CN104311450B - The bis-Schiff base sensor of a kind of monitoring copper ion capable of circulation and synthesis thereof and application - Google Patents
The bis-Schiff base sensor of a kind of monitoring copper ion capable of circulation and synthesis thereof and application Download PDFInfo
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Abstract
The present invention designs the bis-Schiff base sensor having synthesized a kind of detection copper ion capable of circulation, belongs to cation detection field.This sensor is at DMSO H2Can be to Cu in O system2+Carry out high selective colorimetric fluorescence identifying: i.e. when adding Cu in system2+Time, color and the fluorescence of system all change significantly, and add color and the fluorescence to system of other cation all have no significant effect.It addition, as the DMSO H of sensor2O system adds Cu2+Solution, adds H2PO4 ‑Time, the fluorescence of system recovers again (5 times the most capable of circulation), and therefore, bis-Schiff base sensor is the Cu of a kind of good reusable edible2+Sensor.For the ease of quickly detecting copper ion, bis-Schiff base sensor load is fabricated to copper ion test paper on test paper by the present invention.
Description
Technical field
The invention belongs to cation detection field, relate to a kind of copper ion acceptor compound；Particularly relate to the bis-Schiff base sensor of a kind of high selective colorimetric-fluorescence binary channels identification copper ion.The present invention also relates to the synthesis of this copper ion bis-Schiff base sensor and the application in identifying copper ion.
Background technology
Metal cation plays special effect in the metabolic process of organism, and it is to complete under the control combining respective egg white matter in the transmission of intraor extracellular.Ca2+, Mg2+Deng play critically important role in nerve conduction, cell signaling processes, and a series of severe toxicity heavy metals such as lead in metal, mercury, cadmium are widely used in industrial process stream, and they are mostly eventually converted into cation and are discharged into nature.These heavy metal ion can be got up by enrichment in biological tissue by food chain, cation free in being converted into human body cell, also plays an important role, thus Man & Nature circle are caused tremendous influence in biological physiology course.Therefore, it is possible to effectively suffer from great meaning at these metal cations of intracellular detection for biochemistry, environmental science and medical science etc..
In numerous transition metal ions, copper is a kind of required trace element in human body, is also heavy metal element.Cu2+Excess, is possible not only to pollute environment, if too much at people's cylinder accumulation, can cause the most serious disease.In consideration of it, copper ion conveniently detects the extensive concern causing people, and constantly inquire into its detection method.
In numerous cations recognition systems, schiff bases is the host molecule that a class is critically important.Schiff bases is the compounds that a class contains imido grpup (C=N).Research shows, schiff bases and complex thereof have important effect in fields such as spectroscopy, Coordinative Chemistry, analytical chemistry.But, the application for schiff bases Selective recognition copper ion has not yet to see report.
Summary of the invention
It is an object of the invention to provide a kind of can the bis-Schiff base sensor of high selective colorimetric-fluorescence identifying copper ion；
It is a further object of the present invention to provide the synthetic method of the ion bis-Schiff base sensor of a kind of above-mentioned colorimetric-fluorescence identifying copper；
A further object of the invention is just to provide the concrete application of above-mentioned colorimetric-fluorescence identifying copper ion bis-Schiff base sensor.
One, bis-Schiff base sensor and synthesis thereof
Ion bis-Schiff base sensor (L) of colorimetric of the present invention-fluorescence binary channels identification copper, its structural formula is as follows:
The synthesis of bis-Schiff base sensor: solvent made by absolute ethyl alcohol, glacial acetic acid is made catalyst, 2-hydroxyl-1-naphthalene Formaldehyde and the adjacent first benzidine mol ratio with 1.5:1 ~ 1.0:1, is reacted 10～12h, obtain yellow solid at 85～90 DEG C.
The consumption of catalyst glacial acetic acid is the 1.5～2.0% of adjacent first benzidine mole.
