CN108383820A - A kind of cup [4] thiocarbamide cumarin chemical sensor and its preparation method and application - Google Patents
A kind of cup [4] thiocarbamide cumarin chemical sensor and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to supermolecule fluorescence probe field, more particularly to a kind of detection F‑Fluorescence probe and its preparation method and application.More particularly to a kind of identification F‑Cup [4] thiocarbamide cumarin chemical sensor, preparation method is:Using nitration reaction nitro is introduced in calixarenes upper edge, then it is flowed back in methyl alcohol by nitro also at amino by Raney Li and hydrazine hydrate, aminocoumarin forms isothiocyano cumarin with thiophosgene, amino calixarenes and isothiocyano cumarin can react under mild conditions, can obtain target product in high yield.Building-up process of the present invention is relatively simple, easy control of reaction conditions, and the fluorescence probe of preparation has excellent optical property and optical stability.It can be used for being detected fluorine ion.
Description
Technical field
The invention belongs to supramolecular chemistry sensor field, more particularly to a kind of cup [4] thiocarbamide cumarin chemical sensor
And its preparation method and application.
Background technology
Fluorine ion plays important role in human life and food health, can be used as food additives, is people
Body indispensable element plays an important role in bone growth and dental health, but the fluorine ion of human body excess intake can draw
Play the diseases such as osteoporosis, osteosarcoma.Fluoride is easy to be absorbed by the body, but is difficult by body metabolism, and human body excessively connects
Tactile fluoride can cause gastric cancer and some kidney troubles.Contain exceeded fluoride in some less developed countries, drinking water, then
Lead to human body fluoride poisoning, causes the disease in terms of a series of bone.Therefore the fluorine ion tool in detection human body and environment
There are important meaning, synthesis identification F-Acceptor molecule have good potential using value.
Many common analysis methods, such as uv-vis spectra (UV-Vis), cyclic voltammetry (CV), nuclear magnetic resonance
(NMR) and electron paramagnetic resonance (EPR) etc. is not suitable for F-Measurement.F is detected using fluorescent spectrometry-Not only operation letter
Just, and selectivity, sensitivity, real-time in-situ context of detection have outstanding advantages, and will not destroy sample.Therefore, utilization is glimmering
F in the quantitative detection environment of light probe simplicity-, to further appreciating that F-Effect in biosystem is of great significance.
Invention content
It is an object of the present invention to overcome existing detection F-Analysis method on deficiency, a kind of synthesis letter is provided
Single, selectivity is good, can quickly detect F-Cup [4] thiocarbamide cumarin chemical sensor.
The second object of the present invention is to provide a kind of detection F-Cup [4] thiocarbamide cumarin chemical sensor preparation side
Method.
The third object of the present invention is cup obtained [4] thiocarbamide cumarin chemical sensor for detecting F-。
Detection F provided by the invention-Cup [4] thiocarbamide cumarin chemical sensor molecular structural formula it is as follows:
The preparation method of cup [4] thiocarbamide cumarin chemical sensor provided by the invention, synthetic route are as follows:
The specific preparation method of cup [4] thiocarbamide cumarin chemical sensor, carries out as steps described below:
(1) phenolic hydroxyl group of lower edge, is passed through normal-butyl by the tertiary butyl that cup [4] aromatic hydrocarbons is sloughed to upper edge by Fu Ke back reactions
Bromine is etherified entirely, thus obtains exposed upper edge cup [4] aromatic hydrocarbons.
Wherein, cup [4] aromatic hydrocarbons is heated to reflux is condensed under alkaline condition using p-tert-butylphenol and formaldehyde as raw material
It arrives.
(2) exposed upper edge cup [4] aromatic hydrocarbons in step (1) is dissolved in dichloromethane, by with nitric acid and acetic acid to upper
Along nitrification modification is carried out, nitration product is reduced to amino by hydrazine hydrate and Raney-Li, reducing agent is filtered to remove, uses dichloro
Methane wash, revolving can be obtained reduzate 5,17- diamino -25,26,27,28- tetra-n-butyl cup [4] aromatic hydrocarbons.
Wherein, nitric acid and acetic acid volume ratio are 1:2.
