receptor ultraviolet change added before and after anion: after adding fluorion,Pyridine anion receptor solution has significantly new absworption peak to produce at 357nm place. And after adding other aniones (chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate),Pyridine anion receptor solution generates less at the new absworption peak in 357nm place or generates without new absworption peak. ExplanationPyridine anion receptor can pass through ultra-violet absorption spectrum Selective recognition fluorion in DMSO solution.
When adding fluorion, solution gradually becomes colourless solution from yellow solution. The change explanation of colorPyridine anion receptor can realize the bore hole of fluorion and compare colour discrimination. The inventive method can in the condition without 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, is separately added into different amounts of fluorion, and fluorinion concentration is 0mol/L respectively, and 1.0 �� 10-4Mol/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, along with adding fluorinion concentration increase, becomes colorless from yellow gradually, forms the standard color range of color alternation gradually.
Taking 10 �� L liquid to be measured, being equipped with 10mL concentration is 5.0 �� 10-5Mol/L'sIn the identical color comparison tube of pyridine anion receptor DMSO solution. According to adding after liquid to be measured, solution colour and standard sample color contrast, visually find out the standard sample that color and luster is the most close, the normal concentration of fluorion in standard sample, i.e. fluorinion concentration in color comparison tube to be measured. The content of fluorion in liquid to be measured is obtained by calculating.
Standard color range according to addition fluorinion concentration and solution colour is it can be seen that detection method, and lowest detection line is up to 5.0 �� 10-5Mol/L, the best interval of detection is 1.0 �� 10-4mol/L-1.0��10-3Mol/L, can without accurate expensive instrument when, 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, in a series of 10mL volumetric flasks, is separately added into the DMSO solution (5.0 �� 10 of the 4-butyl ammonium of 1.0mL fluorion, chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate-3Mol/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 5.0 �� 10-3Mol/L, i.e. the anion concentration in each solution is 100 times of acceptor density, places overnight after mix homogeneously. With concentration for 5.0 �� 10-6Mol/L'sDMSO: H of pyridine anion receptor2O=9: 1 solution (does not add anion) as comparison. Under 25 DEG C of conditions, 357nm is excitation wavelength, measures the fluorescence emission spectrum of each solution.
As it is shown in figure 5, compare the acceptor fluorescence intensity change added before and after anion, it has been found that: after adding fluorion,The pyridine anion receptor solution fluorescence emission spectrum at 400nm place is obviously enhanced. And add other aniones (e.g., chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate),The fluorescence emission spectrum change at 400nm place of the pyridine anion receptor solution is less or almost constant. ExplanationPyridine anion receptor can 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, being gradually added into concentration is 5.0 �� 10-2Mol/L fluorion 0-20 �� L, in ie in solution, fluorinion concentration increases to 5.0 �� 10 from 0mol/L gradually-4mol/L(100 times of pyridine acceptor density). MeasurePyridine anion receptor solution adds the Fluorescence Increasing process of variable concentrations fluoride solution. As shown in Figure 6, along with the increase adding fluorinion concentration, solution is remarkably reinforced at 400nm place fluorescence emission spectrum. Take 400nm place solution fluorescence intensity, draw the relation curve adding fluorinion concentration and 400nm place solution fluorescence intensity, as it is shown in fig. 7, be the standard curve of fluorion and solution fluorescence intensity.
Taking 2 �� L liquid to be measured, adding 2mL concentration is 5.0 �� 10-6Mol/L'sDMSO: H of pyridine anion receptor2In O=9: 1 solution, measure the fluorescence emission spectral intensity of solution.According to fluorescence intensity, check in fluorinion concentration according to fluorinion concentration is corresponding with the standard curve of solution fluorescence intensity, the content of fluorion in liquid to be measured can be obtained by calculating.
Standard curve according to fluorinion concentration and solution fluorescence intensity is it can be seen that detection mode of the present invention, and lowest detection line is up to 2.5 �� 10-5Mol/L, the best interval of detection is 2.5 �� 10-6mol/L-5.0��10-4Mol/L, can detect low dose fluoride ion with sensitivity.
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, in a series of 10mL volumetric flasks, is separately added into the DMSO solution (5.0 �� 10 of the 4-butyl ammonium of 2.0mL fluorion, chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, 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 1.0 �� 10-3Mol/L, i.e. the anion concentration in solution is 20 times of acceptor density, places overnight after mix homogeneously. With concentration for 5.0 �� 10-5Mol/L'sDMSO: H of pyridine anion receptor2O=9: 1 solution (does not add anion) as comparison. The ultra-violet absorption spectrum of each solution is measured under 25 DEG C of conditions.