The sign data of above-mentioned synthetic product are as follows:
(m.p.>300℃),1HNMR(DMSO-d6,400MHz)δ15.81(d 2H,OH),δ9.39(d 2H,-CH=N),
8.19~8.22(d 2H,Ar) 7.59~7.69(m 4H,ArH)7.70~7.47 (m 6H,Ar) 7 .20~7.22 (m 2H,Ar)
7.00~7.04(m 2H,Ar) 6.66~6.69(m2H,Ar)δ2.18(s6H,-CH3).IR(KBr,cm-1)v:3730(
OH), 3030 (=C-H), 1618 (-C=N), 1327 (CH3), 746 (Ar-H), Anal. Calcd. for
C36H28N2O2: C 83.05, H 5.42; N 5.38,O 6.15. Found: C 83.01, H 5.42; N 5.40,O
6.17.ESI-MS m/z (M+H)+ Calcd for C36H28N2O2521.20;Found521.208。
Two, the performance of bis-Schiff base sensor identification copper ion
1. the ultraviolet colorimetric identification of pair cation
L DMSO is made into 2 × 10-4The bulk solution of mol L；Take the bulk solution of 0.5mL respectively in 13 colorimetric cylinders, be separately added into the different cation (Fe of 0.25mL3+, Hg2+, Ag+, Ca2+, Cu2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, Mg2+) the DMSO solution (10eqv) of perchlorate, sequentially add 1mLpH=7.2 cushioning liquid (with the water of the pH=7.2 that 4-HEPES becomes), finally with DMSO constant volume to 5mL, standing after mixing with TBAH regulating allocation.Now the concentration of sensor is 2 × 10-5Mol/L, the percentage by volume 20% of water in system.Found that: only Cu2+Addition make the color of bulk solution become light green from yellow, and the addition of other cation, make the color of bulk solution become Chinese red from yellow.In corresponding uv-vis spectra, Cu2+Addition make bulk solution occur in that obvious blue shift respectively at 450nm, and the ultraviolet spectra to bulk solution that adds of other cation has no significant effect (see figure 1).Illustrate that bis-Schiff base sensor L can colorimetric detection Cu in the DMSO mixed system with water2+。
2, ultraviolet titration
Below by UV Vis titration experimental study sensor L and the binding constant of copper ion.L DMSO is made into 2 × 10-4The bulk solution of mol L, adds 2mL cushioning liquid (with the water of the pH=7.2 that 4-HEPES becomes with TBAH regulating allocation), with DMSO constant volume to 10mL, shakes up standing.Add the DMSO solution of the perchlorate of copper ion.Find that ultraviolet spectra peak at 480nm is gradually reduced, and the peak at 425nm gradually rises along with in system, copper ion concentration is gradually increased.There is obvious blue shift in peak, meanwhile, 350, occurs in that 3 isobestic points at 380,440nm, shows that this titration process defines stable complex compound (see Fig. 2, wherein illustration is to go out, at 486nm, the scatter diagram that absorbance reduces).From Fig. 2 can be clear and definite find out L and Cu2+Coordination ratio be 1:2.
3, the fluoroscopic examination identification to cation
L DMSO is made into 2 × 10-4The bulk solution of mol L；Take the bulk solution of 0.5mL respectively in 13 colorimetric cylinders, be separately added into the different cation (Fe of 0.25mL3+, Hg2+, Ag+, Ca2+, Cu2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, Mg2+) the DMSO solution (50eqv) of perchlorate, sequentially add 1mLpH=7.2 cushioning liquid (with the water of the pH=7.2 that 4-HEPES becomes) with TBAH regulating allocation, finally use DMSO constant volume is to 5mL.Then with the ultra violet lamp of 365nm, Fe is found3+, Hg2+, Ag+, Ca2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, Mg2+Add on the fluorescence of L all without affecting, and Cu2+After addition, the complete quencher of strong green fluorescence of bulk solution.Meanwhile, by fluorescent emission figure (Fig. 3) it can be seen that bulk solution adds Cu2+, its hyperfluorescence emission peak at 530nm disappears, and adds remaining cation, and it all occurs the strongest emission peak at 530nm.Illustrate that sensor L can be at DMSO(aqueous 20%) in the most single-minded sensitive detection Cu2+。
4, the mensuration of LDL
When 25 DEG C, utilize uv-vis spectra, according to Cu2+Titration experiments to receptor solution, passes through 3sB/ S calculates, and available L is to Cu2+LDL reach 7.25 × 10-8 mol·L-1 。
5, fluorescence interference--free experiments
Fig. 4 is acceptorL (2×10-4 mol·L-1) in DMSO (aqueous 20%) solution to Cu2+The anti-interference figure of fluorescence of ion.As seen from Figure 4, acceptor L identifies Cu2+Do not affected by other ions, therefore anti-interference energy is fabulous, shown that acceptor L can be in the presence of other coexisting ion, interference-free high selective enumeration method Cu2+。
6, reusable edible performance
In order to study acceptor L and Cu2+In conjunction with situation, further it is carried out fluorescence titration and probe into.Along with Cu2+Be gradually added into, at 530nm, fluorescence emission peak is gradually lowered, finally, as the Cu adding 14 equive2+Time, this emission peak is wholly absent.When to the Cu adding 14 equive2+ Solution in add the H of 28 equive2PO4 -Time, fluorescence recovers again, so energy well reciprocation cycle 5 times (Fig. 5), and therefore, L is the Cu of a kind of good reusable edible2+Sensor.