The quality (g) of nitration product is with the volume (mL) of hydrazine hydrate and Raney-Li than being 1:3:3, wherein hydrazine hydrate and
Raney-Li is reducing agent.
(3) 7- amino -4- trifluoromethyl cumarins are dissolved in dichloromethane, are then reacted at room temperature with thiophosgene,
By vacuum pump by remaining thiophosgene extraction system, 7- isothiocyano -4- trifluoromethyl tonka-beans can be obtained in high yield
Element;Since thiophosgene has very high activity and effumability, so the reaction conversion ratio is very high, and its post-processing is simple.
Wherein, the molar ratio of 7- amino -4- trifluoromethyls cumarin and thiophosgene is 1:3.
(4) 5,17- diamino -25,26,27,28- tetra-n-butyls cup [4] aromatic hydrocarbons that step (2) obtains is dissolved in dichloromethane
In alkane, the 7- isothiocyano -4- trifluoromethyl cumarins that step (3) obtains then are added, cup [4] sulphur is obtained by the reaction at room temperature
Urea cumarin chemical sensor, reaction condition is milder, and yield is higher.
The reaction is made solvent with dichloromethane and is reacted at room temperature, and reaction condition is mild, since isothiocyano has
Higher activity is easy to react with amino, and yield is higher.
Wherein, 5,17- diamino -25,26 in step (4), 27,28- tetra-n-butyl cup [4] aromatic hydrocarbons and 7- isothiocyanos -
The molar ratio of 4- trifluoromethyl cumarins is 1:2-3, preferably 1:2.2.
Based on the application of cup [4] thiocarbamide cumarin chemical sensor, chemical sensor produced by the present invention is with highly selective
With high sensitivity to F-It is answered with fluorescence and colorimetric double-bang firecracker, can be used to identify the fluorine ion in solution.
The present invention infers F-In low concentration with probe molecule by interaction of hydrogen bond, two thiourea groups can be same
When and F-More stable Quadrupolar hydrogen bond complex is combined by N-H.Work as F-When concentration is higher, due to F-With stronger
Electronegativity leads to F-The proton in thiourea group can be sloughed, to reach deprotonation, while supervening HF2 -, nitrogen-atoms
On cloud density increase, so as to cause electronics transfer effect enhance, meet PET luminescence mechanisms, so as to cause host molecule
Fluorescence is quenched.
Chemical sensor produced by the present invention has lower detection limit and higher complexation constant, can be used for F in environment-
Analysis detection, feature be it is easy to use, at low cost, be not required to pre-process.
The chemical sensor of the present invention can be used for detecting the F in natural environment-.Simulating natural environment detects F-Method be:
An access 10mL volumetric flask, prepares dimethyl sulfoxide (DMSO) (DMSO) solution of fluorescence probe, and a concentration of 2 × 10-5Mol/L exists successively
The F of various concentration is added in each volumetric flask-It uses DMSO constant volumes to 10mL afterwards, shakes up, after placing 30min at room temperature, use fluorescence
Spectrophotometer, using 387nm as excitation wavelength, slit 5/5nm, 481nm are that launch wavelength tests fluorescence intensity, and test obtains phase
Corresponding fluorescence intensity.
The beneficial effects of the invention are as follows:
(1) fluorescence probe building-up process of the invention is relatively simple, easy control of reaction conditions, by simply post-processing
It can obtain pure product.In addition, the fluorescence probe prepared has excellent optical property and optical stability.
(2) during to Fluoride recognition, significant quenching phenomenon, solution face occur fluorescence probe of the invention for fluorescence
Color also changes, and has colorimetric identification function, is conducive to be detected fluorine ion.
(3) fluorescence probe of the invention has good selectivity the identification of fluorine ion and anti-interference.
Description of the drawings
Fig. 1 is fluorescent probe molecule in the embodiment of the present invention 1 to F-Selective recognition figure;Wherein, abscissa is wavelength
(nm), ordinate is fluorescence intensity.
Fig. 2 is fluorescent probe molecule in the embodiment of the present invention 1 to the anti-interference figure of different anions;Wherein, abscissa
Situation is added for different ions, ordinate is fluorescence intensity.
Fig. 3 is fluorescent probe molecule fluorescence intensity and time-varying relationship figure in the embodiment of the present invention 1;Wherein, abscissa
For the time, ordinate is fluorescence intensity.
