CN106153586A - The europium fluorescent probe based on p-phthalic acid application in detection aniline - Google Patents
The europium fluorescent probe based on p-phthalic acid application in detection aniline Download PDFInfo
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- CN106153586A CN106153586A CN201610428598.3A CN201610428598A CN106153586A CN 106153586 A CN106153586 A CN 106153586A CN 201610428598 A CN201610428598 A CN 201610428598A CN 106153586 A CN106153586 A CN 106153586A
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- aniline
- fluorescent probe
- detection
- phthalic acid
- bdc
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
Abstract
The invention discloses the application in detection aniline of a kind of europium fluorescent probe based on p-phthalic acid, the construction unit of this fluorescent probe is [Eu (BDC) Cl (H2O)], wherein BDC represents the p-phthalic bridge losing proton on two carboxyls, and it has excellent red fluorescence performance, under ultra violet lamp, and the redness that display is bright.In aqueous solution or DMF, aniline has significant quenching effect to the red fluorescence of this fluorescent probe, and therefore it can be used for high sensitivity, high selectivity, anti-interference detection aniline, and it has good recycling for aniline detection.
Description
Technical field
The invention belongs to the detection technique field of aniline, be specifically related to a kind of europium fluorescent probe based on p-phthalic acid and exist
Detection aniline in apply detection aniline in application.
Background technology
Aniline is widely present in medicated cigarette, food and industrial waste gas, it has also become environmental contaminants that a class is serious and carcinogenic
Material.Wherein aniline can increase the sickness rate of pulmonary carcinoma, is also whether a kind of important symbol suffering from pulmonary carcinoma simultaneously.At present, domestic
The outer means for detecting aniline mainly have electrochemical process, spectrophotometer method, gas chromatography, high performance liquid chromatography etc.,
These methods all achieve the detection to aniline, the part but they come with some shortcomings, and such as operation complexity, reaction is slow, spend height.
Therefore, it is achieved the real-time Sensitive Detection of aniline is remained a big challenge.
Fluorescent optical sensor due to easy to operate, analyze that speed is fast, high sensitivity, high selectivity and relatively low detection limit, and
The parent enjoying vast researcher looks at.Fluorescence probe material refers to there is characteristic fluorescence in ultraviolet-visible-near infrared region, and
Its photoluminescent property (exciting and launch wavelength, intensity, life-span, polarization etc.) can with the character of local environment, as polarity, refractive index,
The class fluorescence molecule that viscosity etc. change and change delicately.Lanthanide series metal organic framework materials is by organic ligand and group of the lanthanides
Metallic atom consists of coordinate bond, there is the energy transfer process of ligand metal in its system, can be by exciting part
Realize the luminescence of lanthanide atom, thus the luminescence process of effective sensitization lanthanide atom, effectively strengthen the luminous intensity of lanthanide atom.
Organolanthanide Complexes, due to its distinctive principle of luminosity, can be used to detect various inorganic ions, organic molecule etc., has
Hope and become a kind of quick and easy fluorescent probe.
Summary of the invention
The technical problem to be solved is to provide a kind of new for europium fluorescent probe based on p-phthalic acid
Application.
Solve above-mentioned technical problem and be the technical scheme is that above-mentioned europium fluorescent probe based on p-phthalic acid is in inspection
Surveying the application in aniline, the construction unit of this fluorescent probe is [Eu (BDC) Cl (H2O)], wherein BDC represents mistake on two carboxyls
The p-phthalic bridge of deprotonation, belongs to monoclinic system, and space group is P 21/ c, cell parameter isα=γ=90 °, β=103.352
(4) °, unit cell volumeZ=4, it prepares according to following method:
By EuCl3·6H2O, p-phthalic acid, iodate 1-ethyl-3-methylimidazole ionic liquid are 3:1:7 in molar ratio
Mixing, 170 DEG C are reacted 5 days, are cooled to room temperature, through acetone, ethanol purge, obtain europium fluorescent probe based on p-phthalic acid.
Beneficial effects of the present invention is as follows:
1, the fluorescent probe that the present invention uses is under ultra violet lamp, demonstrates bright redness.Carry out at about 275nm
Fluorescence excitation, has obvious Eu at 579nm, 592nm, 614nm, 653nm and 700nm3+Characteristic emission peak.