Great many of experiments shows, at DMSO-H2In O system, H2The percentage by volume of O is when 15 ~ 20%, and bis-Schiff base sensor L is at DMSO-H2O system can realize the fluorescence to copper ion-colorimetric recognition performance.
Three, Cu2+Test paper and application
For the ease of detection Cu2+, we are prepared for being loaded with sensor L and L-Cu2+Test paper: the filter paper watery hydrochloric acid of 0.5 mol/L is soaked 1 hour, then washs repeatedly, till filter liquor is neutrality with distilled water.L DMSO is made into 2 × 10-3The bulk solution of mol/L, is added drop-wise on the filter paper of above-mentioned process, makes the DMSO solution uniform adsorption of L on filter paper；It is subsequently placed in vacuum drying chamber and is dried, obtain being loaded with the test paper of sensor L.This Test paper is under visible light in crocus, in green under 365nm uviol lamp.Dropping Cu2+After, this Test paper under visible light in light green, fluorescent quenching under uviol lamp；After dripping other cation, test paper color is basically unchanged.
Accompanying drawing explanation
Fig. 1 isL (2×10-4 mol·L-1) ultraviolet-visible absorption spectroscopy figure to cation in DMSO (aqueous 20%) solution；Fig. 2 isL (2×10-4 mol·L-1) in DMSO (aqueous 20%) solution and solution to Cu2+The ultraviolet titration figure of ion.
Fig. 3 isL (2×10-4 mol·L-1) fluorescent emission figure to cation in DMSO (aqueous 20%) solution.
Fig. 4 acceptorL (2×10-4 mol·L-1) in DMSO (aqueous 20%) solution to Cu2+The anti-interference figure of fluorescence of ion.
Fig. 5 acceptorL (2×10-4 mol·L-1) in DMSO (aqueous 20%) solution to Cu2+- H2PO4 -The fluorescence of ion opens the light figure.
Detailed description of the invention
To structure, the synthesis of inventive sensor L below by specific embodiment and copper ion is detected recognition methods, the preparation of Test paper and application it is described in detail.
1, the synthesis of sensor molecule L
Weighing 0.48g(2.4mmol) 2-hydroxyl-1-naphthalene Formaldehyde is placed in the round-bottomed flask of 100mL, add 40mL absolute ethyl alcohol and make solvent, it is slowly added to 0.45g(2mmol under stirring) adjacent first benzidine, catalyst made by 1mL glacial acetic acid, 30min is stirred under room temperature, it is subsequently placed in 85 DEG C of oil bath pans backflow 12h, obtains yellow solid 1.06g.Productivity 80%.
2, the preparation of Test paper
Filter paper is cut into the square of 8 cm × 8 cm, with 0.5 mol L-1Watery hydrochloric acid soak 1 hour.After distilled water washing repeatedly, limit suction strainer limit distilled water washs on a buchner funnel, till filter liquor is neutrality.Suction strainer removes water, is placed in vacuum drying chamber by washed filter paper and is dried.Being dissolved in DMSO solution by sensor L, being configured to concentration is 2.0 × 10-4 mol·L-1DMSO solution.The filter paper handled well is lain against in 10cm plate, drip DMSO solution with dropper in the center of filter paper, make filter paper uniform adsorption DMSO solution.It is placed in vacuum drying chamber dried, is cut into the test strips of 0.5 cm × 4 cm, be placed in containers for future use clean, that be dried.This Test paper is under visible light in crocus, in green under 365nm uviol lamp.
3, the detection of copper ion
By Fe3+, Hg2+, Ag+, Ca2+, Cu2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, Mg2+DMSO(2 × 10 of perchlorate-4 mol·L-1) be added drop-wise to respectively on copper ion test paper.Under visible light, if test paper color is become light green from crocus, under the uviol lamp of 365nm, test paper color is by green to fluorescent quenching, and that dropping is described is Cu2+；If test paper color color under the ultraviolet of visible ray and 365nm does not all have significant change, then explanation dropping room temperature is other cation.
Claims (7)
1. the bis-Schiff base sensor molecule of a detection copper ion capable of circulation is at DMSO-H2O system detects the application of copper ion, it is characterised in that: the structural formula of the bis-Schiff base sensor molecule of described detection copper ion capable of circulation is as follows:
。
The bis-Schiff base sensor molecule of detection copper ion capable of circulation the most as claimed in claim 1 is at DMSO-H2O system detects the application of copper ion, it is characterised in that: at DMSO-H2In O system, only Cu2+Addition make the color of system become light green from yellow, and Fe3+, Hg2+, Ag+, Ca2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, Mg2+Addition, make the color of system become Chinese red from yellow.