Fig. 4 is the linear relationship chart of fluorescent probe molecule fluorescence intensity and probe itself concentration in the embodiment of the present invention 1;Its
In, abscissa is concentration, and ordinate is fluorescence intensity.
Fig. 5 is fluorescent probe molecule and F in the embodiment of the present invention 1-Fluorescence and UV titration chart, wherein the horizontal seats of Fig. 5-a
It is designated as wavelength, ordinate is fluorescence intensity, and Fig. 5-b abscissas are wavelength, and ordinate is ultraviolet absorptivity.
Specific implementation mode
The present invention will be described in detail with reference to embodiments, but the present invention is not limited to these embodiments.
Embodiment 1
The synthesis of chemical sensor L:
(1) four n-butyl ether powder (25.0g, 38.0mmol) of cup [4] aromatic hydrocarbons is sequentially added in the three-necked flask of 250mL,
65% nitric acid (50mL) and glacial acetic acid is slowly added dropwise with constant pressure funnel in dichloromethane (600mL), glacial acetic acid (120mL)
The mixed solution of (100mL), system color gradually become black by claret, stir 1h at room temperature, and water (600mL) is added to be quenched instead
It answers, stirs, be sufficiently mixed liquid separation after concussion, water layer is extracted with dichloromethane (3 × 50mL), merges organic phase, then use water successively
(2 × 200mL), saturated salt solution (2 × 200mL) washing, anhydrous sodium sulfate drying.After evaporation and concentration, thick solid is obtained, is added
Enter a small amount of dichloromethane to dissolve by heating, pour methanol solution under constant stirring, white solid is precipitated, filter, mesh is obtained after dry
Mark product, yield 29%.
1H NMR(300MHz,DMSO):δ=7.91 (d, J=9.0Hz, 2H, ArH), 7.83 (d, J=7.5Hz, 2H,
), ArH 7.76 (t, J=7.5Hz, 2H, ArH), 7.66 (t, J=7.5Hz, 2H, ArH), 5.94 (s, 2H, CH), 4.48 (d, J=
10.6Hz,2H,CH2), 3.94 (d, J=11.3Hz, 2H, CH2), 3.83 (d, J=11.7Hz, 2H, CH2), 3.68 (d, J=
11.6Hz,2H,CH2).
(2) in the two mouth flask of 250mL, the white solid (1.00g, 1.40mmol) of step (1) is added, is then added
20mL methanol is heated to methanol eddy in oil bath as solvent, and 3mL hydrazine hydrates and 3mL then is added dropwise to reaction system
Raney-Ni is reacted under nitrogen protection, after being heated to 80 DEG C of reaction 5h, stops heating, cooling, with suction filtered through kieselguhr,
Filtrate is washed with distilled water to neutrality, obtains oil phase, dichloromethane is evaporated and methanol obtains gray solid, yield 98%.
1H NMR(300MHz,CDCl3):δ=0.95-1.00 (m, 12H, CH3),1.35-1.50(m,8H,CH2),1.80-
1.91(m,8H,CH2), 3.03 (d, J=13.2Hz, 6H, ArCH2Ar+NH2), 3.77 (t, J=7.2Hz, 4H, ArOCH2),
3.88 (t, J=7.5Hz, 4H, ArOCH2), 4.38 (d, J=13.2Hz, 4H, ArCH2Ar),5.92(s,4H,ArH),6.60-
6.74(m,6H,ArH).
(3) in 150mL single-necked flasks, 7- amino -4- trifluoromethyls cumarins (1.40g, 6.11mmol) are added, are added
About 20mL dichloromethane as solvent, with constant pressure funnel to reaction system be slowly added dropwise thiophosgene (2.10g,
18.26mmol).Stop reaction after reacting 2h, then reaction system is vacuumized with diaphragm pump, removes extra sulphur light
Gas, crude product purify (ethyl acetate through column chromatography for separation:Petroleum ether=1:20) beige solid, yield 82% are obtained.