2, the fluorescent probe that the present invention uses all can realize high sensitivity, high selectivity, anti-interference in aqueous solution, DMF
Detection aniline, and for aniline detection, there is good recycling.
Accompanying drawing explanation
Fig. 1 is the structural representation of fluorescent probe of the present invention.
Fig. 2 is the fluorogram of fluorescent probe of the present invention.
Fig. 3 is the design sketch of fluorescent probe of the present invention the highest selective enumeration method aniline.
Fig. 4 is fluorescent probe of the present invention design sketch of high selective enumeration method aniline in DMF.
Fig. 5 is the design sketch of fluorescent probe of the present invention anti-interference in aqueous detection aniline.
Fig. 6 is 10 design sketchs of circulation of fluorescent probe of the present invention detection aniline.
Detailed description of the invention
The present invention is described in more detail with embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
0.5492g(1.5mmol)EuCl3·6H2O, 0.0828g (0.5mmol) p-phthalic acid and 0.8006g
(3.5mmol), during iodate 1-ethyl-3-methylimidazole ionic liquid adds 25mL teflon-lined reactor, mixing is all
Even, then reactor is positioned in baking oven, reacts 5 days at 170 DEG C, be cooled to room temperature, through acetone, ethanol purge, obtain
Water white bulk europium based on p-phthalic acid fluorescent probe, its construction unit is [Eu (BDC) Cl (H2O)], wherein BDC
Representing the p-phthalic bridge losing proton on two carboxyls, belong to monoclinic system, space group is P 21/ c, cell parameter is α=γ=90 °, β=
103.352 (4) °, unit cell volumeZ=4.As shown in Fig. 1, Eu1 takes the coordination mode of seven coordinations, week
Enclose and be connected with the carboxyl of four monatomic chelatings, two μ2-Cl-With a water, constitute single cap triangular prism.
1, fluorescence property test
Inventor uses solid state fluorescence method of testing that at 275nm wavelength, above-mentioned fluorescent probe is carried out fluorescence excitation, carries out glimmering
Optical property is tested, and test result is shown in Fig. 2.From Figure 2 it can be seen that have at 579nm, 592nm, 614nm, 653nm and 700nm significantly
Eu3+Characteristic emission peak, respectively correspondence5D0→7F0、5D0→7F1、5D0→7F2、 5D0→7F3With5D0→7F4Transition, illustrates this fluorescence
Probe glows.
2, selective enumeration method aniline in water
31.7 μ L toluene, 36.6 μ L ethylbenzene, 42.0 μ L third it are separately added in the HEPES buffer that 30mL pH value is 6.5
Benzene, 14.1 μ L methylamines, 29.3 μ L n-butylamines, 39.8 μ L triethanolamine, 20.0 μ L ethylenediamines, 23.1 μ L dimethylformamides,
27.3 μ L aniline, are configured to 10mmoL/L difference organic amine or benzene derivate solution respectively；Take the above-mentioned solution of 3mL respectively, add
Enter the above-mentioned fluorescent probe of 3mg, ultrasonic 30 minutes of room temperature, carry out fluorometric investigation, simultaneously with water (pH value be 6.5 HEPES buffering
Liquid) do blank.Result is shown in Fig. 3.
As seen from Figure 3, at toluene, ethylbenzene, propyl benzene, methylamine, n-butylamine, triethanolamine, ethylenediamine, dimethylformamide
In aqueous solution, the fluorescence intensity of fluorescent probe is with the most essentially identical, but in aniline solution, fluorescent probe redness is glimmering
Light disappears, and fluorescence intensity is obviously reduced.Illustrate that, in above several organic amines and benzene derivate, only aniline can be glimmering to this
Light probe produces fluorescent quenching, i.e. uses this fluorescent probe can the highest selective enumeration method aniline.
3, selective enumeration method aniline in DMF
31.7 μ L toluene, 36.6 μ L ethylbenzene, 42.0 μ L propyl benzene, 14.1 μ L methylamines, 29.3 μ it are separately added in 30mL DMF
L n-butylamine, 39.8 μ L triethanolamine, 20.0 μ L ethylenediamines, 27.3 μ L aniline, be configured to respectively 10mmoL/L difference organic amine or
Benzene derivate solution；Take the above-mentioned solution of 3mL respectively, add the above-mentioned fluorescent probe of 3mg, ultrasonic 30 minutes of room temperature, carry out fluorescence
Test, does blank with DMF simultaneously.Result is shown in Fig. 4.