The bis-Schiff base sensor molecule of detection copper ion capable of circulation the most as claimed in claim 2 is at DMSO-H2O system detects the application of copper ion, it is characterised in that: at DMSO-H2In O system, only Cu2+Addition make the complete quencher of fluorescence of system, and Fe3+, Hg2+, Ag+, Ca2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, Mg2+Add the fluorescence of system had no significant effect.
4. as described in claim 1-3 the bis-Schiff base sensor molecule of detection copper ion capable of circulation at DMSO-H2O system detects the application of copper ion, it is characterised in that: DMSO-H2In O system, H2The percentage by volume of O is 15 ~ 20%.
The bis-Schiff base sensor molecule of detection copper ion capable of circulation the most as claimed in claim 1 is at DMSO-H2O system detects the application of copper ion, it is characterised in that: it is prepared as being loaded with the Test paper of the bis-Schiff base sensor of described detection copper ion capable of circulation.
The bis-Schiff base sensor molecule of detection copper ion capable of circulation the most as claimed in claim 5 is at DMSO-H2O system detects the application of copper ion, it is characterised in that: by Fe3+, Hg2+, Ag+, Ca2+, Cu2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, Mg2+Being added drop-wise on Test paper respectively, if test paper color is become light green from crocus under visible light, that dropping is described is Cu2+；If test paper color does not has significant change, then explanation dropping is other cation.
The bis-Schiff base sensor molecule of detection copper ion capable of circulation the most as claimed in claim 5 is at DMSO-H2O system detects the application of copper ion, it is characterised in that: by Fe3+, Hg2+, Ag+, Ca2+, Cu2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, Mg2+Being added drop-wise on Test paper respectively, if the color that test paper is under uviol lamp is become fluorescent quenching from the strongest green fluorescence, that dropping is described is Cu2+；If test paper color does not has significant change under ultraviolet, then explanation dropping is other cation.
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| CN104914079A (en) * | 2015-05-08 | 2015-09-16 | 西北师范大学 | Two-sided Schiff base sensor, synthesis method thereof, and application thereof in fluorescent colorimetric continuous identification of Cu<2+> and H<2>PO<4><-> |
| CN104961647A (en) * | 2015-06-26 | 2015-10-07 | 西北师范大学 | Fluorescent recognition cupper ion (CU2+) sensor molecules and composition and application thereof |
| CN105044061A (en) * | 2015-07-25 | 2015-11-11 | 渤海大学 | High-selectivity method for detecting p-phenylenediamine in aqueous solution |
| CN105694866B (en) * | 2016-04-01 | 2017-09-29 | 齐齐哈尔大学 | Symmetric form phenanthro- imidazoles Fe3+ fluorescence probes of double-Schiff base link and preparation method thereof |
| CN107827775A (en) * | 2017-11-20 | 2018-03-23 | 西北师范大学 | A kind of sensor molecule for being capable of colorimetric fluorescence cycle detection copper ion and its preparation and application |
| CN113403062B (en) * | 2021-06-18 | 2023-03-14 | 广东药科大学 | Molecular imprinting ratio fluorescent probe and fluorescent test paper for visually detecting quintozene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159682A (en) * | 2013-04-09 | 2013-06-19 | 西北师范大学 | 2-aminobenzimidazole Schiff base based cyanide receptor compound and preparation and applications thereof |
| CN103992292A (en) * | 2014-04-18 | 2014-08-20 | 西北师范大学 | Schiff base sensor molecule, its synthesis, and its application in fluorescent colorimetric detection of CN<-> in water |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159682A (en) * | 2013-04-09 | 2013-06-19 | 西北师范大学 | 2-aminobenzimidazole Schiff base based cyanide receptor compound and preparation and applications thereof |
| CN103992292A (en) * | 2014-04-18 | 2014-08-20 | 西北师范大学 | Schiff base sensor molecule, its synthesis, and its application in fluorescent colorimetric detection of CN<-> in water |
Non-Patent Citations (2)
| Title |
|---|
| Chelates and corrosion inhibition of newly synthesized Schiff bases derived from o-tolidine;Ali M. Ali等;《Transition Metal Chemistry》;20071231;第32卷(第4期);第461页右栏第2-3段 * |
| Poly(Schiff base)s Containing 1,1-Binaphthyl Moieties: Synthesis and Characterization;Mircea Grigoras等;《Macromol. Chem. Phys.》;20011231;第202卷;第2262-2266页 * |
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