1H NMR(300MHz,DMSO-d6):δ=7.12 (s, 1H, C-CH-C=O), 7.50 (dd, 1H, J1=2.1Hz, J2
=8.7Hz, ArH), 7.71 (d, 1H, J=0.6Hz, ArH), 7.73-7.76 (m, 1H, ArH)13C NMR(75MHz,DMSO-
d6):113.00,115.13,118.29,123.65,126.56,134.37,136.87,138.59,139.03,154.83,
158.45ppm.
(4) in 100mL single-necked flasks, the white solid (0.80g, 1.18mmol) of step (2), dichloromethane is added
(15mL) is eventually adding the beige solid (0.68g, 2.50mmol) of step (3), reacts 50min at room temperature, is steamed by rotating
It sends out instrument and removes solvent, crude product purifies (ethyl acetate through column chromatography for separation:Petroleum ether=1:40) production of faint yellow solid target is obtained
Object, yield 82%.
1H NMR(300MHz,DMSO-d6):δ=0.95-1.01 (m, 12H, CH3),1.41-1.49(m,8H,CH2),
1.84-1.91(m,8H,CH2), 3.17 (d, 4H, J=13.2Hz, ArCH2), Ar 3.82 (t, 8H, J=13.2Hz, ArOCH2),
4.33 (d, 4H, J=12.9Hz, ArCH2), Ar 6.54 (t, 2H, J=13.2Hz, ArH), 6.65 (d, 4H, J=7.5Hz,
), ArH 6.83 (s, 4H, ArH), 6.87 (s, 2H, C-CH-C=O), 7.38 (dd, 2H, J1=2.1Hz, J2=8.7Hz, ArH),
7.53 (d, 2H, J=7.5Hz, ArH), 7.94 (d, 2H, J=1.8Hz, ArH), 9.70 (s, 2H, NH), 10.01 (s, 2H, NH)
.13C NMR(75MHz,DMSO-d6):14.36,19.36,30.67,32.29,74.96,108.44,118.76,122.51,
123.84,125.08,128.50,132.84,134.70,135.20,139.45,144.71,154.07,154.57,156.82,
159.04,164.61,178.55ppm.ESI-MS:M/z=1221.4 ([M+H]+).
Embodiment 2
With reference to the method for embodiment 1, step (1) nitric acid and acetic acid volume ratio 1:1 participates in reaction, and the yield of product is
25%.
Embodiment 3
With reference to the method for embodiment 1, step (1) nitric acid and acetic acid volume ratio 1:3 participate in reaction, and the yield of product is
22%.
Embodiment 4
With reference to the method for embodiment 1, step (1) nitric acid and acetic acid volume ratio 3:1 participates in reaction, and the yield of product is
16%.
Embodiment 5
Selectivity of the fluorescence probe that embodiment 1 obtains to F- fluoroscopic examinations.
It is 2.0 × 10 with DMSO compound concentrations-4The fluorescent probe molecule mother liquor of mol/L, take 1mL fluorescent probe molecules in
In 10mL volumetric flasks, 5.0 × 10 are diluted to DMSO-5Mol/L, for use.The F for being 0.1mol/L with DMSO compound concentrations-,Cl-,
Br-,I-,CH3COO-, HSO4 -And H2PO4 -Solion is pipetted with microsyringe in 0.1mL to volumetric flask, anion concentration
It is 100 times of concentration and probe concentration, is response of exciting light detection probe to different anions of 387nm with wavelength, measures knot
Fruit is as shown in Figure 1.
It can be found that the fluorescence intensity of probe molecule system has reached 250a.u. or so from the result of Fig. 1, work as addition
After different anions, F is only added-System fluorescence intensity falls below 20a.u. hereinafter, showing significant fluorescent quenching phenomenon,
And Cl-,Br-,I-Ion pair system fluorescence intensity does not influence, CH3COO-, HSO4 -, H2PO4 -To the fluorescence intensity slightly shadow of system
It rings.Illustrate our host molecule to F-With very strong Selective recognition, there is good specificity, higher sensitivity.
By being observed under 365nm ultraviolet lamps, probe molecule itself sends out strong blue light, and F is added-Probe autofluorescence is quenched
It goes out.Should the result shows that:The fluorescence probe is to F-There is higher sensitivity.
Embodiment 6
Other common ions detect F to the fluorescence probe that embodiment 1 obtains-Interference experiment.