From fig. 4, it can be seen that toluene, ethylbenzene, propyl benzene, methylamine, n-butylamine, triethanolamine, ethylenediamine aqueous solution in, fluorescence
The fluorescence intensity of probe is essentially identical with in DMF, but in aniline solution, fluorescent probe red fluorescence disappears, fluorescence intensity
It is obviously reduced.When detection in DMF is described, do not interfere with the Detection results of this fluorescent probe yet, identical with phenomenon in water, i.e.
Use this fluorescent probe can in DMF high selective enumeration method aniline.
4, anti-interference detection aniline
14.1 μ L methylamines, 29.3 μ L n-butylamines, 39.8 μ L it are sequentially added in the HEPES buffer that 30mL pH value is 6.5
Triethanolamine, 20.0 μ L ethylenediamines, 23.1 μ L dimethylformamides so that methylamine, n-butylamine, triethanolamine, ethylenediamine and two
The concentration of methylformamide is 10mmoL/L；Take the above-mentioned solution of 3mL respectively, add the above-mentioned fluorescent probe of 3mg, room temperature ultrasonic 30
Minute, carry out fluorometric investigation.In above-mentioned solution, add 2.7 μ L aniline again, under the same conditions it is carried out fluorometric investigation again.
Result is shown in Fig. 5.As seen from the figure, in the mixed solution of methylamine, n-butylamine, triethanolamine, ethylenediamine and dimethylformamide, should
The fluorescence intensity of fluorescent probe does not has significant change；After adding aniline, the red fluorescence of fluorescent probe disappears immediately, and fluorescence is strong
Degree is obviously reduced.In the presence of illustrating when aniline and various organic amine while, have no effect on the fluorescent probe detection for aniline, i.e.
This fluorescent probe has high selectivity and anti-interference to aniline.
5, cycle detection aniline
Adding 27.3 μ L aniline in the HEPES buffer that 30mL pH value is 6.5, the aniline being configured to 10mmoL/L is molten
Liquid.Above-mentioned fluorescent probe is coated with on the glass sheet, inserts in the cuvette equipped with 10mmoL/L aniline solution, carry out fluorescence survey
Examination.Then the sheet glass scribbling fluorescent probe is taken out, dry 1 hour at 50 DEG C, the sheet glass dried is placed again into
10mmoL/L aniline solution carries out fluorometric investigation.Circulation 10 times successively, result is shown in Fig. 6.As seen from Figure 6, by this fluorescent probe
Being placed in the detection liquid of aniline, recycle 10 times, the fluorescence intensity of fluorescent probe is basically unchanged, illustrate this fluorescent probe for
Aniline detection has good recycling.
Claims (1)
1. the europium fluorescent probe based on p-phthalic acid application in detection aniline, the construction unit of this fluorescent probe is [Eu (BDC)
Cl(H2O)], wherein BDC represents the p-phthalic bridge losing proton on two carboxyls, belongs to monoclinic system, and space group is P 21/
C, cell parameter is α=γ
=90 °, β=103.352 (4) °, unit cell volumeZ=4.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610428598.3A CN106153586B (en) | 2016-06-16 | 2016-06-16 | Application of the europium fluorescence probe based on terephthalic acid (TPA) in detection aniline |
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| CN201610428598.3A CN106153586B (en) | 2016-06-16 | 2016-06-16 | Application of the europium fluorescence probe based on terephthalic acid (TPA) in detection aniline |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057685A (en) * | 2017-04-20 | 2017-08-18 | 陕西师范大学 | Europium fluorescence probe and test paper based on biphenyl dicarboxylic acid and the application in detection p-phenylenediamine |
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| CN104312578A (en) * | 2014-09-22 | 2015-01-28 | 南开大学 | Fluorescent material with high thermal stability and stable to organic solvent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057685A (en) * | 2017-04-20 | 2017-08-18 | 陕西师范大学 | Europium fluorescence probe and test paper based on biphenyl dicarboxylic acid and the application in detection p-phenylenediamine |
| CN107057685B (en) * | 2017-04-20 | 2019-04-12 | 陕西师范大学 | Europium fluorescence probe and test paper based on biphenyl dicarboxylic acid and the application in detection p-phenylenediamine |
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