As shown in Figure 8, find by comparing the receptor ultraviolet change added before and after anion: after adding fluorion,Pyridine anion receptor solution has significantly new absworption peak to produce at 357nm place. And after adding other aniones (chloride ion, bromide ion, iodide ion, acetate ion, hydrogen sulfate ion, dihydrogen phosphate ions, perchlorate),Pyridine anion receptor solution generates less at the new absworption peak in 357nm place or generates without new absworption peak. ExplanationPyridine anion receptor can pass through ultra-violet absorption spectrum Selective recognition fluorion.
When adding fluorion, solution gradually becomes colourless solution from yellow solution. The change explanation of colorPyridine anion receptor can realize the bore hole of fluorion and compare colour discrimination. The inventive method can without the condition of precision equipment, conveniently and efficiently recognition detection fluorion.
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 0mol/L respectively, and 5.0 �� 10-4Mol/L, 1.0 �� 10-3Mol/L, 1.5 �� 10-3Mol/L, 2.0 �� 10-3Mol/L, 2.5 �� 10-3Mol/L, 3.0 �� 10-3Mol/L, 3.5 �� 10-3Mol/L, 4.0 �� 10-3Mol/L, 4.5 �� 10-3Mol/L, 5.0 �� 10-3Mol/L. Solution colour in color comparison tube, along with adding fluorinion concentration increase, becomes colorless from yellow gradually, forms the standard color range of color alternation gradually.
Taking 10 �� 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. According to adding after liquid to be measured, solution colour and standard sample color contrast, visually find out the standard sample that color and luster is the most close, the normal concentration of fluorion in standard sample, i.e. fluorinion concentration in color comparison tube to be measured. The content of fluorion in liquid to be measured is obtained by calculating.
Standard color range according to addition fluorinion concentration and solution colour is it can be seen that detection mode of the present invention, and lowest detection line is up to 5.0 �� 10-4Mol/L, the best interval of detection is 5.0 �� 10-4mol/L-5.0��10-3Mol/L, can without accurate expensive instrument when, 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 containingThe DMSO solution of pyridine anion receptor or DMSO: H2In O=9: 1 solution, adding testing sample, if detecting the Fluorescence Increasing of described solution, then showing in this testing sample containing fluorion;
Wherein, described inShown in the structure of pyridine anion receptor such as formula (I):
Formula (I).
2. the method for claim 1, it is characterised in that described inPyridine anion receptor concentration in DMSO solution is 5.0 �� 10-6Mol/L��5.0 �� 10-3Mol/L; Described testing sample concentration in DMSO solution is 0��1.0 �� 10-1Mol/L; The fluorescence emission spectrum of described solution strengthens.
3. the method for claim 1, it is characterised in that described inPyridine anion receptor is DMSO: H2Concentration in O=9: 1 solution is 5.0 �� 10-6Mol/L��5.0 �� 10-3Mol/L; Described testing sample is DMSO: H2Concentration in O=9: 1 solution 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 containingThe DMSO solution of pyridine anion receptor or DMSO: H2In O=9: 1 solution, add testing sample, if the color from yellow of described solution becomes colorless, then show in this testing sample containing fluorion;
Wherein, described inShown in the structure of pyridine anion receptor such as formula (I):
Formula (I).
5. method as claimed in claim 4, it is characterised in that described inPyridine 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.
6. method as claimed in claim 4, it is characterised in that described inPyridine anion receptor is DMSO: H2Concentration in O=9: 1 solution is 5.0 �� 10-5Mol/L��5.0 �� 10-2Mol/L; Described testing sample is DMSO: H2Concentration in O=9: 1 solution is 5.0 �� 10-3Mol/L��5.0mol/L; The color from yellow of described solution becomes colorless.
7. formula (I)Pyridine anion receptor is at DMSO solution or DMSO: H2The application of selectivity fluorescence identifying fluorion in O=9: 1 solution.
8. formula (I)Pyridine anion receptor is at DMSO solution or DMSO: H2The application of selectivity ratios colour discrimination fluorion in O=9: 1 solution.
9. formula (I)Pyridine anion receptor is in the application of aqueous phase Fluoride recognition, and wherein, described application is to identify in testing sample whether contain fluorion in the mixed solution of DMSO and water.
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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 CN201410491423.8A patent/CN105651743A/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 |
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| 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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