Ion interference--free experiments are can to pass through ion interference reality as the important performance indicator of fluorescence probe to ion
Test the selectivity and sensitivity that can study probe to anion.
Experimental procedure:Taking 8 10mL volumetric flasks to mark 1-8 respectively, (No. 1 is a concentration of 2.0 × 10-5Mol/L host molecules
Solution).A concentration of 0.1mol/L anion solutions (F of 0.2mL are pipetted respectively-,Cl-,Br-,I-,CH3COO-,HSO4-,H2PO4 -) arrive
In 2 to No. 8 volumetric flasks, a concentration of 0.1mol/L F of 0.2mL are then pipetted-Solution is to 3 to No. 8 volumetric flasks.It is fixed with DMSO solvents
Hold, fluorometric investigation (E is under equal conditions carried out after ready to balance 20minx=387nm, scanning voltage 600V, temperature 298K).
It can be found that Cl is added into system from the result of Fig. 2-,Br-,I-,CH3COO-,HSO4 -,H2PO4 -Afterwards, adding
When entering other anion, it has been found that as addition Cl-,Br-,I-When, system color does not change, but as addition CH3COO-,
HSO4 -,H2PO4 -When, system color is slightly faded, it is presumed that Cl-,Br-,I-Almost without interference, CH3COO-,HSO4 -With
H2PO4 -Slightly interfere.We have found that the fluorescence intensity that other ion pair host molecules are added does not change significantly, but to system
Middle addition F-When, the fluorescence intensity of system drastically declines, and it is very big to reduce degree.Such ion coexists experiment and shows main body point
Son is to F-It with stronger recognition specificity, has good selectivity, is hardly influenced by other coexisting ions.
Embodiment 7
Reaction time detects F to the fluorescence probe that embodiment 1 obtains-Influence.
A 10mL volumetric flask is taken, 1mL host molecules mother liquor is pipetted with 1mL pipettes and is pipetted with microsyringe
0.2mL F-Into volumetric flask, constant volume then is carried out with DMSO, and carry out fluorometric investigation rapidly.Since 0.5min, and
1.5min, 3min, 4min, 6min, 7min, 8min, 10min, 12min, 15min time with carried out under above-mentioned the same terms it is glimmering
Optical tests extend reaction time fluorescent quenching degree and tend towards stability substantially state, see Fig. 3.
Embodiment 8
The fluorescence intensity and F for the probe that embodiment 1 obtains-The linear relationship of concentration.
In a natural environment, the F of different low concentrations is taken-, with Fluorescence Spectrometer, obtain a working curve, such as Fig. 4, knot
Fruit shows the fluorescence intensity of solution 2.0 × 10-6Mol/L to 2.0 × 10-5It is in a linear relationship in the range of mol/L, to F-Inspection
Survey is limited to 3.5 × 10-6mol/L。(R2=0.99072)
Embodiment 9
Probe molecule and F-Fluorescent ultraviolet titration
It is glimmering by being carried out in DMSO solution as shown in Fig. 5-a in order to further study the complexation property between Subjective and Objective
Light titration experiments, when excitation wavelength is 387nm, probe molecule itself has stronger fluorescence, molten by the DMSO in probe
The F of various concentration is added in liquid-, with F-Concentration be continuously increased, the fluorescent emission intensity at 481nm is gradually reduced, to visit
Needle molecule is to F-Show on-off responses.
It equally also studied the ultraviolet-visible absorption drop for the fluorine ion that different equivalents are added in the DMSO solution of probe
Fixed experiment, as shown in Fig. 5-b, with F-Concentration gradually increases, and absorption intensity of the probe molecule at 366nm gradually weakens, companion
With going out a new absorption peak in 475nm red shifts, and there is a new isobestic point in 400nm or so, illustrates
Titration process in there is new complex compound, and with F-Concentration gradually increases, and the absorption peak strength that red shift goes out gradually increases
By force, work as F-When concentration increases to 100 times of the concentration of probe molecule, ultraviolet-visible spectral absorption intensity tends towards stability.Illustration
It indicates under natural light, can with the naked eye observe F-Addition solution can be caused to become crocus by colourless moment,
Has the function of bore hole identification.
Claims (9)
1. a kind of cup [4] thiocarbamide cumarin chemical sensor, it is characterised in that:The chemical sensor has following structure:
2. a kind of preparation method of cup as described in claim 1 [4] thiocarbamide cumarin chemical sensor, it is characterised in that:Institute
Stating preparation method, steps are as follows:
(1) cup [4] aromatic hydrocarbons is sloughed to the tertiary butyl of upper edge by Fu Ke back reactions, the phenolic hydroxyl group of lower edge is carried out by n-butyl bromide
Full etherificate, obtains exposed upper edge cup [4] aromatic hydrocarbons;
(2) exposed upper edge cup [4] aromatic hydrocarbons in step (1) is dissolved in dichloromethane, upper edge is carried out by nitric acid and acetic acid
Nitrification modification, then nitration product is reduced to amino by hydrazine hydrate and Raney-Li, it is filtered to remove reducing agent, uses dichloromethane
Washing, revolving obtain 5,17- diamino -25,26,27,28- tetra-n-butyl cup [4] aromatic hydrocarbons;
(3) 7- amino -4- trifluoromethyl cumarins are dissolved in dichloromethane, then react, passes through at room temperature with thiophosgene
Remaining thiophosgene extraction system is obtained 7- isothiocyano -4- trifluoromethyl cumarins by vacuum pump;
(4) 5,17- diamino -25,26,27,28- tetra-n-butyls cup [4] aromatic hydrocarbons that step (2) obtains is dissolved in dichloromethane
In, the 7- isothiocyano -4- trifluoromethyl cumarins that step (3) obtains then are added, cup [4] thiocarbamide perfume is obtained by the reaction at room temperature
Legumin fluorescence probe.
3. the preparation method of cup [4] thiocarbamide cumarin chemical sensor as claimed in claim 2, it is characterised in that:Step (1)
Described cup [4] aromatic hydrocarbons is heated to reflux is condensed to yield under alkaline condition using p-tert-butylphenol and formaldehyde as raw material.
4. the preparation method of cup [4] thiocarbamide cumarin chemical sensor as claimed in claim 2, it is characterised in that:Step (2)
The quality of the nitration product is 1 with the volume ratio of hydrazine hydrate and Raney-Li:3:3.
5. the preparation method of cup [4] thiocarbamide cumarin chemical sensor as claimed in claim 2, it is characterised in that:Step (2)
The volume ratio of the nitric acid and acetic acid is 1:2.
6. the preparation method of cup [4] thiocarbamide cumarin chemical sensor as claimed in claim 2, it is characterised in that:Step (3)
The molar ratio of the 7- amino -4- trifluoromethyls cumarin and thiophosgene is 1:3.
7. the preparation method of cup [4] thiocarbamide cumarin chemical sensor as claimed in claim 2, it is characterised in that:Step (4)
5,17- diamino -25,26,27,28- tetra-n-butyls cup [4] aromatic hydrocarbons and 7- isothiocyano -4- trifluoromethyl cumarins
Molar ratio be 1:2-3.
8. a kind of application of cup as described in claim 1 [4] thiocarbamide cumarin chemical sensor, it is characterised in that:The cup
[4] thiocarbamide cumarin chemical sensor is used as detection F-Fluorescence probe.
9. the application of cup [4] thiocarbamide cumarin chemical sensor as claimed in claim 8, it is characterised in that:The chemistry passes
Sensor detects F-Method be:10mL volumetric flasks are taken, prepare the DMSO solution of fluorescence probe, a concentration of 2 × 10-5Mol/L is holding
The F of various concentration is added in measuring bottle-It uses DMSO constant volumes to 10mL afterwards, shakes up, after placing 30min at room temperature, with fluorescence spectrophotometer light
Degree meter, using 387nm as excitation wavelength, slit 5/5nm, 481nm are that launch wavelength tests fluorescence intensity, and test obtains corresponding
Fluorescence intensity.
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CN109655436A (en) * | 2018-12-07 | 2019-04-19 | 武汉工程大学 | Cryanide ion fluorescence detection test of a kind of column aromatic hydrocarbons modification and preparation method thereof, detection method |
CN109655436B (en) * | 2018-12-07 | 2021-03-30 | 武汉工程大学 | Column aromatic modified cyanide ion fluorescence detection test paper, and preparation method and detection method thereof |
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